Shape memory polyarylene ether nitrile composite material with cross-linked amino side chain as well as preparation method and application of shape memory polyarylene ether nitrile composite material

Abstract

The invention belongs to the field of shape memory of high polymer materials, and particularly relates to an amino side chain cross-linked shape memory polyarylene ether nitrile composite material as well as a preparation method and application of the amino side chain cross-linked shape memory polyarylene ether nitrile composite material. The preparation method of the composite material comprises the following steps: in an inert gas atmosphere, enabling a monomer containing a bisphenol group, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, a water-carrying agent, an organic solvent, 2, 6-dihalobenzonitrile and a salt-forming agent to form a reaction system, so as to prepare a polyarylene ether nitrile copolymer with an amino side chain; and adding the obtained poly (arylene ether nitrile) copolymer and a monomer containing a terminal carboxyl group into an N, N-dimethylformamide solvent, adding a dehydrating agent, uniformly stirring to obtain a blend, stirring at 40-60 DEG C to enable the amino group and the carboxyl group to be subjected to dehydration, polycondensation and cross-linking, and synthesizing the shape memory poly (arylene ether nitrile) composite material with amino side chain cross-linking. The composite material has good mechanical properties and thermal stability, and also has a toughening function.

Description

Technical Field

[0001] The invention belongs to the field of shape memory polymer materials, and in particular relates to a shape memory polyarylethernitrile composite material with amino side chain cross-linking, and a preparation method and application thereof. Background Art

[0002] Shape memory polymers, as a unique type of stimulus-responsive smart materials, can exhibit responsive deformation capabilities according to changes in the external environment and the stimuli they receive. This property makes shape memory polymers show great potential in a variety of application scenarios, such as in adaptive structures, smart drives, biomedical devices, and sensors. By carefully designing and regulating their chemical composition and microstructure, the performance of shape memory polymers can be further optimized to meet the specific needs of different fields. However, the shape memory polymer materials currently widely used have deficiencies in mechanical strength and thermal stability, which seriously restricts their application potential in specific fields such as engineering manufacturing and aerospace. Therefore, the development of new shape memory polymers with high strength and high heat resistance is of great significance for promoting the application of such materials in the fields of spatial deformable components, load-bearing structural parts, and engineering intelligent drive devices.

[0003] Polyarylethernitrile, as a class of thermoplastic polyarylether compounds containing a large number of aromatic rings, ether bonds and pendant cyanide groups, has abundant benzene rings and ether oxygen bonds on its molecular chain, which endows it with many excellent properties such as high strength, high temperature resistance, flame retardancy, corrosion resistance, easy processing and insulation. These comprehensive properties make polyarylethernitrile highly regarded in the field of engineering applications. However, the rigid structure of the main chain of polyarylethernitrile leads to its insufficient toughness, high brittleness and poor deformation ability, which seriously limits its application range in real life. Therefore, how to improve the flexibility and deformation ability of polyarylethernitrile while maintaining its original mechanical properties, and then give it shape memory properties to expand its wide application in the field of smart materials, has become a research topic of great significance. Summary of the invention

[0004] The invention provides a shape memory polyarylethernitrile composite material with amino side chain crosslinking, a preparation method and application thereof. The composite material has good mechanical properties and thermal stability and also has a toughening function.

[0005] The present invention is achieved through the following technical solutions: In a first aspect, the present invention provides a shape memory poly(arylether nitrile) composite material having amino side chain crosslinking, wherein the composite material is obtained by polymerizing a monomer containing a bisphenol group, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,6-dihalobenzonitrile and a monomer containing a terminal carboxyl group to obtain a structure of formula (I); Formula (I): , Wherein, n is an integer between 80 and 100; the molecular weight of Ar2 is 2000-4000; The -Ar1- can be selected from the following structures: , , , or ; The -Ar2- may optionally have the following structure: , , or .

[0006] Furthermore, in a preferred embodiment of the present invention, the molar ratio of the above-mentioned monomer containing bisphenol groups to 2,2-bis(3-amino-4-hydroxyphenyl)propane is 7:3 to 9:1.

[0007] Furthermore, in a preferred embodiment of the present invention, the glass transition temperature of the poly(arylene ether nitrile) composite material is 100-120° C., and the tensile strength is 55-75 MPa.

[0008] Furthermore, the composite material is first synthesized from monomers containing bisphenol groups, 2,2-bis(3-amino-4-hydroxyphenyl)propane and 2,6-dihalobenzonitrile to obtain a polyarylethernitrile copolymer having amino side chains; and then the polyarylethernitrile copolymer and the monomer containing terminal carboxyl groups are polymerized under the action of a dehydrating agent to obtain a shape memory polyarylethernitrile composite material having amino side chain crosslinks.

