CN108892768B - A kind of self-healing light-controlled plastic polyurethane elastomer material, its preparation and application - Google Patents
A kind of self-healing light-controlled plastic polyurethane elastomer material, its preparation and application Download PDFInfo
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Abstract
本发明公开了一种聚氨酯弹性体材料及其制备方法，通过以六芳基联咪唑(HABI)类光致变色分子和多元醇作为弹性体材料的交联剂，构筑出有双交联网络结构的聚氨酯弹性体材料，相应地获得了一种对紫外光有快速响应的智能变形聚氨酯材料，且该材料具有自愈合功能。本发明的聚氨酯弹性体有着很好的韧性、延展性和抗疲劳性等机械物理性能，作为一种智能材料，在驱动器、软体机器人、人造生物器官、传感器、制造业、医疗保健、可穿戴设备和医疗器械等方面有着潜在的应用市场。
The invention discloses a polyurethane elastomer material and a preparation method thereof. By using hexaaryl biimidazole (HABI) photochromic molecules and polyhydric alcohol as the cross-linking agent of the elastomer material, a double-cross-linked network structure is constructed. The obtained polyurethane elastomer material correspondingly obtained an intelligent deformable polyurethane material with rapid response to ultraviolet light, and the material has a self-healing function. The polyurethane elastomer of the present invention has good mechanical and physical properties such as toughness, ductility and fatigue resistance. As a smart material, it can be used in actuators, soft robots, artificial biological organs, sensors, manufacturing, medical care, wearable devices. and medical devices have potential application markets.
Description
Technical Field
The invention belongs to the technical field of flexible intelligent driving materials, and particularly relates to a self-healing light-operated plastic polyurethane elastomer material, and a preparation method and application thereof.
Background
Self-healing light-operated plastic polyurethane elastomers fall into the category of polymeric smart driver materials, also known as actuators or artificial muscles, which respond to external stimuli and change their shape and size. In recent years, with the development of research and the increasing demand for production and living, research on flexible actuators and stimuli-responsive materials is vigorously developed, and among them, polymer materials play a leading role in the field of development of smart materials due to advantages such as low manufacturing cost and easy processing. These materials have the potential to revolutionize healthcare, wearable devices, artificial biological organs, manufacturing, and flexible robotics.
Compared with the traditional rigid material, the flexible material is easy to deform, can adapt to the changing environment and the setting of dynamic tasks, adapts to high load, accords with the production and life safety of human beings, allows cheap mass production, and has better biodegradability and biocompatibility. The material is required to respond to some external stimulus on the macroscopic scale, and one or more functional molecules are necessarily contained in the material on the microscopic scale; in order to make the material have quick response and reversible property, the design of the internal molecular structure of the material is important. The existing intelligent driving material is complex in structural design, so that the synthesis of the material becomes extremely difficult, the application cost is increased, the response to external stimulation is slow or irreversible, and the actual production and living application of the intelligent material is limited to a great extent.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention provides a self-healing light-operated plastic polyurethane elastomer material, a preparation method and application thereof, and aims to construct a polyurethane elastomer material with a double-crosslinking network structure by using Hexaarylbiimidazole (HABI) photochromic molecules and polyol as crosslinking agents of the elastomer material, so that an intelligent deformable polyurethane material with quick response to ultraviolet light is correspondingly obtained, and the material has a self-healing function, thereby solving the technical problems of slow response to external stimuli, irreversible reaction, complex structural design and the like of the intelligent driving material in the prior art.
In order to achieve the above object, according to one aspect of the present invention, a polyurethane elastomer material is provided, which is a polyurethane elastomer material having a double-crosslinked network structure obtained by mixing and reacting an oligomer diol and a diisocyanate as raw materials, and a tetrahydroxy-functionalized hexaarylbiimidazole molecular switch and a polyol as crosslinking agents, wherein hexaarylbiimidazole is a dynamic crosslinking point in the network structure, and the polyol is a fixed crosslinking point; the molecular weight of the oligomer dihydric alcohol is less than 10000 g/mol.
