CN111333812B - 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 PDFInfo
- Publication number
- CN111333812B CN111333812B CN202010195260.4A CN202010195260A CN111333812B CN 111333812 B CN111333812 B CN 111333812B CN 202010195260 A CN202010195260 A CN 202010195260A CN 111333812 B CN111333812 B CN 111333812B
- Authority
- CN
- China
- Prior art keywords
- shape memory
- aggregation
- self
- memory polymer
- induced emission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000002776 aggregation Effects 0.000 title claims abstract description 115
- 238000004220 aggregation Methods 0.000 title claims abstract description 114
- 229920000431 shape-memory polymer Polymers 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004020 luminiscence type Methods 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 20
- -1 9, 10-bis (4-hydroxystyryl) anthracene compound Chemical class 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 49
- 230000008569 process Effects 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 230000001939 inductive effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 239000012781 shape memory material Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000003446 memory effect Effects 0.000 description 3
- 230000007334 memory performance Effects 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940083761 high-ceiling diuretics pyrazolone derivative Drugs 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003967 siloles Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000001420 substituted heterocyclic compounds Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008846 dynamic interplay Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C08G2280/00—Compositions for creating shape memory
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
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
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:
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.
Drawings
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:
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 (4)
1. A preparation method of an aggregation-induced emission self-repairing shape memory polymer is characterized by comprising 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 then heating to remove the solvent in the mixed solution B to obtain the aggregation-induced emission self-repairing shape memory polymer, wherein the content of the aggregation-induced emission compound in the aggregation-induced emission self-repairing shape memory polymer is 0.1-10%, the aggregation-induced emission compound is a 9, 10-bis (4-hydroxystyryl) anthracene compound, and the self-repairing shape memory polymer is a polyurethane prepolymer terminated by isocyanate.
2. The method of making an aggregation-induced emission self-repairing shape memory polymer of claim 1, wherein the solvent comprises N, N-methylene formamide.
3. The method for preparing an aggregation-induced emission self-repairing shape memory polymer as claimed in claim 1, 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.
4. The application of the aggregation induced emission self-repairing shape memory polymer prepared by the preparation method of the aggregation induced emission self-repairing shape memory polymer as claimed in claim 1 in the fields of image display, information storage, optical memory, coating early warning and luminescent devices.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010195260.4A CN111333812B (en) | 2020-03-19 | 2020-03-19 | Aggregation-induced luminescence self-repairing shape memory polymer and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010195260.4A CN111333812B (en) | 2020-03-19 | 2020-03-19 | Aggregation-induced luminescence self-repairing shape memory polymer and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111333812A CN111333812A (en) | 2020-06-26 |
CN111333812B true CN111333812B (en) | 2022-02-22 |
Family
ID=71178864
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010195260.4A Active CN111333812B (en) | 2020-03-19 | 2020-03-19 | Aggregation-induced luminescence self-repairing shape memory polymer and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111333812B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113307943B (en) * | 2021-05-31 | 2022-05-13 | 中国科学院大学 | Actuator material with fluorescence tunable, shape memory and self-repairing properties |
CN113683766B (en) * | 2021-07-06 | 2022-05-24 | 华南理工大学 | Polymer material with shape and color memory function and preparation method and application thereof |
CN114920904B (en) * | 2022-05-31 | 2024-01-30 | 郑州大学 | Preparation method and application of colorless transparent high-strength polyurethane anti-counterfeiting material |
CN115612056B (en) * | 2022-10-20 | 2024-10-15 | 吉林大学 | Polyurethane elastomer with high toughness and high mechanical strength and water resistance, repairable and recyclable functions and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4772745A (en) * | 1986-08-18 | 1988-09-20 | The United States Of America As Represented By The Secretary Of Commerce | Polymer-reactive photosensitive anthracenes |
JP2006028064A (en) * | 2004-07-14 | 2006-02-02 | Kawasaki Kasei Chem Ltd | 9,10-bis(2-hydroxyethoxy)anthracene and its manufacturing method |
CN106381555A (en) * | 2016-08-26 | 2017-02-08 | 华南理工大学 | Composite fiber containing aggregation-induced luminescent molecules, preparation method thereof and application thereof |
CN109528352A (en) * | 2019-01-15 | 2019-03-29 | 哈尔滨工业大学 | A kind of shape-memory polymer carries medicine intestinal stent and preparation method thereof |
-
2020
- 2020-03-19 CN CN202010195260.4A patent/CN111333812B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4772745A (en) * | 1986-08-18 | 1988-09-20 | The United States Of America As Represented By The Secretary Of Commerce | Polymer-reactive photosensitive anthracenes |
JP2006028064A (en) * | 2004-07-14 | 2006-02-02 | Kawasaki Kasei Chem Ltd | 9,10-bis(2-hydroxyethoxy)anthracene and its manufacturing method |
CN106381555A (en) * | 2016-08-26 | 2017-02-08 | 华南理工大学 | Composite fiber containing aggregation-induced luminescent molecules, preparation method thereof and application thereof |
CN109528352A (en) * | 2019-01-15 | 2019-03-29 | 哈尔滨工业大学 | A kind of shape-memory polymer carries medicine intestinal stent and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111333812A (en) | 2020-06-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111333812B (en) | Aggregation-induced luminescence self-repairing shape memory polymer and preparation method thereof | |
CN111040110B (en) | Force-induced response dynamic polymer and application thereof | |
CN104497208B (en) | Self-healing sulfobetaine zwitterionic nano composite aquagel and preparation method thereof | |
Yu et al. | Photomechanical response of polymer-dispersed liquid crystals/graphene oxide nanocomposites | |
Zhao et al. | Self-healing metallo-supramolecular polymers showing luminescence off/on switching based on lanthanide ions and terpyridine moieties | |
Pan et al. | From fragile plastic to room-temperature self-healing elastomer: Tuning quadruple hydrogen bonding interaction through one-pot synthesis | |
CN102532892B (en) | Conductive polymer film and preparation method thereof | |
CN111040204B (en) | Force-induced response dynamic polymer and application thereof | |
CN109913977B (en) | Nucleic acid gel fiber and preparation method thereof | |
CA3186761A1 (en) | Carbon quantum dot and synthesis method therefor, thin film and electronic device | |
Ji et al. | A fluorescent supramolecular crosslinked polymer gel formed by crown ether based host-guest interactions and aggregation induced emission | |
CN111378137A (en) | Force-induced responsive polymer with multi-network structure | |
Jiang et al. | Blue-emitting thermoreversible oligourethane gelators with aggregation-induced emission properties | |
CN111378143A (en) | Energy absorption method based on force-induced response supramolecular polymer | |
CN110423346A (en) | A kind of polyamide liquid crystal macromolecule and preparation method thereof with aggregation-induced emission property | |
CN111378140A (en) | Force-induced response supramolecular polymer | |
CN111378178A (en) | Energy absorption method based on force-induced response polymer | |
CN111378141B (en) | Force-induced response supramolecular polymer | |
CN115926026A (en) | Organic phosphorescent material and preparation method and application thereof | |
CN111378174A (en) | Force-induced responsive polymer with multi-network cross-linked structure | |
CN113997650A (en) | Multilayer structure assembly with force-induced responsiveness | |
CN113045771A (en) | Aspartic acid-based self-repairing antibacterial hydrogel and preparation method and application thereof | |
CN111378172A (en) | Force-induced responsive polymer with multi-hybrid network structure | |
CN111378175A (en) | Force-induced response polymer with cross-linked structure | |
CN111378181A (en) | Force-induced responsive polymer with single-hybrid network structure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |