CN109440212B - Preparation method of high-orientation high-toughness regenerated cellulose fiber and high-orientation high-toughness regenerated cellulose fiber - Google Patents
Preparation method of high-orientation high-toughness regenerated cellulose fiber and high-orientation high-toughness regenerated cellulose fiber Download PDFInfo
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- CN109440212B CN109440212B CN201811436865.7A CN201811436865A CN109440212B CN 109440212 B CN109440212 B CN 109440212B CN 201811436865 A CN201811436865 A CN 201811436865A CN 109440212 B CN109440212 B CN 109440212B
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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Abstract
The invention provides a preparation method of high-orientation high-toughness regenerated cellulose fibers and the high-orientation high-toughness regenerated cellulose fibers, and relates to the technical field of fibers, wherein the preparation method comprises the following steps: (a) mixing the regenerated cellulose solution with a cross-linking agent to obtain a mixed solution of the regenerated cellulose and the cross-linking agent; (b) spinning the mixed solution, and solidifying the mixed solution through a coagulating bath to obtain wet regenerated cellulose fibers; (c) carrying out limited drying on the wet regenerated cellulose fibers to obtain high-orientation high-toughness regenerated cellulose fibers; the preparation method provided by the invention has the advantages of simple process, low raw material cost and environmental friendliness, and the regenerated cellulose fibers prepared at different times have high orientation degree, high strength and high toughness, show obvious optical anisotropy under polarized light, and are potential functional fiber materials.
Description
Technical Field
The invention relates to the technical field of fibers, in particular to a preparation method of high-orientation high-toughness regenerated cellulose fibers and the high-orientation high-toughness regenerated cellulose fibers.
Background
The consumption of non-renewable resources and environmental pollution problems caused by petroleum-based polymer materials have made the use of bio-based polymers to manufacture new materials increasingly urgent. The use of renewable resources to replace petroleum-based polymeric materials for the production of plastics and fibers is currently a trend in future material development. Cellulose is a renewable resource with the most abundant sources on the earth, has the advantages of low cost, excellent thermal stability, degradability and the like, and is widely concerned by researchers.
The regenerated cellulose fiber is widely applied to daily life of people, and relates to industries of surgical medical supplies, textile, water treatment, automobile industry and the like. But the existing regenerated cellulose fiber has harsh preparation conditions, expensive solvent and easy environmental pollution.
Therefore, there is a need for developing a method for preparing regenerated cellulose fiber with environmental protection and low cost.
Disclosure of Invention
The invention aims to provide a preparation method of high-orientation high-toughness regenerated cellulose fibers, which aims to solve the technical problems that the existing regenerated cellulose fibers are harsh in preparation conditions, expensive in solvent and easy to cause environmental pollution.
The preparation method of the high-orientation high-toughness regenerated cellulose fiber provided by the invention comprises the following steps:
(a) mixing the regenerated cellulose solution with a cross-linking agent to obtain a mixed solution of the regenerated cellulose and the cross-linking agent;
(b) spinning the mixed solution of regenerated cellulose and a cross-linking agent, and solidifying the mixed solution through a coagulating bath to obtain wet regenerated cellulose fibers;
(c) and (3) carrying out limited drying on the wet regenerated cellulose fiber to obtain the high-orientation high-toughness regenerated cellulose fiber.
Further, in the step (a), the mass ratio of the cross-linking agent to the regenerated cellulose is (0.5-6): (3-7);
preferably, the regenerated cellulose solution has a concentration of 3 to 7 wt.%.
Further, the regenerated cellulose has a degree of polymerization of 200-2000;
preferably, the regenerated fiber is derived from one or more of cotton linter pulp, absorbent cotton pulp, straw pulp, wood pulp, bagasse pulp, alginate cellulose and animal cellulose.
Further, the cross-linking agent is selected from epoxy compounds and/or aldehyde compounds;
preferably, the epoxy compound comprises epichlorohydrin and chloroepoxybutane;
preferably, the aldehyde compounds include glutaraldehyde and succinaldehyde.
Further, in the step (b), the cross-linked regenerated cellulose solution is extruded into a coagulating bath through a spinning nozzle;
preferably, the diameter of the wet regenerated cellulose fibers is 50 to 200 μm.
