CN112095159B - High-strength coarse denier polyvinyl alcohol fiber spun by wet method and preparation method thereof - Google Patents
High-strength coarse denier polyvinyl alcohol fiber spun by wet method and preparation method thereof Download PDFInfo
- Publication number
- CN112095159B CN112095159B CN202010770659.0A CN202010770659A CN112095159B CN 112095159 B CN112095159 B CN 112095159B CN 202010770659 A CN202010770659 A CN 202010770659A CN 112095159 B CN112095159 B CN 112095159B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- fiber
- temperature
- wet
- stretching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/10—Filtering or de-aerating the spinning solution or melt
- D01D1/103—De-aerating
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D4/00—Spinnerette packs; Cleaning thereof
- D01D4/02—Spinnerettes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
Abstract
The invention relates to a high-strength coarse denier polyvinyl alcohol fiber prepared by wet spinning and a preparation method thereof, wherein polyvinyl alcohol with the polymerization degree of 3000-3500 and the alcoholysis degree of 98-99% is dissolved in DMSO, and La is added 2 O 3 Obtaining a spinning solution after the polyvinyl alcohol is completely dissolved (the content of the polyvinyl alcohol is 20-22 wt%, and La is used) 2 O 3 The content of (b) is 0.8-1.0 wt%); and then carrying out wet spinning (the diameter of a spinneret orifice is 0.42-0.45 mm), and sequentially carrying out primary coagulation bath (at the temperature of-12 to-10 ℃), primary stretching (with the stretching multiple being 2.0-2.2 times) and secondary coagulation bath (at the temperature of-2 to 0 ℃), carrying out primary hot stretching, extraction and secondary hot stretching to obtain the fiber, wherein the titer of the fiber is 19.2-21.1 dtex, the breaking strength is 13.1-14.6 cN/dtex, and the elastic modulus is 320-339 cN/dtex.
Description
Technical Field
The invention belongs to the technical field of polyvinyl alcohol (PVA) fibers, and relates to a high-strength coarse denier polyvinyl alcohol fiber obtained by wet spinning and a preparation method thereof.
Background
The high-strength concrete has the characteristics that the high-strength concrete has quite wide application prospect in the fields of road bridges, water conservancy municipal administration, marine engineering equipment, military industry national defense and the like. However, it is known that ordinary concrete itself has disadvantages such as brittle cracking and insufficient toughness. The high-strength high-modulus polyvinyl alcohol fiber is usually used for cement-based reinforcing materials due to the advantages of high strength, large modulus, strong adhesive force and the like, but because the fineness of the common high-strength high-modulus polyvinyl alcohol fiber is lower, the maximum fiber mixing amount of each ton of concrete is only about 1.5 kilograms, and the maximum fiber mixing amount of the high-strength coarse-denier polyvinyl alcohol fiber of each ton of concrete can reach about 20 kilograms, the defects of high brittleness and insufficient toughness can be well overcome, and the performance requirements of the high-strength concrete can be met.
At present, the polyvinyl alcohol fiber with higher fiber degree can be prepared only by a melt spinning method, but the prepared polyvinyl alcohol fiber has low strength modulus (breaking strength is generally less than or equal to 10cN/dtex, and elastic modulus is generally less than or equal to 190cN/dtex), and the high-strength coarse-denier polyvinyl alcohol fiber is difficult to be industrially prepared due to special production process and the like.