[0009] In a second aspect, the present invention provides a method for preparing a shape memory poly(arylene ether nitrile) composite material having amino side chain crosslinking, characterized in that the method comprises the following steps: S1: Under an inert gas atmosphere, a monomer containing a bisphenol group, 2,2-bis(3-amino-4-hydroxyphenyl)propane, a water-carrying agent, an organic solvent, 2,6-dihalobenzonitrile and a salt-forming agent are formed into a reaction system to prepare a polyarylethernitrile copolymer having an amino side chain; S2: Add the obtained polyarylethernitrile copolymer and the monomer containing terminal carboxyl group to N,N-dimethylformamide solvent, add dehydrating agent and stir to obtain a blend, stir at 40-60°C to dehydrate and polycondense the amino group and the carboxyl group to crosslink, and synthesize a shape memory polyarylethernitrile composite material with amino side chain crosslinking.

[0010] Furthermore, in a preferred embodiment of the present invention, a method for preparing a polyarylethernitrile composite material comprises the following steps: (a) in a nitrogen atmosphere, a monomer containing a bisphenol group, 2,2-bis(3-amino-4-hydroxyphenyl)propane, a water-carrying agent, an organic solvent and a salt-forming agent are uniformly mixed to form a reaction system; (b) heating the reaction system and repeatedly performing a dehydration treatment during the heating process until a bisphenolate is formed; (c) After the bisphenolate is fully formed, the system is cooled; after the temperature is cooled to 100-120° C., 2,6-dihalobenzonitrile is added to the system, and then the temperature is slowly increased to 160-170° C. to allow the system to fully react and obtain a viscous polymer solution; (d) pouring the obtained viscous polymer solution into deionized water, repeatedly washing to remove impurities, and then drying to finally obtain a polyarylene ether nitrile copolymer having an amino side chain; (e) Adding the obtained polyarylether nitrile copolymer and the monomer containing terminal carboxyl groups to N, N-dimethylformamide solvent, and continuously adding a dehydrating agent, stirring evenly to obtain a blend, and then stirring the blend at a temperature of 40-60° C. to allow the amino groups and carboxyl groups to fully dehydrate and polycondense to crosslink, and after drying, synthesizing a shape memory polyarylether nitrile composite material having amino side chain crosslinking.

[0011] Furthermore, in a preferred embodiment of the present invention, the above-mentioned monomer containing a bisphenol group is selected from bisphenol AF, bisphenol A, resorcinol, hydroquinone, biphenol or 4,4'-dihydroxydiphenyl ether.

[0012] More preferably, the above-mentioned monomer containing a bisphenol group is selected from bisphenol AF, bisphenol A or hydroquinone; more preferably, the monomer containing a bisphenol group is selected from bisphenol AF.

[0013] Furthermore, in a preferred embodiment of the present invention, the above-mentioned monomer containing a terminal carboxyl group is selected from carboxyl-terminated polybutadiene, dicarboxyl polyethylene glycol, carboxyl-terminated polyester or carboxyl-terminated polyether.

[0014] Furthermore, the carboxyl-terminated polyester comprises carboxyl-terminated polycaprolactone, carboxyl-terminated polylactic acid or carboxyl-terminated polyethylene glycol sebacate.

[0015] Furthermore, the carboxyl-terminated polyether includes carboxyl-terminated polyethylene oxide, carboxyl-terminated polypropylene glycol or polypropylene glycol dicarboxylate.

[0016] More preferably, the above-mentioned monomer containing a terminal carboxyl group is selected from terminal carboxyl polybutadiene or dicarboxyl polyethylene glycol.

[0017] More preferably, the above-mentioned monomer containing a terminal carboxyl group is selected from terminal carboxyl polybutadiene.

[0018] Further, in a preferred embodiment of the present invention, the organic solvent is one or more of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, and sulfolane; The water-carrying agent is toluene or xylene; The salt-forming agent is at least one of anhydrous potassium carbonate, potassium hydroxide, sodium carbonate and sodium hydroxide; The dehydrating agent is N,N'-dicyclohexylcarbocyanine.

[0019] Further, in a preferred embodiment of the present invention, the amount of the above organic solvent is 4-6 times the total mass of the monomer containing bisphenol groups and 2,2-bis(3-amino-4-hydroxyphenyl)propane; The amount of the salt-forming agent is 1-2 times the molar number of 2,6-dihalobenzonitrile; The volume ratio of the water-carrying agent to the organic solvent is 3-4:10.

[0020] Furthermore, in a preferred embodiment of the present invention, the amount of the carboxyl-terminated monomer added in the above step S2 is 5%-30% of the mass of the poly(arylene ether nitrile) copolymer.

[0021] In a third aspect, the present invention provides an application of a shape memory poly(arylethernitrile) composite material having amino side chain crosslinking, wherein the application includes application in the fields of aerospace, medical equipment, electronic equipment or smart textiles.