Preferably, the molar ratio of oligomeric diol, diisocyanate, polyol to tetrahydroxy functionalized hexaarylbiimidazole is 12.5: (12-14): (1-5): (0.5 to 4).
Preferably, the molar ratio of oligomeric diol, diisocyanate, polyol to tetrahydroxy functionalized hexaarylbiimidazole is 12.5: (12-14): 3: 1.
further preferably, the molar ratio of the oligomeric diol, diisocyanate, polyol, and tetrahydroxy-functionalized hexaarylbiimidazole is 12.5: 13.7: 3: 1.
preferably, the polyol is a triol or tetraol.
Preferably, the polyol is glycerol triol or pentaerythritol.
Preferably, the tetrahydroxy functionalized hexaarylbisimidazole molecular switch is obtained by modifying and designing 2-Cl-HABI as a molecular main body, wherein the 2-Cl-HABI has a structure shown as a formula (I):
preferably, the tetrahydroxy functionalized hexaarylbisimidazole molecular switch has a structural formula shown as any one of (two) to (ten):
r in the formulas (two) to (ten) is an alkyl chain containing 2 hydroxyl groups.
Preferably, R in the formulae (two) to (ten) is-CH2CHOHCH2OH。
Preferably, the oligomer dihydric alcohol is polyether dihydric alcohol with the molecular weight of 400-8000 g/mol or polyester dihydric alcohol with the molecular weight of 400-8000 g/mol.
Preferably, the diisocyanate is an aliphatic diisocyanate or an aromatic diisocyanate.
Preferably, the diisocyanate is hexamethylene diisocyanate or diphenylmethane diisocyanate.
According to another aspect of the present invention, there is provided a method for preparing the polyurethane elastomer material, comprising the steps of:
(1) under the light shielding condition and under the protection of inert gas, mixing and stirring an organic solution of tetrahydroxy functionalized hexaarylbisimidazole molecules, a catalyst, polyol and dried oligomer dihydric alcohol to obtain a mixed solution; wherein the molar ratio of oligomeric diol, diisocyanate, polyol to tetrahydroxy functionalized hexaarylbiimidazole is 12.5: (12-14): (1-5): (0.5 to 4);
(2) mixing diisocyanate with the mixed solution obtained in the step (1), stirring, and removing the solvent at the temperature lower than 35 ℃ to obtain a solvent-removed mixed solution;
(3) and (3) transferring the mixed solution subjected to solvent removal in the step (2) into a mold, and solidifying and molding the mixed solution under the condition of vacuumizing.
Preferably, the drying treatment in step (1) comprises the following specific steps: and (3) vacuumizing and drying the oligomer dihydric alcohol at the temperature of 70-90 ℃ for 1-3 hours.
Preferably, the organic solvent in the organic solution in step (1) is anhydrous tetrahydrofuran.
Preferably, step (3) is specifically: and (3) transferring the mixed solution of which the solvent is removed in the step (2) into a mould, and reacting for 12-48 hours at the temperature of 40-80 ℃ under the condition of vacuum pumping to solidify and form the mixed solution.
According to another aspect of the invention, the polyurethane elastomer material is used as a light-control plastic intelligent material or a self-healing intelligent material.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the polyurethane material provided by the invention is a light-operated plastic polyurethane elastomer material which is in a double-crosslinking network structure, a tetrahydroxy functionalized hexaaryl biimidazole molecular switch and polyol are used as crosslinking agents, hexaaryl biimidazole in the network structure serves as a dynamic crosslinking point, and the polyol is a fixed crosslinking point. When the polyurethane elastomer is subjected to a certain load, the material can continuously elongate under ultraviolet illumination. This process is reversible. When the load is removed, the material rebounds due to the existence of the fixed cross-linking point, but cannot rebound to the original length, and the material further rebounds to the original length by using the ultraviolet irradiation again.
(2) The polyurethane elastomer material provided by the invention has excellent self-healing effect and short healing time, and the mechanical properties of the healed material can be comparable to those of the material without damage initially.
