CN115651196A - Body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds and preparation method thereof - Google Patents
Body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000004044 response Effects 0.000 title claims abstract description 25
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- PFRGXCVKLLPLIP-UHFFFAOYSA-N diallyl disulfide Chemical compound C=CCSSCC=C PFRGXCVKLLPLIP-UHFFFAOYSA-N 0.000 claims description 12
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical group SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- XNZOTQPMYMCTBZ-UHFFFAOYSA-N allyl methyl disulfide Chemical compound CSSCC=C XNZOTQPMYMCTBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- DJLRNCWMAKPXJF-UHFFFAOYSA-N 3-(ethyldisulfanyl)prop-1-ene Chemical compound CCSSCC=C DJLRNCWMAKPXJF-UHFFFAOYSA-N 0.000 claims description 4
- JSOVZQSFWPMPKN-UHFFFAOYSA-N 4-(3-sulfanylpropanoyloxy)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCCCOC(=O)CCS JSOVZQSFWPMPKN-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005057 refrigeration Methods 0.000 claims description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 claims description 3
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- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- IPNDIMIIGZSERC-UHFFFAOYSA-N 4-(2-sulfanylacetyl)oxybutyl 2-sulfanylacetate Chemical compound SCC(=O)OCCCCOC(=O)CS IPNDIMIIGZSERC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds and a preparation method thereof. The invention introduces the synthesized long-chain soft segment molecule PHG into the liquid crystal polymer molecular chain, increases the soft segment ratio in the molecular chain, reduces the energy required by the movement of the liquid crystal elastomer molecular chain, and effectively reduces the phase transition temperature of the liquid crystal elastomer because the liquid crystal polymer has phase transition at lower temperature; hydrogen bonds formed among the contained dynamic amido bonds can effectively maintain the breaking tensile strength of the liquid crystal elastomer, and the problem that the liquid crystal elastomer is T NI The problem of a sharp decrease in tensile strength at break at the above ambient temperature; the contained dynamic disulfide bonds also endow the fabric with excellent programmable and self-healing properties. Meanwhile, the single-domain liquid crystal elastomer can be driven by body temperature and has obvious reversible shrinkage deformation; the invention provides a flexible wearable device for application in the field of flexible wearable devicesAnd (4) a feasible scheme is adopted.
Description
Technical Field
The invention belongs to the field of preparation of flexible intelligent materials, and particularly relates to a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds and a preparation method thereof.
Background
The liquid crystal elastomer serving as a flexible polymer material with good biocompatibility has the advantages of reversible deformation, large tensile strain, stress and the like, and has wide application prospects in the fields of actuators, soft robots, optical elements, wearable equipment and the like.
The precondition of the liquid crystal elastomer having the driving performance is to form a single-domain liquid crystal elastomer. The monodomain refers to the orderly arrangement of the mesogens in the cross-linked network to form uniform orientation. The monodomain liquid crystalline elastomer is in an anisotropic phase (liquid crystal phase) at or below the liquid crystal transition temperature (Ti) and has mesogens arranged in order, and is in an isotropic phase at or above Ti and has mesogens arranged in disorder. When being stimulated by the outside, the polymer chains generate the phase state change between the isotropic phase and the anisotropic phase, thereby generating reversible deformation. However, the liquid crystal elastomer can be reversibly deformed by an external temperature stimulus, but the phase transition temperature T of the liquid crystal elastomer has been reported NI Most are above 60 ℃, and the temperature at which the reversible deformation occurs is far higher than the body temperature. Meanwhile, although the driving strain can reach more than 50% at high temperature, it is at T NI The tensile strength at break at temperatures above this level decreases rapidly. Therefore, these drawbacks further limit the practical application of liquid crystal elastomer materials.
At present, the soft segment is introduced into the liquid crystal polymer network to replace the rigid element in the liquid crystal polymer, so that the energy required by the motion of the segment is reduced, and the purpose of reducing the phase transition temperature is achieved. However, the introduction of the soft segment reduces the phase transition temperature of the material, and simultaneously, the partial driving performance and mechanical property of the liquid crystal elastomer are sacrificed, so that the overall performance of the liquid crystal elastomer is greatly influenced.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is known to a person skilled in the art.
Disclosure of Invention
One of the purposes of the invention is to design a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds based on the above problems of the liquid crystal elastomer and by innovating from the structure of a liquid crystal polymerization network. The single-domain liquid crystal elastomer can realize reversible driving at body temperature, and simultaneously ensure the driving performance and the mechanical performance of the liquid crystal elastomer, and improve the driving performance at T NI The tensile strength at break at temperature is drastically reduced.
