CN106832172B - Light/heat grading response shape memory polymer and preparation method and application thereof - Google Patents
Light/heat grading response shape memory polymer and preparation method and application thereof Download PDFInfo
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- CN106832172B CN106832172B CN201611234855.6A CN201611234855A CN106832172B CN 106832172 B CN106832172 B CN 106832172B CN 201611234855 A CN201611234855 A CN 201611234855A CN 106832172 B CN106832172 B CN 106832172B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3836—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing azo groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2280/00—Compositions for creating shape memory
Abstract
The invention is applicable to the field of intelligent high polymer materials, and provides a light/heat grading response shape memory polymer and a preparation method and application thereof. The light/heat grading response shape memory polymer is formed by polymerizing a monomer A, a monomer B and a monomer C; wherein the structural formula of the monomer A is
The monomer B is hexamethylene diisocyanate, and the monomer C is N-methyldiethanolamine. The light/heat grading response shape memory polymer provided by the invention has a unique light/heat grading response shape memory effect and has independent deformation response to ultraviolet light and thermal stimulation respectively.
Description
Technical Field
The invention belongs to the field of intelligent high polymer materials, and particularly relates to a light/heat grading response shape memory polymer, and a preparation method and application thereof.
Background
In recent decades of research on Shape Memory Polymers (SMPs), the research and application of thermotropic shape memory polymeric materials (TSMPs) have been greatly developed. However, TSMPs are not easily controlled remotely, and deformation is achieved by directly heating to induce phase change of materials, which greatly limits the application of TSMPs in shielding systems and non-contact systems. On the other hand, photo-SMPs have received high attention from researchers because of the excellent characteristics of environmental friendliness, remote controllability, instantaneity, and the like due to light stimulation. The photoinduced SMPs have the unique advantages of non-contact regulation and control deformation, fixed-point regulation and control deformation, high speed, clean regulation and control deformation and the like, and can directly convert light energy into mechanical energy and improve the utilization efficiency of light. However, SMPs stimulated by ordinary light have strong dependence on light, and are deformed when irradiated with light, and are restored when not irradiated with light, and thus cannot fix a temporary shape. In addition, to further expand the versatility and practical application range of SMPs, domestic and foreign research on SMPs is focusing on realizing multiple responsiveness and multiple shape memory effects. However, the current multiple shape memory effect is to realize triple or multiple shape memory by temperature control of multiple reversible phases or by using a wide range of glass transition as a reversible equivalent means, which is limited by temperature. There have also been some studies on the triple shape memory performance by heat generated by electric or light action, which is attributed to the single thermally induced triple shape memory effect.
Accordingly, the prior art is deficient and needs improvement.
Disclosure of Invention
In order to solve the technical problems, the invention provides an optical/thermal grading response shape memory polymer, and a preparation method and application thereof, aiming at improving the temporary shape fixing effect of the existing shape memory polymer and developing the shape fixing controllability of the existing shape memory polymer, thereby realizing the development and application of multifunctional SMPs.
The invention is realized by the following steps that the light/heat grading response shape memory polymer is formed by polymerizing a monomer A, a monomer B and a monomer C;
wherein the structural formula of the monomer A is
The monomer B is hexamethylene diisocyanate, and the monomer C is N-methyldiethanolamine.
The invention also provides a preparation method of the light/heat grading response shape memory polymer, which comprises the following steps:
carrying out polymerization reaction on the monomer A and the monomer B to obtain a shape memory polymer prepolymer containing an azobenzene structural unit;
and adding a monomer C and a monomer B into the shape memory polymer prepolymer to obtain the high-molecular-weight shape memory polymer.
Compared with the prior art, the invention has the beneficial effects that: the light/heat grading response shape memory polymer provided by the embodiment of the invention utilizes the photoinduced configuration isomerization change of azobenzene molecules to construct a polymer high molecular material with shape memory and shape change. The light/heat grading response shape memory polymer obtained by the method has a unique light/heat grading response shape memory effect and has independent deformation response to ultraviolet light and thermal stimulation respectively. Under the irradiation of ultraviolet light, the shape memory polymer can actively deform; after the ultraviolet light is cancelled, the deformation is kept unchanged under the normal temperature and the visible light environment, and a temporary shape is obtained; when the temperature is raised above the glass transition temperature of the shape memory polymer by thermal stimulation, the shape memory polymer can actively recover the deformation from the temporary shape to the original shape.