(3) The polyurethane elastomer provided by the invention has good mechanical and physical properties such as toughness, ductility and fatigue resistance, can be used as an intelligent material, and has potential application markets in the aspects of drivers, soft robots, artificial biological organs, sensors, manufacturing industry, medical care, wearable equipment, medical appliances and the like.
(4) The preparation method of the self-healing light-operated plastic polyurethane elastomer material provided by the invention has the advantages that the pretreatment of the raw materials is very simple, the reaction process is completed in one step, and the industrial large-scale production is easy to realize.
Drawings
Fig. 1 is an optical image of the self-healing light-controlled plastic polyurethane elastomer of example 1, which is repeatedly deformed by ultraviolet light induction when the polyurethane elastomer is loaded;
FIG. 2 is an optical image of two cut self-healing light-controlled plastic polyurethane elastomers self-healing in example 2;
FIG. 3 is a stress strain diagram of the elastomer and the initial damage-free elastomer after self-healing in different time periods under visible light for the polyurethane elastomer material prepared in example 2.
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. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a polyurethane elastomer material, which is a polyurethane elastomer material with a double-crosslinking network structure obtained by taking low-polymer dihydric alcohol, diisocyanate, polyol and a tetrahydroxy functionalized hexaaryl biimidazole (HABI) molecular switch as raw materials and a tetrahydroxy functionalized hexaaryl biimidazole molecular switch and polyol as crosslinking agents through reaction. The molar ratio of oligomer diol, diisocyanate, polyol to tetrahydroxy functionalized hexaarylbiimidazole is 12.5: (12-14): (1-5): (0.5 to 4), preferably 12.5: (12-14): 3: 1, more preferably 12.5: 13.7: 3: 1. The proportion of the four raw materials is important, the proportion range needs to be strictly controlled to form the polyurethane elastomer material, wherein the content of diisocyanate is more critical, the content of diisocyanate is too low, the material cannot be cured, the content of diisocyanate is too high, the strength of the obtained material is too high, the elastomer material cannot be formed, and the corresponding light control plasticity is not obvious.
In the above raw materials, the polyhydric alcohol is a trihydric alcohol or tetrahydric alcohol, and is preferably glycerol trihydric alcohol or pentaerythritol. The oligomer is a polymer composed of fewer repeating units, and the relative molecular mass of the polymer is generally less than 10000g/mol, wherein the oligomer diol is preferably polyether diol or polyester diol with the molecular weight of 400-8000 g/mol, and is further preferably oligomer diol such as polyethylene glycol (PEG) or polytetrahydrofuran ether glycol (PTMG). The diisocyanate is aliphatic diisocyanate or aromatic diisocyanate, preferably hexamethylene diisocyanate HDI or diphenylmethane diisocyanate MDI. The invention particularly selects a tetrahydroxy functionalized Hexaarylbiimidazole (HABI) molecular switch as a dynamic cross-linking agent, the tetrahydroxy functionalized hexaarylbiimidazole molecular switch is a series of molecules which are obtained by modifying and designing 2-Cl-HABI as a molecular main body, and the 2-Cl-HABI has a structure shown as a formula (I):
for example, the tetrahydroxy functionalized hexaarylbisimidazole molecular switch may have a structural formula as shown in any one of (di) to (ten):
r in the formulae (di) to (ten) is an alkyl chain containing 2 hydroxyl groups, preferably-CH2CHOHCH2And (5) OH. In the case of molecules of the formula (II), where R is-CH2CHOHCH2When OH, the preparation method of the molecule of the formula (II) is as follows:
(1) adding 2-chloro-4-hydroxybenzaldehyde and 3-chloro-1, 2-propylene glycol into an aqueous solution of sodium hydroxide to react for 12 hours at the temperature of 80 ℃ in a nitrogen atmosphere, then cooling to room temperature, adding a certain amount of concentrated hydrochloric acid, and carrying out liquid separation chromatography to prepare 2-chloro-4- (2, 3-dihydroxypropoxy) benzaldehyde;
(2) adding the product of the first step, benzil and ammonium acetate into a certain amount of acetic acid solution at 90 ℃ for reaction for 12 hours, separating, crystallizing and purifying to obtain 2-chloro tetrahydroxy triphenylimidazole;
(3) and (3) at room temperature, adding the product obtained in the second step, the hematite solid and potassium hydroxide into an organic solution of dichloromethane, reacting for 8 hours, and separating and purifying to obtain the molecule shown in the formula (II).