Further, the coagulating bath is an acidic aqueous solution or ethanol;
preferably, the solute of the acidic aqueous solution is selected from at least one of hydrochloric acid, sulfuric acid, acetic acid, phytic acid, nitric acid, and benzoic acid;
preferably, the concentration of the solute in the acidic aqueous solution is 0.1 to 2 mol/L.
Further, in the step (b), the pressure applied to the crosslinked regenerated cellulose solution during spinning is 0.2-1 MPa.
Further, in the step (c), the zone-limited drying is drying under 2D tension environment.
The second purpose of the invention is to provide a high-orientation high-toughness regenerated cellulose fiber which is obtained by the preparation method of the high-orientation high-toughness regenerated cellulose fiber.
The invention also aims to provide application of the high-orientation high-toughness regenerated cellulose fiber in a functional fiber material.
The preparation method of the high-orientation high-toughness regenerated cellulose fiber provided by the invention firstly carries out crosslinking on a regenerated cellulose solution, and then carries out spinning solidification and limited-area drying, so that the preparation method is simple in process, low in raw material cost, green and environment-friendly, and free of environmental pollution, and the prepared regenerated cellulose fiber simultaneously has covalent bond and non-covalent bond crosslinking points, so that the regenerated cellulose fiber has high orientation degree, high strength and high toughness, shows obvious optical anisotropy under polarized light, and is a potential functional fiber material.
The high-orientation high-toughness regenerated cellulose fiber provided by the invention has covalent bond and non-covalent bond crosslinking points, not only has high orientation degree, high strength and high toughness, but also shows obvious optical anisotropy under polarized light, is a potential functional fiber material, and has wide application prospect.
Drawings
FIG. 1 is a polarization micrograph of regenerated cellulose fibers provided in example 6;
FIG. 2(a) is a low-magnification scanning electron micrograph of regenerated cellulose fibers provided in example 3;
FIG. 2(b) is an enlarged view of a portion of the curve in FIG. 2 (a);
FIG. 3 is an atomic force microscope photomicrograph of regenerated cellulose fibers provided in example 5;
fig. 4 is an XRD pattern of the regenerated cellulose fibers provided in example 6, the regenerated cellulose fibers provided in comparative example 1, and the regenerated cellulose fibers provided in comparative example 2.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that:
in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is only a shorthand representation of the combination of these numerical values.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
According to one aspect of the invention, the invention provides a preparation method of high-orientation high-toughness regenerated cellulose fibers, which comprises the following steps:
(a) mixing the regenerated cellulose solution with a cross-linking agent to obtain a mixed solution of the regenerated cellulose and the cross-linking agent;
(b) spinning the mixed solution of regenerated cellulose and a cross-linking agent, and solidifying the mixed solution through a coagulating bath to obtain wet regenerated cellulose fibers;
(c) and (3) carrying out limited drying on the wet regenerated cellulose fiber to obtain the high-orientation high-toughness regenerated cellulose fiber.
In step (a), the crosslinking reaction is carried out under the temperature condition of the regenerated fiber glue.
The preparation method of the high-orientation high-toughness regenerated cellulose fiber provided by the invention firstly carries out crosslinking on a regenerated cellulose solution, and then carries out spinning solidification and limited-area drying, so that the preparation method is simple in process, low in raw material cost, green and environment-friendly, and free of environmental pollution, and the prepared regenerated cellulose fiber simultaneously has covalent bond and non-covalent bond crosslinking points, so that the regenerated cellulose fiber has high orientation degree, high strength and high toughness, shows obvious optical anisotropy under polarized light, and is a potential functional fiber material.
In a preferred embodiment of the present invention, in step (a), the mass ratio of the crosslinking agent to the regenerated cellulose is (0.5 to 6): (3-7). The mass ratio of the cross-linking agent to the regenerated cellulose is controlled to ensure that the regenerated cellulose can be cross-linked more completely.
Typically, but not by way of limitation, the mass ratio of the cross-linking agent to the regenerated cellulose is, for example, 0.5:6, 0.5:1, 0.5:7, 1:4, 1:5, 1:6, 1:7, 1:8, 1:3, 4:3, 2:1, 3:7, 2:7 or 4: 7.
In a preferred embodiment of the invention, the concentration of the regenerated cellulose solution is 3 to 7 wt.%. The concentration of the regenerated cellulose solution is controlled to ensure that the regenerated cellulose crosslinking reaction is carried out more completely.
Typically, but not by way of limitation, the regenerated cellulose solution has a concentration of, for example, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, or 7 wt%.
