CN111269386A - Ionic shape memory polyurethane, crystal form A, preparation method and application thereof - Google Patents

Ionic shape memory polyurethane, crystal form A, preparation method and application thereof Download PDF

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CN111269386A
CN111269386A CN202010224581.2A CN202010224581A CN111269386A CN 111269386 A CN111269386 A CN 111269386A CN 202010224581 A CN202010224581 A CN 202010224581A CN 111269386 A CN111269386 A CN 111269386A
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shape memory
memory polyurethane
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polyurethane
tertiary amine
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CN111269386B (en
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陈少军
李永成
卓海涛
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Shenzhen University
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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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Abstract

The invention relates to the technical field of intelligent high polymer materials, in particular to ionic shape memory polyurethane, a crystal form A, a preparation method and application thereof, wherein the ionic shape memory polyurethane comprises a structure shown as the following formula:
Figure DDA0002427219460000011
wherein R1, R2 and R3 are defined in the specification; the ionic shape memory polyurethane provided by the invention has a stable ionic bond structure formed by ammonium ions and carboxylate ions, solves the problems of unstable hydrogen bonds and easy dissociation in the shape memory polyurethane in the prior art, has good photo-thermal graded response shape memory performance, keeps a shape fixed state under visible light, and has better practical application value.

Description

Ionic shape memory polyurethane, crystal form A, preparation method and application thereof
Technical Field
The invention relates to the technical field of intelligent high polymer materials, in particular to ionic shape memory polyurethane, a crystal form A, a preparation method and application thereof.
Background
Shape memory polymers are smart materials that deform and set a temporary shape when subjected to an external stimulus, and change shape back to the original shape when subjected to a corresponding stimulus change (e.g., temperature, light, electricity, magnetism, solvent, etc.). And may be classified into a thermal type, a photo type, a magnetic type, a chemical induction type, etc. according to the response type. The shape memory polymer has the characteristics of light weight, low price, convenient processing, easy deformation, various stimulation modes and the like, and is widely applied to the fields of medical treatment, spinning, biosensing, aerospace, intelligent wearing and the like. The development of multiple stimulus responses has been a major research direction for shape memory polymers; however, the current common photoresponse shape memory polymer has no fixed performance, is deformed under the action of ultraviolet light, and returns to the original shape after the ultraviolet light is removed; therefore, the development of stimulus responsive shape memory polymers that combine light response with other stimulus responses is one of the current developments.
The liquid crystal polymer is also a very important functional polymer material, has distinctive liquid crystal characteristics, and also shows distinctive functional characteristics such as light response characteristics, two-way shape memory performance and the like along with the change of a liquid crystal orientation structure. However, the liquid crystal photoresponse material or the shape memory polymer material has complex preparation process, expensive raw materials and poor structure adjustability. How to rapidly and efficiently prepare the liquid crystal shape memory polymer material is a problem which needs to be solved urgently in the current market.
In recent years, researchers have adopted hydrogen bond supramolecular action to rapidly connect a liquid crystal element into a shape memory polymer, realize the combination of liquid crystal characteristics and shape memory characteristics, and prepare hydrogen bond supramolecular liquid crystal shape memory polymers (polymers, 2019, 127: 121671), however, hydrogen bonds are unstable and are easy to dissociate, and the combination effect is influenced, so that the supramolecular polymers are required to be further improved.
Disclosure of Invention
It is therefore one of the objects of the present invention to provide an ionic shape memory polyurethane comprising the structure shown below:
Figure BDA0002427219440000021
wherein R is1、R2And R3Independently of one another, from: a linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue having up to 40 carbon atoms, which may comprise a residue selected from the group consisting of-O-, -C (O) -, -NH-and-NR3-one or more groups;
y is selected from: a linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue having up to 40 carbon atoms, which may comprise a residue selected from the group consisting of-O-, -C (O) -, -NH-and-NR3-one or more groups;
m and n are integers from 1 to 20.
Further, the compound comprises a structure shown in the following formula:
Figure BDA0002427219440000031
wherein R is4is-CH3、-CH2CH3or-CH2CH2CH2NH2；
Y is selected from: a linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue having up to 40 carbon atoms, which may comprise a residue selected from the group consisting of-O-, -C (O) -, -NH-and-NR3-one or more groups;
m and n are integers from 1 to 20.
