CN111363116A - Shape memory polyurethane based on hydrogen bond interaction and preparation method thereof - Google Patents
Shape memory polyurethane based on hydrogen bond interaction and preparation method thereof Download PDFInfo
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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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- 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
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
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- 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
- C08J2375/06—Polyurethanes from polyesters
Abstract
The invention provides shape memory polyurethane based on hydrogen bond interaction, which has a structural formula as follows:
wherein n represents the degree of polymerization. The shape memory polyurethane prepared by the invention based on the hydrogen bond interaction adopts the hydrogen bond interaction, can promote the interaction between molecules and improve the materialMechanical properties.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to shape memory polyurethane based on hydrogen bond interaction and a preparation method thereof.
Background
Shape memory polymers, also known as shape memory polymers, are polymeric materials that can recover their original shape after an article having the original shape is fixed after its original condition is changed under certain conditions, and stimulated by external conditions (e.g., heat, electricity, light, chemical induction, etc.). At present, the polymers with shape memory properties are mainly polyurethane, polynorbornene, and the like.
Shape Memory Polyurethane (SMPU) is a novel functional polymer material, which is a block copolymer polymerized by a hard segment with high glass transition temperature and a soft segment with low glass transition temperature, and different glass transition temperatures can be obtained by adjusting the composition and proportion of polyurethane raw materials. SMPU has excellent mechanical property and biocompatibility, wide designable range of memory temperature, large deformation, good shape memory effect and good processability, and attracts the interest of a plurality of scientific researchers.
However, the shape memory property of the existing shape memory polyurethane is poor, mainly linear structure, and the mechanical property is not high, so that the requirement of production cannot be met.
Disclosure of Invention
In view of the above-mentioned disadvantages in the prior art, the present invention aims to provide a shape memory polyurethane based on hydrogen bond interaction and a preparation method thereof, wherein the shape memory polyurethane is a hydrogen bond type crosslinking thermotropic shape memory polyurethane, and has high mechanical properties and good shape memory properties.
In order to achieve the purpose, the invention provides the following technical scheme: a shape memory polyurethane based on hydrogen bonding interactions, the structural formula of the shape memory polyurethane is as follows:
wherein n represents the degree of polymerization.
The preparation method of the shape memory polyurethane based on hydrogen bond interaction comprises the following steps:
(1) prepolymerization reaction: weighing 5-10g of PCL, placing the PCL in a reactor, adding DMF (dimethyl formamide) and a catalyst, placing the reactor in an oil bath, stirring and heating to 70-85 ℃, keeping the stirring speed at 400-500 r/min, continuing heating to 80-90 ℃, adding 0.8-1.2mL of hexamethylene diisocyanate into the reactor, and reacting for 1-1.5 h;
(2) chain extension reaction: weighing 1.3-1.8g of solid N, N-dihydroxyethyl isonicotine, and dissolving with DMF to obtain liquid N, N-dihydroxyethyl isonicotine; slowly dripping the liquid N, N dihydroxyethyl isonicotinite into a reactor, adding 1-2mL of hexamethylene diisocyanate, and reacting for 2-4h at the temperature of 80-90 ℃;
(3) film forming: and (3) quickly pouring the reacted liquid into a preheated mould to uniformly distribute the liquid on the mould, and placing the mould in an oven at 80 ℃ for drying for 8-20h to obtain the shape memory polyurethane SMPUn with different hard segment contents.
Further, n in the shape memory polyurethane SMPUn based on hydrogen bond interaction represents the hard segment content in the polyurethane, and n is 5,10 or 15.
Furthermore, the molecular weight of the PCL is 2000, and the PCL needs to be placed in an oven at 80 ℃ for drying treatment before use.
Further, the catalyst is dibutyltin dilaurate.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a solution polymerization method through hydrogen bond action, takes Polycaprolactone (PCL), N dihydroxyethyl isonicotinite (BINA) and Hexamethylene Diisocyanate (HDI) as main raw materials, and prepares three different hydrogen bond type crosslinking thermotropic shape memory polyurethanes (SMPUn, N is the hard segment content, and N is 5,10 and 15) with different hard segment contents by changing the content ratio of the BINA and the HDI; and the structure and the shape memory performance of the material are represented by infrared ray, TG, DSC, XRD and the like. The result shows that the hydrogen bond type crosslinking thermotropic shape memory polyurethane has good shape memory performance, and the interaction between molecules can be promoted by adopting the hydrogen bond action, so that the mechanical property of the material is improved.
