Fluorescent high-strength and high-toughness sodium alginate fiber material and preparation method thereof

Abstract

The present application relates to the technical field of biological materials and fiber materials, and mainly relates to a fluorescent high-strength and high-toughness sodium alginate fiber material and a preparation method thereof.The fluorescent high-strength and high-toughness sodium alginate fiber material is prepared by first injecting a mixed solution of sodium alginate and a quaternary ammonium salt containing a tetraphenyl ethylene structure into a calcium chloride aqueous solution to obtain a water-containing fiber material, and then stretching and drying the obtained water-containing fiber material to obtain an ionic composite material.The fluorescent high-strength and high-toughness sodium alginate fiber material prepared by the present application has high strength, high toughness and good fluorescent performance, and can withstand a wide range of pH and temperature conditions.The fluorescent high-strength and high-toughness sodium alginate fiber material prepared by the present application can be applied to the fields of textiles and medical materials.

Description

Technical Field

[0001] The present invention relates to the technical fields of biomaterials and fiber materials, and mainly relates to a fluorescent high-strength and high-toughness sodium alginate fiber material and a preparation method thereof. Background Art

[0002] Biomaterials have a wide range of applications in the fields of textiles, chemical engineering, and medical materials. Good material properties are crucial for the practical applications of biomaterials. Among material properties, strength and toughness are two very important mechanical properties. Strength measures the ability of a material to withstand loads without being damaged, while toughness measures the ability of a material to withstand elastic and plastic deformations.

[0003] In the design and manufacture of materials, how to simultaneously improve the strength and toughness of materials is one of the long-standing challenges in the field of materials science. In the currently developed biomaterials, two main methods are used to improve the strength and toughness of materials. One method is to enhance the ability of the material to absorb energy during deformation through plastic deformation before the material fractures, and the other method is to repair the fracture points after the material fractures. Comparing the two methods, the former can maintain the integrity of the material and has received more attention in the design of biomaterials.

[0004] Polysaccharide biological macromolecules such as cellulose and sodium alginate have a linear sugar chain molecular structure. Due to the excellent mechanical strength properties of their sugar chains, they become an ideal choice for developing biofiber materials. However, when using polysaccharide biological molecules to prepare fiber materials, it is found that the obtained fiber materials are difficult to achieve the mechanical strength of the sugar chains at the nanoscale level. In order to enhance the mechanical strength of such biofiber materials, metal ions such as calcium ions and aluminum ions are often used to enhance the cross-linking between sugar chains. This strategy can effectively improve the strength of the material, but at the same time reduces the strain of the material, which is not conducive to the improvement of toughness performance. So far, polysaccharide biofiber materials with both high strength and high toughness have been rarely reported, especially fiber materials with a strength above gigapascals (GPa) will exhibit relatively weak material toughness.

[0005] Excellent fluorescence properties can endow fiber materials with characteristics such as easy identification, easy detection, and easy tracking, which is conducive to the expansion of the application scenarios of fiber materials. However, due to the lack of fluorescent groups in the molecular structure, polysaccharide fiber materials are difficult to have good fluorescence properties. Developing fluorescent polysaccharide fiber materials requires modifying polysaccharide molecules with fluorescent dyes, which needs to overcome the fluorescence quenching phenomenon of fluorescent dye molecules in the solvent-free aggregation state. Therefore, developing high-strength and high-toughness polysaccharide fiber materials with stable fluorescence properties in various environments is of great significance for expanding the applications of polysaccharide-based biomaterials in basic scientific research and technical fields. Summary of the Invention

[0006] In view of this, the object of the present invention is to provide a fluorescent high-strength and high-toughness sodium alginate fiber material and a preparation method thereof.

[0007] The technical solution of the present invention is as follows:

[0008] The present invention provides a fluorescent high-strength and high-toughness sodium alginate fiber material, and the preparation raw materials thereof include sodium alginate, calcium chloride and a quaternary ammonium salt containing a tetraphenylethylene structure.

[0009] In the present invention, the sodium alginate is a mixture of polysaccharide polymers with the molecular formula (C6H7O6Na)n.

