CN111333812A - Aggregation-induced luminescence self-repairing shape memory polymer and preparation method thereof - Google Patents

Aggregation-induced luminescence self-repairing shape memory polymer and preparation method thereof Download PDF

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CN111333812A
CN111333812A CN202010195260.4A CN202010195260A CN111333812A CN 111333812 A CN111333812 A CN 111333812A CN 202010195260 A CN202010195260 A CN 202010195260A CN 111333812 A CN111333812 A CN 111333812A
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刘彦菊
冷劲松
何阳
王晓飞
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Harbin Institute of Technology
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Abstract

The invention provides an aggregation-induced emission self-repairing shape memory polymer and a preparation method thereof. According to the invention, the aggregation-induced emission compound and the self-repairing shape memory polymer are crosslinked into an interpenetrating network in a grafting or block chemical bonding mode, so that the dispersibility of the aggregation-induced emission compound in the self-repairing shape memory polymer is effectively improved, and the material has better fluorescence performance; because the aggregation-induced emission compound is grafted or blocked in the self-repairing shape memory polymer matrix, the shape memory and self-repairing processes of the material can be monitored in real time by using the fluorescence property of AIE, the damage or crack of the shape memory polymer can be early warned, the damage position of the material can be indicated, and the application prospect of the aggregation-induced emission self-repairing shape memory polymer can be improved.

Description

Aggregation-induced luminescence self-repairing shape memory polymer and preparation method thereof
Technical Field
The invention relates to the technical field of preparation methods of intelligent macromolecules, in particular to a gathering induced luminescence self-repairing shape memory polymer and a preparation method thereof.
Background
In 2001, Tang-loyal courier et al found a heteropentadiene compound which hardly emitted fluorescence in ethanol solution and increased fluorescence signal once prepared as a thin film or added to a mixed solution of ethanol and water; this phenomenon is quite contrary to the aggregation-induced quenching (ACQ) phenomenon in conventional fluorescent materials, and this particular fluorescence emission phenomenon is known as aggregation-induced emission (AIE) by down et al. The aggregation-induced emission molecules have almost no fluorescence in a dilute solution, but have strong fluorescence in a high-concentration or aggregation state, so that the defect that the traditional organic fluorescent material has low luminous efficiency or even does not emit light in a high-concentration solution state is effectively overcome, and the new material with a specific fluorescence effect can be obtained by combining the aggregation-induced emission molecules with other high-molecular materials by utilizing the characteristics of the aggregation-induced emission molecules.
The Self-repairing shape memory material (Self-healing material) is an intelligent Shape Memory Polymer (SMP) with a Self-repairing function after the material is damaged by an external force, can prolong the service life of the shape memory material, has the advantages of short repairing time and no toxicity of the Self-repairing shape memory material with non-covalent bonds, and has wide application prospect in the field of biomedicine.
The aggregation-induced emission compound and the self-repairing shape memory polymer are combined, so that the application fields of the material can be expanded, and the material has wide application prospects in image display, information storage, optical memory, coating early warning, light-emitting devices and the like. However, the compatibility between the AIE compound and the SMP is poor, so that the AIE compound cannot be uniformly dispersed in a matrix, and agglomeration and crystallization phenomena are easy to occur along with the increase of the dosage of the AIE, so that the fluorescence effect of the composite material is reduced.
Disclosure of Invention
The invention aims to solve the problem of how to simply and effectively prepare the aggregation-induced emission self-repairing shape memory polymer with better performance to a certain extent.
In order to solve the problems, the invention provides an aggregation-induced emission self-repairing shape memory polymer, wherein an aggregation-induced emission compound is chemically bonded on the self-repairing shape memory polymer through grafting or block, and the structural formula of the aggregation-induced emission self-repairing shape memory polymer is as follows:
Figure BDA0002417373630000021
wherein the content of the first and second substances,
Figure BDA0002417373630000022
n＝5000。
optionally, the aggregation-inducing luminescent compound comprises a hydroxyl group and the self-healing shape memory polymer comprises an isocyanate group.