The invention provides a body temperature responsive single-domain liquid crystal elastomer with double dynamic covalent bonds, which is synthesized by taking a liquid crystal monomer RM257, a chain extender, a long-chain soft segment PHG, a cross-linking agent, a disulfide compound, a photoinitiator and a catalyst as raw materials through a two-step method, wherein the unit structure of the molecular structure of the liquid crystal elastomer is as follows:
preferably, the molecular structure of the single-domain liquid crystal elastomer simultaneously contains a dynamic disulfide bond and a dynamic amide bond, wherein the dynamic disulfide bond is disconnected and reconnected at 150 ℃ or UV (ultraviolet), the self-healing is realized, and the dynamic amide bond and secondary amine on the dynamic amide bond can form a hydrogen bond. The formed hydrogen bond can effectively maintain the breaking tensile strength of the liquid crystal elastomer; solves the problem that the liquid crystal elastomer is at T NI The tensile strength at break at the above ambient temperature sharply decreases.
The invention also aims to provide a preparation method of the body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds. Through the design of a liquid crystal polymerization network structure, the liquid crystal elastomer has body temperature driving, programmable and self-repairing performances.
A preparation method of a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds specifically comprises the following preparation steps:
s1, weighing the following components in proportion: the liquid crystal composition comprises a liquid crystal monomer RM257, a chain extender, a long-chain soft segment PHG, a cross-linking agent, a disulfide compound, a photoinitiator and a catalyst;
s2, preparing long-chain soft segment PHG: placing polyethylene glycol (PEG), isocyano Ethyl Methacrylate (IEMA) and dibutyltin dilaurate (T12) serving as a catalyst into a three-neck flask, adding 20mL Tetrahydrofuran (THF) solvent, and completely dissolving for N 2 Reacting for 4-8h at 55-65 ℃ in the atmosphere to obtain a long-chain soft-segment PHG solution; under the process, the long-chain soft-segment PHG can be prepared mildly, and the PHG solution can be directly used for preparing the liquid crystal elastomer without further purification, filtration and other processes, so that the utilization rate of the long-chain soft-segment PHG is improved.
S3, preparing a liquid crystal elastomer: dissolving a liquid crystal monomer RM257, a chain extender, a catalyst, a photoinitiator UV-651 and the long-chain soft-segment PHG solution prepared in the step S1 in Tetrahydrofuran (THF), and stirring for reaction for 12-24 hours; adding a cross-linking agent PETMP, a disulfide compound and a catalyst to continuously react for 4-6 h to obtain a liquid crystal elastomer solution; according to the invention, the long-chain soft-segment PHG molecular chain and the disulfide compound are simultaneously introduced into the main-chain type liquid crystal elastomer, so that the structure, functional design and performance optimization of the liquid crystal elastomer are expanded, the single-domain liquid crystal elastomer can realize reversible driving at body temperature, and the driving performance and mechanical performance of the liquid crystal elastomer are ensured.
S4, defoaming and drying: pouring the liquid crystal elastomer solution obtained in the step S2 into a polytetrafluoroethylene groove, putting the polytetrafluoroethylene groove into a refrigerator for refrigeration, eliminating bubbles in the solution, putting the solution at normal temperature until the solvent is completely volatilized, and continuously drying the solution in an oven at the temperature of 40-80 ℃ to obtain a liquid crystal elastomer film;
s5, alignment of the liquid crystal elastomer: and (4) pre-stretching the liquid crystal elastomer film dried in the step (S3) to 100-200% of the original length, stretching and collimating at 80 ℃, and finally curing by using ultraviolet light (UV) to obtain the single-domain liquid crystal elastomer.
Preferably, in step S1, the molar ratio of the liquid crystal monomer RM257, the chain extender, the long-chain soft segment PHG, the crosslinking agent, and the disulfide compound is 1 to 1.15: 0.085-1.15: 0.01 to 0.2: 0.045-0.07: 0.01 to 0.1; the content of the catalyst is 0.5 to 1.5 weight percent of the mass of the liquid crystal monomer RM 257; the content of the photoinitiator is 1.0wt% -2.0 wt% of the mass of the liquid crystal monomer RM 257.
By the above-set ratio, on the one hand, sufficient reaction between raw materials and crosslinking of oligomers can be facilitated; on the other hand, as the content of the long-chain soft segment PHG is more, the occupation ratio of the soft segment molecular chain in the liquid crystal polymer molecular chain is more, the crosslinking density in the liquid crystal polymer molecular network and the energy required by the segment motion of the molecular chain can be reduced, and the tensile strength and the isotropic transition temperature of the liquid crystal elastomer are reduced; when the content of the long-chain soft segment PHG is too low, the phase transition temperature of the formed liquid crystal polymer is higher, and the requirement of body temperature response is difficult to meet; when the content of the long-chain soft segment PHG is excessive, the phase transition temperature of the formed liquid crystal polymer can be further reduced, but the ratio of the soft segment molecular chain is increased, the breaking tensile strength is reduced, and meanwhile, the chain segment slip of the liquid crystal polymer molecular chain in the mechanical stretching pre-alignment process can also exist, so that the orientation degree of a liquid crystal element is reduced, and the driving strain of the liquid crystal polymer is initiated; therefore, within the proportion range, the liquid crystal elastomer prepared by the invention can keep the breaking tensile strength and the driving strain property within a small variation range under the condition of reducing the phase transition temperature.
