Photoresponsive high-strength and high-toughness sodium alginate fiber materials and their preparation methods
By combining sodium alginate with a double-chain azobenzene surfactant, a photoresponsive high-strength and high-toughness sodium alginate fiber material was prepared, solving the problem that it is difficult for materials to simultaneously possess high strength and high toughness, and realizing the regulation of mechanical properties and environmental adaptability under light conditions.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QINGDAO UNIV OF SCI & TECH
- Filing Date
- 2024-01-29
- Publication Date
- 2026-04-21
AI Technical Summary
Existing technologies struggle to combine high strength and high toughness in the same material, especially in polysaccharide-based biocellulose materials, and there are few reports on photocontrolled biocellulose materials with azobenzene as the crosslinking point.
A photoresponsive, high-strength, and high-toughness sodium alginate fiber material was prepared by combining sodium alginate with a double-chain azobenzene surfactant and regulating the molecular structure of azobenzene through light stimulation to form cross-linking points.
This study demonstrated that sodium alginate fiber materials can rapidly and efficiently change their mechanical properties under light conditions, exhibiting high strength and high toughness while maintaining stable performance under a wide range of environmental conditions.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to the fields of bio-fiber materials and stimulus-responsive materials, and mainly to a photoresponsive high-strength and high-toughness sodium alginate fiber material and its preparation method. Background Technology
[0002] Combining mutually exclusive mechanical properties within a single material has long been a challenge in materials science. For instance, it's typically difficult for a material to simultaneously possess both high strength and high toughness. To achieve this, two strategies have been developed: intrinsic and extrinsic material design mechanisms. Compared to extrinsic mechanisms, intrinsic mechanisms effectively prevent material fracture during use, offering certain advantages.
[0003] Materials prepared using intrinsic material design mechanisms can enhance strength and toughness by increasing plastic deformation before fracture occurs. Intrinsic material design mechanisms have been widely applied in the design of strong biomaterials based on polysaccharide biomolecules. These materials effectively enhance the strength and toughness of polysaccharide materials by strengthening interchain hydrogen bonds, cross-linking protein molecules, and doping with inorganic nanoparticles. To date, strategies for preparing stimulus-responsive, high-strength, and high-toughness fiber materials by using functional organic molecules as glycan cross-linking points have been rarely reported.
[0004] Azobenzene molecules are commonly used photosensitive functional molecules, capable of rapid response to light stimulation. Specifically, ultraviolet light irradiation drives azobenzene from a planar trans structure to a non-planar cis structure, while visible light irradiation drives it back to the trans structure. In the molecular aggregated state, planar trans azobenzene molecules can form strong π-π forces, while the formation of a non-planar cis structure disrupts these forces. Therefore, the trans-cis structural transition can effectively alter the forces between azobenzene molecules; that is, the magnitude of these forces can be effectively controlled by light irradiation. If an azobenzene molecule that can efficiently bind to polysaccharide biomolecules can be designed, it can be used as a crosslinking point in bio-fiber materials. This azobenzene crosslinking point, existing in a planar trans structure, can effectively improve the strength and toughness of the fiber material, while existing in a non-planar cis structure, it can reduce the strength and toughness. This mechanism allows for the photomodulation of high-strength, high-toughness fiber materials. However, to date, there are few reports on bio-fiber materials using azobenzene as a crosslinking point. Developing photosensitive bio-fiber materials based on azobenzene is of great significance for expanding the applications of azobenzene-based materials and stimulus-responsive bio-fiber materials in basic research and related technological fields. Summary of the Invention
[0005] In view of this, the purpose of the present invention is to provide a photoresponsive high-strength and high-toughness sodium alginate fiber material and its preparation method.
[0006] The technical solution of the present invention is as follows:
[0007] This invention provides a photoresponsive, high-strength, and high-toughness sodium alginate fiber material, the raw materials for which include sodium alginate and a double-chain azobenzene surfactant.
[0008] In this invention, the sodium alginate is a mixture of polysaccharide polymers with the molecular formula (C6H7O6Na)n.
[0009] In this invention, the double-chain azobenzene surfactant is N,N-dimethyl-N-(4-(4-((4-n-octyloxyphenyl)diazepine)phenoxy)n-butyl)-3,6,9,12-tetraoxatridecylammonium bromide.