[0010] In the present invention, the quaternary ammonium salt containing a tetraphenylethylene structure is any one of N,N-dimethyl-N-(8-(4-(2-(4-octyloxyphenyl)-1,2-diphenylethenyl)phenoxy)n-octyl)-2,5-dioxaheptyl ammonium bromide and N,N-dimethyl-N-(8-(4-(2-(4-octyloxyphenyl)-1,2-diphenylethenyl)phenoxy)n-octyl)-3,6,9,12-tetraoxatridecyl ammonium bromide.

[0011] In the present invention, the preparation method of the fluorescent high-strength and high-toughness sodium alginate fiber material includes:

[0012] Mix an aqueous solution of sodium alginate and an aqueous solution of a quaternary ammonium salt containing a tetraphenylethylene structure at room temperature, inject the above-mentioned mixed solution into an aqueous solution of calcium chloride in an S-shaped moving manner, let the obtained fiber material stand in the aqueous solution of calcium chloride and then collect and take it out, stretch the obtained fiber material with a strain of 110%, and finally dry the obtained fiber material under the conditions of room temperature and a relative humidity of less than 50% to obtain a fluorescent high-strength and high-toughness sodium alginate fiber material.

[0013] In the preparation method of the fluorescent high-strength and high-toughness sodium alginate fiber material in the present invention, based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na, the concentration of the aqueous solution of sodium alginate is 20-30 mmol / L, the concentration of the aqueous solution of the quaternary ammonium salt containing a tetraphenylethylene structure is 5-10 mmol / L, and the mass concentration of calcium chloride in the aqueous solution of calcium chloride is 0.5%.

[0014] In the preparation method of the fluorescent high-strength and high-toughness sodium alginate fiber material in the present invention, in the mixed solution, based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na, the molar ratio of sodium alginate to the quaternary ammonium salt containing a tetraphenylethylene structure is 30:1.

[0015] In the present invention, in the preparation method of the fluorescent high-strength and high-toughness sodium alginate fiber material, the rate at which the mixed solution is injected into the aqueous calcium chloride solution in an S-shaped movement manner is 0.1 - 1.0 mL / s, the time for leaving the fiber material standing in the aqueous calcium chloride solution is 5 - 10 minutes, and the time for drying the fiber material under the conditions of room temperature and a relative humidity of less than 5% is 20 - 30 minutes.

[0016] The present invention provides a fluorescent high-strength and high-toughness sodium alginate fiber material and a preparation method thereof, and the fluorescent high-strength and high-toughness sodium alginate fiber material and the preparation method thereof have the following characteristics:

[0017] 1. The obtained fluorescent high-strength and high-toughness sodium alginate fiber material of the present invention is a sodium alginate fiber material with a quaternary ammonium salt containing a tetraphenyl ethylene structure and calcium ions as cross-linking points.

[0018] 2. The obtained fluorescent high-strength and high-toughness sodium alginate fiber material of the present invention has both high strength and high toughness, and the tensile strength and toughness of the fluorescent high-strength and high-toughness sodium alginate fiber material can reach 1.27 GPa and 150.48 MJ / m 3 , which is comparable to the performance of natural spider dragline silk.

[0019] 3. The obtained fluorescent high-strength and high-toughness sodium alginate fiber material of the present invention has good fluorescence properties.

[0020] 4. The obtained fluorescent high-strength and high-toughness sodium alginate fiber material of the present invention can provide stable fluorescence properties and tensile strength within the range of pH 1 - 10.

[0021] 5. The obtained fluorescent high-strength and high-toughness sodium alginate fiber material of the present invention can provide stable fluorescence properties and high-strength mechanical properties within the range of -196 - 100 °C. Description of the Drawings

[0022] Figure 1 It is the stress-strain curve of the fluorescent high-strength and high-toughness sodium alginate fiber material described in Example 1 under tensile conditions.

[0023] Figure 2 It is the scanning electron microscope picture of the fluorescent high-strength and high-toughness sodium alginate fiber material described in Example 1 under room temperature conditions.