[0022] Compared with the prior art, the present invention has at least the following technical effects: The shape memory poly(arylethernitrile) composite material with amino side chain crosslinking provided by the present invention adopts a poly(arylethernitrile) prepolymer with side chain amino functionalization and a difunctional carboxyl-terminated flexible chain segment to carry out a controllable amidation reaction through a solution polycondensation method to construct a three-dimensional crosslinked network system with phase separation characteristics; in the system, the physical crosslinking points formed by the rigid poly(arylethernitrile) main chain and the amide bond together constitute a fixed phase, giving the material a stable permanent shape; and the flexible chain segment with a low glass transition temperature serves as a reversible phase, giving the material an excellent shape memory effect.

[0023] The present invention provides a method for preparing a shape memory polyarylether nitrile composite material with amino side chain crosslinking, wherein the composite material is prepared by a nucleophilic polycondensation reaction, wherein an amide bond is formed by dehydration polycondensation of an amino group and a carboxyl group, and a polyarylether nitrile containing an amino side chain is free radical polymerized with a carboxyl-terminated monomer to construct a three-dimensional crosslinked network, thereby obtaining a composite material with good mechanical properties and thermal stability. In addition, the combination of the polyarylether nitrile containing an amino side chain and a carboxyl-terminated monomer can increase the crosslinking density of the polyarylether nitrile polymer, thereby ensuring that the material has good mechanical properties and thermal stability, and also has a toughening function.

[0024] The shape memory poly(arylethernitrile) composite material with amino side chain crosslinking provided by the present invention has high shape fixation rate, fast recovery rate and wide temperature range response characteristics, and has potential application value in the fields of petroleum engineering, aerospace, biomedical equipment and flexible electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The infrared spectra of the polyarylethernitrile composite material of Comparative Example 1 and the shape memory polyarylethernitrile composite material of Example 1; Figure 2 is a stress-strain curve diagram of the poly(arylene ether nitrile) composite material of Example 1; Figure 3 is a stress-strain curve diagram of the poly(arylene ether nitrile) composite material of Example 2; Figure 4 is a stress-strain curve diagram of the poly(arylene ether nitrile) composite material of Example 5; Figure 5 is a stress-strain curve diagram of the poly(arylene ether nitrile) composite material of Comparative Example 1; Figure 6 is a stress-strain curve diagram of the polyarylethernitrile composite material of comparative example 2; Figure 7 This is a thermogravimetric analysis diagram of the poly(arylene ether nitrile) composite material of Example 1; Figure 8 This is a thermogravimetric analysis diagram of the poly(arylene ether nitrile) composite material of Example 5; Fig. 9 is a differential scanning calorimetry diagram of the poly(arylene ether nitrile) composite material of Example 1; Fig.10 is a differential scanning calorimetry diagram of the poly(arylene ether nitrile) composite material of Example 5; Fig.11 This is a macroscopic shape memory test diagram of the poly(arylene ether nitrile) composite material of Example 1; Fig.12 This is a macroscopic shape memory test diagram of the poly(arylene ether nitrile) composite material of Example 5; DETAILED DESCRIPTION The embodiments of the present invention will be described in detail below in conjunction with examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. The specific conditions not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased commercially.

[0026] The abbreviation for 2,2-bis(3-amino-4-hydroxyphenyl)propane is BAP; N,N'-dicyclohexylcarbodiimide is abbreviated as DCC; The technical solution of the specific implementation mode of the present invention is: The present invention provides a method for preparing a shape memory poly(arylether nitrile) composite material having amino side chain crosslinking, comprising the following steps: S1: Under an inert gas atmosphere, a monomer containing a bisphenol group, 2,2-bis(3-amino-4-hydroxyphenyl)propane, a water-carrying agent, an organic solvent, 2,6-dihalobenzonitrile and a salt-forming agent are formed into a reaction system to prepare a polyarylethernitrile copolymer having an amino side chain; S2: Add the obtained polyarylethernitrile copolymer and the monomer containing terminal carboxyl group to N,N-dimethylformamide solvent, add dehydrating agent and stir to obtain a blend, stir at 40-60°C to dehydrate and polycondense the amino group and the carboxyl group to crosslink, and synthesize a shape memory polyarylethernitrile composite material with amino side chain crosslinking. Monomers containing terminal carboxyl groups must be flexible alkyl long chains with two carboxyl groups at the end positions. Carboxylic acids and amines form amide bonds in the presence of a dehydrating agent. The reaction conditions are mild, and the amino and carboxyl groups have strong reaction specificity, avoiding side reactions with other functional groups (such as cyano groups and ether bonds) to ensure the purity of the cross-linked network.