In a preferred embodiment of the present invention, the regenerated cellulose has a degree of polymerization of 200-2000. By selecting the regenerated cellulose with the polymerization degree of 200-2000 as the raw material, the raw material is cheaper and is easier to carry out crosslinking reaction with the crosslinking agent. Typically, but not by way of limitation, the regenerated cellulose has a degree of polymerization of, for example, 200, 300, 400, 5000, 800, 1000, 1200, 1500, 1800, or 2000.
In a preferred embodiment of the invention, the regenerated cellulose is derived from one or more of linter pulp, degreased cotton pulp, straw pulp, wood pulp, bagasse pulp, alginate cellulose and animal cellulose. The regenerated cellulose prepared by the raw materials is changed into valuable, and the cost of the raw materials is further reduced.
In a preferred embodiment of the invention, the crosslinking agent is selected from epoxy compounds and/or aldehyde compounds.
The epoxy compound and the aldehyde compound are more easily subjected to a crosslinking reaction with the regenerated cellulose so as to improve the strength and toughness of the generated crosslinked regenerated fiber.
In a further preferred embodiment of the present invention, the epoxy compound is selected from epichlorohydrin and/or chloroepoxybutane, and particularly, when epichlorohydrin is selected, the epoxy compound is more likely to undergo a crosslinking reaction with the regenerated cellulose, which is more beneficial to improving the strength and toughness of the crosslinked regenerated fiber.
In a further preferred embodiment of the present invention, the aldehyde compound is selected from glutaraldehyde and/or succinaldehyde, and particularly glutaraldehyde is selected, which is more likely to undergo a crosslinking reaction with the regenerated cellulose, and is more beneficial to improve the strength and toughness of the crosslinked regenerated cellulose.
In a preferred embodiment of the present invention, in step (b), the crosslinked regenerated cellulose solution is extruded into a coagulation bath through a spinning nozzle. And spinning the crosslinked regenerated cellulose solution through a spinning nozzle, extruding the spun solution into a coagulating bath for solidification and forming to obtain the wet regenerated cellulose fiber.
In a preferred embodiment of the invention, the diameter of the wet regenerated cellulose fibres is between 50 and 200 μm. Typically, but not by way of limitation, the diameter of the wet regenerated cellulose fibers is, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 μm.
In a preferred embodiment of the present invention, the diameter of the spinning nozzle is 90 to 200 μm to control the diameter of the produced wet regenerated cellulose fiber to 50 to 200 μm. Typically, but not by way of limitation, the diameter of the spinning nozzle is, for example, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 μm.
In a preferred embodiment of the invention, the coagulation bath is an acidic aqueous solution or ethanol. The acidic aqueous solution or ethanol is selected as the coagulating bath, so that the cost is lower, and the wet regenerated cellulose fiber is easier to form and coagulate.
In a further preferred embodiment of the invention, the solute of the acidic aqueous solution is selected from one or more of hydrochloric acid, sulfuric acid, acetic acid, phytic acid, nitric acid and benzoic acid.
In a preferred embodiment of the invention, the concentration of the solute in the acidic aqueous solution is 0.1 to 2 mol/L. The concentration of solute in the acidic aqueous solution is controlled to improve the solidification rate of the wet regenerated cellulose fiber and improve the preparation efficiency. Typical but non-limiting concentrations of solute in the acidic aqueous solution are, for example, 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8 or 2 mol/L.
In a preferred embodiment of the present invention, in the step (b), the pressure applied to the crosslinked regenerated cellulose solution during spinning is 0.2 to 1.2 MPa. Preferably, the cross-linked regenerated fiber solution is pressurized by a metering pump, so that the cross-linked breeding fiber solution is extruded out through a spinning nozzle and enters a coagulation bath for coagulation. Typically, but not by way of limitation, the pressure exerted by the metering pump on the cross-linked regenerated cellulose is, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1 or 1.2 MPa.
In a preferred embodiment of the present invention, in step (c), the zone-limited drying is drying under 2D tension. After the wet regenerated cellulose fiber is wound on a silk winding drum, two ends are fixed, and the two ends are subjected to limited drying to improve the orientation degree of the fiber, so that the high-orientation high-toughness regenerated cellulose fiber is obtained.