Optionally, the aggregation-induced emission self-repair shape memory polymer has an aggregation-induced emission compound content of 0.1% to 10%.
The invention also aims to provide a preparation method of the aggregation-induced emission self-repairing shape memory polymer, so as to simply and effectively prepare the aggregation-induced emission self-repairing shape memory polymer with better performance.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of the aggregation-induced emission self-repairing shape memory polymer comprises the following steps:
dissolving an aggregation-induced emission compound in a solvent to form a mixed solution A, adding a self-repairing shape memory polymer into the mixed solution A, carrying out chemical grafting or chemical block reaction to form a mixed solution B, and heating to remove the solvent in the mixed solution B, thus obtaining the aggregation-induced emission self-repairing shape memory polymer.
Optionally, the aggregation-inducing luminescent compound comprises one or more of a polyaryl-substituted heterocyclic compound, a polyaryl-substituted vinylic compound and a compound containing hydrogen bonds and having an aggregation-inducing luminescent phenomenon;
wherein, the polyaryl substituted heterocyclic compound comprises one or more of aminated silole derivatives, thiophene derivatives, pyrazolone derivatives and imidazole derivatives;
the polyaryl substituted ethylene compound comprises one or more of a tetra-styrene derivative, distyrylanthracene and a distyrylanthracene derivative;
the compound containing hydrogen bonds and having aggregation-induced emission phenomenon includes one or more of carborane derivatives having a three-dimensional aromatic structure, cyanostyrene, and onium salts.
Optionally, the self-healing shape memory polymer includes one or more of an ethylene-vinyl acetate copolymer, a poly-caprolactone-based polymer, a polylactic acid-based polymer, and a polyurethane-based polymer.
Optionally, the stimulus-responsive type of the self-healing shape memory polymer includes one or more of a thermotropic type, a photoinduced type, an electroluminescent type, a magnetic type, and a chemical solvent-responsive type.
Alternatively, the solvent comprises N, N-methylene formamide.
Optionally, further comprising: and pouring the mixed solution B into a mold, then placing the mold in a vacuum oven, and removing the solvent in the mixed solution B to obtain the aggregation-induced luminescence self-repairing shape memory polymer film.
The third purpose of the invention is to provide the application of the aggregation induced emission self-repairing shape memory polymer in the fields of image display, information storage, optical memory, coating early warning and light-emitting devices.
Compared with the prior art, the aggregation-induced emission self-repairing shape memory polymer and the preparation method thereof provided by the invention have the following advantages:
(1) according to the invention, the aggregation-induced emission compound and the self-repairing shape memory polymer are crosslinked into an interpenetrating network in a grafting or block chemical bonding mode, so that on one hand, the dispersibility of the aggregation-induced emission compound in the self-repairing shape memory polymer is effectively improved, and the material has better fluorescence performance; on the other hand, because the aggregation-induced emission compound is grafted or blocked into the self-repairing shape memory polymer matrix, the shape memory and self-repairing processes of the material can be monitored in real time by using the fluorescence property of AIE, and meanwhile, the damage or crack of the shape memory polymer is early warned, the damage position of the material is indicated, the same position is prevented from being damaged again, and the application prospect of the aggregation-induced emission self-repairing shape memory polymer is improved.
(2) The preparation method of the aggregation-induced emission self-repairing shape memory polymer provided by the invention is simple and efficient, is suitable for large-scale industrial production, has simple and easily designed chemical process, has no complex post-treatment process, and simultaneously has the advantages of abundant and easily obtained raw materials, moderate price and easy popularization.
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FIG. 1 is a reaction scheme for chemically grafting an aggregation-induced emission compound to a self-healing shape memory polymer according to an embodiment of the present invention;
FIG. 2 is a self-healing process of an aggregation-induced emission self-healing shape memory polymer film according to an embodiment of the present invention;
FIG. 3 illustrates a shape memory process of a aggregation-induced emission self-healing shape memory polymer film according to an embodiment of the present invention;
FIG. 4 is a fluorescence intensity spectrum of the shape memory process of the aggregation-induced emission self-healing shape memory polymer film according to an embodiment of the present invention;
FIG. 5 is a mechanism of aggregation-induced emission compounds according to an embodiment of the present invention;
FIG. 6 is a flow chart of a method for preparing an aggregation-induced emission self-repairing shape memory polymer according to an embodiment of the present invention;
FIG. 7 is a schematic structural diagram of a aggregation-induced emission self-repairing shape memory polymer according to an embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In addition, the terms "comprising," "including," "containing," and "having" are intended to be non-limiting, i.e., that other steps and other ingredients can be added that do not affect the results. Materials, equipment and reagents are commercially available unless otherwise specified.