[0027] (a) under a nitrogen atmosphere, a monomer containing a bisphenol group, 2,2-bis(3-amino-4-hydroxyphenyl)propane, a water-carrying agent, an organic solvent and a salt-forming agent are uniformly mixed to form a reaction system; Wherein, the organic solvent is one or more of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, and sulfolane; The water-carrying agent is toluene or xylene; The salt-forming agent is at least one of anhydrous potassium carbonate, potassium hydroxide, sodium carbonate and sodium hydroxide; The amount of the organic solvent used is 4-6 times the total mass of the monomer containing the bisphenol group and 2,2-bis(3-amino-4-hydroxyphenyl)propane; The amount of the salt-forming agent is 1-2 times the molar number of 2,6-dihalobenzonitrile; The volume ratio of the aqueous agent to the organic solvent is 3-4:10.

[0028] (b) heating the reaction system and repeatedly performing a dehydration treatment during the heating process until the system temperature reaches 140-150° C.; within this temperature range, repeatedly performing a water-carrying operation with the aid of a water-carrying agent, and the water-carrying time is controlled to be 2-3 hours, thereby forming a bisphenol salt; (c) After the bisphenolate is fully formed, the system is cooled; after the temperature is cooled to 100-120° C., 2,6-dihalobenzonitrile is added to the system, and then the temperature is slowly increased to 160-170° C. to allow the system to fully react and obtain a viscous polymer solution; The above 2,6-dihalobenzonitrile is 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile.

[0029] (d) pouring the obtained viscous polymer solution into deionized water, repeatedly washing to remove impurities, and then drying to finally obtain a polyarylene ether nitrile copolymer having an amino side chain; (e) Adding the obtained polyarylether nitrile copolymer and the monomer containing terminal carboxyl groups to N, N-dimethylformamide solvent, continuing to add a dehydrating agent, stirring evenly to obtain a blend, and then stirring the blend at a temperature of 40-60° C. for 12-15 hours to allow the amino group and the carboxyl group to fully dehydrate and condense to crosslink, thereby synthesizing a shape memory polyarylether nitrile composite material with amino side chain crosslinking.

[0030] In the above step, the amount of the terminal carboxyl monomer added is 5%-30% of the mass of the polyarylethernitrile copolymer. The polarity of the amide bond is high and the intermolecular hydrogen bonding is strong. Therefore, the crosslinking degree is controlled by adjusting the ratio of the amino group and the carboxyl group, thereby optimizing the performance of the material. In addition, the material after amide bond crosslinking usually has a high tolerance to organic solvents and acid-base environments, and is suitable for harsh working environments.

[0031] The dehydrating agent is N,N'-dicyclohexylcarbodiimide (DCC). DCC is selected as the dehydrating agent because it has good solubility in N,N-dimethylformamide (DMF), ensuring the uniformity of the reaction system and avoiding uneven local cross-linking. Moreover, the use of DCC for dehydration at 40-60°C will not cause the degradation of the main chain of the polyarylethernitrile, completely ensuring the main chain structure of the polyarylethernitrile, and the monomer with the terminal carboxyl group must be a flexible alkyl long chain containing two carboxyl groups at the terminal position, so that a three-dimensional network structure with shape memory can be formed under the action of the dehydrating agent.

[0032] The amount of the dehydrating agent is 10%-20% of the added mass of the terminal carboxyl monomer.

[0033] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0034] Example 1 This embodiment prepares a shape memory poly(arylether nitrile) composite material having amino side chain crosslinking. (a) under a nitrogen atmosphere, 7.56 g of bisphenol AF, 0.65 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 10 ml of toluene, 30 ml of N-methylpyrrolidone and 4.2 g of anhydrous potassium carbonate as a salt-forming agent were mixed uniformly to form a reaction system; (b) heating the reaction system and repeatedly performing a dehydration treatment during the heating process until the system temperature reaches 145° C.; within this temperature range, repeatedly performing a water-carrying operation with the aid of a water-carrying agent, and the water-carrying time is controlled to be 2.5 hours, thereby forming a bisphenol salt; (c) After the bisphenolate is fully formed, the system is cooled; after cooling to 115° C., water and the water-carrying agent are removed, 3.48 g of 2,6-dihalobenzonitrile is added to the system, and then the temperature is slowly raised to 170° C. to allow the system to fully react, thereby obtaining a viscous polymer solution; (d) pouring the obtained viscous polymer solution into deionized water, repeatedly washing to remove impurities, and then drying to finally obtain a polyarylene ether nitrile copolymer having an amino side chain; (e) 1 g of the poly(arylene ether nitrile) copolymer obtained in step d and 0.1 g of carboxyl-terminated polybutadiene were added to 10 ml of N, N-dimethylformamide solvent, and 0.0105 g of a dehydrating agent was added, and the mixture was stirred to obtain a blend. The mixture was stirred and reacted at 40-60° C. for 15 h under a nitrogen atmosphere to allow the amino group and the carboxyl group to undergo dehydration and polycondensation for cross-linking. The resulting solution was poured into a mold and dried at 60° C. for 24 h to synthesize a shape memory poly(arylene ether nitrile) composite material having amino side chain cross-linking.