Preferably, in step S2, the molecular weight of polyethylene glycol (PEG) is 400 to 8000, and the molar ratio of polyethylene glycol (PEG) to isocyanatoethyl methacrylate (IEMA) is 1:2. the invention enables the preparation reaction of the long-chain soft segment PHG to be carried out more fully by controlling the molar ratio of each component; when the polyethylene glycol (PEG) is excessive, the content of the long-chain soft-segment PHG is reduced due to insufficient reaction of raw materials, the proportion of the PHG in the liquid crystal polymer is further reduced, and the phase transition temperature is difficult to reduce; when the amount of Isocyano Ethyl Methacrylate (IEMA) is excessive, the raw material IEMA in the PHG is excessive, and the excessive IEMA participates in the preparation reaction of the liquid crystal oligomer, affects further chain extension and crosslinking of the polymer network, and even causes the mechanical property of the liquid crystal elastomer to be reduced.
Further, in the step S3, the molar ratio of RM257 to the chain extender to the cross-linking agent is 1 to 1.15:0.085 to 1.15: 0.045-0.07; RM257: PHG: the molar ratio of the disulfide bond compounds is 1-1.15: 0.01 to 0.2:0.01 to 0.1; the content of the catalyst is 0.5 to 1.5 weight percent of the mass of the liquid crystal monomer RM 257; the content of the photoinitiator is 1.0 to 2.0 weight percent of the mass of the liquid crystal monomer RM 257.
Further, in step S4, the defoaming treatment mode is: pouring the liquid crystal elastomer solution in the step S2 into a polytetrafluoroethylene groove, putting the polytetrafluoroethylene groove into a refrigerator for refrigerating at-20 ℃ for 1-2h, recovering to the normal temperature, continuing to volatilize the solvent for 24-48 h, continuing to dry in a baking oven at 40 ℃ for 1-2h, and then gradually heating to 80 ℃ for 6-10h. In the drying process, through gradient heating treatment, bubbles formed in the film when the solvent is volatilized too fast can be eliminated on one hand, and the volatilization process of the solvent can be effectively slowed down on the other hand, so that a liquid crystal polymer network in the film is fully crosslinked, and a compact liquid crystal elastomer film is formed.
Further, in step S5, mechanically stretching the dried liquid crystal elastomer to 100% -200% of the original length, heating and collimating for 0.5-2 h at 80 ℃, and then curing for 0.2-1 h by using ultraviolet light (UV), thus obtaining the single-domain liquid crystal elastomer. In the alignment process, the liquid crystal elements in the liquid crystal elastomer can be effectively fully oriented in the pre-stretching process, and simultaneously, the liquid crystal elements are further polymerized and cured under ultraviolet light. The single domain liquid crystal elastomer with excellent reversible driving strain and tensile strength at break can be obtained.
Preferably, the chain extender is at least one of 3, 6-dioxa-1, 8-octane dithiol, 1, 4-butanediol bis (3-mercaptopropionate), and 1, 4-butanediol bis (mercaptoacetate). The cross-linking agent is pentaerythritol tetrakis (3-mercaptopropionate). The disulfide compound is at least one of diallyl disulfide, allyl methyl disulfide and ethyl allyl disulfide. The catalyst is at least one of di-n-propylamine, triethylamine and diethylenetriamine.
The technical scheme of the invention is that a two-step method is adopted to prepare the liquid crystal elastomer, and the three chain extenders adopted contain flexible molecular chains (-O-), so as to increase the soft segment proportion of the liquid crystal polymer; the three chain extenders and the liquid crystal monomer need to carry out addition reaction under the action of a catalyst to form liquid crystal oligomer which continues to react with a disulfide compound and a cross-linking agent; wherein, the disulfide compounds are all selected to have dialkenyl disulfide compounds, which can play a role in bridging the oligomer and the crosslinking agent; in this process, the catalyst is at least one of di-n-propylamine, triethylamine and diethylenetriamine, so that the reaction can be slowed and more sufficiently. The liquid crystal elastomer prepared by the method contains amido bonds and disulfide bonds, and is positioned on the main chain of liquid crystal polymer molecules, so that the requirements of the required body temperature driving strain and breaking tensile strength performance can be met.
Preparing a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds based on the technical scheme; when the phase transition temperature is high, the reversible driving strain and fracture tensile strength performance is excellent, the self-healing and programmable performance is also realized, and the driving behaviors comprise stretching, bending, twisting and spiraling;
wherein,
through the scheme, the invention has the beneficial effects that:
1. the invention prepares a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds, introduces synthesized long-chain soft segment molecules PHG into a liquid crystal polymer molecular chain, increases the soft segment ratio in the molecular chain, reduces the energy required by the movement of the molecular chain of the liquid crystal elastomer, and enables the liquid crystal polymer to generate phase change at lower temperature, thereby effectively reducing the isotropic transition temperature of the liquid crystal elastomer; because the introduced long-chain soft segment molecule PHG contains dynamic amido bonds, hydrogen bonds formed among the amido bonds can effectively maintain the breaking tensile strength of the liquid crystal elastomer; solves the problem that the liquid crystal elastomer is at T NI The tensile strength at break at the above ambient temperature sharply decreases. Warp beamThe degree of orientation of the single-domain liquid crystal elastomer is 0.41-0.45 through tests NI At 39-43.6 ℃; the driving strain is 11.1 to 31.6 percent at the temperature of 35 to 45 ℃; the fracture tensile strength can not obviously change within the range of 25-45 ℃, and the maximum fracture tensile strength can reach 3.5 MPa.