And the concentration of spinning solution in the common wet spinning process is low, the aperture of a spinneret plate is small, and the titer of the fiber is lower through technological processes of solidification, extraction bath, high-power hot stretching and the like. On the basis of the existing equipment and process, the polyvinyl alcohol fiber with high strength and thick denier is difficult to prepare by adopting wet spinning. Therefore, it is necessary to research the wet-spun high-strength coarse denier polyvinyl alcohol fiber and the preparation method thereof.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a wet-spun high-strength coarse denier polyvinyl alcohol fiber and a preparation method thereof, wherein the high-strength coarse denier polyvinyl alcohol fiber is prepared from La with the particle size of 20-40 nm 2 O 3 The nano particles are used as a cross-linking agent, polyvinyl alcohol with the polymerization degree of 3000-3500 and the alcoholysis degree of 98-99% is used as a raw material for wet spinning, and the nascent fiber is obtainedSequentially carrying out two-stage coagulation bath and two-time hot stretching to obtain high-strength coarse denier polyvinyl alcohol fibers;
in order to achieve the purpose, the technical scheme is as follows:
a preparation method of a wet spinning high-strength coarse denier polyvinyl alcohol fiber comprises the steps of dissolving polyvinyl alcohol with polymerization degree of 3000-3500 and alcoholysis degree of 98-99% in DMSO, and adding La with particle size of 20-40 nm 2 O 3 Dissolving nano particles into polyvinyl alcohol completely to obtain high-concentration spinning solution; then carrying out wet spinning, and sequentially carrying out primary coagulation bath, primary stretching, secondary coagulation bath, primary hot stretching, extraction and secondary hot stretching on the obtained primary fiber to obtain the high-strength coarse denier polyvinyl alcohol fiber; the polyvinyl alcohol spinning with medium and high polymerization degree is selected because the polyvinyl alcohol spinning with too high polymerization degree is complex in process and difficult to produce, and the diameter of the fiber after high-power drawing is large in thinning range, so that the preparation of coarse denier fiber is not facilitated; and too low polymerization degree is not favorable for preparing high-strength polyvinyl alcohol fiber due to more end defects. The high alcoholysis degree is also beneficial to preparing high-strength fibers, the improvement of the crystallinity of the fibers is influenced because macromolecules have larger side groups due to the small alcoholysis degree, and the process is difficult to realize due to the higher alcoholysis degree;
the temperature of the first-stage coagulating bath is-12 to-10 ℃; the temperature of the secondary coagulating bath is-2 to 0 ℃; the solvents of the first-stage coagulating bath and the second-stage coagulating bath are both methanol or ethanol;
in the high-concentration spinning solution, the mass fraction of polyvinyl alcohol is 20-22 wt%, and La is used 2 O 3 The mass fraction of the nano particles is 0.8-1.0 wt%; in the wet spinning process, the aperture of a spinneret orifice is 0.42-0.45 mm;
the stretching ratio of the first stretching is 2.0-2.2 times. At this time, a certain tension is required to be applied in order to maintain the extensibility of the macromolecular chain, and because the nascent fiber is thick, the retraction of the fiber can be overcome by a slightly larger tension, so that the straightened state of the macromolecular chain is maintained as much as possible, but the fiber just comes out of the low-temperature coagulation bath, and the brittle failure is easily caused by an excessively high stretching ratio.
As a preferred technical scheme:
according to the preparation method of the wet-spinning high-strength coarse denier polyvinyl alcohol fiber, the curing time of the primary coagulation bath is 2.8-3.0 min; the curing time of the second-stage coagulating bath is 2.8-3.0 min. Because this nascent fibre titer is great, the difficult solidification thoroughly in the short time of comparing the fibre of ordinary titer, so extension curing time can play better solidification effect in first order and second level coagulation bath, but curing time overlength is unfavorable to production efficiency.
According to the preparation method of the wet-spinning high-strength coarse denier polyvinyl alcohol fiber, the temperature of the first hot drawing is 190-200 ℃. Compared with polyvinyl alcohol with common titer, the coarse denier polyvinyl alcohol fiber has larger titer, so that the inner and outer macromolecules of the fiber can form uniform folding chain crystals under the action of temperature and stress, the temperature is slightly higher than that of the common fiber, but the fiber is easy to melt due to overhigh temperature, thereby being not beneficial to the improvement of the subsequent stretching multiple; the temperature of the second hot stretching is 200-210 ℃, and the higher the hot stretching temperature is, the larger the hot stretching multiple of the fiber is, the larger the total stretching multiple is, the larger the heavy denier fiber can properly increase the second hot stretching temperature, but when the temperature is too high, the fiber can be fused and cannot be continuously stretched. The main reason is that the activation energy of macromolecular chains in the polyvinyl alcohol fiber is increased along with the rise of the hot stretching temperature, the movement of chain segments is accelerated, and the macromolecular conformation is changed due to the internal rotation of single bonds on the main chain and the movement of the chain segments, so that the macromolecular chains of the fiber are easier to straighten and orient under the action of external force, the hot stretching multiple of the fiber is increased, the orientation degree and the crystallinity degree of the fiber are increased, and finally the mechanical property of the fiber is improved, but when the temperature is too high, the fiber is easy to be locally melted and broken, and the mechanical property of the fiber is influenced on the contrary.