Drawings
FIG. 1 is an infrared spectrum of a shape memory polyurethane based on hydrogen bonding interactions according to the present invention;
FIG. 2 is an X-ray diffraction analysis chart of the shape memory polyurethane based on hydrogen bond interaction according to the present invention;
FIG. 3 is a thermogravimetric plot of a shape memory polyurethane based on hydrogen bonding interactions in accordance with the present invention;
FIG. 4 is a DSC graph of a shape memory polyurethane based on hydrogen bonding interactions according to the present invention;
FIG. 5 is a force versus displacement graph of a shape memory polyurethane tensile test based on hydrogen bonding interactions in accordance with the present invention;
FIG. 6 is a photo of the shape memory polyurethane shape memory recovery based on hydrogen bonding interaction according to the present invention.
Detailed Description
The process of the present invention will be described in detail with reference to specific examples. The shape memory polyurethane based on hydrogen bond interaction can be abbreviated as SMPUn, and the final product is subjected to a series of characterization such as infrared, TG, DSC and XRD. The PCL is named as polycaprolactone in the invention, hexamethylene diisocyanate is abbreviated as HDI, N, N-dihydroxyethyl isonicotine is abbreviated as BINA, dibutyltin dilaurate is abbreviated as DBTL, and N, N-dimethylformamide is abbreviated as DMF.
Firstly, the invention discloses a preparation method of shape memory polyurethane based on hydrogen bond interaction
Example 1
A preparation method of shape memory polyurethane based on hydrogen bond interaction comprises the following steps:
(1) prepolymerization reaction: 5.0g of PCL with molecular weight of 2000 is weighed and put into an oven with temperature of 80 ℃ for drying before use. Slowly adding the dried PCL into a three-neck flask with the specification of 250mL, then adding 20-30mL of DMF solvent into the three-neck flask by using a dropper, and then dropwise adding 3-5 drops of catalyst dibutyltin dilaurate; plugging bottle mouths on two sides of a three-neck flask by using rubber mouths to prevent solvent volatilization and contact of medicine air, placing two thirds of the three-neck flask into an oil bath pot, setting the temperature of the oil bath pot to be 70 ℃, setting the stirring speed to be 400r/min, turning on an electric stirrer to stir, heating to 70 ℃, resetting the temperature of the oil bath pot to be 80 ℃, waiting for the temperature of the oil bath pot to reach 80 ℃, and slowly injecting 0.8mL of HDI into the flask by using a syringe injector; maintaining the temperature of the oil bath kettle at 80 ℃, and keeping the reaction between HDI and PCL to be fully carried out, wherein the prepolymerization reaction time is about 1.5 h;
(2) chain extension reaction: weighing 1.32g of solid N, N-dihydroxyethyl isonicotinine (BINA), and dissolving with 20mL of DMF to obtain liquid N, N-dihydroxyethyl isonicotinine; slowly dripping the liquid N, N dihydroxyethyl isonicotinite into a three-neck flask, wherein the liquid BINA serves as an expansion chain in a reaction system, and then adding 1mL of hexamethylene diisocyanate for adjusting the ratio of PCL to BINA; in order to ensure that the chain extension reaction is fully carried out, the reaction is carried out for 4 hours at the temperature of 80 ℃;
(3) film forming: preheating a mould when the system in the flask is about to react completely; after the reaction is finished, the prepared polyurethane is quickly poured into a mold, the polyurethane is uniformly distributed on the mold pasted with the transparent adhesive in the pouring process, the temperature of an oven is set to be 80 ℃, the mold is placed in the oven, and the time is 8 hours, so that the N, N-Dimethylformamide (DMF) solvent is completely evaporated to dryness, and the SMPU5 film is obtained.