According to a second aspect of the invention, the invention provides a high-orientation high-toughness regenerated cellulose fiber which is obtained according to the preparation method of the high-orientation high-toughness regenerated cellulose fiber provided by the invention.
The high-orientation high-toughness regenerated cellulose fiber provided by the invention has covalent bond and non-covalent bond crosslinking points, not only has high orientation degree, high strength and high toughness, but also shows obvious optical anisotropy under polarized light, is a potential functional fiber material, and has wide application prospect.
According to a third aspect of the invention, the invention provides the application of the highly oriented high-tenacity regenerated cellulose fiber in functional fiber materials.
The technical solution provided by the present invention is further described below with reference to examples and comparative examples.
Example 1
This example provides a regenerated cellulose fiber prepared as follows:
(1) adding 30mL of epichlorohydrin (with the mass concentration of 99%) into 1000mL of regenerated cellulose (with the number average molecular weight of 100000) solution with the concentration of 5 wt% at 0 ℃, uniformly stirring, and performing centrifugal deaeration to obtain a mixed solution;
(2) putting the mixed solution into a charging barrel of a wet spinning machine, applying pressure of 0.8MPa to the charging barrel, enabling the mixed solution to pass through a spinning nozzle with the diameter of 120 mu m, entering a sulfuric acid solution coagulating bath with the concentration of 0.2mol/L to rapidly terminate the chemical crosslinking reaction and solidify, and obtaining wet regenerated cellulose fibers;
(3) and (3) washing the wet regenerated cellulose fiber, winding the wet regenerated cellulose fiber on a spinning drum, fixing two ends of the wet regenerated cellulose fiber, and performing limited drying to obtain the high-orientation high-toughness regenerated cellulose fiber.
Example 2
This example provides a regenerated cellulose fiber prepared as follows:
(1) adding 10mL of epichlorohydrin (with the mass concentration of 99%) into 1000mL of regenerated cellulose (with the number average molecular weight of 100000) solution with the concentration of 6 wt% at the temperature of 5 ℃, uniformly stirring, and then performing centrifugal deaeration to obtain a mixed solution;
(2) putting the mixed solution into a charging barrel of a wet spinning machine, applying pressure of 0.4MPa to the charging barrel, enabling the mixed solution to pass through a spinning nozzle with the diameter of 160 mu m, entering a phytic acid solution coagulating bath with the concentration of 0.5 mol/L to rapidly terminate the chemical crosslinking reaction and solidify, and obtaining wet regenerated cellulose fibers;
(3) and (3) washing the wet regenerated cellulose fiber, winding the wet regenerated cellulose fiber on a spinning drum, fixing two ends of the wet regenerated cellulose fiber, and performing limited drying to obtain the high-orientation high-toughness regenerated cellulose fiber.
Example 3
This example provides a regenerated cellulose fiber prepared as follows:
(1) adding 20mL of epoxy chloropropane (with the mass concentration of 99%) into 1000mL of regenerated cellulose (with the number average molecular weight of 10000) solution with the concentration of 4.5 wt% at the temperature of 5 ℃, uniformly stirring, and then performing centrifugal deaeration to obtain a mixed solution;
(2) putting the mixed solution into a charging barrel of a wet spinning machine, applying pressure of 0.6MPa to the charging barrel, enabling the mixed solution to pass through a spinning nozzle with the diameter of 200 mu m, entering a hydrochloric acid solution coagulation bath with the concentration of 0.5 mol/L to rapidly terminate the chemical crosslinking reaction and solidify, and obtaining wet regenerated cellulose fibers;
(3) and (3) washing the wet regenerated cellulose fiber, winding the wet regenerated cellulose fiber on a spinning drum, fixing two ends of the wet regenerated cellulose fiber, and performing limited drying to obtain the high-orientation high-toughness regenerated cellulose fiber.
Example 4
This example provides a regenerated cellulose fiber prepared as follows:
(1) adding 60mL of epichlorohydrin (with the mass concentration of 99%) into 1000mL of regenerated cellulose (with the number average molecular weight of 100000) solution with the concentration of 5 wt% at 0 ℃, uniformly stirring, and performing centrifugal deaeration to obtain a mixed solution;
(2) putting the mixed solution into a charging barrel of a wet spinning machine, applying 1MPa pressure to the charging barrel, enabling the mixed solution to enter a nitric acid solution coagulating bath with the concentration of 0.1mol/L through a spinning nozzle with the diameter of 90 mu m to quickly terminate the chemical crosslinking reaction and solidify, and obtaining wet regenerated cellulose fibers;
(3) and (3) washing the wet regenerated cellulose fiber, winding the wet regenerated cellulose fiber on a spinning drum, fixing two ends of the wet regenerated cellulose fiber, and performing limited drying to obtain the high-orientation high-toughness regenerated cellulose fiber.