[0010] In this invention, the preparation method of the photoresponsive high-strength and high-toughness sodium alginate fiber material includes:
[0011] An aqueous solution of sodium alginate and an aqueous solution of a double-chain azobenzene surfactant were mixed at room temperature. The resulting mixture was injected into an aqueous solution of calcium chloride in an S-shaped motion. The resulting fiber material was left to stand in the calcium chloride aqueous solution for 5 minutes and then collected. The collected wet fiber material was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and at a relative humidity of less than 50% to obtain a photoresponsive high-strength and high-toughness sodium alginate fiber material.
[0012] In the preparation method of the photoresponsive high-strength and high-toughness sodium alginate fiber material of the present invention, the aqueous solution of sodium alginate is calculated based on the repeating monosaccharide unit of sodium alginate as C6H7O6Na, the concentration of the aqueous solution of sodium alginate is 20-30 mmol / L, the concentration of the aqueous solution of the double-chain azobenzene surfactant is 10-15 mmol / L, and the mass concentration of calcium chloride in the aqueous solution of calcium chloride is 0.6%.
[0013] In the preparation method of the photoresponsive high-strength and high-toughness sodium alginate fiber material of the present invention, in the obtained mixture, the sodium alginate is calculated as C6H7O6Na as the repeating monosaccharide unit of sodium alginate, and the molar ratio of sodium alginate to double-chain azobenzene surfactant is 20:1.
[0014] In the preparation method of the photoresponsive high-strength and high-toughness sodium alginate fiber material of the present invention, the rate at which the obtained mixture is injected into the aqueous solution of calcium chloride in an S-shaped movement is 0.1 to 0.5 mL / s, and the drying time of the stretched wet fiber material at room temperature and relative humidity below 50% is 20 to 30 minutes.
[0015] In this invention, after obtaining the photoresponsive high-strength and high-toughness sodium alginate fiber material, the process further includes regulating the mechanical properties of the photoresponsive high-strength and high-toughness sodium alginate fiber material under room temperature conditions by light irradiation.
[0016] In this invention, the process of regulating the mechanical properties of the photoresponsive high-strength and high-toughness sodium alginate fiber material under room temperature conditions by light irradiation includes: ultraviolet light irradiation, inducing the strength and toughness of the photoresponsive high-strength and high-toughness sodium alginate fiber material to decrease to less than 50% of the initial value; and visible light irradiation, inducing the strength and toughness of the photoresponsive high-strength and high-toughness sodium alginate fiber material to recover to the initial level.
[0017] In this invention, during the process of controlling the mechanical properties of the photoresponsive high-strength and high-toughness sodium alginate fiber material at room temperature through light irradiation: the ultraviolet light irradiation conditions are a wavelength of 365 nm and an intensity of 30 mW / cm². 2 The exposure time was 5 minutes; the visible light irradiation conditions were a wavelength of 520 nm and an intensity of 90 mW / cm². 2 Time: 5 minutes.
[0018] This invention provides a photoresponsive high-strength and high-toughness sodium alginate fiber material and its preparation method. The photoresponsive high-strength and high-toughness sodium alginate fiber material and its preparation method have the following characteristics:
[0019] 1. The photoresponsive high-strength and high-toughness sodium alginate fiber material obtained in this invention is a sodium alginate fiber material with double-chain azobenzene surfactant and calcium ions as crosslinking points.
[0020] 2. The photoresponsive high-strength and high-toughness sodium alginate fiber material obtained by this invention possesses both high strength and high toughness. The average tensile strength and toughness of the photoresponsive high-strength and high-toughness sodium alginate fiber material can reach 732 MPa and 112 MJ / m, respectively. 3 .
[0021] 3. The photoresponsive high-strength and high-toughness sodium alginate fiber material obtained by the present invention can rapidly and efficiently change its mechanical strength and toughness properties through light stimulation.
[0022] 4. The photoresponsive high-strength and high-toughness sodium alginate fiber material obtained by the present invention can maintain high strength in the pH range of 1 to 14.
[0023] 5. The photoresponsive high-strength and high-toughness sodium alginate fiber material obtained by the present invention can maintain high strength in the range of -196 to 100℃. Attached Figure Description
[0024] Figure 1 The stress-strain curve of the photoresponsive high-strength and high-toughness sodium alginate fiber material described in Example 1 under tensile conditions.