2. According to the invention, a disulfide bond is introduced into a liquid crystal polymer network molecular chain, self-healing is realized by placing a sheared mLCEs stripe sample in a 150 ℃ or UV environment, and due to the introduction of a dynamic amido bond, a hydrogen bond formed between amido bonds and the dynamic disulfide bond have a synergistic effect, so that the self-healing capability of the liquid crystal elastomer is promoted. After self-healing, the breaking tensile strength of the mLCEs can be restored to 90% of the original tensile strength before shearing; meanwhile, the disulfide bonds endow the mLCEs with programmable performance, and reversible deformation of the programmed shape and the original shape is realized at 150 ℃ or UV.
3. The single-domain liquid crystal elastomer designed by the invention can realize driving at body temperature (36.8 ℃) and also has excellent performances of programmability and self-healing. The reversible shrinkage deformation after driving reaches 11.1 percent; the body temperature response type single-domain liquid crystal elastomer provides a feasible scheme for application in the field of intelligent wearable equipment.
Drawings
FIG. 1 is a nuclear magnetic spectrum of PHG in sample mLCEs of example 1 of the present invention;
FIG. 2 shows Raman spectra of mLCEs of example 1 and comparative example 1;
FIG. 3 is a differential thermal scanning analysis (DSC) profile of mLCEs of examples 1-3 of the present invention and comparative examples 1-3;
FIG. 4 is a graph of the driving strain and tensile strength at break at 45 ℃ for mLCEs of examples 1-3 of the present invention and comparative examples 1-3;
FIG. 5 is a graph of tensile strength at break versus strain at 25 ℃ for mLCEs of examples 1-3 of the present invention and comparative examples 1-3;
FIG. 6 is a graph of 5 cycles of tensile strain at 25 ℃ and 45 ℃ for sample mLCEs of example 1 of the present invention;
FIG. 7 is a driving strain cycle curve and a stability curve of 10 cycle length changes of sample mLCEs at temperature rising and temperature falling respectively in the embodiment 1 of the invention;
FIG. 8 is an SEM image of self-healing conditions of mLCEs at 150 ℃ and UV for different time periods of sample 1 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention more clear, the present invention is described in detail with reference to specific embodiments below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the examples of the present invention, the specific sources of the various materials required are as follows:
polyethylene glycol 400: shanghai Michelin Biochemical technology, inc.;
polyethylene glycol 800: shanghai Maxin Biochemical technologies, inc.;
polyethylene glycol 2000: shanghai Michelin Biochemical technology, inc.;
isocyanatoethyl methacrylate (98%): shanghai Maxin Biochemical technologies, inc.;
dibutyltin dilaurate: shanghai Michelin Biochemical technology, inc.;
liquid crystalline monomer RM257 (97%): 2-methyl-1, 4-phenylenebis (4- (3- (acryloyloxy) propoxy) benzoate), shijia scany fine chemical ltd;
chain extender BBT (97%): 1, 4-butanediol bis (thioglycolate), shanghai Aladdin Biotechnology, inc.;
chain extender EDDET (97%): 3, 6-dioxa-1, 8-octanedithiol, shanghai Allantin Biotech Co., ltd;
the chain extender BDMP (97 percent) is 1,4 butanediol di (3-mercaptopropionate), shanghai Aladdin Biotechnology GmbH;
catalyst di-n-propylamine: shanghai Michelin Biochemical technology, inc.;
catalyst triethylamine: shanghai Maxin Biochemical technologies, inc.;
catalyst diethylenetriamine: shanghai Maxin Biochemical technologies, inc.;
tetrahydrofuran: shanghai Lingfeng Chemicals, inc.;
diallyl disulfide (85%): shanghai Maxin Biochemical technologies, inc.;
allyl methyl disulfide (85%): shanghai Maxin Biochemical technologies, inc.;
ethyl allyl disulfide (85%): shanghai Michelin Biochemical technology, inc.;
photoinitiator (2): 2, 2-dimethoxy-2-phenylacetophenone, shanghai alatin biochem technologies, ltd;
crosslinking agent PETMP (90%): pentaerythritol tetrakis (3-mercaptopropionate), shanghai Aladdin Biotechnology Ltd.
Example 1
A preparation method of a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds specifically comprises the following preparation steps:
s1, preparing long-chain soft segment molecules: 1.665mmol of polyethylene glycol (average molecular weight 400) and 3.33mmol of isocyanatoethyl methacrylate were dissolved in 20mL of tetrahydrofuran solvent, 20. Mu.L of the catalyst dibutyltin dilaurate, N 2 Oil bath is carried out at 60 ℃ under the atmosphere for reaction for 6h, and the PHG-400 solution with the concentration of 0.083mmol/mL is prepared.