Example 5
This example provides a regenerated cellulose fiber prepared as follows:
(1) adding 0.5mL of epoxy chloropropane (with the mass concentration of 99%) into 1000mL of regenerated cellulose (with the number-average molecular weight) solution with the concentration of 6 wt% at 0 ℃, uniformly stirring, and performing centrifugal deaeration to obtain a mixed solution;
(2) putting the mixed solution into a charging barrel of a wet spinning machine, applying pressure of 0.2MPa to the charging barrel, enabling the mixed solution to enter a coagulating bath of acetic acid solution with the concentration of 1mol/L through a spinning nozzle with the diameter of 180 mu m to quickly terminate the chemical crosslinking reaction and solidify, and obtaining wet regenerated cellulose fibers;
(3) and (3) washing the wet regenerated cellulose fiber, winding the wet regenerated cellulose fiber on a spinning drum, fixing two ends of the wet regenerated cellulose fiber, and performing limited drying to obtain the high-orientation high-toughness regenerated cellulose fiber.
Example 6
This example provides a regenerated cellulose fiber prepared as follows:
(1) adding 5mL of epichlorohydrin (with the mass concentration of 99%) into 1000mL of regenerated cellulose (with the number average molecular weight of 100000) solution with the concentration of 7 wt% at 0 ℃, uniformly stirring, and performing centrifugal deaeration to obtain a mixed solution;
(2) putting the mixed solution into a charging barrel of a wet spinning machine, applying 1MPa pressure to the charging barrel, enabling the mixed solution to enter a coagulating bath of acetic acid solution with the concentration of 1mol/L through a spinning nozzle with the diameter of 120 mu m to quickly terminate the chemical crosslinking reaction and solidify, and obtaining wet regenerated cellulose fibers;
(3) and (3) washing the wet regenerated cellulose fiber, winding the wet regenerated cellulose fiber on a spinning drum, fixing two ends of the wet regenerated cellulose fiber, and performing limited drying to obtain the high-orientation high-toughness regenerated cellulose fiber.
Example 7
This example provides a regenerated cellulose fiber prepared as follows:
(1) adding 3mL of epichlorohydrin (with the mass concentration of 99%) into 1000mL of regenerated cellulose (with the number average molecular weight of 100000) solution with the concentration of 3 wt% at 0 ℃, uniformly stirring, and performing centrifugal deaeration to obtain a mixed solution;
(2) putting the mixed solution into a charging barrel of a wet spinning machine, applying pressure of 0.3MPa to the charging barrel, enabling the mixed solution to enter a benzoic acid solution coagulating bath with concentration of 0.2mol/L through a spinning nozzle with the diameter of 150 mu m to quickly terminate the chemical crosslinking reaction and solidify, and obtaining wet regenerated cellulose fibers;
(3) and (3) washing the wet regenerated cellulose fiber, winding the wet regenerated cellulose fiber on a spinning drum, fixing two ends of the wet regenerated cellulose fiber, and performing limited drying to obtain the high-orientation high-toughness regenerated cellulose fiber.
Example 8
This example provides a regenerated cellulose fiber, which differs from example 6 in that: in the step (1), 0.3mL of epichlorohydrin (with a mass concentration of 99%) is added into 1000mL of regenerated cellulose (with a number average molecular weight of 100000) solution with a concentration of 7 wt% at 0 ℃, and after uniform stirring, centrifugal deaeration is carried out to obtain a mixed solution; the rest of the steps (2) and (3) are the same as those in embodiment 6, and are not described herein again.
Example 9
This example provides a regenerated cellulose fiber, which differs from example 6 in that: in the step (1), 0.1mL of epichlorohydrin (with a mass concentration of 99%) is added into 1000mL of regenerated cellulose (with a number average molecular weight of 100000) solution with a concentration of 1.5 wt% at 0 ℃, and after uniform stirring, centrifugal deaeration is carried out to obtain a mixed solution; the rest of the steps (2) and (3) are the same as those in embodiment 6, and are not described herein again.