[0035] Example 2 This embodiment prepares a shape memory poly(arylether nitrile) composite material having amino side chain crosslinking. (a) under a nitrogen atmosphere, 7.56 g of bisphenol AF, 0.65 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 10 ml of toluene, 30 ml of N-methylpyrrolidone and 4.2 g of anhydrous potassium carbonate as a salt-forming agent were mixed uniformly to form a reaction system; (b) heating the reaction system and repeatedly performing a dehydration treatment during the heating process until the system temperature reaches 150° C.; within this temperature range, repeatedly performing a water-carrying operation with the aid of a water-carrying agent, and the water-carrying time is controlled to be 3 hours, thereby forming a bisphenol salt; (c) After the bisphenol salt is fully formed, the system is cooled; after cooling to 120° C., water and the water-carrying agent are removed, 3.48 g of 2,6-dihalobenzonitrile is added to the system, and then the temperature is slowly raised to 170° C. to allow the system to fully react, thereby obtaining a viscous polymer solution; (d) pouring the obtained viscous polymer solution into deionized water, repeatedly washing to remove impurities, and then drying to finally obtain a polyarylene ether nitrile copolymer having an amino side chain; (e) 1 g of the poly(arylene ether nitrile) copolymer obtained in step d and 0.2 g of the carboxyl-terminated polybutadiene were added to 10 ml of N, N-dimethylformamide solvent, and 0.021 g of a dehydrating agent was added, and the mixture was stirred to obtain a blend. The mixture was stirred and reacted at 60° C. for 14 h under a nitrogen atmosphere to allow the amino group and the carboxyl group to fully dehydrate and condense for cross-linking. The reaction solution was poured into a mold and dried at 60° C. for 25 h to synthesize a shape memory poly(arylene ether nitrile) composite material with amino side chain cross-linking.

[0036] Example 3 This embodiment prepares a shape memory poly(arylether nitrile) composite material having amino side chain crosslinking. (a) under a nitrogen atmosphere, 6.72 g of bisphenol AF, 1.3 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 10 ml of toluene, 30 ml of N-methylpyrrolidone and 4.2 g of anhydrous potassium carbonate as a salt-forming agent were mixed uniformly to form a reaction system; (b) heating the reaction system and repeatedly performing a dehydration treatment during the heating process until the system temperature reaches 150° C.; within this temperature range, repeatedly performing a water-carrying operation with the aid of a water-carrying agent, and the water-carrying time is controlled to be 2-3 hours, thereby forming a bisphenol salt; (c) After the bisphenol salt is fully formed, the system is cooled; after cooling to 120° C., water and the water-carrying agent are removed, 3.48 g of 2,6-dihalobenzonitrile is added to the system, and then the temperature is slowly raised to 170° C. to allow the system to fully react, thereby obtaining a viscous polymer solution; (d) pouring the obtained viscous polymer solution into deionized water, repeatedly washing to remove impurities, and then drying to finally obtain a polyarylene ether nitrile copolymer having an amino side chain; (e) 1 g of the poly(arylene ether nitrile) copolymer obtained in step d and 0.2 g of the carboxyl-terminated polybutadiene were added to 10 ml of N, N-dimethylformamide solvent, and 0.021 g of a dehydrating agent was added, and the mixture was stirred to obtain a blend. The mixture was stirred and reacted at 60° C. under a nitrogen atmosphere for 12-15 h to allow the amino group and the carboxyl group to fully dehydrate and condense for cross-linking. The reaction solution was poured into a mold and dried at 60° C. for 26 h to synthesize a shape memory poly(arylene ether nitrile) composite material with amino side chain cross-linking.

[0037] Example 4 This embodiment prepares a shape memory poly(arylether nitrile) composite material having amino side chain crosslinking. (a) under a nitrogen atmosphere, 5.88 g of bisphenol AF, 1.72 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 10 ml of toluene, 30 ml of N-methylpyrrolidone and 4.2 g of anhydrous potassium carbonate as a salt-forming agent were mixed uniformly to form a reaction system; (b) heating the reaction system and repeatedly performing a dehydration treatment during the heating process until the system temperature reaches 140° C.; within this temperature range, repeatedly performing a water-carrying operation with the aid of a water-carrying agent, and the water-carrying time is controlled to be 2 hours, thereby forming a bisphenol salt; (c) After the bisphenolate is fully formed, the system is cooled; after cooling to 100° C., water and the water-carrying agent are removed, 3.48 g of 2,6-dihalobenzonitrile is added to the system, and then the temperature is slowly raised to 160° C. to allow the system to fully react, thereby obtaining a viscous polymer solution; (d) pouring the obtained viscous polymer solution into deionized water, repeatedly washing to remove impurities, and then drying to finally obtain a polyarylene ether nitrile copolymer having an amino side chain; (e) 1 g of the poly(arylene ether nitrile) copolymer obtained in step d and 0.2 g of the carboxyl-terminated polybutadiene were added into 10 ml of N, N-dimethylformamide solvent, and 0.021 g of a dehydrating agent was added thereto, and the mixture was stirred to obtain a blend. The mixture was stirred and reacted at 50° C. in a nitrogen atmosphere for 12 hours to allow the amino group and the carboxyl group to undergo sufficient dehydration and polycondensation for cross-linking. The resulting solution was poured into a mold, and then dried at 60° C. for 22 hours to synthesize a shape memory poly(arylene ether nitrile) composite material having amino side chain cross-linking.