S2, preparing a liquid crystal elastomer: dissolving 3.33mmol of liquid crystal monomer RM257, 3.28mmol of chain extender 3, 6-dioxa-1, 8-octane dithiol and 0.02g of photoinitiator in 4g of tetrahydrofuran solvent at 25 ℃, and adding 20 mu L of n-dipropylamine to obtain a precursor solution;
adding PHG-400 solution according to 5% of liquid crystal monomer RM257 mol, namely adding 2mLPHG-400 into the precursor solution, reacting for 18h to obtain liquid crystal elastomer prepolymer, adding 0.187mmol of cross-linking agent pentaerythritol tetrakis (3-mercaptopropionate), 0.333mmol of diallyl disulfide and 10 mu L of n-dipropylamine, mixing and reacting for 6h to obtain liquid crystal elastomer solution.
S3, defoaming and drying: and pouring the obtained liquid crystal elastomer solution into a polytetrafluoroethylene plate, defoaming, placing the liquid crystal elastomer solution in a fume hood, naturally drying the liquid crystal elastomer solution for 24 hours, placing the liquid crystal elastomer solution in a 40 ℃ drying oven for drying for 2 hours, heating the liquid crystal elastomer solution to 60 ℃ for drying for 8 hours, and heating the liquid crystal elastomer solution to 80 ℃ for drying for 2 hours to obtain the liquid crystal elastomer.
S4, aligning the liquid crystal elastomer: and cutting off a part of the strip-shaped liquid crystal elastomer, stretching the strip-shaped liquid crystal elastomer along the length direction by 100%, heating and collimating the strip-shaped liquid crystal elastomer at 80 ℃ for 1h, and then continuously using UV light for 0.5h to finally obtain the single-domain liquid crystal elastomer.
Example 2
A preparation method of a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds specifically comprises the following preparation steps:
s1, preparing long-chain soft segment molecules: 1.665mmol of polyethylene glycol (average molecular weight: 800) and 3.33mmol of isocyanoethyl methacrylate were dissolved in 20mL of tetrahydrofuran solvent, and 20. Mu.L of dibutyltin dilaurate, N as a catalyst, was added 2 Reacting for 6h under the atmosphere at 60 ℃ in an oil bath to prepare a PHG-800 solution with the concentration of 0.083 mmol/mL.
S2, preparing a liquid crystal elastomer: dissolving 3.33mmol of liquid crystal monomer RM257, 3.35mmol of chain extender 1, 4-butanediol di (3-mercaptopropionate) and 0.02g of photoinitiator in 3g of tetrahydrofuran solvent at 25 ℃, and adding 20 mu L of di-n-propylamine to obtain a precursor solution;
adding PHG-800 solution with the molar weight of 2.5 percent of that of the liquid crystal monomer RM257, namely adding 1ml of PHG-800 into the precursor solution, reacting for 12h to obtain a liquid crystal elastomer prepolymer, adding 0.194mmol of cross-linking agent pentaerythritol tetrakis (3-mercaptopropionate), 0.333mmol of allyl methyl disulfide and 10 mu L of di-n-propylamine, mixing and reacting for 6h to obtain the liquid crystal elastomer solution.
S3, defoaming and drying: pouring the obtained liquid crystal elastomer solution into a polytetrafluoroethylene plate, defoaming, placing the liquid crystal elastomer solution in a fume hood for naturally drying for 48h, drying in a 40 ℃ oven for 1h, heating to 60 ℃ for drying for 5h, and heating to 80 ℃ for drying for 1h to obtain the liquid crystal elastomer.
S4, liquid crystal elastomer alignment: and cutting off a part of the strip-shaped liquid crystal elastomer, stretching the strip-shaped liquid crystal elastomer along the length direction by 150%, heating and collimating the strip-shaped liquid crystal elastomer at 80 ℃ for 2 hours, and then continuously using UV light for 1 hour to finally obtain the single-domain liquid crystal elastomer.
Example 3
A preparation method of a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds specifically comprises the following preparation steps:
s1, preparing long-chain soft segment molecules: 1.665mmol of polyethylene glycol (average molecular weight 2000) and 3.33mmol of isocyanatoethyl methacrylate were dissolved in 20mL of tetrahydrofuran solvent, and 20. Mu.L of the catalyst dibutyltin dilaurate, N, were added 2 Oil bath is carried out at 60 ℃ under the atmosphere for reaction for 6h, and the PHG-2000 solution with the concentration of 0.083mmol/mL is prepared.
S2, preparing a liquid crystal elastomer: mixing 3.33mmol of liquid crystal monomer RM257, 3.43mmol of chain extender 1, 4-butanediol bis (mercaptoacetate) and 0.02g of photoinitiator at 25 ℃, adding 2g of tetrahydrofuran solvent, adding 20 mu L of di-n-propylamine, and carrying out catalytic reaction to obtain a precursor solution;
adding a PHG-2000 solution (3 mLPHG-2000) which is 7.5 percent of the molar weight of a liquid crystal monomer RM257 into the precursor solution, reacting for 12 hours to obtain a liquid crystal elastomer prepolymer, adding 0.204mmol of a cross-linking agent pentaerythritol tetrakis (3-mercaptopropionate) and 0.333mmol of dynamic covalent bond ethyl allyl disulfide 10 mu L of di-n-propylamine, mixing and reacting for 6 hours to obtain a liquid crystal elastomer solution.