According to the preparation method of the wet-spinning high-strength coarse denier polyvinyl alcohol fiber, the stretching multiple of the first hot stretching is 2.4-2.5 times, and the stretching multiple of the second hot stretching is 3.0-3.5 times. When the stretching multiple of the first stretching is too low, the pre-orientation degree of the fiber is insufficient, the crystal form is easily changed into monoclinic crystal which is difficult to stretch, so that the second stretching is not uniform, the elongation of the fiber is low due to the effect of crosslinking points in the fiber, and molecular chains are easy to break during high-power stretching; under the condition of reasonably distributing the stretching ratio twice, the total stretching ratio can be improved as much as possible. The second thermal stretch is the maximum stretch that the fiber can bear at this time, and the total stretch of the fiber is the product of the third stretch.
According to the preparation method of the wet-spinning high-strength coarse denier polyvinyl alcohol fiber, the extracted solvent is methanol or ethanol, the temperature is 25-30 ℃, the time is 23-24 hours (the solvent can be replaced every 12 hours or so to increase the extraction efficiency), and the purpose of extraction at a higher temperature is to remove the solvent in the coarse denier fiber to the maximum extent and increase the hot stretching multiple.
The preparation method of the wet-spinning high-strength coarse denier polyvinyl alcohol fiber comprises the following steps: the extrusion rate of the spinneret orifice is 4.0-4.2 ml/min, and the spinning temperature is 85-90 ℃.
According to the preparation method of the wet-spinning high-strength coarse denier polyvinyl alcohol fiber, the spinning solution is subjected to defoaming treatment at 78-80 ℃ for 3.0-3.5 hours before wet spinning. If the spinning solution contains bubbles, the thickness of the fiber is uneven, the stretching ratio is influenced, and certain damage can be caused to spinning equipment. The deaeration of the spinning solution with higher concentration is difficult, the deaeration time needs to be properly prolonged, and the time is meaningless after the spinning solution is fully deaerated.
The invention also provides the high-strength coarse-denier polyvinyl alcohol fiber prepared by the preparation method of the wet-spun high-strength coarse-denier polyvinyl alcohol fiber, wherein the fineness of the high-strength coarse-denier polyvinyl alcohol fiber is 19.2-21.1 dtex, the breaking strength is 13.1-14.6 cN/dtex, and the elastic modulus is 320-339 cN/dtex.
The mechanism of the invention is as follows:
in order to prepare the high-strength coarse denier polyvinyl alcohol fiber by adopting a wet spinning process, the concentration (20-22 wt%) of a spinning solution prepared firstly is higher than that (12-15 wt%) of a spinning solution prepared by adopting a wet spinning method with DMSO as a solvent, correspondingly,the aperture (0.42-0.45 mm) of the spinneret orifice is also higher than that of the spinneret orifice (0.2-0.3 mm) in the common wet spinning process, the requirement of large diameter of the nascent fiber is met under the condition, and in addition, La with higher concentration is also added into the spinning solution 2 O 3 The nano particles (0.8-1.0 wt%) are used as a cross-linking agent, and the amount of the cross-linking agent is 0.5-0.8 wt% higher than that of the cross-linking agent used in the common spinning;
the invention adopts two-stage coagulating bath with certain stretching ratio to solidify nascent fiber, which comprises the following steps: when the polyvinyl alcohol spinning solution is extruded from the spinneret orifices, the macromolecular chains tend to be in a straight chain state under the action of shearing force of the spinneret orifices, and when the polyvinyl alcohol spinning solution directly enters a low-temperature first-stage coagulating bath, the thermal motion of the macromolecular chains is rapidly reduced due to large temperature difference, and nascent fibers are instantly solidified, so that the straight chain state of the macromolecular chains is kept; mechanical stretching is carried out between the first-stage coagulating bath and the second-stage coagulating bath in a lower multiple, wherein the stretching is to avoid that macromolecular chains are retracted to a greater extent due to the rise of temperature when the fibers enter air; after entering a second-stage moderate temperature (the temperature is between the temperature of the first-stage coagulating bath and the room temperature), the macromolecular chains are slightly retracted along with the slow increase of the temperature, the fiber diameter is thickened, the solvent is preliminarily removed, the fibers are further solidified, and the macromolecular chains are not greatly retracted and tangled due to the drastic change of the temperature when entering the room temperature, so that the strength is favorably improved;