Drawings
FIG. 1 is a schematic diagram of the optical/thermal grading response shape change and recovery process of L HSMPU prepared in example 2 of the present invention;
FIG. 2 is a schematic diagram showing structural changes of an azobenzene structural unit of L HSMPU prepared in example 3 of the present invention under the stimulation of ultraviolet light at different times.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first embodiment of the invention provides a light/heat grading response shape memory polymer, which is formed by polymerizing a monomer A, a monomer B and a monomer C;
wherein the structural formula of the monomer A is
The monomer B is hexamethylene diisocyanate, and the monomer C is N-methyldiethanolamine.
The first embodiment of the present invention provides a photo/thermal grading response shape memory polymer, which is prepared by polymerizing azobenzene dicarboxylic acid, hexamethylene diisocyanate and N-methyldiethanolamine. Respectively carrying out polyaddition reaction on azobenzene dicarboxylic acid and partial hexamethylene diisocyanate under the action of a catalyst to construct an azobenzene soft segment chain; carrying out polyaddition reaction on N-methyldiethanolamine and the rest hexamethylene diisocyanate under the action of a catalyst to construct a hard segment of the N-methyldiethanolamine; and then, the azobenzene soft segment chain is connected with the N-methyldiethanolamine hard segment chain through chemical bonds, and the polymer high polymer material with shape memory and shape change is constructed by utilizing the photoinduced configuration isomerization change of azobenzene molecules. The light/heat grading response shape memory polymer obtained by the method has a unique light/heat grading response shape memory effect and has independent deformation response to ultraviolet light and thermal stimulation respectively.
Referring to fig. 1, the shape memory polymer can be actively deformed under the irradiation of ultraviolet light; after the ultraviolet light is cancelled, the deformation is kept unchanged under the normal temperature and the visible light environment, and a temporary shape is obtained; when the temperature is raised above the glass transition temperature of the shape memory polymer by thermal stimulation, the shape memory polymer can actively recover the deformation from the temporary shape to the original shape.
Specifically, the structural formula of the shape memory polymer is as follows:
wherein n is more than or equal to 10, and m is more than or equal to 10. In the light/heat hierarchical response shape memory polymer provided by the first embodiment of the present invention, a polyurethane main chain is introduced into an azobenzene structural unit, and the light/heat hierarchical response shape memory polymer has a light response function. The polyurethane hard segment provides a physical crosslinking point for thermal recovery, and the azobenzene structure generates structural change under the action of thermal stimulation to cause main chain motion and generate elastic recovery to recover to an initial state.
Specifically, the mass ratio of the monomer A, the monomer B and the monomer C is (10-20): 30-40): 40-60. By regulating the dosage of the monomer A, the monomer B and the monomer C, the mass percentage of the monomer A in the shape memory polymer is 10-20 wt%, the mass percentage of the monomer C is 30-40 wt%, and the mass percentage of the monomer B is 40-60 wt%. Thereby realizing the control of the deformation of the photoresponse of the shape memory polymer by regulating and controlling the content of the monomer A; the control of the temperature response range of the thermal response of the shape memory polymer is realized by regulating the content of B and C.
Specifically, the monomer B includes at least one of aliphatic diisocyanates. The monomer C comprises at least one of N-methyldiethanolamine and N-methyldimethanolamine.
Specifically, the mole number a of carboxyl groups in the monomer A, the mole number B of isocyanate groups in the monomer B and the mole number C of hydroxyl groups in the monomer C satisfy the following relationship:
and r is b/(a + c), and the value range of r is 0.95-1.05.
The number average molecular weight of the polymerized shape memory polymer is larger than 5000 by limiting the number relation of the mole number a of carboxyl in the monomer A, the mole number B of isocyanate groups in the monomer B and the mole number C of hydroxyl groups in the monomer C, so that the shape memory polymer has better moldability.
Specifically, the glass transition temperature of the light/heat grading response shape memory polymer is 30-90 ℃. The content of the monomers A, B and C in the shape memory polymer is regulated and controlled, so that the glass transition temperature of the polyurethane is kept at 30-90 ℃.