In addition, although the invention has described the forms of S1, S2, S3 and the like for each step in the preparation, the description is only for the convenience of understanding, and the forms of S1, S2, S3 and the like do not represent the limitation of the sequence of each step.
The traditional fluorescent luminescent material has stronger luminous efficiency in solution, but the luminous intensity is reduced in an aggregation state, even the luminescence is completely quenched, and the aggregation fluorescence quenching effect (ACQ) is obtained. In the practical application process, the ACQ phenomenon causes the materials to meet the bottleneck, and the application field of the fluorescent materials is greatly limited. The discovery of the aggregation-induced emission molecules fundamentally overcomes the defect that the traditional fluorescent material has fluorescence quenching in practical application, and leads people to turn to a brand-new angle on the understanding of the organic luminescent material.
Shape Memory Polymers (SMP) are stimulus-responsive intelligent materials with shape memory effect, and when the SMP is subjected to external stimulus, such as heat, light, electricity, magnetism, chemical solvents and the like, the materials can be restored to the initial shape from a temporary shaping state, so that the SMP can be widely applied to the fields of aerospace, biomedicine, sensing braking and the like. However, crystalline polymer segments are susceptible to fatigue from the shape memory effect of the material and to breakage at the stressed site after undergoing frequent shape memory cycles. At present, a shape memory polymer material with self-repairing capability constructed by introducing intermolecular dynamic interaction into a polymer system is reported, and the shape memory polymer not only has better shape memory effect and higher mechanical strength, but also has the capability of repairing mechanical damage and functional fatigue.
How to better combine the aggregation-induced emission molecule with the self-repairing shape memory polymer to obtain a polymer with better fluorescence performance and self-warning and self-repairing shape memory performance, thereby expanding the application field of the shape memory material, is a problem to be solved at present.
In order to solve the problems, the invention provides an aggregation-induced emission self-repairing shape memory polymer, which is endowed with an aggregation-induced emission effect by chemically grafting or chemically blocking an aggregation-induced emission compound into a self-repairing shape memory polymer matrix; due to the fact that the aggregation-induced emission compound and the shape memory polymer are chemically bonded, the problem that the shape memory polymer is poor in performance due to the fact that materials are not uniformly mixed and the aggregation-induced emission compound is agglomerated can be effectively solved.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
With reference to fig. 1, an embodiment of the present invention provides an aggregation-induced emission self-repairing shape memory polymer, where an aggregation-induced emission compound is chemically bonded to a shape memory polymer through grafting or block bonding, and a structural formula of the aggregation-induced emission self-repairing shape memory polymer is as follows:
Figure BDA0002417373630000061
wherein the content of the first and second substances,
Figure BDA0002417373630000062
n＝5000。
as shown in fig. 1 and 7, the aggregation-induced emission compound (AIE) includes a hydroxyl group, the self-repair shape memory polymer includes an isocyanate group, and a carbamate is generated by the reaction of the hydroxyl group and the isocyanate group, so that the aggregation-induced emission compound is blocked or grafted onto the self-repair shape memory polymer and an interpenetrating network is formed, so that the self-repair shape memory polymer has an aggregation-induced emission effect.
In addition, the aggregation-induced emission compound (AIE) can also comprise an acrylate group, and is mixed with self-repairing shape memory ethylene-vinyl acetate, then the C ═ C double bond free radical reaction is carried out, and the mixture is chemically grafted to the self-repairing shape memory ethylene-vinyl acetate copolymer to form the aggregation-induced emission self-repairing shape memory polymer.