meanwhile, La added in the present invention 2 O 3 The nano particles can be uniformly dispersed in the spinning solution due to better dispersibility, and the La is 2 O 3 The nano particles have small particle size (20-40 nm), large specific surface area and high activity, the surface contains a large number of hydroxyl groups, and after part of the solvent in the spinning solution is removed in a solid bath, La in the fiber 2 O 3 The nano particles can generate a large amount of hydrogen bond crosslinking with hydroxyl on a polyvinyl alcohol macromolecular chain, and can inhibit the formation of the hydrogen bonds of the macromolecular chain and the macromolecular chains; in the process of curing the nascent fiber by the two-stage coagulation bath, the entanglement among macromolecular chains can be avoided, and the state of straightening the molecular chains is favorably kept; in addition, theLa in an organic coagulation bath 2 O 3 The La which is generally soluble and is not easily removed remains in the fiber 2 O 3 The nano particles can form permanent cross-linking points in the fiber and form network cross-linking with macromolecular chains, so that the fiber has higher titer, and the external force applied to the fiber can be dispersed due to the network cross-linking effect, thereby improving the strength of the fiber.
Has the advantages that:
(1) the preparation method of the high-strength coarse denier polyvinyl alcohol fiber through wet spinning adopts high-concentration spinning solution, special cross-linking agent, a spinneret plate with large aperture and spinning solidified by two-stage coagulating bath containing a certain stretching multiple to prepare the high-strength coarse denier polyvinyl alcohol fiber with the titer of 19.2-21.1 dtex, the breaking strength of 13.1-14.6 cN/dtex and the elastic modulus of 320-339 cN/dtex;
(2) the high-strength coarse denier polyvinyl alcohol fiber prepared by the method disclosed by the invention can have quite wide application prospects in the fields of road bridges, water conservancy municipal administration, marine engineering equipment, military industry and national defense and the like.
Drawings
FIG. 1 is a schematic drawing of a coagulation bath and drawing;
FIG. 2 is a schematic drawing of hot stretching;
wherein, 1-a propulsion pump, 2-a spinning nozzle, 3-guide rollers I, 4-guide rollers II, 5-guide rollers III, 6-a first-stage coagulating bath and 7-a second-stage coagulating bath.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of wet spinning high-strength coarse denier polyvinyl alcohol fiber comprises the following steps:
(1) firstly, the polymerization degree is 3200 and the alcoholysis degreeDissolving 98% polyvinyl alcohol in DMSO, adding La 2 O 3 Preparing a high-concentration spinning solution from the nano particles; in the high-concentration spinning solution, the mass fraction of polyvinyl alcohol is 21 wt%, and La is added 2 O 3 The mass fraction of the nano particles is 0.9 wt%;
(2) defoaming the spinning solution at 79 ℃ for 3.2 h;
(3) performing wet spinning, and sequentially passing the obtained nascent fiber through a first-stage coagulating bath (the solvent is methanol and the curing time is 2.9min) with the temperature of-11 ℃, a first-stage drawing (the drawing multiple is 2.1 times) and a second-stage coagulating bath (the solvent is methanol and the curing time is 2.8min) with the temperature of-1 ℃; as shown in fig. 1, a spinning solution is extruded by a propulsion pump 1, a nascent fiber is extruded through a large-aperture spinneret 2, enters a first-stage coagulation bath 6, is stretched for the first time (the stretching ratio is controlled by adjusting the rotating speed of guide rollers I3 and II 4), then enters a second-stage coagulation bath 7, and is subjected to subsequent hot stretching through a guide roller III 5 after the second coagulation is finished;
the thermal stretching process is that the solidified fiber is subjected to first thermal stretching (stretching multiple is 2.5 times) at the temperature of 198 ℃, extraction (solvent is methanol, temperature is 26 ℃, time is 24 hours) and second thermal stretching (stretching multiple is 3.2 times) at the temperature of 205 ℃ to prepare the high-strength coarse denier polyvinyl alcohol fiber; wherein, the wet spinning process comprises the following steps: the extrusion rate of the spinneret plate is 4.1ml/min, the spinning temperature is 86 ℃, and the aperture of the spinneret orifice is 0.43 mm; as shown in fig. 2, a drawing apparatus for the first hot drawing and the second hot drawing is schematically illustrated.