The second embodiment of the present invention provides a method for preparing the above-mentioned optical/thermal grading response shape memory polymer, which comprises the following steps:
carrying out polymerization reaction on the monomer A and the monomer B to obtain a shape memory polymer prepolymer containing an azobenzene structural unit;
and adding a monomer C and a monomer B into the shape memory polymer prepolymer to obtain the high-molecular-weight shape memory polymer.
The preparation method of the photo/thermal grading response shape memory polymer provided by the second embodiment of the invention is to perform polymerization synthesis by using azobenzene dicarboxylic acid, diisocyanate and N-methyldiethanolamine as raw materials. Firstly, alternately copolymerizing azobenzene dicarboxylic acid and partial diisocyanate to construct an azobenzene soft segment chain, wherein a catalyst for the reaction of the azobenzene dicarboxylic acid and the diisocyanate is dibutyltin dilaurate; and (3) alternately copolymerizing N-methyldiethanolamine and the rest diisocyanate to construct an azobenzene hard segment, connecting an azobenzene soft segment chain with the azobenzene hard segment through a chemical bond, and constructing the polymer high polymer material with shape memory and shape change by utilizing photoinduced configuration isomerization change of azobenzene molecules.
Specifically, the chemical structural formula of the shape memory polymer prepolymer is as follows:
In a second embodiment of the present invention, a method for preparing a light/heat grading response shape memory polymer is provided, and a chemical structural formula of the light/heat grading response shape memory polymer obtained by the method is:
the preparation method is simple in process and suitable for large-scale production.
The third embodiment of the invention provides an application of the light/heat grading response shape memory polymer, wherein the application is that the light/heat grading response shape memory polymer is used for preparing an intelligent nano device, an intelligent drug controlled release agent or an intelligent sensor.
The third embodiment of the invention applies the azobenzene compound as the photoresponse group to a device or a preparation for converting light energy into mechanical motion, and has wide application prospect.
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1
Adding 0.37g of 4,4 '-azobenzene dicarboxylic acid and 10.0g N, N' -dimethylformamide into a three-neck flask for dissolving, then dropwise adding 1.5g of hexamethylene diisocyanate and 0.6m of L dibutyltin dilaurate, reacting for 30min at 80 ℃, then adding 1.96g N-methyldiethanolamine and 1.5g of hexamethylene diisocyanate, reacting for 30min at 80 ℃, pouring the solution into a polytetrafluoroethylene mold after the reaction is finished, and drying in an air-blast drying oven at 80 ℃ for 24h to obtain the optical/thermal grading response shape memory polyurethane (L HSMPU). the azobenzene structural unit is introduced into a polyurethane main chain and has an optical response function, a physical cross-linking point is provided for thermal recovery by a polyurethane hard segment, and the azobenzene structure can also generate structural change under the action of thermal stimulation to cause the main chain movement and elastic recovery to restore to the initial state.
Example 2
Adding 0.54g of 4,4 '-azobenzene dicarboxylic acid and 12.0g N, N' -dimethylformamide into a three-neck flask for dissolving, then dropwise adding 1.5g of hexamethylene diisocyanate and 0.6m of L dibutyltin dilaurate, reacting at 80 ℃ for 30min, then adding 1.89g N-methyldiethanolamine and 1.5g of hexamethylene diisocyanate, reacting at 80 ℃ for 30min, pouring the solution into a polytetrafluoroethylene mold after the reaction is finished, and drying in an air-blast drying oven at 80 ℃ for 24h to obtain the optical/thermal grading response shape memory polyurethane (L HSMPU). The diagram of FIG. 1 is a schematic diagram of the optical/thermal grading response shape change and the recovery process of the prepared L HSMPU, and can be seen from FIG. 1, under the irradiation of ultraviolet light, the polyurethane main chain is curled shape and has photoinduced shape deformation, after the ultraviolet light stops, the curled shape is kept stable at room temperature, has a good shape fixing function, and in the temperature rising process, the curled shape is gradually recovered to the initial flat state without irradiation, and the shape recovery is realized.