Example 2
A preparation method of shape memory polyurethane based on hydrogen bond interaction comprises the following steps:
(1) prepolymerization reaction: 7.0g of PCL with molecular weight of 2000 is weighed and put into an oven with temperature of 80 ℃ for drying before use. Slowly adding the dried PCL into a three-neck flask with the specification of 250mL, then adding 20-30mL of DMF solvent into the three-neck flask by using a dropper, and then dropwise adding 3-5 drops of catalyst dibutyltin dilaurate; plugging bottle mouths on two sides of a three-neck flask by using rubber mouths to prevent solvent volatilization and contact of medicine air, placing two thirds of the three-neck flask into an oil bath pot, setting the temperature of the oil bath pot to be 80 ℃, setting the stirring speed to be 450r/min, turning on an electric stirrer to stir, heating to 80 ℃, resetting the temperature of the oil bath pot to be 85 ℃, waiting for the temperature of the oil bath pot to reach 85 ℃, and slowly injecting 1.0mL of HDI into the flask by using a syringe injector; maintaining the temperature of the oil bath kettle at 85 ℃, and keeping the reaction between HDI and PCL to be fully carried out, wherein the prepolymerization reaction time is about 1.2 h;
(2) chain extension reaction: weighing 1.65g of solid N, N-dihydroxyethyl isonicotine (BINA), and dissolving with 25mL of DMF to obtain liquid N, N-dihydroxyethyl isonicotine; slowly dripping the liquid N, N dihydroxyethyl isonicotinite into a three-neck flask, wherein the liquid BINA serves as an expansion chain in a reaction system, and then adding 1.5mL of hexamethylene diisocyanate for adjusting the ratio of PCL to BINA; in order to ensure that the chain extension reaction is fully carried out, the reaction is carried out for 2 hours at the temperature of 90 ℃;
(3) film forming: preheating a mould when the system in the flask is about to react completely; after the reaction is finished, the prepared polyurethane is quickly poured into a mold, the polyurethane is uniformly distributed on the mold pasted with the transparent adhesive in the pouring process, the temperature of an oven is set to be 80 ℃, the mold is placed in the oven, the mold is waited for 15 hours, so that the N, N-Dimethylformamide (DMF) solvent is completely evaporated to dryness, and the SMPU10 film is obtained.
Example 3
A preparation method of shape memory polyurethane based on hydrogen bond interaction comprises the following steps:
(1) prepolymerization reaction: 10.0g of PCL with molecular weight of 2000 is weighed and put into an oven with temperature of 80 ℃ for drying before use. Slowly adding the dried PCL into a three-neck flask with the specification of 250mL, then adding 20-30mL of DMF solvent into the three-neck flask by using a dropper, and then dropwise adding 3-5 drops of catalyst dibutyltin dilaurate; plugging bottle mouths on two sides of a three-neck flask by using rubber mouths to prevent solvent volatilization and contact of medicine air, placing two thirds of the three-neck flask into an oil bath pot, setting the temperature of the oil bath pot to be 85 ℃, setting the stirring speed to be 500r/min, turning on an electric stirrer to stir, heating to 85 ℃, resetting the temperature of the oil bath pot to be 90 ℃, waiting for the temperature of the oil bath pot to reach 90 ℃, and slowly injecting 1.2mL of HDI into the flask by using a syringe injector; maintaining the temperature of the oil bath kettle at 90 ℃, and keeping the reaction between HDI and PCL to be fully carried out, wherein the time of the prepolymerization reaction is about 1 h;
(2) chain extension reaction: weighing 1.8g of solid N, N-dihydroxyethyl isonicotinine (BINA), and dissolving with 30mL of DMF to obtain liquid N, N-dihydroxyethyl isonicotinine; slowly dripping the liquid N, N dihydroxyethyl isonicotinite into a three-neck flask, wherein the liquid BINA serves as an expansion chain in a reaction system, and then adding 2mL of hexamethylene diisocyanate for adjusting the ratio of PCL to BINA; in order to ensure that the chain extension reaction is fully carried out, the reaction is carried out for 3 hours at the temperature of 85 ℃;
(3) film forming: preheating a mould when the system in the flask is about to react completely; after the reaction is finished, the prepared polyurethane is quickly poured into a mold, the polyurethane is uniformly distributed on the mold pasted with the transparent adhesive in the pouring process, the temperature of an oven is set to be 80 ℃, the mold is placed in the oven, and the time is 20 hours, so that the N, N-Dimethylformamide (DMF) solvent is completely evaporated to dryness, and the SMPU15 film is obtained.