The fineness of the prepared high-strength coarse denier polyvinyl alcohol fiber is 19.9dtex, the breaking strength is 13.9cN/dtex, and the elastic modulus is 331 cN/dtex.
Comparative example 1
A method for preparing polyvinyl alcohol fiber by wet spinning, which has the same process as that of the embodiment 1, except that, in the wet spinning, the high concentration spinning solution is changed into a spinning solution with a lower concentration and a mass fraction of 14%, and the prepared polyvinyl alcohol fiber has a fineness of 13.9dtex, a breaking strength of 10.2cN/dtex, and an elastic modulus of 287 cN/dtex; comparing comparative example 1 with example 1, it can be seen that the fineness, breaking strength and elastic modulus in comparative example 1 are all smaller, because under the same spinning conditions, with the decrease of the concentration of the spinning solution, the number of polyvinyl alcohol molecular chains contained in a single fiber is reduced, and when the fiber is coagulated and formed, the number of holes formed by the diffusion of the solvent into the coagulation bath is increased, and the defects in the fiber are increased, thereby reducing the mechanical properties of the fiber. On the contrary, a higher concentration of the spinning solution is beneficial to the improvement of the mechanical properties of the fiber, but when the concentration of the spinning solution is too high, the viscosity of the solution is too high, and the fiber cannot be stably and continuously produced.
Comparative example 2
A process for preparing wet-spun polyvinyl alcohol fibers substantially the same as in example 1, except that the wet-spun raw material contained no La was used 2 O 3 The fineness of the prepared polyvinyl alcohol fiber is 15.9dtex, the breaking strength is 11.4cN/dtex, and the elastic modulus is 295 cN/dtex; as can be seen by comparing comparative example 2 with example 1, the fineness, breaking strength and elastic modulus in comparative example 2 are smaller because La 2 O 3 The nano particles can form a complex with polyvinyl alcohol macromolecules to play a role in permanent crosslinking, not only can reduce the mutual crosslinking in and among the macromolecules and overcome the entanglement of macromolecular chains, but also can play a role in dispersing external force by a certain number of crosslinking points, thereby being beneficial to improving the mechanical property of the fiber, simultaneously enabling the diameter of the fiber to be thicker and finally being beneficial to preparing the high-strength coarse denier polyvinyl alcohol fiber.
Comparative example 3
The preparation method of a wet spinning polyvinyl alcohol fiber, its process is basically the same as example 1, the difference is only that the fiber is solidified through the first-stage coagulating bath during the wet spinning, the temperature and the coagulating time of the first-stage coagulating bath are the same as example 1, the titer of the finally prepared polyvinyl alcohol fiber is 20.3dtex, the breaking strength is 12.5cN/dtex, the elastic modulus is 312 cN/dtex; comparing comparative example 3 with example 1, it can be seen that the fineness of comparative example 3 is slightly increased, but the strength and modulus are smaller, because the fiber is easier to retract due to the lack of one drawing and larger temperature difference action in the middle of the one-stage coagulation bath compared with the two-stage coagulation bath, and the large amount of solvent contained in the fiber is not removed, which affects the increase of the drawing multiple, thus the diameter of the fiber is thicker, and the improvement of the mechanical property of the fiber is not good.