The aggregation-induced emission compound (AIE) can also comprise a hydroxyl group, the self-repairing shape memory polymer poly-caprolactone contains dihydroxy, and the two poly-caprolactone are blocked into the same polymer system through isocyanate to obtain the self-repairing shape memory poly-caprolactone polymer with the aggregation-induced emission effect.
Although the block grafting reaction is described as an example of the reaction of hydroxyl and isocyanate groups to form carbamate, in other embodiments, the aggregation-induced emission compound may be chemically bonded to the self-healing shape memory polymer by grafting or blocking through other reactions, which is not limited herein.
With reference to fig. 2, the self-repairing shape memory polymer is shaped into a temporary shape at the material transition temperature, and then the crystalline structure of the material is opened under the response of external stimuli, and the motion capability of the polymer chain segment is re-excited, so that the shape of the material is spontaneously recovered, that is, the self-repairing shape memory polymer is crosslinked through the physical forces of hydrogen bonds, crystallization of the polymer chain segment and the like, so that the material has good repairing capability. In the embodiment of the invention, the self-repairing bonds of the self-repairing shape memory polymer are non-covalent bonds, including hydrogen bonds, ionic bonds, pi-pi interaction and the like.
Therefore, the aggregation-induced emission compound and the self-repairing shape memory polymer are crosslinked into an interpenetrating network in a grafting or block chemical bonding mode, on one hand, the dispersibility of the aggregation-induced emission compound in the self-repairing shape memory polymer is effectively improved, and the material has better fluorescence performance; on the other hand, because the aggregation-induced emission compound is grafted or blocked into the self-repairing shape memory polymer matrix, the shape memory and self-repairing processes of the material can be monitored in real time by using the fluorescence property of AIE, and meanwhile, the damage or crack of the shape memory polymer is early warned, the damage position of the material is indicated, the same position is prevented from being damaged again, and the application prospect of the aggregation-induced emission self-repairing shape memory polymer is improved.
It can be understood that, because the aggregation-induced emission compound is a hard segment which is terminated by isocyanate groups and comprises a benzene ring, the hard segment is introduced onto a flexible chain segment of the self-repairing shape memory polymer, the crosslinking density of the self-repairing shape memory polymer is increased, and the length of the molecular chain segment between crosslinking points is reduced to a certain extent, so that the molecular structure of the aggregation-induced emission self-repairing shape memory polymer has two molecular chain segment structures of a hard segment and a soft segment, the fixed phase of physical crosslinking or chemical crosslinking realizes the positioning of an initial state and provides restoring force to enable a reversible phase to return to the initial state, and the soft segment as the reversible phase of the material can realize solidification and softening along with the change of temperature, thereby ensuring the deformability of the material.
Therefore, when the addition amount of the aggregation-inducing luminescent compound is too large, the crystallization performance of the matrix is affected, the shape memory performance is reduced, and the preparation cost is too high; if the addition amount of the aggregation-induced emission compound is too low, the fluorescence property of the matrix is poor, and the deformation process of the material cannot be effectively monitored. In the embodiment of the invention, preferably, the content of the aggregation-induced emission compound in the aggregation-induced emission self-repair shape memory polymer is 0.1% -10%, and within the range, the material has better self-repair shape memory performance and fluorescence imaging effect.
In combination with FIG. 6, another embodiment of the present invention provides a method for preparing an aggregation-induced emission self-repairing shape memory polymer, comprising:
s1, dissolving the aggregation-induced emission compound in a solvent to form a mixed solution A;
s2, adding the shape memory polymer into the mixed solution A, carrying out chemical grafting or chemical block reaction to form mixed solution B, and then heating to remove the solvent in the mixed solution B, thus obtaining the aggregation induced luminescence self-repairing shape memory polymer.