The synthetic route of the shape memory polyurethane is as follows:
In order not to affect the mechanical performance test of the SMPUn film, if the SMPUn film prepared has more broken or bubbles, a film re-forming method can be used, and the specific method is as follows:
the method comprises the steps of cutting an SMPUn membrane into powder, weighing 2-3 g of the powder by using an electronic balance, transferring the powder into a 250mL glass container, dripping 8-10 mL of DMF (dimethyl formamide) by using a dropper, putting a rotor using magnetic stirring, covering a cover to prevent volatilization of a solvent, setting the temperature of a heating table to be 80 ℃, putting the whole container into the heating table, stirring by using the magnetic rotor to accelerate dissolution of the powder of the SMPUn membrane in the DMF, and fully dissolving the powder. Slowly pouring the liquid in the container into a preheated culture dish, setting the temperature of an oven to be 80 ℃, putting the culture dish, drying for 8 hours, and fully evaporating the N, N-Dimethylformamide (DMF) solvent. After drying, wait for the evaporating dish to cool to room temperature. Finally, the film was carefully cut with a small knife along the edge of the film and gently lifted to obtain a thin SMPUn film which was reformed into a thin film. This process was repeated until no air bubbles appeared in the prepared sample.
Secondly, the performance test of the shape memory polyurethane based on the hydrogen bond interaction prepared by the invention
1. Infrared test (FT-IR)
Selecting a smooth SMPUn film (comprising SMPU5, SMPU10 and SMPU15) with uniform thickness, and taking out the SMPUn film to cut a square sample with an area of about 1 square centimeter. And (4) placing the prepared sample into an instrument sample chamber, placing a clamp down, and covering the box. The method comprises the steps that the infrared spectrogram can be tested only by setting parameters of software before the infrared spectrometer operates, an optical path background signal is scanned firstly when the infrared spectrometer operates, then a sample is scanned, and finally the infrared spectrogram of the sample is obtained through Fourier transform. As can be seen from fig. 1, the infrared spectrum of the polyurethane is very distinct, and it can be checked from the infrared spectrum whether the structure of the sample has obtained the desired product. Since the molecular structure of SMPUn is the same, the infrared spectrum of SMPU5 is selected as an example, and it can be inferred from FIG. 1 that the prepared product has N-H bond and C ═ O bond, a wider absorption peak exists in the graph, and the absorption peak appears at 3337cm-1Near this peak, the peak is the stretching vibration absorption peak of the N-H bond and is at 1726cm-1A relatively clear absorption peak can be observed, and the peak is a stretching vibration absorption peak of C ═ O bonds, so that the product can be determined to be polyurethane according to the characteristic. In the range of 2500-1900 cm-1Does not have an absorption peak of isocyanate group (-N ═ C ═ O), and has a value of 2936cm-1Nearby observation of CH2From this, it was presumed that-OH reacted with the isocyanate group in HDI and HDI in the system had completely reacted. The product prepared by the method of the invention is polyurethane.
2. X-ray diffraction analysis (XRD)
Selecting a proper SMPUn film to cut a small square sample with the area of about 1 square centimeter, clamping the sample by using tweezers, moving the sample on a glass slide filled with plasticine, and flattening the glass slide as much as possible to fix the sample. After the steps are completed, the glass slide can be placed into an X-ray diffractometer for testing so as to further study and observe the structure of the SMPUn. As can be seen from fig. 2, in the wide-angle region of 2 θ of 10 ° to 40 °, a sharp diffraction peak is observed, which proves that the sample is a crystalline polymer, and it can be seen that the diffraction peak is increased with the increase of BINA added into the system, which indicates that the increase of the hard segment content ratio is helpful to enhance the crystallinity of SMPUn.