Example 2
A preparation method of wet spinning high-strength coarse denier polyvinyl alcohol fiber comprises the following steps:
(1) firstly, polyvinyl alcohol with the polymerization degree of 3400 and the alcoholysis degree of 98 percent is dissolved in DMSO, and La is added 2 O 3 Obtaining high-concentration spinning solution by the nano particles; in the high-concentration spinning solution, the mass fraction of polyvinyl alcohol is 21 wt%, and La is added 2 O 3 The mass fraction of the nano particles is 0.8 wt%;
(2) defoaming the spinning solution at 78 deg.C for 3.4 h;
(3) performing wet spinning, and sequentially treating the obtained nascent fiber by a first-stage coagulating bath (the solvent is methanol and the curing time is 2.8min) with the temperature of-12 ℃, a first-stage drawing (the drawing multiple is 2.0 times), a coagulating bath (the solvent is methanol and the curing time is 2.9min) with the second-stage temperature of 0 ℃, a first-stage hot drawing (the drawing multiple is 2.4 times) with the temperature of 199 ℃, extraction (the solvent is methanol and the temperature is 27 ℃ and the time is 24h) and a second-stage hot drawing (the drawing multiple is 3.3 times) with the temperature of 203 ℃ to obtain the high-strength coarse denier polyvinyl alcohol fiber; wherein, the wet spinning process comprises the following steps: the extrusion rate of the spinneret plate is 4ml/min, the spinning temperature is 86 ℃, and the aperture of a spinneret orifice is 0.44 mm;
the fineness of the prepared high-strength coarse denier polyvinyl alcohol fiber is 20.1dtex, the breaking strength is 14.1cN/dtex, and the elastic modulus is 334 cN/dtex.
Example 3
A preparation method of wet spinning high-strength coarse denier polyvinyl alcohol fiber comprises the following steps:
(1) firstly, polyvinyl alcohol with polymerization degree of 3500 and alcoholysis degree of 99 percent is dissolved in DMSO, and La is added 2 O 3 Obtaining high-concentration spinning solution by the nano particles; quality of polyvinyl alcohol in high concentration spinning solutionThe amount fraction is 22wt%, La 2 O 3 The mass fraction of the nano particles is 1.0 wt%;
(2) defoaming the spinning solution at the temperature of 80 ℃ for 3.5 h;
(3) performing wet spinning, and sequentially treating the obtained nascent fiber by a first-stage coagulating bath (the solvent is methanol and the curing time is 3min) with the temperature of minus 11 ℃, a first-stage drawing (the drawing multiple is 2.2 times), a coagulating bath (the solvent is methanol and the curing time is 2.8min) with the second-stage temperature of 0 ℃, a first-stage hot drawing (the drawing multiple is 2.4 times) with the temperature of 200 ℃, extraction (the solvent is ethanol and the temperature is 28 ℃ and the time is 23h) and a second-stage hot drawing (the drawing multiple is 3.5 times) with the temperature of 210 ℃ to obtain the high-strength coarse denier polyvinyl alcohol fiber; wherein, the wet spinning process comprises the following steps: the extrusion rate of a spinneret plate is 4.2ml/min, the spinning temperature is 87 ℃, and the aperture of a spinneret orifice is 0.42 mm;
the fineness of the prepared high-strength coarse-denier polyvinyl alcohol fiber is 19.2dtex, the breaking strength is 14.6cN/dtex, and the elastic modulus is 339 cN/dtex.
Example 4
A preparation method of wet spinning high-strength coarse denier polyvinyl alcohol fiber comprises the following steps:
(1) firstly, polyvinyl alcohol with the polymerization degree of 3000 and the alcoholysis degree of 99 percent is dissolved in DMSO, and La is added 2 O 3 Obtaining high-concentration spinning solution by the nano particles; in the high-concentration spinning solution, the mass fraction of polyvinyl alcohol is 20 wt%, and La 2 O 3 The mass fraction of the nano particles is 0.8 wt%;
(2) defoaming the spinning solution at 78 deg.C for 3.0 h;
(3) performing wet spinning, and sequentially treating the obtained nascent fiber by a first-stage coagulating bath (the solvent is ethanol and the curing time is 2.9min) with the temperature of minus 10 ℃, a first-stage drawing (the drawing multiple is 2.0 times), a coagulating bath (the solvent is ethanol and the curing time is 2.9min) with the second-stage temperature of minus 2 ℃, a first-stage hot drawing (the drawing multiple is 2.5 times) with the temperature of 190 ℃, extraction (the solvent is methanol and the temperature is 30 ℃ and the time is 24h) and a second-stage hot drawing (the drawing multiple is 3.0 times) with the temperature of 200 ℃ to obtain the high-strength coarse denier polyvinyl alcohol fiber; wherein, the wet spinning process comprises the following steps: the extrusion rate of the spinneret plate is 4.1ml/min, the spinning temperature is 88 ℃, and the aperture of the spinneret orifice is 0.45 mm;
the fineness of the prepared high-strength coarse denier polyvinyl alcohol fiber is 21.1dtex, the breaking strength is 13.1cN/dtex, and the elastic modulus is 320 cN/dtex.