[0038] Example 5 This embodiment prepares a shape memory poly(arylether nitrile) composite material having amino side chain crosslinking. (a) under a nitrogen atmosphere, 2.48 g of hydroquinone, 0.65 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 10 ml of toluene, 30 ml of N-methylpyrrolidone and 4.2 g of anhydrous potassium carbonate as a salt-forming agent were mixed uniformly to form a reaction system; (b) heating the reaction system and repeatedly performing a dehydration treatment during the heating process until the system temperature reaches 145° C.; within this temperature range, repeatedly performing a water-carrying operation with the aid of a water-carrying agent, and the water-carrying time is controlled to be 2-3 hours, thereby forming a bisphenol salt; (c) After the bisphenol salt is fully formed, the system is cooled; after cooling to 110° C., water and the water-carrying agent are removed, 3.48 g of 2,6-dihalobenzonitrile is added to the system, and then the temperature is slowly raised to 170° C. to allow the system to fully react, thereby obtaining a viscous polymer solution; (d) pouring the obtained viscous polymer solution into deionized water, repeatedly washing to remove impurities, and then drying to finally obtain a polyarylene ether nitrile copolymer having an amino side chain; (e) 1 g of the poly(arylene ether nitrile) copolymer obtained in step d and 0.1 g of dicarboxyl polyethylene glycol were added to 10 ml of N, N-dimethylformamide solvent, and 0.0105 g of a dehydrating agent was added, and the mixture was stirred to obtain a blend. The mixture was stirred and reacted at 60° C. for 15 h under a nitrogen atmosphere to allow the amino group and the carboxyl group to fully dehydrate and polycondense for cross-linking. The reaction solution was poured into a mold and dried at 60° C. for 24 h to synthesize a shape memory poly(arylene ether nitrile) composite material with amino side chain cross-linking.

[0039] Comparative Example 1 In this comparative example, a polyarylether nitrile composite material having an amino side chain is prepared. The steps of this comparative example are the same as those of Example 1 (a) to (d). After preparing the polyarylether nitrile copolymer having an amino side chain in step d, 1 g of the polyarylether nitrile copolymer is added with 10 ml of N, N-dimethylformamide solvent, and the mixture is stirred evenly to obtain a blend. The blend is then poured into a mold and dried at 60° C. for 24 h to synthesize the polyarylether nitrile composite material having an amino side chain.

[0040] Comparative Example 2 In this comparative example, a polyarylethernitrile composite material having an amino side chain is prepared. (a) under a nitrogen atmosphere, 7.56 g of bisphenol AF, 0.65 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 10 ml of toluene, 30 ml of N-methylpyrrolidone and 4.2 g of anhydrous potassium carbonate as a salt-forming agent are mixed uniformly to form a reaction system; (b) heating the reaction system and repeatedly performing a dehydration treatment during the heating process until the system temperature reaches 150° C.; within this temperature range, repeatedly performing a water-carrying operation with the aid of a water-carrying agent, and the water-carrying time is controlled to be 3 hours, thereby forming a bisphenol salt; (c) After the bisphenol salt is fully formed, the system is cooled; after cooling to 120° C., water and the water-carrying agent are removed, 3.48 g of 2,6-dihalobenzonitrile is added to the system, and then the temperature is slowly raised to 170° C. to allow the system to fully react, thereby obtaining a viscous polymer solution; (d) pouring the obtained viscous polymer solution into deionized water, repeatedly washing to remove impurities, and then drying to finally obtain a polyarylene ether nitrile copolymer having an amino side chain; (e) 1 g of the poly(arylene ether nitrile) copolymer obtained in step d and 0.1 g of the carboxyl-terminated polybutadiene were added into 10 ml of N, N-dimethylformamide solvent, and the mixture was stirred to obtain a blend. The mixture was then stirred and reacted at 60° C. for 15 h under a nitrogen atmosphere to allow the amino group and the carboxyl group to undergo sufficient dehydration and polycondensation for cross-linking. The resulting solution was poured into a mold and dried at 60° C. for 18-26 h to synthesize a shape memory poly(arylene ether nitrile) composite material having amino side chain cross-linking.