Comparative example 1
This comparative example provides a regenerated cellulose fiber, which is the same as the regenerated cellulose type number used in example 6, and which was prepared by a method comprising the steps of:
(1) putting 1000mL of regenerated cellulose (with the number average molecular weight of 100000) solution with the concentration of 7 wt% into a cylinder of a wet spinning machine, applying the pressure of 1MPa to the cylinder, enabling the mixed solution to enter a coagulation bath of acetic acid solution with the concentration of 1mol/L through a spinning nozzle with the diameter of 120 mu m to rapidly terminate the chemical crosslinking reaction and solidify, and obtaining wet regenerated cellulose fibers;
(2) and (3) washing the wet regenerated cellulose fiber, winding the wet regenerated cellulose fiber on a spinning reel, fixing two ends of the wet regenerated cellulose fiber, and performing limited drying to obtain the regenerated cellulose fiber.
Comparative example 2
This comparative example 2 provides a regenerated cellulose fiber prepared as follows: adding 5mL of epichlorohydrin (with the mass concentration of 99%) into 1000mL of regenerated cellulose (with the number average molecular weight of 100000) solution with the concentration of 7 wt% at 0 ℃, uniformly stirring, and performing centrifugal deaeration to obtain a mixed solution;
(2) and (3) placing the mixed solution into a charging barrel of a wet spinning machine, applying 1MPa pressure to the charging barrel, enabling the mixed solution to pass through a spinning nozzle with the diameter of 120 mu m, entering a water bath for regeneration and solidification, and drying to obtain the wet regenerated cellulose fibers.
Test example 1
The regenerated cellulose fibers provided in examples 1 to 9 and comparative examples 1 to 2 were observed by a polarization microscope, and the results showed that the regenerated cellulose fibers provided in examples 1 to 9 all had iridescent anisotropic behavior, whereas the regenerated cellulose fibers provided in comparative examples 1 to 2 did not have iridescent anisotropic behavior, and that the iridescent anisotropic behavior of the regenerated cellulose fibers provided in examples 1 to 7 was significantly superior to that of examples 8 to 9.
Fig. 1 is a polarization microscope photograph of the regenerated cellulose fiber provided in example 6, and it can be seen from fig. 1 that the regenerated cellulose fiber provided in example 6 has a color anisotropic behavior.
Test example 2
The regenerated cellulose fibers provided in examples 1 to 9 and comparative examples 1 to 2 were observed by scanning electron microscopy, and the results showed that the regenerated cellulose fibers provided in examples 1 to 9 and comparative example 1 all had orientation, whereas the regenerated cellulose fibers provided in comparative example 2 did not have orientation, and the orientation of the regenerated cellulose fibers provided in examples 1 to 7 was significantly higher than that of examples 8 to 9 and comparative example 1.
FIG. 2(a) is a low-magnification scanning electron micrograph of regenerated cellulose fibers provided in example 3; FIG. 2(b) is an enlarged view of a portion of the curve in FIG. 2 (a); as can be seen from fig. 2(a) and 2(b), example 3 provides a regenerated cellulose fiber surface having high orientation.
Test example 3
Atomic force microscope observation of the regenerated cellulose fibers provided in examples 1 to 9 and comparative examples 1 to 2 revealed that the regenerated cellulose fibers provided in examples 1 to 9 and comparative example 1 all had orientation, whereas the regenerated cellulose fibers provided in comparative example 2 did not have orientation, and the orientation of the regenerated cellulose fibers provided in examples 1 to 7 was significantly higher than that of examples 8 to 9 and comparative example 1.
Fig. 3 is an atomic force microscope photograph of the regenerated cellulose fibers provided in example 5, and it can be seen from fig. 3 that the regenerated cellulose fibers provided in example 5 have high orientation.
Test example 4
The regenerated cellulose fibers provided in examples 1 to 9 and comparative examples 1 to 2 were subjected to mechanical property tests, and the results are shown in table 1, in which 4 samples were measured for each example, and the average value was taken.
TABLE 1 regenerated cellulose fiber mechanical property data sheet
As can be seen from the table, the elastic modulus of the regenerated cellulose fibers provided in examples 1-9 is significantly higher than that of comparative examples 1-2, which shows that the strength and toughness of the regenerated cellulose fibers prepared by the preparation method of the highly oriented and high-toughness regenerated cellulose fibers provided by the invention are significantly improved by crosslinking the regenerated cellulose solution, spinning, solidifying and zone-limited drying.