Further, Y is selected from: hydrocarbon residues of linear, cyclic or branched, saturated or unsaturated aliphatic diisocyanates or polyisocyanates having up to 15 carbon atoms; or the like, or, alternatively,
the Y is selected from: hydrocarbon residues of aromatic diisocyanates or polyisocyanates having up to 15 carbon atoms.
Further, the Y is selected from at least one of the structures shown in the following formulas:
Figure BDA0002427219440000041
Figure BDA0002427219440000042
or
Figure BDA0002427219440000043
Further, the ionic shape memory polyurethane is selected from at least one of formulas (III), (IV), (V), or (VI):
Figure BDA0002427219440000044
Figure BDA0002427219440000051
further, n is an integer of 1 to 20.
The invention also provides a method for preparing the ionic shape memory polyurethane, which comprises the following steps:
(1) carrying out polymerization reaction on dihydric alcohol containing tertiary amine and diisocyanate or polyisocyanate to generate polyurethane containing tertiary amine;
(2) mixing the polyurethane containing tertiary amine with azo liquid crystal element containing carboxyl to obtain the ionic shape memory polyurethane.
Further, at least one of the following items (1) to (8) is also satisfied:
(1) in the step 1), the number of carbon atoms in the tertiary amine-containing dihydric alcohol is 2-120, preferably, the tertiary amine-containing dihydric alcohol is at least one of N-methyldiethanolamine, N-ethyldiethanolamine and N- (3-aminopropyl) diethanolamine;
(2) in the step 1), the diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, 4' -diphenylmethane diisocyanate and 2, 6-toluene diisocyanate;
(3) in the step 1), the molar ratio of isocyanate groups in the diisocyanate and/or polyisocyanate to hydroxyl groups in the tertiary amine nitrogen-containing diol is (0.90-1.5): 1;
(4) in the step 1), the temperature of the polymerization reaction is 80-100 ℃, and the reaction time is 4-6 h;
(5) in the step 1), organic solvent is adopted to dissolve dihydric alcohol containing tertiary amine, diisocyanate and/or polyisocyanate are added, and under the action of catalyst, N2Under the protection of (2), carrying out polymerization reaction, wherein the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and dimethyl sulfoxide, and the catalyst is a dibutyltin dilaurate catalyst;
(6) in the step 2), the carboxyl-containing azo liquid crystal element is alkoxy azo benzoic acid, and the number of alkane carbon atoms is 1-25; preferably at least one of octoxy azobenzoic acid, dodecyloxy azobenzoic acid and tetradecyloxy azobenzoic acid;
(7) in the step 2), the molar ratio of the carboxyl azo liquid crystal element to the polyurethane containing the tertiary amine is (0.02-1.20): 1;
(8) in the step 2), the ionic shape memory polyurethane is dried at the temperature of 60-120 ℃ for 12-36 h.
The invention also provides a crystal form A of the ionic shape memory polyurethane shown in the formula (VI), wherein Cu-K alpha radiation is used, and X-ray powder diffraction is expressed by a2 theta angle, and the crystal form A has characteristic peaks at 23.9 +/-0.2 degrees, 25.0 +/-0.2 degrees, 26.6 +/-0.2 degrees and 27.5 +/-0.2 degrees;
Figure BDA0002427219440000061
further, said form a has a characteristic endothermic peak at a temperature of 51-59 ℃ using differential scanning calorimetry; and/or, the TGA profile of form a has a loss on heat before 160 ℃ of less than 5%.
The invention also provides the application of the ionic shape memory polyurethane, the ionic shape memory polyurethane prepared by the preparation method, or the crystal form A of the ionic shape memory polyurethane in intelligent control devices, optical components, electronic components, display panels, textiles and daily necessities.
The technical scheme of the invention has the following advantages:
1. the ionic shape memory polyurethane provided by the invention has a stable ionic bond structure formed by ammonium ions and carboxylate ions, solves the problems of unstable hydrogen bonds and easy dissociation in the shape memory polyurethane in the prior art, has good photo-thermal graded response shape memory performance, keeps a shape fixed state under visible light, and has better practical application value.