Specifically, in step S1, the aggregation inducing luminescent compound (AIE) contains a hydroxyl group, and specifically includes one or more of a polyarylate-substituted heterocyclic compound, a polyarylate-substituted vinylic compound, and a compound having a hydrogen bond and having an aggregation-induced luminescent phenomenon. Wherein, the polyaryl substituted heterocyclic compound comprises one or more of aminated silole derivatives, thiophene derivatives, pyrazolone derivatives and imidazole derivatives; one or more of polyaryl substituted ethylene compound tetrastyrene derivatives, distyrylanthracene and distyrylanthracene derivatives; the compound containing hydrogen bond and having aggregation-induced emission phenomenon includes one or more of carborane derivative, cyanostyrene and onium salt having three-dimensional aromatic structure.
As shown in connection with fig. 5, these AIE molecules generally have a twisted molecular configuration that dissipates energy through free rotation and molecular vibration in dilute solutions, thereby reducing fluorescence emission; but in the solid or aggregate state, its luminescence is significantly enhanced due to its confinement of intramolecular rotation and vibration.
The solvent comprises N, N-methylene formamide, dimethyl sulfoxide and the like, and only the aggregation-induced emission compound and the self-repairing shape memory compound are ensured to be soluble in the solvent. In the present embodiment, preferably, the solvent is N, N-methylene formamide.
In step S2, the shape memory polymer is added to the mixed solution a, mixed uniformly and reacted for 1-3 hours, so that the hydroxyl group and the isocyanate are fully reacted.
The content of the aggregation-inducing luminescent compound greatly affects the shape memory property and the fluorescence property, and in the embodiment of the invention, the mass ratio of the aggregation-inducing luminescent compound to the solvent to the shape memory polymer is as follows: (0.1-10):(100:100).
The self-repairing shape memory polymer comprises one or more of ethylene-vinyl acetate copolymer, poly-caprolactone polymer, polylactic acid polymer and polyurethane polymer; and the self-repairing bonds of the self-repairing shape memory polymer are non-covalent bonds and comprise hydrogen bonds, ionic bonds, pi-pi interaction and the like. Namely, the thermoplastic self-repairing shape memory material comprises materials with biocompatibility, such as thermoplastic self-repairing shape memory ethylene-vinyl acetate copolymer, thermoplastic self-repairing shape memory polylactones, thermoplastic self-repairing shape memory polylactic acid, thermoplastic self-repairing shape memory polyurethane and the like.
The stimulus response type of the self-repairing shape memory polymer includes one or more of a thermal type, a photo type, an electro type, a magneto type and a chemical solvent response type, as long as the self-repairing shape memory polymer can spontaneously recover the shape of the material in response to the external stimulus, which is not particularly limited herein.
According to the preparation method provided by the embodiment of the invention, the aggregation induced emission compound is chemically grafted or chemically blocked on the self-repairing shape memory polymer, so that the prepared aggregation induced emission self-repairing shape memory polymer has better thermal stability and mechanical property, and the use of a fluorescent material is ensured; namely, the aggregation-induced emission self-repairing shape memory polymer has the properties of a high-performance polymer and aggregation-induced emission properties, and has a good application prospect. In addition, the preparation method is simple and efficient, is suitable for large-scale industrial production, has simple chemical process, easy design and no complex post-treatment process, and simultaneously has the advantages of abundant and easily-obtained raw materials, moderate price and easy popularization.
Because the fluorescent material required in daily life is generally in a solid state or a thin film state, in order to expand the application scenario of the aggregation-induced emission self-repairing shape memory polymer, the preparation method described in this embodiment further includes the steps of:
s3, pouring the mixed solution B into a mold, then placing the mold in a vacuum oven, and removing the solvent in the mixed solution B at the temperature of 60-100 ℃ to obtain the aggregation induced luminescence self-repairing shape memory polymer film.
Certainly, the prepared aggregation-induced emission self-repairing shape memory polymer is dissolved in a solvent, poured into a mold, and the solvent is removed after reaction, so that the aggregation-induced emission self-repairing shape memory polymer film can also be obtained.
Specifically, 0.01-1g of aggregation-induced emission compound is dissolved in a solvent for later use; then 5-20g of shape memory polymer, namely the self-repairing shape memory polymer blocked by isocyanate is dissolved in the solvent. And then, uniformly mixing the two solutions, fully reacting hydroxyl and isocyanate in a reaction kettle, pouring into a polytetrahydrofuran mould, placing in a vacuum oven at 60-100 ℃, preserving the temperature for 20-28h, and removing the solvent to obtain the aggregation induced luminescence self-repairing shape memory polymer film.