The tetrahydroxy functionalized hexaarylbisimidazole molecular switch of the formulas (III) to (ten) can be prepared according to similar ideas of the preparation methods.
The invention provides a preparation method of a polyurethane elastomer material, which comprises the following steps:
(1) under the light shielding condition and under the protection of inert gas nitrogen, mixing and stirring the dried oligomer dihydric alcohol, the organic solution of the tetrahydroxy functionalized hexaaryl bisimidazole molecule, the catalyst and the polyol to obtain a mixed solution; the drying treatment comprises the following specific steps: and (3) vacuumizing and drying the oligomer dihydric alcohol at the temperature of 70-90 ℃ for 1-3 hours. The organic solvent adopted in the organic solution is anhydrous Tetrahydrofuran (THF), and the catalyst is dibutyltin dilaurate (DBTDL). The oligomer diol is dried to remove water therefrom so as to prevent water molecules from reacting with diisocyanate, resulting in failure to obtain the polyurethane elastomer material of the present invention. The inert gas protection is to avoid oxygen in the air from participating in the reaction, so that the self-healing light-controlled plastic polyurethane elastomer material cannot be obtained.
(2) Mixing diisocyanate with the mixed solution obtained in the step (1), stirring, and removing the solvent at the temperature lower than 35 ℃ to obtain a solvent-removed mixed solution; the solvent removal method can be, for example, to reduce the boiling point of the solvent to evaporate the solvent under the condition of vacuum, and the temperature for removing the solvent is not preferably too high, because once the diisocyanate is added to the mixed solution in step (1), the reaction is started, the temperature is too high, the reaction is too fast, so that the diisocyanate is cured in the process of removing the solvent, and finally, the cured material may contain the solvent or a molded elastomer material meeting the requirements cannot be obtained. And controlling the rotary evaporation temperature to ensure that the reaction system is still in a liquid state after the solvent is removed, so that the next step of curing and forming in a proper mould is facilitated.
(3) And (3) transferring the mixed solution of which the solvent is removed in the step (2) into a mould, and reacting for 12-48 hours at the temperature of 40-80 ℃ under the condition of vacuum pumping to solidify and form the mixed solution. The curing and molding are carried out under the vacuum pumping condition to avoid oxygen in the air from participating in the reaction, so that the self-healing light-control plastic polyurethane elastomer material cannot be obtained.
The invention provides a self-healing light-operated plastic polyurethane elastomer material and a preparation method thereof, wherein the elastomer material is prepared from the following raw materials: oligomer dihydric alcohol, diisocyanate, polyalcohol and tetrahydroxy functionalized Hexaarylbiimidazole (HABI) molecular switch. According to the invention, tetrahydroxy functionalized hexaaryl imidazole photochromic molecules are introduced into a polymer system, the prepared polyurethane material is in a double-crosslinking network structure, a tetrahydroxy functionalized hexaaryl imidazole photochromic molecule switch and polyhydric alcohol are crosslinking agents, hexaaryl imidazole in the network structure serves as a dynamic crosslinking point, and the polyhydric alcohol serves as a fixed crosslinking point. The dynamic cross-linking point refers to a molecule which serves as a cross-linking point under an external condition such as an illumination condition, wherein a bond in the molecule is dissociated to form two separated free radicals which are disconnected; and when the light is removed, the free radicals are combined again to form cross-linking points of a cross-linking structure. The fixed crosslinking point refers to a crosslinking point at which no linkage is broken under light irradiation.