[0024] Figure 3 It is the bar chart of the tensile strength of the fluorescent high-strength and high-toughness sodium alginate fiber material described in Example 1 under the conditions of pH 1, 7, and 10. Detailed Embodiments

[0025] The present invention provides a fluorescent high-strength and high-toughness sodium alginate fiber material and a preparation method thereof. Those skilled in the art can draw on the content of this article and appropriately improve the process parameters to achieve it. It should be noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are all regarded as included in the present invention. The methods and applications of the present invention have been described through preferred embodiments. Those skilled in the art can obviously make changes or appropriate modifications and combinations to the methods and applications in this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0026] The following further elaborates the present invention in conjunction with embodiments:

[0027] Example 1:

[0028] Mix 5 mL of an aqueous sodium alginate solution with a concentration of 30 mmol / L (calculated based on the repeating monosaccharide unit of sodium alginate as C6H7O6Na) and 1 mL of an aqueous solution of N,N-dimethyl-N-(8-(4-(2-(4-octyloxyphenyl)-1,2-diphenylethenyl)phenoxy)octyl)-2,5-dioxoheptyl ammonium bromide with a concentration of 5 mmol / L. Inject the above mixture into 500 mL of an aqueous calcium chloride solution with a mass concentration of 0.5% in an S-shaped moving manner (rate: 0.2 mL / s) through a syringe. Let the obtained fiber material stand in the aqueous calcium chloride solution for 5 minutes, then collect and take it out. Stretch the obtained fiber material with a strain of 110%. Finally, dry the obtained fiber material at room temperature and a relative humidity of less than 50% for 20 minutes to prepare a fluorescent high-strength and high-toughness sodium alginate fiber material.

[0029] For the prepared fluorescent high-strength and high-toughness sodium alginate fiber material, at room temperature, the stress-strain diagram of the fluorescent high-strength and high-toughness sodium alginate fiber material in the tensile test is as Figure 1 shown. According to Figure 1 , it is obtained that: the tensile strength and toughness of the fluorescent high-strength and high-toughness sodium alginate fiber material can reach 1.27 GPa and 150.48 MJ / m 3 , indicating that the fluorescent high-strength and high-toughness sodium alginate fiber material simultaneously possesses two mechanical properties of high strength and high toughness, and the strength and toughness of the fluorescent high-strength and high-toughness sodium alginate fiber material are comparable to those of natural spider dragline silk.

[0030] For the prepared fluorescent high-strength and high-toughness sodium alginate fiber material, the scanning electron microscope image at room temperature is as Figure 2 shown. According to Figure 2 , it is obtained that: the fluorescent high-strength and high-toughness sodium alginate fiber material has a smooth surface structure and a solid internal structure, and is uniform in thickness.

[0031] The tensile strength change diagram of the prepared fluorescent high-strength and high-toughness sodium alginate fiber material after being soaked in aqueous solutions with different pH strengths for 5 minutes and then redried is as follows Figure 3 shown. According to Figure 3 , it is obtained that the fluorescent high-strength and high-toughness sodium alginate fiber material can maintain high-strength performance within the range of pH 1 - 10.

[0032] The prepared fluorescent high-strength and high-toughness sodium alginate fiber material, after testing, can maintain high-strength mechanical properties within the range of -196 to 100 °C.

[0033] The prepared fluorescent high-strength and high-toughness sodium alginate fiber material, after testing, can exhibit stable fluorescent performance within the range of pH 1 - 10, and the fluorescent high-strength and high-toughness sodium alginate fiber material can exhibit stable fluorescent performance within the range of -196 to 100 °C.

[0034] Example 2:

[0035] Mix 5 mL of an aqueous sodium alginate solution with a concentration of 30 mmol / L (calculated based on the repeating monosaccharide unit of sodium alginate as C6H7O6Na) and 1 mL of an aqueous solution of N,N-dimethyl-N-(8-(4-(2-(4-octyloxyphenyl)-1,2-diphenylethenyl)phenoxy)octyl)-3,6,9,12-tetraoxatridecylammonium bromide with a concentration of 5 mmol / L. Inject the above mixture into 500 mL of an aqueous calcium chloride solution with a mass concentration of 0.5% in an S-shaped moving manner (at a rate of 0.2 mL / s) through a syringe. Let the obtained fiber material stand in the aqueous calcium chloride solution for 5 minutes, then collect and take it out. Stretch the obtained fiber material with a strain of 110%. Finally, dry the obtained fiber material at room temperature and a relative humidity of less than 50% for 20 minutes to prepare a fluorescent high-strength and high-toughness sodium alginate fiber material.