Referring to fig. 3 and 4, fig. 3 shows a shape memory process of the self-repairing shape memory polymer film with aggregation-induced emission, and fig. 4 shows a fluorescence emission intensity spectrum of the self-repairing shape memory polymer film with aggregation-induced emission, which shows that the fluorescence intensity of the film is strong in an initial state, the fluorescence intensity is weak when the film is stretched and formed into a temporary shape, and the fluorescence intensity is increased again when the film returns to the initial state in response to an external stimulus.
The self-repairing shape memory polymer film is in a solid state at the initial stage of shape memory, so that molecular motion and molecular rotation of the AIE compound are hindered, and the fluorescence intensity of the material is high. When the material is stretched and shaped, the self-repairing shape memory polymer film is forced to deform in a high elastic mode under the action of external force, chain segments in the material move, the molecular motion and the molecular rotation of the AIE compound are accelerated, and therefore the fluorescence intensity of the material is weakened. When the shape of the self-repairing shape memory polymer film is recovered, when the soft segment crystals of the material are melted or dissolved in a solvent, the free volume of molecules is increased, the molecular rotation of the AIE compound is weakened, phenyl can rotate freely, the emission intensity is reduced, and the fluorescence intensity is weakened and even becomes colorless.
Therefore, the fluorescence intensity of the aggregation-induced emission compound in the self-repairing deformation process is different, and the state of the display film can be monitored in real time according to the difference of the fluorescence intensity. Namely, in the process that the shape of the aggregation induced luminescence self-repairing shape memory polymer film is damaged and repaired, the shape of the material is imaged in real time through fluorescence detection, the repairing state of the material is monitored in real time, the repairing degree of the material is displayed, meanwhile, the damage or crack of the shape memory polymer is early warned, the damage position of the material is indicated, and the same position is prevented from being damaged again.
The aggregation-induced emission self-repairing shape memory polymer prepared by the embodiment of the invention can be applied to the fields of image display, information storage, optical memory, coating early warning and luminescent devices; in addition, the nano-composite material has good biocompatibility, and can be widely applied to the fields of biological material imaging, biosensors and biomedicine.
The following describes a specific preparation method of an aggregation induced emission self-repairing solvent-based shape memory polymer film by using different embodiments, the embodiments of the present invention are only described by using a shape memory polymer containing a hydrophilic chain segment as an example, and can also use different self-repairing shape memory polymers according to external stimulus response types, wherein an aggregation induced emission compound is selected from a 9, 10-bis (4-hydroxystyrene-based) anthracene compound, a solvent is selected from N, N-methylene formamide (DMF), and a self-repairing shape memory polymer is selected from a polyurethane prepolymer terminated by isocyanate:
example 1
0.01g of 9, 10-bis (4-hydroxystyryl) anthracene compound was dissolved in DMF solvent for use.
5g of isocyanate-terminated polyurethane prepolymer was dissolved in DMF; and then, uniformly mixing the two solutions, fully reacting hydroxyl and isocyanate in a reaction kettle, pouring the mixture into a polytetrahydrofuran mold, placing the mold in a vacuum oven at the temperature of 60 ℃ for 20 hours, preserving the heat, and removing the solvent to obtain the self-repairing solvent type shape memory polyurethane film with aggregation-induced luminescence.
Example 2
1g of 9, 10-bis (4-hydroxystyryl) anthracene compound was dissolved in DMF solvent for further use.
Dissolving 20g of polyurethane prepolymer terminated with isocyanate in DMF; and then, uniformly mixing the two solutions, fully reacting hydroxyl and isocyanate in a reaction kettle, pouring the mixture into a polytetrahydrofuran mold, placing the mold in a vacuum oven at 100 ℃, preserving heat for 28 hours, and removing the solvent to obtain the self-repairing solvent type shape memory polyurethane film with aggregation-induced luminescence.