The elastic modulus of the polyurethane elastomer material with the double-crosslinked-network structure is changed under the irradiation of ultraviolet light, the elastic modulus of the material is continuously reduced along with the increase of the ultraviolet light irradiation time, and the polyurethane elastomer material can be used as a light-controllable plastic intelligent material, such as artificial muscle responding to the ultraviolet light. When the polyurethane elastomer is subjected to a certain load, the material can continuously elongate under ultraviolet illumination. This process is reversible. When the load is removed, the material rebounds due to the existence of the fixed cross-linking point, but cannot rebound to the original length, and the material further rebounds to the original length by using the ultraviolet irradiation again. Specifically, under ultraviolet irradiation, C-N bonds between two imidazole rings of a hexaarylbiimidazole molecular switch are broken, so that two triphenylimidazole free radicals (TPIR) which are difficult to stably exist are formed, and after the ultraviolet irradiation is removed, the triphenylimidazole free radicals (TPIR) form hexaarylbiimidazole again. By utilizing the property of the hexaaryl bisimidazole molecular switch, when the polyurethane elastomer bears a certain load, two triphenyl imidazole free radicals are dislocated under the irradiation of ultraviolet light, so that the material is continuously elongated, and the network structure is rearranged. The deformation of the material can be well controlled by the light, the longer the light time, the larger the deformation, and the process is reversible. Due to the existence of the fixed cross-linking points, the material has good elasticity, the load is removed, the material rebounds, but due to the dislocation rearrangement of the triphenyl imidazole free radical, the material cannot rebound to the initial length, and the triphenyl imidazole free radical which originally undergoes the dislocation rearrangement can seek the triphenyl imidazole free radical at the initial position and is combined with the triphenyl imidazole free radical again by using the ultraviolet irradiation, so that the material can further rebound to the initial length.
In addition, the polyurethane elastomer material with the double-crosslinked network structure has excellent self-healing capability under visible light, and can be used as a self-healing intelligent material. The polyurethane elastomer material has excellent self-healing effect and short healing time, and the mechanical property of the healed material can be compared with that of the material without damage initially. Because the HABIS and TPIRs have thermodynamic equilibrium, the material with physical damage is placed under visible light, the material heals by itself, and the healing effect in a short time is excellent. Compared with most of the existing self-healing materials, the material has short healing time and does not need too harsh external conditions.
The polyurethane elastomer prepared by the invention has good mechanical and physical properties such as toughness, ductility and fatigue resistance, and has potential application markets in the aspects of drivers, soft robots, artificial biological organs, sensors, manufacturing industry, medical care, wearable equipment, medical appliances and the like as an intelligent material.
The starting materials used in the examples of the present invention are commercially available, or can be obtained by well-established methods known in the art, except for the self-synthesized tetrahydroxy functionalized hexaarylbisimidazole molecular switch.
The following are examples:
example 1
PTMG is used as oligomer dihydric alcohol, and 2-Cl-4-diol-HABI molecular switches and glycerol are used as cross-linking agents to synthesize the double-cross-linked self-healing light-controlled plastic polyurethane elastic material. The molecular structure of 2-Cl-4-diol-HABI is as follows.
PTMG (1.9 g; 1.9mmol) is weighed into a round-bottom flask, dried under vacuum at 70 ℃ for about 1h and cooled to room temperature under the protection of nitrogen. Weighing glycerol (42 mg; 0.456mmol) and injecting into the round bottom flask, then weighing 2-Cl-4-diol-HABI (128 mg; 0.152mmol), dissolving with 10ml anhydrous THF, mixing with PTMG, and adding catalyst DBTDL and stirring vigorously for half an hour; 0.33ml of HDI was added to the above mixed solution by drawing with a 1ml syringe; and vacuumizing the mixed solution for three to four times, stirring for about ten minutes, performing rotary evaporation, completely removing THF, and pouring into a mold. Putting the mixture into a vacuum drying oven, reacting for 24 hours at 45 ℃ under vacuum, cooling to room temperature and taking out. Finally obtaining the dumbbell-shaped orange translucent polyurethane elastomer, and carrying out the ultraviolet light induced tensile deformation test. The weight was 100 g. The relevant tensile deformation test procedure is presented in fig. 1, with an initial sample having a length; when a weight is added, the material is elastically deformed and extends for a certain distance; then ultraviolet radiation is carried out on the material, the material is subjected to certain plastic deformation and is stretched again; removing the illumination and the weight, wherein the material retracts for a certain distance due to certain elasticity, but can not rebound to the initial length, and the difference is several millimeters; finally, the material is again subjected to ultraviolet irradiation under the condition of no load, and is placed in a dark environment for a period of time, and the material is further restored to the original length.