As can be seen from the comparison of examples 1 to 7 with examples 8 to 9, by selecting the regenerated cellulose at a concentration and a mass ratio of the crosslinking agent to the regenerated cellulose of (0.5 to 6): (3-7), the regenerated cellulose fiber obtained has higher strength and toughness.
Test example 5
XRD tests were performed on the regenerated cellulose fibers provided in example 6, the regenerated cellulose fibers provided in comparative example 1, and the regenerated cellulose fibers provided in comparative example 2, and the test results are shown in fig. 4.
As can be seen from fig. 4, the regenerated cellulose fiber provided in comparative example 2 has an amorphous peak, which indicates that the regenerated cellulose fiber provided in comparative example 2 has covalent bond crosslinking points, the regenerated cellulose fiber provided in comparative example 1 has a crystalline peak, which indicates that the regenerated cellulose fiber provided in comparative example 1 has non-covalent bond crosslinking, and the regenerated cellulose fiber provided in example 5 has both an amorphous peak and a crystalline peak, which indicates that the regenerated cellulose fiber provided in example 5 has both covalent bond and non-covalent bond crosslinking points.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (15)
1. A preparation method of high-orientation high-toughness regenerated cellulose fibers is characterized by comprising the following steps:
(a) mixing the regenerated cellulose solution with a cross-linking agent to obtain a mixed solution of the regenerated cellulose and the cross-linking agent;
(b) spinning the mixed solution of regenerated cellulose and a cross-linking agent, and solidifying the mixed solution through a coagulating bath to obtain wet regenerated cellulose fibers;
(c) carrying out limited drying on the wet regenerated cellulose fibers to obtain high-orientation high-toughness regenerated cellulose fibers;
in the step (a), the mass ratio of the cross-linking agent to the regenerated cellulose is (0.5-6): (3-7);
in the step (c), the limited drying is drying in a 2D tension environment; the method specifically comprises the following steps: and winding the wet regenerated cellulose fiber on a silk tube, fixing two ends, and performing limited drying.
2. The method according to claim 1, wherein the regenerated cellulose has a concentration of 3 to 7 wt%.
3. The production method according to claim 1, wherein the regenerated cellulose has a degree of polymerization of 200-2000.
4. The method according to claim 1, wherein the regenerated fiber is derived from one or more of cotton linter pulp, cotton wool pulp, straw pulp, wood pulp, bagasse pulp, algal cellulose and animal cellulose.
5. The method according to claim 1, wherein the crosslinking agent is selected from epoxy compounds and/or aldehyde compounds.
6. The process according to claim 5, characterized in that said epoxy compound comprises epichlorohydrin and chloroepoxybutane.
7. The method according to claim 5, wherein the aldehyde compounds include glutaraldehyde and succinaldehyde.
8. The method according to claim 1, wherein in the step (b), the crosslinked regenerated cellulose solution is extruded into the coagulation bath through a spinning nozzle.
9. The method according to claim 1, wherein the diameter of the wet regenerated cellulose fiber is 50 to 200 μm.
10. The method of claim 1, wherein the coagulation bath is an aqueous acidic solution or ethanol.
11. The method according to claim 1, wherein the solute of the acidic aqueous solution is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, phytic acid, nitric acid, and benzoic acid.
12. The method according to claim 11, wherein the concentration of the solute in the acidic aqueous solution is 0.1 to 2 mol/L.
13. The method according to claim 1, wherein in the step (b), the pressure applied to the crosslinked regenerated cellulose solution during spinning is 0.2 to 1 MPa.
14. Highly oriented high tenacity regenerated cellulose fibers, characterized in that they are obtainable by the process according to any one of claims 1 to 13.
15. Use of highly oriented high tenacity regenerated cellulose fibers according to claim 14 in functional fiber materials.
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| CN107417934A (en) * | 2017-08-09 | 2017-12-01 | 武汉大学 | It is a kind of that there is power to cause the high-strength of optics anisotropic approach, high-ductility cellulose aquagel and preparation method thereof |
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| CN107417934A (en) * | 2017-08-09 | 2017-12-01 | 武汉大学 | It is a kind of that there is power to cause the high-strength of optics anisotropic approach, high-ductility cellulose aquagel and preparation method thereof |
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