Example 3
1g of 9, 10-bis (4-hydroxystyryl) anthracene compound was dissolved in DMF solvent for further use.
Dissolving 13g of polyurethane prepolymer terminated with isocyanate in DMF; and then, uniformly mixing the two solutions, fully reacting hydroxyl and isocyanate in a reaction kettle, pouring the mixture into a polytetrahydrofuran mold, placing the mold in a vacuum oven at 80 ℃, preserving heat for 24 hours, and removing the solvent to obtain the self-repairing solvent type shape memory polyurethane film with aggregation-induced luminescence.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.

Claims (10)

1. An aggregation-induced emission self-repairing shape memory polymer is characterized in that an aggregation-induced emission compound is chemically bonded on the self-repairing shape memory polymer through grafting or block, and the structural formula of the aggregation-induced emission self-repairing shape memory polymer is as follows:
Figure FDA0002417373620000011
wherein the content of the first and second substances,
Figure FDA0002417373620000012
n＝5000。
2. the aggregation-induced emission self-healing shape memory polymer of claim 1, wherein the aggregation-induced emission compound comprises a hydroxyl group and the self-healing shape memory polymer comprises an isocyanate group.
3. The aggregation-induced emission self-repairing shape memory polymer of claim 1, wherein the aggregation-induced emission compound is present in the aggregation-induced emission self-repairing shape memory polymer in an amount of 0.1% to 10%.
4. A method of making an aggregation-induced emission self-healing shape memory polymer according to any one of claims 1 to 3, comprising:
dissolving an aggregation-induced emission compound in a solvent to form a mixed solution A, adding a self-repairing shape memory polymer into the mixed solution A, carrying out chemical grafting or chemical block reaction to form a mixed solution B, and heating to remove the solvent in the mixed solution B, thus obtaining the aggregation-induced emission self-repairing shape memory polymer.
5. The method for preparing the aggregation-induced emission self-repairing shape memory polymer as claimed in claim 4, wherein the aggregation-induced emission compound comprises one or more of a polyaryl-substituted heterocyclic compound, a polyaryl-substituted vinylic compound and a compound containing hydrogen bonds and having an aggregation-induced emission phenomenon; wherein the content of the first and second substances,
the polyaryl substituted heterocyclic compound comprises one or more of aminated silole derivatives, thiophene derivatives, pyrazolone derivatives and imidazole derivatives;
the polyaryl-substituted vinylic compounds include: one or more of a stilbene derivative, distyrylanthracene, and distyrylanthracene derivative;
the compound containing hydrogen bonds and having aggregation-induced emission phenomenon includes one or more of carborane derivatives having a three-dimensional aromatic structure, cyanostyrene, and onium salts.
6. The method for preparing the aggregation-induced emission self-repairing shape memory polymer as claimed in claim 4, wherein the self-repairing shape memory polymer comprises one or more of ethylene-vinyl acetate copolymer, poly-caprolactone polymer, polylactic acid polymer and polyurethane polymer.
7. The method of making an aggregation-induced emission self-healing shape memory polymer of claim 6, wherein the stimulus response type of the self-healing shape memory polymer comprises one or more of a thermotropic type, a photoinduced type, an electroluminescent type, a magnetic type, and a chemical solvent responsive type.
8. The method of making an aggregation-induced emission self-repairing shape memory polymer of claim 4, wherein the solvent comprises N, N-methylene formamide.
9. The method for preparing an aggregation-induced emission self-repairing shape memory polymer as claimed in claim 4, further comprising:
and pouring the mixed solution B into a mold, then placing the mold in a vacuum oven, and removing the solvent in the mixed solution B to obtain the aggregation-induced luminescence self-repairing shape memory polymer film.
10. Use of the aggregation induced emission self-healing shape memory polymer of any one of claims 1 to 3 in the fields of image display, information storage, optical memory, coating forewarning, and light emitting devices.
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CN115612056A (en) * 2022-10-20 2023-01-17 吉林大学 High-toughness and high-mechanical-strength polyurethane elastomer with excellent water resistance and repairable and recyclable functions and preparation method thereof

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