3. Thermal Property analysis (TG-DSC)
3.1) TGA test analysis
One of the evaluation criteria of the upper limit of the service temperature of the polymer is the thermal stability of the polymer, and the stronger the thermal stability of the polymer, the polymer is not easy to melt, soften or even degrade when heated, and the performance of the polymer can be maintained at higher temperature. Thermal stability of SMPUn was studied using thermogravimetric analysis.
About 6-8mg of the sample was weighed and placed in a crucible. The crucible was placed in an environment with nitrogen for testing. The crucible containing the sample was placed in the sample furnace of the thermogravimetric analyzer and the empty crucible was placed in the reference furnace. After setting the various parameters of the software, the test of the sample was started.
From the TG curve of SMPUn (n-5, 10,15) in fig. 3(a), it is evident that the curves of SMPU5, SMPU10, and SMPU15 all show 2 decomposition platforms. Taking SMPU5 as an example, the soft segment decomposition platform of polyurethane is between 250 and 335 ℃, and the hard segment decomposition platform of polyurethane is between 340 and 490 ℃. Comparing the three curves, it can be observed that the thermal stability of SMPUn is related to the hard segment content in polyurethane, the hard segment content is high, and the thermal stability is slightly higher. The reason for this may be that as the hard segment content increases, the hydrogen bonding action increases, the thermal stability is improved, and the initial decomposition temperature of the polyurethane slightly increases.
As can be seen from the DTG curve of fig. 3 (b): the hard segment content of the polyurethane is related to the decomposition rate of the SMPUn, and the latter tends to decrease with the increase of the former. Due to the increase of intermolecular hydrogen bonds, the intermolecular force of the SMPUn is enhanced, so that the decomposition rate of the SMPU5 with low hard segment content is higher than that of the other two, which shows that the decomposition rate is reduced on the contrary due to the high hard segment content. SMPUn, unlike other polymers, undergoes multi-stage decomposition, indicating microphase separation between soft and soft segments, which is responsible for its shape memory properties.
3.2) DSC test analysis
The sample was subjected to DSC measurement to analyze the glass transition temperature of the sample. Weighing about 6mg of sample, placing the sample in a crucible, flattening, setting the air inlet speed of nitrogen to be 40mL/min, and the temperature rise speed to be 10 ℃/min, and then starting the test. Fig. 4 is DSC diagrams of SMPU5, SMPU10, and SMPU15 at a temperature decrease and a temperature increase, respectively.
As shown in fig. 4, polymer SMPUn (n is the hard segment content ratio, n is 5,10,15) exhibits one melting point and one crystallization point. The melting point here represents the melting of the soft segment portion of PCL in the polymer, and the crystallization point represents the crystallization of the soft segment portion of PCL in the polymer. It can be seen that the melting point does not change much as the hard segment content ratio in the polymer increases.
4. Mechanical Property test
4.1) tensile test
The tensile test can clearly understand the relationship between the proportion of hard segments in SMPUn and the tensile strength and flexibility thereof.
Respectively taking SMPUn films with different proportions, cutting the SMPUn films into rectangular sample strips with the length of 3cm and the width of 1.3cm, measuring the thickness of the sample strips, putting the sample strips into a testing machine for clamping, inputting data of an original gauge length, the width and the thickness, setting the stretching speed to be 2 mm per minute, and starting testing.
The results of the tensile test are shown in fig. 5, from which it is evident that: all three curves are of a brittle and hard type. Comparing the three force versus displacement curves, it can be seen that as the hard segment content increases, the flexibility increases and the energy absorption increases.