[0025] Figure 2 The image is a scanning electron microscope image of the photoresponsive high-strength and high-toughness sodium alginate fiber material described in Example 1, taken at room temperature.
[0026] Figure 3 The mechanical strength change of the photoresponsive high-strength and high-toughness sodium alginate fiber material described in Example 1 during cyclic irradiation with ultraviolet and visible light.
[0027] Figure 4 The toughness properties of the photoresponsive high-strength and high-toughness sodium alginate fiber material described in Example 1 change during cyclic irradiation with ultraviolet and visible light. Detailed Implementation
[0028] This invention provides a photoresponsive, high-strength, and high-toughness sodium alginate fiber material and its preparation method. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the same result. It should be noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments. Those skilled in the art can obviously make modifications or appropriate alterations and combinations to the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.
[0029] The present invention will be further illustrated below with reference to the embodiments:
[0030] Example 1:
[0031] At room temperature, 5 mL of a 30 mmol / L sodium alginate aqueous solution (based on the sodium alginate repeating monosaccharide unit being C6H7O6Na) and 0.75 mL of a 10 mmol / L N,N-dimethyl-N-(4-(4-((4-n-octyloxyphenyl)diazeninyl)phenoxy)n-butyl)-3,6,9,12-tetraoxatridecylammonium bromide aqueous solution were mixed. The resulting mixture was injected into 500 mL of a 0.6% calcium chloride aqueous solution using a syringe in an S-shaped motion (at a rate of 0.2 mL / s). The resulting fiber material was allowed to stand in the calcium chloride aqueous solution for 5 minutes and then collected. The collected wet fiber material was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and a relative humidity of less than 50% for 20 minutes to obtain a photoresponsive high-strength and high-toughness sodium alginate fiber material.
[0032] The stress-strain diagram of the prepared photoresponsive high-strength and high-toughness sodium alginate fiber material in tensile testing at room temperature is shown below. Figure 1 As shown, according to Figure 1 The results show that the average tensile strength and toughness of the photoresponsive high-strength and high-toughness sodium alginate fiber material can reach 732 MPa and 112 MJ / m, respectively. 3 This indicates that the photoresponsive high-strength and high-toughness sodium alginate fiber material possesses both high strength and high toughness as mechanical properties.
[0033] The prepared photoresponsive high-strength and high-toughness sodium alginate fiber material, as shown in the scanning electron microscope image at room temperature, is as follows. Figure 2 As shown, according to Figure 2 It was found that the photoresponsive high-strength and high-toughness sodium alginate fiber material has a smooth surface structure and a solid internal structure, with uniform thickness.
[0034] The prepared photoresponsive high-strength and high-toughness sodium alginate fiber material, under room temperature conditions, exhibits changes in mechanical strength during cyclic irradiation with ultraviolet and visible light, such as... Figure 3 As shown, according to Figure 3 It was found that the photoresponsive high-strength and high-toughness sodium alginate fiber material can adjust its mechanical strength to less than 50% of its initial value under ultraviolet light irradiation, and the photoresponsive high-strength and high-toughness sodium alginate fiber material can adjust its mechanical strength to recover to its initial level under visible light irradiation.
[0035] The prepared photoresponsive high-strength and high-toughness sodium alginate fiber material exhibits the following toughness changes during cyclic irradiation with ultraviolet and visible light at room temperature: Figure 4 As shown, according to Figure 4 It was found that the photoresponsive high-strength and high-toughness sodium alginate fiber material can adjust its toughness to less than 50% of its initial value under ultraviolet light irradiation, and the photoresponsive high-strength and high-toughness sodium alginate fiber material can adjust its toughness to recover to its initial level under visible light irradiation.
[0036] The prepared photoresponsive high-strength and high-toughness sodium alginate fiber material was tested and found to maintain high strength mechanical properties within the pH range of 1 to 14.
[0037] The prepared photoresponsive high-strength and high-toughness sodium alginate fiber material was tested and found to maintain high strength mechanical properties within the temperature range of -196 to 100℃.