[0041] Comparative Example 3 In this comparative example, a polyarylether nitrile composite material having an amino side chain is prepared. The steps of this comparative example are the same as those of Example 5 (a) to (d). After preparing the polyarylether nitrile copolymer having an amino side chain in step d, 1 g of the polyarylether nitrile copolymer is added with 10 ml of N, N-dimethylformamide solvent, and the mixture is stirred evenly to obtain a blend. The blend is then poured into a mold and dried at 60° C. for 24 h to synthesize the polyarylether nitrile composite material having an amino side chain.

[0042] In order to illustrate that the poly(arylene ether nitrile) composite material provided by the present application has good mechanical properties and thermal stability, the following experiments are conducted: Experimental Example 1: Fourier Transform Infrared Spectroscopy (FTIR) Analysis The structure of the composite materials prepared in Example 1 and Comparative Example 1 was characterized by using a NICOLET-6700 infrared spectrometer. The specific test method is as follows: Example 1 and Comparative Example 1 were placed in an oven at 70°C and dried for 24 h, taken out and cooled to room temperature, pressed into tablets using potassium bromide, and the FTIR spectrum of the samples was tested by a Fourier transform infrared spectrometer, with the instrument scanning wave number range of 4000-400 cm -1 , resolution 2cm -1 The results are as follows Figure 1 Infrared spectrum.

[0043] from Figure 1 It can be seen that the poly(arylether nitrile) composite material prepared in Comparative Example 1 has a -1 The double peak of stretching vibration of amino group proves that BAP is successfully introduced into poly(arylether nitrile). -1 The stretching vibration peak of methyl group is 2330cm -1 The stretching vibration peak of cyano group is 1200-1270cm -1 It is a double peak of stretching vibration of the benzene ring skeleton structure, proving the successful synthesis of poly(arylether nitrile). In the shape memory poly(arylether nitrile) composite material prepared in Example 1, it can be seen from the figure that the peaks at 3500-3300cm -1 The amino stretching vibration doublet at 3343 cm -1 and 1524cm -1 There is a single peak of NH stretching vibration at 1684 cm -1 The characteristic peak at corresponds to the stretching vibration absorption peak of carbonyl C=O, proving the formation of amide bonds (carboxyl-terminated polybutadiene successfully forms a three-dimensional cross-linked network structure with poly(arylether nitrile)); Experimental Example 2: Mechanical Properties Test Test method: The mechanical properties of the samples were tested by a universal testing machine at room temperature of 25°C and relative humidity of 25%. The dried samples were cut into dumbbell shapes and the strain rate was set to 20 mm / min. The mechanical properties of the composite materials prepared in Examples 1-2 and 5 and Comparative Examples 1-2 were tested respectively. The results are shown in Table 1. Figure 2-6 The stress-strain curve is shown in Figure 2 The tensile strength of the composite material of Example 1 is 57.2 MPa, and the elongation at break is 12.9%; Figure 3 The tensile strength of the composite material of Example 2 is 63.1 MPa, and the elongation at break is 26.1%; Figure 4 The tensile fracture curve of the composite material of Example 5: the tensile strength of the composite material is 65.8 MPa, and the elongation at break is 13.94%; Figure 5 The tensile strength of the polyarylethernitrile material of Comparative Example 1 is 54 MPa, and the elongation at break is 6.5%. Figure 6 The tensile strength of the composite material of Comparative Example 2 is 38.4 MPa, and the elongation at break is 20.1%. It can be seen that the composite material using carboxyl-terminated polybutadiene or dicarboxyl polyethylene glycol to construct a three-dimensional cross-linked network structure improves toughness while maintaining good mechanical properties.

[0044] Experimental Example 3: Thermal Performance Test The test method is: using a TGA / SDTA85 thermogravimetric analyzer to examine the thermal stability of shape memory poly(arylethernitrile) in a nitrogen atmosphere and using a STARe system from Mettler Toledo to perform DSC analysis. The sample of Example 1 was subjected to a thermogravimetric test, with a test temperature range of 40-600°C, a heating rate of 10°C / min, and a nitrogen flow rate of 50mL / min during the test; The samples of Examples 1 and 5 were subjected to DSC analysis. The specific test method was as follows: first, the sample was heated to 40°C at a rate of 10°C / min and kept at 40°C for 5 min; then, the sample was heated to 180°C at a rate of 10°C / min and kept at 180°C for 2 min; then, the sample was cooled to 40°C at a rate of 10°C / min and kept at 40°C for 2 min; finally, the sample was heated to 180°C at a rate of 10°C / min. During the test, the nitrogen flow rate was always maintained at 50 mL / min. The results are shown in FIG. Figure 7-10 shown.