5. Testing of shape memory and self-healing Properties
5.1) shape memory Performance testing
The SMPUn film is adopted to verify the thermal response shape memory performance. A bubble-free, non-damaged SMPUn film (SMPU 15 film was selected in the figure) was cut into rectangles at room temperature, which were painted blue on one side and orange on the other side (for easy observation), to obtain the original shape (FIG. 6-a). The sample was placed on a heating table and heated to 50 ℃ and the sample started to soften (FIG. 6-b); when the temperature was raised to 70 ℃, the film curled along one side of the rectangle, rapidly cooled at room temperature, and fixed in shape, thereby obtaining a temporary shape (fig. 6-c). As is apparent from fig. 6, the temporary shape of the SMPUn film was set as an egg roll, and then the sample was slowly heated on a heating stage, and as the temperature rose to 50 ℃, the egg roll was gradually unrolled (fig. 6-d), and the shape of the sample changed to an arch bridge shape over two minutes of continuous heating (fig. 6-e); when the heating stage temperature was heated to 70 c, the shape of the sample was restored to the original shape after about 20 seconds at this temperature (fig. 6-a). The whole process only needs about 3 minutes to completely unfold the sample. Thus, it can be demonstrated that the SMPUn film has a thermally responsive shape memory function.
5.2) Effect of temperature on its shape memory Properties
The same sample was placed in a stand and heated to 70 ℃ until it softened, curled along the original trace, and cooled again while still maintaining its egg roll shape, and then placed in a 70 ℃ heating stand, and after about 20 seconds, the sample was gradually unfolded for about 50 seconds, the sample was completely unfolded, and the sample recovered to a long strip shape, i.e., the original shape, which took about one minute for the entire process.
Under the condition of gradually raising the temperature from 50 ℃ to 70 ℃, the same sample is placed in a heating table for heating, curling and cooling to obtain the same egg roll shape, then the egg roll shape is placed in a heating table at 50 ℃, after about 40 seconds, the sample is gradually unfolded, about one and a half minutes, the sample is completely unfolded, the sample is recovered to be a strip shape, namely the initial shape, and the whole process needs about two minutes.
By comparing the shape recovery rate of the sample with the shape recovery rate at 70 ℃ under the condition of gradually increasing the temperature from 50 ℃ to 70 ℃, it is obvious that the temperature at which the shape recovery rate is faster is 70 ℃.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (5)
1. A shape memory polyurethane based on hydrogen bonding interactions, wherein the structural formula of the shape memory polyurethane is as follows:
wherein n represents the degree of polymerization.
2. A method for preparing a shape memory polyurethane based on hydrogen bonding interaction according to claim 1, comprising the steps of:
(1) prepolymerization reaction: weighing 5-10g of PCL, placing the PCL in a reactor, adding DMF (dimethyl formamide) and a catalyst, placing the reactor in an oil bath, stirring and heating to 70-85 ℃, keeping the stirring speed at 400-500 r/min, continuing heating to 80-90 ℃, adding 0.8-1.2mL of hexamethylene diisocyanate into the reactor, and reacting for 1-1.5 h;
(2) chain extension reaction: weighing 1.3-1.8g of solid N, N-dihydroxyethyl isonicotine, and dissolving with DMF to obtain liquid N, N-dihydroxyethyl isonicotine; slowly dripping the liquid N, N dihydroxyethyl isonicotinite into a reactor, adding 1-2mL of hexamethylene diisocyanate, and reacting for 2-4h at the temperature of 80-90 ℃;
(3) film forming: and (3) quickly pouring the reacted liquid into a preheated mould to uniformly distribute the liquid on the mould, and placing the mould in an oven at 80 ℃ for drying for 8-20h to obtain the shape memory polyurethane SMPUn with different hard segment contents.
3. The preparation method of the shape memory polyurethane based on hydrogen bonding interaction as claimed in claim 2, wherein n in the SMPUn of the shape memory polyurethane based on hydrogen bonding interaction represents the hard segment content in the polyurethane, and n is 5,10 or 15.
4. The preparation method of shape memory polyurethane based on hydrogen bonding interaction as claimed in claim 2, wherein the molecular weight of PCL is 2000, and it is dried in 80 deg.C oven before use.
5. The method of claim 2, wherein the catalyst is dibutyltin dilaurate.
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| CN115010900A (en) * | 2022-05-16 | 2022-09-06 | 广东石油化工学院 | Azobenzene liquid crystal elastomer with photo-thermal double response and reversible deformation and preparation method thereof |
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