[0038] Comparative Example 1:
[0039] At room temperature, 5 mL of a 30 mmol / L sodium alginate aqueous solution (based on the sodium alginate repeating monosaccharide unit being C6H7O6Na) and 1.5 mL of a 10 mmol / L N,N-dimethyl-N-(4-(4-((4-n-octyloxyphenyl)diazeninyl)phenoxy)n-butyl)-3,6,9,12-tetraoxatridecylammonium bromide aqueous solution were mixed. The resulting mixture was injected into 500 mL of a 0.6% calcium chloride aqueous solution using a syringe in an S-shaped motion (at a rate of 0.2 mL / s). The resulting fiber material was allowed to stand in the calcium chloride aqueous solution for 5 minutes and then collected. The collected wet fiber material was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and relative humidity below 50% for 20 minutes to obtain a sodium alginate fiber material containing a double-chain azobenzene surfactant.
[0040] The sodium alginate fiber material containing a double-chain azobenzene surfactant prepared in Comparative Example 1 was tested and found to have an average mechanical strength below 400 MPa and an average toughness value of 30 MJ / m. 3 The sodium alginate fiber material containing a double-chain azobenzene surfactant prepared in Comparative Example 1 is not a high-strength, high-toughness sodium alginate fiber material.
[0041] Comparative Example 2:
[0042] At room temperature, 5 mL of sodium alginate aqueous solution with a concentration of 30 mmol / L (calculated as sodium alginate repeating monosaccharide unit C6H7O6Na) was injected into 500 mL of calcium chloride aqueous solution with a mass concentration of 0.6% using a syringe in an S-shaped movement (rate of 0.2 mL / s). The resulting fiber material was allowed to stand in the calcium chloride aqueous solution for 5 minutes and then collected. The collected wet fiber material was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and relative humidity below 50% for 20 minutes to obtain sodium alginate fiber material.
[0043] The sodium alginate fiber material prepared in Comparative Example 2, after testing, showed an average tensile strength of less than 400 MPa and a toughness of less than 15 MJ / m at room temperature. 3 Its strength and toughness are far lower than those of the photoresponsive high-strength and high-toughness sodium alginate fiber material described in Example 1.
[0044] The sodium alginate fiber material prepared in Comparative Example 2 was tested and found to lack photostimulation response performance.
[0045] The above are merely preferred embodiments of the present invention. It should be noted that those skilled in the art can make several improvements without departing from the principle of the present invention, and these improvements should also be considered within the scope of protection of the present invention.
Claims
1. A photoresponsive high-strength, high-toughness sodium alginate fiber material and its preparation method, characterized in that, The raw materials for its preparation include sodium alginate and a double-chain azobenzene surfactant. The sodium alginate is a mixture of polysaccharide polymers with the molecular formula (C6H7O6Na)n, and the double-chain azobenzene surfactant is... N,N -dimethyl- N -(4-(4-((4-n-octyloxyphenyl)diazeninyl)phenoxy)n-butyl)-3,6,9,12-tetraoxatridecylammonium bromide, wherein the preparation method of the photoresponsive high-strength and high-toughness sodium alginate fiber material includes: mixing an aqueous solution of sodium alginate with an aqueous solution of a double-chain azobenzene surfactant at room temperature; injecting the resulting mixture into an aqueous solution of calcium chloride in an S-shaped motion; collecting and removing the generated fiber material after standing in the aqueous solution of calcium chloride for 5 minutes; stretching the removed wet fiber material to a strain of 110%; and finally drying the stretched wet fiber material at room temperature and a relative humidity of less than 50% to obtain the photoresponsive high-strength and high-toughness sodium alginate fiber material. In the resulting mixture, the sodium alginate is calculated as C6H7O6Na as the repeating monosaccharide unit; the molar ratio of sodium alginate to the double-chain azobenzene surfactant is 20:1; and the mass concentration of calcium chloride in the aqueous solution of calcium chloride is 0.6%.
2. The method for preparing the photoresponsive high-strength and high-toughness sodium alginate fiber material according to claim 1, characterized in that, The aqueous solution of sodium alginate has a concentration of 20-30 mmol / L, calculated based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na, and the aqueous solution of the double-chain azobenzene surfactant has a concentration of 10-15 mmol / L.
3. The method for preparing the photoresponsive high-strength and high-toughness sodium alginate fiber material according to claim 1, characterized in that, The rate at which the obtained mixture is injected into the aqueous solution of calcium chloride in an S-shaped motion is 0.1~0.5 mL / s, and the drying time of the stretched wet fiber material at room temperature and relative humidity below 50% is 20~30 minutes.