[0036] Comparative Example 1:

[0037] Inject 5 mL of an aqueous sodium alginate solution with a concentration of 30 mmol / L (calculated based on the repeating monosaccharide unit of sodium alginate as C6H7O6Na) into 500 mL of an aqueous calcium chloride solution with a mass concentration of 0.5% in an S-shaped moving manner (at a rate of 0.2 mL / s) through a syringe. Let the obtained fiber material stand in the aqueous calcium chloride solution for 5 minutes, then collect and take it out. Stretch the obtained fiber material with a strain of 110%. Finally, dry the obtained fiber material at room temperature and a relative humidity of less than 50% for 20 minutes to prepare a sodium alginate fiber material.

[0038] The sodium alginate fiber material prepared in Comparative Example 1 was tested. At room temperature, the tensile strength and toughness of the sodium alginate fiber material prepared in Comparative Example 1 were 0.30 GPa and 11.78 MJ / m 3 , which were much lower than the tensile strength and toughness of the fluorescent high-strength and high-toughness sodium alginate fiber material described in Example 1.

[0039] The sodium alginate fiber material prepared in Comparative Example 1 was tested and found not to have fluorescence properties.

[0040] The above are only the preferred embodiments of the present invention. It should be noted that for those skilled in the art in this technical field, several improvements can be made without departing from the principle of the present invention, and these improvements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing fluorescent high-strength and high-toughness sodium alginate fiber material, characterized in that, The raw materials for its preparation include sodium alginate, calcium chloride, and a quaternary ammonium salt containing a tetraphenylethylene structure. The sodium alginate is a mixture of polysaccharide polymers with the molecular formula (C6H7O6Na)n, and the quaternary ammonium salt containing a tetraphenylethylene structure is... N,N -dimethyl- N -(8-(4-(2-(4-octyloxyphenyl)-1,2-diphenylvinyl)phenoxy)n-octyl)-2,5-dioxaheptaylammonium bromide and N,N -dimethyl- N - (8-(4-(2-(4-octoxyphenyl)-1,2-diphenylvinyl)phenoxy)n-octyl)-3,6,9,12-tetraoxatridecylammonium bromide), wherein the preparation method of the fluorescent high-strength and high-toughness sodium alginate fiber material includes: mixing an aqueous solution of sodium alginate with an aqueous solution of a quaternary ammonium salt containing a tetraphenylethylene structure at room temperature; injecting the above mixture into an aqueous solution of calcium chloride in an S-shaped motion; collecting and removing the obtained fiber material after it has been allowed to stand in the aqueous solution of calcium chloride; stretching the obtained fiber material with a strain of 110%; and finally drying the obtained fiber material at room temperature and a relative humidity of less than 50% to obtain the fluorescent high-strength and high-toughness sodium alginate fiber material, wherein in the mixture, the sodium alginate is calculated based on the sodium alginate repeating monosaccharide unit being C6H7O6Na, and the molar ratio of sodium alginate to the quaternary ammonium salt containing a tetraphenylethylene structure is 30:

1.

2. The method for preparing fluorescent 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. The aqueous solution of sodium alginate has a concentration of 5-10 mmol / L, and the aqueous solution of the quaternary ammonium salt containing a tetraphenylethylene structure has a mass concentration of 0.5% in the aqueous solution of calcium chloride.

3. The method for preparing fluorescent high-strength and high-toughness sodium alginate fiber material according to claim 1 or 2, characterized in that, The mixture is injected into the calcium chloride aqueous solution at a rate of 0.1~1.0 mL / s in an S-shaped motion. The fiber material is left to stand in the calcium chloride aqueous solution for 5~10 minutes. The fiber material is dried at room temperature and at a relative humidity of less than 50% for 20~30 minutes.

Images