Example 3
Adding 0.96g of 4,4 '-azobenzene dicarboxylic acid and 15.0g N, dissolving in N' -dimethylformamide, then dropwise adding 1.5g of hexamethylene diisocyanate and 0.6m of L dibutyltin dilaurate, reacting at 80 ℃ for 30min, then adding 1.69g N-methyldiethanolamine and 1.5g of hexamethylene diisocyanate, reacting at 80 ℃ for 30min, pouring the solution into a polytetrafluoroethylene mold after the reaction is finished, and drying in an air-blast drying oven at 80 ℃ for 24h to obtain the optical/thermal grading response shape memory polyurethane (L HSMPU). fig. 2 shows that the ultraviolet absorption spectrum is adopted to track the change of the azobenzene structure unit structure in L HSMPU prepared under the ultraviolet light stimulation at different times, as shown in fig. 2, the absorption peak of the pi-N-electron (isomer) of nitrogen double bond (-N-) in the azobenzene group at 362nm is gradually reduced along with the ultraviolet light stimulation time, and the trans-benzene group is gradually changed from the cis-pi electron (isomer) electron transition peak to trans-benzene) electron transition peak, namely, and the trans-benzene group is gradually changed into a macroscopic isomer, and the roll material under the ultraviolet light stimulation.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. The light/heat grading response shape memory polymer is characterized in that the light/heat grading response shape memory polymer is formed by polymerizing a monomer A, a monomer B and a monomer C;
wherein the structural formula of the monomer A is
The monomer B comprises at least one of aliphatic diisocyanate, and the monomer C comprises at least one of N-methyldiethanolamine and N-methyldimethanolamine;
the shape memory polymerThe structural formula of (A) is:
n≥10,m≥10。
2. the photo/thermal grading response shape memory polymer of claim 1, wherein monomer a has the formula
The monomer B is hexamethylene diisocyanate, and the monomer C is N-methyldiethanolamine;
the structural formula of the shape memory polymer is as follows:
3. the photo/thermal grading response shape memory polymer as in claim 2, wherein the mass ratio of the monomer A, the monomer B and the monomer C is (10-20): (30-40): (40-60).
4. The photo/thermal grading response shape memory polymer according to claim 1, wherein the mole number of carboxyl groups a in the monomer a, the mole number of isocyanate groups B in the monomer B and the mole number of hydroxyl groups C in the monomer C satisfy the following relationship:
and r is b/(a + c), and the value range of r is 0.95-1.05.
5. The light/heat-grading responsive shape memory polymer of claim 1, wherein the light/heat-grading responsive shape memory polymer has a glass transition temperature of 30 to 90 ℃.
6. The method for preparing an optical/thermal grading responsive shape memory polymer according to any of claims 1 to 5, comprising the steps of:
carrying out polymerization reaction on the monomer A and the monomer B to obtain a shape memory polymer prepolymer containing an azobenzene structural unit;
and adding the monomer C and the monomer B into the shape memory polymer prepolymer to obtain the shape memory polymer with high molecular weight.
7. The method of claim 6, wherein the catalyst for polymerizing the monomer A and the monomer B is dibutyltin dilaurate.
8. The use of the light/heat grading response shape memory polymer according to any one of claims 1 to 5, wherein the use is to use the light/heat grading response shape memory polymer in the preparation of intelligent nano devices, intelligent drug controlled release agents or intelligent sensors.
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| CN107337780A (en) * | 2017-07-20 | 2017-11-10 | 深圳大学 | A kind of preparation method for the shape memory elastic body that light heat double-bang firecracker is answered |
| CN110922561B (en) * | 2019-12-13 | 2022-01-04 | 广东石油化工学院 | Light/heat triple shape memory star polymer and preparation method thereof |
| CN111269386B (en) * | 2020-03-26 | 2021-09-28 | 深圳大学 | Ionic shape memory polyurethane, crystal form A, preparation method and application thereof |
| CN111875765B (en) * | 2020-07-16 | 2022-07-12 | 复旦大学 | Linear azobenzene polymer containing hydrogen bond and preparation method and application thereof |
| CN116694066B (en) * | 2023-08-07 | 2023-09-29 | 苏州易昇光学材料股份有限公司 | GPU (graphic processing unit) optical film and preparation method thereof |
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