[0045] It can be seen from the figure that the polyarylethernitrile composite material prepared in Example 1 has excellent thermal properties, and its temperature when the mass loss is 5% is 397.67°C, and the glass transition temperature is 117.2°C. The temperature when the mass loss of the polyarylethernitrile composite material prepared in Example 5 is 412.3°C, and the glass transition temperature is 122.8°C.

[0046] Experimental Example 4: Shape Memory Test Test method: The shape memory composite materials prepared in Examples 1 and 5 were made into 20 mm × 2 mm × 0.2 mm rectangular parallelepiped strips, placed in an oven, heated at different temperatures, then bent into a "U" shape with external force, and then cooled to room temperature to obtain a temporary shape. The deformation angle was recorded as θ. f The deformed spline is heated again to restore its original shape, and the angle (θr) of the spline is recorded over time. Fig.11As shown, the shape memory composite material of Example 1 has an excellent shape memory recovery rate, and can recover to its original shape within 21 seconds at a temperature of 110°C, with a shape memory fixation rate of 95.71% and a shape memory recovery rate of 98.43%. Fig.12 As shown, the macroscopic shape memory of Example 5 can be restored to the original shape within 42 s at a temperature of 110°C, the shape memory fixation rate is 94.02%, and the shape memory recovery rate is 95.51%.

[0047] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A shape memory poly(arylene ether nitrile) composite material having amino side chain crosslinking, characterized in that: The composite material is obtained by polymerizing a monomer containing a bisphenol group, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,6-dihalobenzonitrile and a monomer containing a terminal carboxyl group to form a structure of formula (I); Formula (I): , Wherein, n is an integer between 80 and 100; the molecular weight of Ar2 is 2000-4000; The -Ar1- can be selected from the following structures: , , , or ; The -Ar2- may optionally have the following structure: , , or .

2. The polyarylethernitrile composite material according to claim 1, characterized in that: The molar ratio of the monomer containing bisphenol groups to 2,2-bis(3-amino-4-hydroxyphenyl)propane is 7:3 to 9:

1.

3. The polyarylethernitrile composite material according to claim 2, characterized in that: The polyarylethernitrile composite material has a glass transition temperature of 100-120° C. and a tensile strength of 55-75 MPa.

4. The method for preparing the poly(arylene ether nitrile) composite material according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1: Under an inert gas atmosphere, a monomer containing a bisphenol group, 2,2-bis(3-amino-4-hydroxyphenyl) propane, a water-carrying agent, an organic solvent, 2,6-dihalobenzonitrile and a salt-forming agent are formed into a reaction system to prepare a polyarylethernitrile copolymer having an amino side chain; S2: Add the obtained polyarylethernitrile copolymer and the monomer containing terminal carboxyl group to N,N-dimethylformamide solvent, add dehydrating agent and stir to obtain a blend, stir at 40-60°C to dehydrate and polycondense the amino group and the carboxyl group to crosslink, and synthesize a shape memory polyarylethernitrile composite material with amino side chain crosslinking.

5. The method for preparing the polyarylethernitrile composite material according to claim 4, characterized in that: The monomer containing a bisphenol group is selected from bisphenol AF, bisphenol A, resorcinol, hydroquinone, biphenol or 4,4'-dihydroxydiphenyl ether.

6. The method for preparing the polyarylethernitrile composite material according to claim 4, characterized in that: The monomer containing a terminal carboxyl group is selected from the group consisting of terminal carboxyl polybutadiene, dicarboxyl polyethylene glycol, terminal carboxyl polyester or terminal carboxyl polyether.

7. The method for preparing the polyarylethernitrile composite material according to claim 5, characterized in that: The organic solvent is one or more of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, and sulfolane; The water-carrying agent is toluene or xylene; The salt-forming agent is at least one of anhydrous potassium carbonate, potassium hydroxide, sodium carbonate and sodium hydroxide; The dehydrating agent is N,N'-dicyclohexylcarbocyanine.

8. The method for preparing the polyarylethernitrile composite material according to claim 5, characterized in that: The amount of the organic solvent used is 4-6 times the total mass of the monomer containing the bisphenol group and 2,2-bis(3-amino-4-hydroxyphenyl)propane; The amount of the salt-forming agent is 1-2 times the molar number of 2,6-dihalobenzonitrile; The volume ratio of the water-carrying agent to the organic solvent is 3-4:

10.

9. The method for preparing the polyarylethernitrile composite material according to claim 4, characterized in that: In the step S2, the amount of the carboxyl-terminated monomer added is 5%-30% of the mass of the poly(arylene ether nitrile) copolymer.

10. Use of the polyarylethernitrile composite material according to any one of claims 1 to 3 or the polyarylethernitrile composite material prepared by the preparation method according to any one of claims 4 to 9, characterized in that: The materials are used in fields including petroleum, aerospace, medical devices, electronic devices or smart textiles.

Images