S3, defoaming and drying: and pouring the obtained liquid crystal elastomer solution into a polytetrafluoroethylene plate, defoaming, placing the polytetrafluoroethylene plate in a fume hood for natural drying 36h, drying the polytetrafluoroethylene plate in a 40 ℃ drying oven for 1.5h, heating to 60 ℃ for drying for 4h, and heating to 80 ℃ for drying for 3h to obtain the liquid crystal elastomer.
S4, liquid crystal elastomer alignment: and cutting off a part of the strip-shaped liquid crystal elastomer, stretching the strip-shaped liquid crystal elastomer along the length direction by 200%, heating and collimating the strip-shaped liquid crystal elastomer at 80 ℃ for 0.5h, and then continuously using UV light for 1h to finally obtain the single-domain liquid crystal elastomer.
Comparative example 1
A preparation method of a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds specifically comprises the following preparation steps:
s1, preparing long-chain soft segment molecules: 1.665mmol of polyethylene glycol (average molecular weight 400) and 3.33mmol of isocyanatoethyl methacrylate were dissolved in 20mL of tetrahydrofuran solvent, 20. Mu.L of the catalyst dibutyltin dilaurate, N 2 Oil bath is carried out at 60 ℃ under the atmosphere for reaction for 6h, and the PHG-400 solution with the concentration of 0.083mmol/mL is prepared.
S2, preparing a liquid crystal elastomer: at 25 ℃, 3.33mmol of liquid crystal monomer RM257, 3.28mmol of chain extender 3, 6-dioxa-1, 8-octane dithiol and 0.02g of photoinitiator are dissolved in 4g of tetrahydrofuran solvent, and 20 mu L of n-dipropylamine is added to obtain a precursor solution;
adding PHG-400 solution according to 5% of liquid crystal monomer RM257 mol, namely adding 2mLPHG-400 into the precursor solution, reacting for 18h to obtain liquid crystal elastomer prepolymer, adding 0.187mmol of cross-linking agent pentaerythritol tetrakis (3-mercaptopropionate) and 10 mu L of n-dipropylamine, mixing and reacting for 6h to obtain liquid crystal elastomer solution.
S3, defoaming and drying: and pouring the obtained liquid crystal elastomer solution into a polytetrafluoroethylene plate, defoaming, placing the liquid crystal elastomer solution in a fume hood, naturally drying for 24 hours, placing the liquid crystal elastomer solution in a 40 ℃ drying oven, drying for 2 hours, heating to 60 ℃, drying for 8 hours, and heating to 80 ℃ to dry for 2 hours to obtain the liquid crystal elastomer.
S4, liquid crystal elastomer alignment: and (3) cutting off a part of the strip-shaped liquid crystal elastomer, stretching the strip-shaped liquid crystal elastomer by 100 percent along the length direction, heating and collimating the strip-shaped liquid crystal elastomer for 1 hour at the temperature of 80 ℃, and then continuously using UV light for illumination for 0.5 hour to finally obtain the single-domain liquid crystal elastomer.
Comparative example 2
A preparation method of a body temperature response type single-domain liquid crystal elastomer specifically comprises the following preparation steps:
s1, preparing a liquid crystal elastomer: dissolving 3.33mmol of liquid crystal monomer RM257, 3.28mmol of chain extender 3, 6-dioxa-1, 8-octane dithiol and 0.02g of photoinitiator in 4g of tetrahydrofuran solvent at 25 ℃, and adding 20 mu L of n-dipropylamine to obtain a precursor solution; and (3) reacting for 12 hours without adding a long-chain soft segment to obtain a liquid crystal elastomer prepolymer, adding 0.187mmol of a cross-linking agent pentaerythritol tetrakis (3-mercaptopropionate), 0.333mmol of diallyl disulfide and 10 mu L of n-dipropylamine, and mixing and reacting for 6 hours to obtain a liquid crystal elastomer solution.
S3, defoaming and drying: and pouring the obtained liquid crystal elastomer solution into a polytetrafluoroethylene plate, defoaming, placing the liquid crystal elastomer solution in a fume hood, naturally drying for 24 hours, placing the liquid crystal elastomer solution in a 40 ℃ drying oven, drying for 2 hours, heating to 60 ℃, drying for 8 hours, and heating to 80 ℃ to dry for 2 hours to obtain the liquid crystal elastomer.
S4, liquid crystal elastomer alignment: and cutting off a part of the strip-shaped liquid crystal elastomer, stretching the strip-shaped liquid crystal elastomer along the length direction by 100%, heating and collimating the strip-shaped liquid crystal elastomer at 80 ℃ for 1h, and then continuously using UV light for 0.5h to finally obtain the single-domain liquid crystal elastomer.