Example 2
PTMG is used as oligomer dihydric alcohol, and 2-Cl-4-diol-HABI molecular switches and glycerol are used as cross-linking agents to synthesize the double-cross-linked self-healing light-controlled plastic polyurethane elastic material.
PTMG (3.8 g; 3.8mmol) is weighed into a round-bottom flask, dried under vacuum at 70 ℃ for about 1h and cooled to room temperature under the protection of nitrogen. Weighing glycerol (112 mg; 1.216mmol) and injecting into the round bottom flask, then weighing 2-Cl-4-diol-HABI (128 mg; 0.152mmol), dissolving with 10ml anhydrous THF, mixing with PTMG, and adding catalyst DBTDL and stirring vigorously for half an hour; 0.66ml of HDI was added to the above mixed solution by drawing with a 1ml syringe; and vacuumizing the mixed solution for three to four times, stirring for about ten minutes, performing rotary evaporation, completely removing THF, and pouring into a mold. Putting the mixture into a vacuum drying oven, reacting for 24 hours at 45 ℃ under vacuum, cooling to room temperature and taking out. Finally obtaining the dumbbell-shaped orange semitransparent polyurethane elastomer, and carrying out self-healing related experiments. The self-healing experiments were performed at room temperature under visible light. The related self-healing experimental process is shown in fig. 2, in order to observe the self-healing phenomenon visually and vividly, two samples marked with different colors are cut and spliced together, and then are placed under visible light, so that the situation that the cut cannot be broken even if pulled by manpower after a period of time is found, and the self-healing phenomenon is shown; fig. 3 is a representation of stress strain of the material in example 2 after different time periods of the initial state and the self-healing by light, and another means different from the optical image is used to illustrate the recovery of the mechanical and physical properties of the material after the self-healing, and the stress strain diagram of the prepared polyurethane elastomer material after the self-healing and the initial damage-free elastomer in different time periods under visible light is used, and the specific recovery degree can be finally compared with the stress strain diagram in fig. 3, the fracture strain of the self-healing sample after the polyurethane elastomer material is placed under visible light for different time periods (1h, 6h, 12h) is increased along with the time extension, the fracture strain of the sample after the polyurethane elastomer material is healed for 12h is even slightly larger than that of the initial sample (origin), which indicates that the healing degree of the material is already high, and the recovery degree of the mechanical and physical properties of the self-healing sample.
Example 3
PTMG is used as oligomer dihydric alcohol, and 2-Cl-4-diol-HABI molecular switches and glycerol are used as cross-linking agents to synthesize the double-cross-linked self-healing light-controlled plastic polyurethane elastic material.
PTMG (3.8 g; 3.8mmol) is weighed into a round-bottom flask, dried under vacuum at 70 ℃ for about 1h and cooled to room temperature under the protection of nitrogen. Weighing glycerol (56 mg; 0.608mmol) and injecting into the round bottom flask, weighing 2-Cl-4-diol-HABI (128 mg; 0.152mmol), dissolving with 10ml anhydrous THF, mixing with PTMG, adding catalyst DBTDL and stirring vigorously for half an hour; 0.66ml of HDI was added to the above mixed solution by drawing with a 1ml syringe; and vacuumizing the mixed solution for three to four times, stirring for about ten minutes, performing rotary evaporation, completely removing THF, and pouring into a mold. Putting the mixture into a vacuum drying oven, reacting for 24 hours at 45 ℃ under vacuum, cooling to room temperature and taking out. Finally obtaining the dumbbell-shaped orange translucent polyurethane elastomer, and carrying out corresponding ultraviolet light induced tensile deformation test.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
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