2. According to the preparation method of the ionic shape memory polyurethane provided by the invention, the polyurethane main chain is polymerized by dihydric alcohol containing tertiary amine and diisocyanate and/or polyisocyanate, alkoxy azobenzoic acid with different alkane chain lengths is selected to be added into the system, and the salt ion group is formed by carboxylic acid and tertiary amine, so that the preparation method is simple in preparation process, easy to regulate and control in structure and performance and low in cost.
3. According to the preparation method of the ionic shape memory polyurethane provided by the invention, researches show that when the molar ratio of the carboxyl-containing azo liquid crystal element to the polyurethane of the tertiary amine is too large, the polymer chain segment spacing is easily increased, the structure is loose, and the bonding force is insufficient, and when the molar ratio of the carboxyl-containing azo liquid crystal element to the polyurethane of the tertiary amine is too small, an ionic structure cannot be effectively formed. The invention controls the molar ratio of the carboxyl-containing azo mesogen to the polyurethane of the tertiary amine to be (0.02-1.20): 1, the structure and the performance can be well matched, and the photoinduced shape memory effect is realized.
4. According to the preparation method of the ionic shape memory polyurethane provided by the invention, researches show that when the molar ratio of isocyanate groups in diisocyanate and/or polyisocyanate to hydroxyl groups in tertiary amine nitrogen-containing dihydric alcohol is too large, the crosslinking degree is easily increased or the molecular weight is insufficient, and when the molar ratio of isocyanate groups in diisocyanate and/or polyisocyanate to hydroxyl groups in tertiary amine nitrogen-containing dihydric alcohol is too small, the molecular weight of the polymer is easily too low. The invention controls the mole ratio of isocyanate group in diisocyanate and/or polyisocyanate to hydroxyl group in diol containing tertiary amine nitrogen to be (0.90-1.5): 1, relatively excellent performance can be achieved.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing the shape memory effect of the ionic shape memory polyurethane film prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of an ionic shape memory polyurethane film prepared in example 2 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the ionic shape memory polyurethane film prepared in example 2 of the present invention;
FIG. 4 is an X-ray diffraction pattern of the ionic shape memory polyurethane film prepared in example 4 of the present invention;
FIG. 5 is an X-ray photoelectron spectrum of the ionic shape memory polyurethane film prepared in example 4 of the present invention;
FIG. 6 is a thermal analysis (DSC) curve of the ionic shape memory polyurethane film prepared in example 4 of the present invention;
FIG. 7 is a thermal stability curve of the ionic shape memory polyurethane film prepared in example 4 of the present invention.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
(1) Adding 1.33g N-ethyldiethanolamine (EDEA) into a three-neck flask, dissolving by using dimethyl sulfoxide (DMSO) as a solvent, adding 1.44g of p-phenylene diisocyanate (PPDI) according to the molar ratio of isocyanate groups in the p-phenylene diisocyanate (PPDI) to hydroxyl groups in tertiary amine nitrogen-containing dihydric alcohol of 0.90, uniformly stirring, adding two drops of dibutyltin dilaurate for catalysis, raising the temperature to 80 ℃, and reacting for 4 hours by mechanical stirring under the protection of nitrogen to prepare a polyurethane solution containing 10 wt% of tertiary amine.
(2) 0.82g (0.002mol) of DABA was added to the tertiary amine-containing polyurethane solution at a ratio of 0.2(r ═ 0.2) mole ratio of dodecyloxyazobenzoic acid (DABA) to EDEA, and the mixture was sufficiently reacted with mechanical stirring to obtain a uniform solution, i.e., an ionic shape memory polyurethane solution containing an ionic shape memory polyurethane having the following structure:
Figure BDA0002427219440000101
(3) and pouring the ionic liquid crystal polyurethane solution into a polytetrafluoroethylene mold to form a film, drying the film in an air-blast drying oven at the temperature of 60 ℃ for 24 hours, and then drying the film in vacuum at the temperature of 60 ℃ for 12 hours to obtain the dry ionic shape memory polyurethane film.
The shape memory effect diagram of the prepared graded-response ionic supramolecular liquid crystal shape memory polyurethane is shown in figure 1, molecular chains of the ionic type shape memory polyurethane film are oriented and arranged after pre-stretching treatment, oriented sample strips are subjected to curling deformation under the stimulation of ultraviolet light, the stimulation of the ultraviolet light is removed, the curling deformation is fixed under the conditions of room temperature and visible light, and when the temperature is raised to 50 ℃ again, the curling shape is gradually recovered to the initial shape.
Example 2
(1) Adding 1.19g N-Methyldiethanolamine (MDEA) into a three-neck flask, dissolving by using N, N-Dimethylformamide (DMF) as a solvent, adding 2.50g of 4,4 '-diphenylmethane diisocyanate (MDI) according to the molar ratio of isocyanate groups in the 4,4' -diphenylmethane diisocyanate to hydroxyl groups in tertiary amine nitrogen-containing dihydric alcohol of 1.00, uniformly stirring, adding two drops of dibutyltin dilaurate for catalysis, controlling the temperature to be 100 ℃, and mechanically stirring for reaction for 4 hours under the protection of nitrogen to prepare a polyurethane solution containing 10 wt% of tertiary amine.
(2) Adding 0.35g (0.001mol) of octoxyazobenzoic acid into a polyurethane solution containing tertiary amine according to the proportion that the molar ratio of the octoxyazobenzoic acid (OABA) to MDEA is 0.1(r is 0.1), and fully reacting under mechanical stirring to obtain a uniform solution, namely an ionic shape memory polyurethane solution, which comprises ionic shape memory polyurethane with the following structure:
Figure BDA0002427219440000111
(3) and pouring the ionic liquid crystal polyurethane solution into a polytetrafluoroethylene mold to form a film, drying the film in an air-blast drying oven at the temperature of 60 ℃ for 24 hours, and then drying the film in vacuum at the temperature of 60 ℃ for 12 hours to obtain the dry ionic shape memory polyurethane film.
The infrared spectrum and the nuclear magnetic resonance hydrogen spectrum of the prepared ionic shape memory polyurethane film are respectively shown in figure 2 and figure 3. As can be seen from FIG. 2, the length of the region of 3300cm-1The wider N-The stretching vibration peak of H is 1705cm-1A characteristic carbonyl peak is found, indicating the presence of a carbamate group; from fig. 3, it can be seen that δ -7.09 and δ -7.35 are the hydrogen proton signals on the MDI phenyl ring and δ -8.13 ppm is the hydrogen proton signal on the OABA phenyl ring, indicating successful grafting of the complex, both confirming the successful synthesis of the ionic shape memory polyurethane.
Example 3
(1) Adding 1.33g N-ethyldiethanolamine (EDEA) into a three-neck flask, dissolving by using N, N-Dimethylformamide (DMF) as a solvent, adding 2.44g of isophorone diisocyanate (IPDI) according to the molar ratio of isocyanate groups in isophorone diisocyanate (IPDI) to hydroxyl groups in tertiary amine nitrogen-containing dihydric alcohol of 1.10, uniformly stirring, adding two drops of stannous octoate for catalysis, controlling the temperature to be 80 ℃, and mechanically stirring for reaction for 4 hours under the protection of nitrogen to prepare the tertiary amine-containing polyurethane solution with the mass fraction of 10 wt%.
(2) 0.22g (0.005mol) of tetradecoxyazobenzoic acid was added to a tertiary amine-containing polyurethane solution at a molar ratio of tetradecoxyazobenzoic acid (TABA) to EDEA of 0.05 (r: 0.05), and the mixture was sufficiently reacted with mechanical stirring to obtain a uniform solution, i.e., an ionic shape memory polyurethane solution, containing an ionic shape memory polyurethane having the following structure:
Figure BDA0002427219440000121
(3) and pouring the ionic liquid crystal polyurethane solution into a polytetrafluoroethylene mold to form a film, drying the film in an air-blast drying oven at the temperature of 60 ℃ for 24 hours, and then drying the film in vacuum at the temperature of 60 ℃ for 12 hours to obtain the dry ionic shape memory polyurethane film.
Example 4
(1) Adding 1.19g N-Methyldiethanolamine (MDEA) into a three-neck flask, adopting N, N-Dimethylacetamide (DMAC) as a solvent, then adding 2.02g of hexamethylene diisocyanate according to the molar ratio of isocyanate groups in the hexamethylene diisocyanate to hydroxyl groups in tertiary amine nitrogen-containing dihydric alcohol of 1.20, adding two drops of stannous octoate for catalysis after uniformly stirring, then controlling the temperature to be 80 ℃, and mechanically stirring for 4 hours under the protection of nitrogen to prepare a polyurethane solution with the mass fraction of 10 wt%.
(2) Adding 0.53g (0.015mol) of octoxyazobenzoic acid into a polyurethane solution containing tertiary amine according to the proportion that the molar ratio of the octoxyazobenzoic acid (OABA) to MDEA is 0.15(r is 0.15), and fully reacting under mechanical stirring to obtain a uniform solution, namely an ionic shape memory polyurethane solution, which comprises ionic shape memory polyurethane with the following structure:
Figure BDA0002427219440000122
(3) and pouring the ionic liquid crystal polyurethane solution into a polytetrafluoroethylene mold to form a film, drying in an air-blowing drying oven at the temperature of 120 ℃ for 12 hours, and then drying in vacuum at the temperature of 60 ℃ for 12 hours to obtain the dry ionic shape memory polyurethane film.
The XRPD pattern of the ionic shape memory polyurethane film prepared in this example was measured using an X-ray powder diffraction (XRPD) instrument, wherein the instrument type: japan science (Rigaku) Uitima IV; the method comprises the following steps: cu target Ka, voltage 40KV, current 40mA, test angle 3-50 degrees, step size 0.02, exposure time 0.2S, light tube slit width 2mm, and a Dtex detector. The results are shown in FIG. 4. The X-ray powder diffraction expressed by the angle of 2 theta has characteristic peaks at 23.9 +/-0.2 degrees, 25.0 +/-0.2 degrees, 26.6 +/-0.2 degrees and 27.5 +/-0.2 degrees, which indicates that the ionic shape memory polyurethane film has good crystallinity and is named as a crystal form A.
An X-ray photoelectron spectrometer is adopted to measure the X-ray photoelectron spectrum of the ionic shape memory polyurethane film prepared by the embodiment, wherein the model of the instrument is PHI Quantera SXM (scanning X-ray Microprobe), a monochromator is adopted, an Al anode target is selected, the energy resolution is 0.5eV, the sensitivity is 3M CPS, the incidence angle is 45 degrees, and the vacuum degree of an analysis chamber is 6.7 multiplied by 10 < -8 > Pa; the bulk silicon-titanium ratio is measured by 3271E type X-ray fluorescence spectrometer of Japan science and electronics Co., Ltd, rhodium target, excitation voltage of 50kV and excitation current of 50mA, the spectral line intensity of each element is detected by a scintillation counter and a proportional counter, a certain amount of sample is taken after the sample is roasted by a powder tabletting method, the sample is put into a mortar and ground to be less than 300 meshes, and the sample is prepared by tabletting. The results are shown in fig. 5, where a peak of quaternary amine nitrogen appears at 402eV, confirming the formation of ionic bonds.
The DSC curve of the ionic shape memory polyurethane film prepared in this example was measured using a differential thermal scanner, instrument type: TA instruments TA2000, USA; the method comprises the following steps: the temperature rise rate is 10 ℃/min, and the result is shown in figure 6, wherein the crystal form A has a characteristic endothermic peak at the temperature of 51-59 ℃. As shown in fig. 7, the TGA profile of form a shows less than 5% loss on heat before 160 ℃, showing a glass transition point and good thermal stability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. An ionic shape memory polyurethane comprising the structure of the formula:
Figure FDA0002427219430000011
wherein R is1、R2And R3Independently of one another, from linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residues having up to 40 carbon atoms, which may comprise a radical chosen from the group consisting of-O-, -C (O) -, -NH-and-NR3-one or more groups;
y is selected from the group consisting of linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residues having up to 40 carbon atoms, which may comprise a radical selected from the group consisting of-O-, -C (O) -, -NH-and-NR3-one or more groups;
m and n are integers from 1 to 20.
2. The ionic shape memory polyurethane of claim 1, comprising a structure of the formula:
Figure FDA0002427219430000021
wherein R is4is-CH3、-CH2CH3or-CH2CH2CH2NH2；
Y is selected from the group consisting of linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residues having up to 40 carbon atoms, which may comprise a radical selected from the group consisting of-O-, -C (O) -, -NH-and-NR3-one or more groups;
m and n are integers from 1 to 20.
3. The ionic shape memory polyurethane of claim 1 or 2, wherein Y is selected from hydrocarbon residues of linear, cyclic or branched, saturated or unsaturated aliphatic di-or polyisocyanates having up to 15 carbon atoms;
the Y is selected from the hydrocarbon residues of aromatic diisocyanates or polyisocyanates having up to 15 carbon atoms.
4. The ionic shape memory polyurethane of any one of claims 1-3, wherein Y is selected from at least one of the structures represented by the following formulae:
Figure FDA0002427219430000031
Figure FDA0002427219430000032
or
Figure FDA0002427219430000033
5. The ionic shape memory polyurethane of any one of claims 1-4, wherein the ionic shape memory polyurethane is selected from at least one of formulas (III), (IV), (V), or (VI):
Figure FDA0002427219430000034
Figure FDA0002427219430000041
6. a method for preparing ionic shape memory polyurethane, which is characterized by comprising the following steps:
1) carrying out polymerization reaction on dihydric alcohol containing tertiary amine and diisocyanate or polyisocyanate to generate polyurethane containing tertiary amine;
2) mixing the polyurethane containing tertiary amine with azo liquid crystal element containing carboxyl to obtain the ionic shape memory polyurethane.
7. The production method according to claim 6, characterized by further satisfying at least one of the following items (1) to (8):
(1) in the step 1), the number of carbon atoms in the tertiary amine-containing dihydric alcohol is 2-120, preferably, the tertiary amine-containing dihydric alcohol is at least one of N-methyldiethanolamine, N-ethyldiethanolamine and N- (3-aminopropyl) diethanolamine;
(2) in the step 1), the diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, 4' -diphenylmethane diisocyanate and 2, 6-toluene diisocyanate;
(3) in the step 1), the molar ratio of isocyanate groups in the diisocyanate and/or polyisocyanate to hydroxyl groups in the tertiary amine nitrogen-containing diol is (0.90-1.5): 1;
(4) in the step 1), the temperature of the polymerization reaction is 80-100 ℃, and the reaction time is 4-6 h;
(5) in the step 1), organic solvent is adopted to dissolve dihydric alcohol containing tertiary amine, diisocyanate and/or polyisocyanate are added, and under the action of catalyst, N2Under the protection of (2), carrying out polymerization reaction, wherein the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and dimethyl sulfoxide, and the catalyst is a dibutyltin dilaurate catalyst;
(6) in the step 2), the carboxyl-containing azo liquid crystal element is alkoxy azo benzoic acid, and the number of alkane carbon atoms is 1-25; preferably at least one of octoxy azobenzoic acid, dodecyloxy azobenzoic acid and tetradecyloxy azobenzoic acid;
(7) in the step 2), the molar ratio of the carboxyl azo liquid crystal element to the polyurethane containing the tertiary amine is (0.02-1.20): 1;
(8) and in the step 2), drying the ionic shape memory polyurethane, wherein the drying mode is blast drying and/or vacuum drying, the drying temperature is 60-120 ℃, and the drying time is 12-36 h.
8. The crystal form A of the ionic shape memory polyurethane shown in the formula (VI) is characterized in that Cu-K alpha radiation is used, and X-ray powder diffraction is expressed by a2 theta angle, and the crystal form A has characteristic peaks at 23.9 +/-0.2 degrees, 25.0 +/-0.2 degrees, 26.6 +/-0.2 degrees and 27.5 +/-0.2 degrees;
Figure FDA0002427219430000051
9. form a according to claim 8, characterized in that it has a characteristic endothermic peak at a temperature of 51-59 ℃ using differential scanning calorimetry; and/or, the TGA profile of form a has a loss on heat before 160 ℃ of less than 5%.
10. The ionic shape memory polyurethane of any one of claims 1 to 5, the ionic shape memory polyurethane prepared by the preparation method of claim 6 or 7, or the crystal form A of claim 8 or 9 is applied to intelligent control devices, optical components, electronic components, display panels, textiles and daily necessities.
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