Comparative example 3
A preparation method of a body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds specifically comprises the following preparation steps:
3.33mmol of a liquid crystal monomer RM257, 3.14mmol of a chain extender 3, 6-dioxa-1, 8-octane dithiol and 0.02g of a photoinitiator were dissolved in 6g of a tetrahydrofuran solution at 25 ℃ and 20. Mu.L of n-dipropylamine was added to obtain a precursor solution. The long-chain soft segment is not added, the reaction is carried out for 12 hours to obtain a liquid crystal elastomer prepolymer, 0.175mmol of a cross-linking agent of pentaerythritol tetra (3-mercaptopropionate) and 10 mu L of n-dipropylamine are added, the mixture is mixed and reacted for 6 hours, and finally the liquid crystal elastomer solution is obtained.
Pouring the obtained liquid crystal elastomer solution into a polytetrafluoroethylene plate, defoaming, placing the polytetrafluoroethylene plate in a fume hood, and naturally drying for about 24 hours after the solvent is completely volatilized; drying at 40 ℃ for 2h in a drying oven, heating to 60 ℃ for drying for 8h, heating to 80 ℃ for drying for 2h, cutting out a part of strip, stretching 100% along the length direction, heating at 80 ℃ for collimation for 1h, and then continuously using UV light for 0.5h to finally obtain the single-domain liquid crystal elastomer.
Performance testing
The examples 1 to 3 and comparative examples 1 to 3 were subjected to the performance test, respectively, and the results are shown in table 1:
TABLE 1 liquid Crystal elastomer Performance test results
As can be seen from the data in Table 1, the introduction of the long-chain soft segment PHG can effectively lower the phase transition temperature (T) of the liquid crystal elastomer NI ). The combination of the test performance results of figures 2-8, examples 1-3 and comparative examples 1-3 shows that the monodomain liquid crystal elastomer prepared in example 1 has the best performance, low driving temperature, good driving strain and tensile strength at break, stable performance and excellent self-healing and programmable performance.
In comparative example 1, diallyl disulfide was used in an amount of 0g, and it was found from the data that the phase transition temperature was increased by 5.8 ℃, the driving strain was decreased by 12.2% at 45 ℃, and that it did not have the self-healing property, as compared with example 1. The introduction of disulfide bonds is illustrated, self-healing can be realized, meanwhile, the disulfide bonds also endow mLCEs with programmable performance, and reversible deformation of programmed shapes and original shapes is realized at 150 ℃ or UV.
Compared with the embodiment 1, the consumption of the long-chain soft segment PHG-400 is 0g, and the data show that the phase transition temperature is increased by 21.2 ℃, the driving strain at 45 ℃ is reduced by 21.5 percent, and the breaking tensile strength at 45 ℃ is reduced by 2.4MPa, which shows that the soft segment is introduced into a liquid crystal polymer network to replace a rigid element in a liquid crystal polymer, the energy required by segment motion is reduced, and the purpose of reducing the phase transition temperature is achieved. In the invention, the breaking tensile strength of the liquid crystal elastomer can be effectively maintained through hydrogen bonds formed between amide bonds; and the self-healing capability of the liquid crystal elastomer is promoted by the synergistic effect of the disulfide bond.
Comparative example 3 compared to example 1, without addition of the disulfide compound and the long chain soft segment PHG, it can be seen from the data that the phase transition temperature was increased by 34.3 ℃, the driving strain at 45 ℃ was reduced by 25.3%, the tensile strength at break at 45 ℃ was reduced by 2.5MPa, and it did not contain self-healing property. The invention is demonstrated by combining comparative example 1 and comparative example 2, and the liquid crystal elastomer is endowed with body temperature driving, programmability and self-repairing performance through the arrangement of double dynamic covalent bonds and the design of a liquid crystal polymerization network structure.
Claims (10)
1. A body temperature response type single-domain liquid crystal elastomer with double dynamic covalent bonds is characterized in that: the unit structure of the liquid crystal elastomer is specifically as follows:
2. the double dynamic covalent bond body temperature responsive monodomain liquid crystal elastomer according to claim 1, characterized in that: the double dynamic covalent bonds are dynamic disulfide bonds and dynamic amide bonds.
3. The method for preparing a double dynamic covalent bond body temperature responsive single domain liquid crystal elastomer according to claim 1 or 2, wherein the method comprises the following steps: the preparation method specifically comprises the following preparation steps:
s1, weighing the following components in proportion: the liquid crystal composite material comprises a liquid crystal monomer RM257, a chain extender, a long-chain soft segment PHG, a cross-linking agent, a disulfide compound, a photoinitiator and a catalyst;
s2, preparing long-chain soft segment PHG: putting polyethylene glycol, isocyano ethyl methacrylate and a catalyst dibutyltin dilaurate into a three-neck flask, adding tetrahydrofuran solvent to completely dissolve, and keeping N 2 Reacting for 4-8h at 55-65 ℃ in the atmosphere to obtain a long-chain soft-segment PHG solution;
s3, preparing a liquid crystal elastomer: dissolving a liquid crystal monomer RM257, a chain extender, a catalyst, a photoinitiator UV-651 and the long-chain soft-segment PHG solution prepared in the step S1 in tetrahydrofuran, and stirring for reaction for 12-24 hours; adding a crosslinking agent, a disulfide compound and a catalyst, and continuously reacting for 4-6 h to obtain a liquid crystal elastomer solution;
s4, defoaming and drying: pouring the liquid crystal elastomer solution obtained in the step S2 into a polytetrafluoroethylene groove, putting the polytetrafluoroethylene groove into a refrigerator for refrigeration, eliminating bubbles in the solution, putting the polytetrafluoroethylene groove into the refrigerator for refrigeration, putting the refrigerator at normal temperature until the solvent is completely volatilized, and continuously drying the liquid crystal elastomer solution in an oven at the temperature of 40-80 ℃ to obtain a liquid crystal elastomer film;
s5, aligning the liquid crystal elastomer: pre-stretching the liquid crystal elastomer film dried in the step S3 to 100% -200% of the original length, stretching and collimating at 80 ℃, and finally curing by using ultraviolet light (UV) to obtain the single-domain liquid crystal elastomer.
4. The method for preparing the double dynamic covalent bond body temperature response type single domain liquid crystal elastomer according to claim 3, wherein the method comprises the following steps: in the step S1, the molar ratio of the liquid crystal monomer RM257, the chain extender, the long-chain soft segment PHG, the cross-linking agent and the disulfide compound is 1-1.15: 0.085-1.15: 0.01 to 0.2: 0.045-0.07: 0.01 to 0.1; the content of the catalyst is 0.5wt% -1.5 wt% of the mass of the liquid crystal monomer RM 257; the content of the photoinitiator is 1.0wt% -2.0 wt% of the mass of the liquid crystal monomer RM 257.
5. The method for preparing the double dynamic covalent bond body temperature response type single domain liquid crystal elastomer according to claim 4, wherein the method comprises the following steps: in the step S2, the molecular weight of the polyethylene glycol is 400-8000, and the molar ratio of the polyethylene glycol to the isocyano ethyl methacrylate is 1:2.
6. the preparation method of the double dynamic covalent bond body temperature response type single domain liquid crystal elastomer according to claim 3, characterized in that: in step S4, the defoaming and drying treatment mode is as follows: and (3) pouring the liquid crystal elastomer solution obtained in the step (S2) into a polytetrafluoroethylene groove, putting the polytetrafluoroethylene groove into a refrigerator to refrigerate for 1-2h at the temperature of-20 ℃, recovering to the normal temperature, continuing to volatilize the solvent for 24-48 h, continuing to dry for 1-2h in a drying oven at the temperature of 40 ℃, and then gradually heating to 80 ℃ for 6-10h.
7. The method for preparing the double dynamic covalent bond body temperature response type single domain liquid crystal elastomer according to claim 3, wherein the method comprises the following steps: in the step S5, the liquid crystal elastomer film dried in the step S4 is pre-stretched to 100% -200% of the original length, then is stretched and collimated for 0.5-2 h at 80 ℃, and finally is irradiated for 0.2-1 h under ultraviolet light UV for curing to obtain the single-domain liquid crystal elastomer.
8. The method for preparing the double dynamic covalent bond body temperature response type single domain liquid crystal elastomer according to claim 4, wherein the method comprises the following steps: the chain extender is at least one of 3, 6-dioxa-1, 8-octane dithiol, 1, 4-butanediol di (3-mercaptopropionate) and 1, 4-butanediol bis (mercaptoacetate); the cross-linking agent is pentaerythritol tetrakis (3-mercaptopropionate).
9. The method for preparing the double dynamic covalent bond body temperature response type single domain liquid crystal elastomer according to claim 4, wherein the method comprises the following steps: the disulfide compound is at least one of diallyl disulfide, allyl methyl disulfide, and ethyl allyl disulfide.
10. The preparation method of the double dynamic covalent bond body temperature response type single domain liquid crystal elastomer according to claim 4, characterized in that: the catalyst is at least one of di-n-propylamine, triethylamine and diethylenetriamine.
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| CN113461903A (en) * | 2020-03-31 | 2021-10-01 | 豪雅镜片泰国有限公司 | Polymerizable composition for optical material, transparent resin and method for producing same, and lens base material and method for producing same |
| CN113527686A (en) * | 2021-07-01 | 2021-10-22 | 清华大学 | Preparation method of liquid crystal elastomer and liquid crystal driving element |
| CN113527687A (en) * | 2021-07-01 | 2021-10-22 | 清华大学 | Liquid crystal elastomer, preparation method thereof and liquid crystal driving element |
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| CN113461903A (en) * | 2020-03-31 | 2021-10-01 | 豪雅镜片泰国有限公司 | Polymerizable composition for optical material, transparent resin and method for producing same, and lens base material and method for producing same |
| CN113527686A (en) * | 2021-07-01 | 2021-10-22 | 清华大学 | Preparation method of liquid crystal elastomer and liquid crystal driving element |
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