Example 5
A preparation method of wet spinning high-strength coarse denier polyvinyl alcohol fiber comprises the following steps:
(1) firstly, polyvinyl alcohol with the polymerization degree of 3100 and the alcoholysis degree of 99 percent is dissolved in DMSO, and La is added 2 O 3 Obtaining high-concentration spinning solution by the nano particles; in the high-concentration spinning solution, the mass fraction of polyvinyl alcohol is 22wt%, and La is added 2 O 3 The mass fraction of the nano particles is 0.9 wt%;
(2) defoaming the spinning solution at 78 deg.C for 3.5 h;
(3) performing wet spinning, and sequentially treating the obtained nascent fiber by a first-stage coagulating bath (the solvent is methanol and the curing time is 3min) with the temperature of-10 ℃, a first-stage drawing (the drawing multiple is 2.1 times), a coagulating bath (the solvent is methanol and the curing time is 3min) with the second-stage temperature of-1 ℃, a first-stage hot drawing (the drawing multiple is 2.5 times) with the temperature of 194 ℃, extraction (the solvent is ethanol and the temperature is 25 ℃ and the time is 24h) and a second-stage hot drawing (the drawing multiple is 3.0 times) with the temperature of 202 ℃ to obtain the high-strength coarse denier polyvinyl alcohol fiber; wherein, the wet spinning process comprises the following steps: the extrusion rate of the spinneret plate is 4.1ml/min, the spinning temperature is 90 ℃, and the aperture of the spinneret orifice is 0.43 mm;
the fineness of the prepared high-strength coarse denier polyvinyl alcohol fiber is 20.7dtex, the breaking strength is 13.7cN/dtex, and the elastic modulus is 325 cN/dtex.
Claims (6)
1. A preparation method of wet spinning high-strength coarse denier polyvinyl alcohol fiber is characterized by comprising the following steps: firstly, polyvinyl alcohol with the polymerization degree of 3000-3500 and the alcoholysis degree of 98-99% is dissolved in DMSO, and La is added 2 O 3 Dissolving nano particles into polyvinyl alcohol completely to obtain high-concentration spinning solution; then carrying out wet spinningSequentially carrying out primary coagulation bath, primary stretching, secondary coagulation bath, primary hot stretching, extraction and secondary hot stretching on the obtained nascent fiber to obtain high-strength coarse denier polyvinyl alcohol fiber;
the temperature of the first-stage coagulation bath is-12 to-10 ℃; the temperature of the second-stage coagulating bath is-2-0 ℃; the solvents of the first-stage coagulating bath and the second-stage coagulating bath are both methanol or ethanol;
in the high-concentration spinning solution, the mass fraction of polyvinyl alcohol is 20-22 wt%, and La 2 O 3 The mass fraction of the nano particles is 0.8-1.0 wt%; in the wet spinning process, the aperture of a spinneret orifice is 0.42-0.45 mm; the stretching ratio of the first stretching is 2.0-2.2 times;
the temperature of the first hot stretching is 190-200 ℃, and the temperature of the second hot stretching is 200-210 ℃;
the stretching ratio of the first hot stretching is 2.4-2.5 times, and the stretching ratio of the second hot stretching is 3.0-3.5 times.
2. The method for preparing the wet-spun high-strength coarse denier polyvinyl alcohol fiber according to claim 1, wherein the curing time of the first-stage coagulation bath is 2.8-3.0 min; the curing time of the second-stage coagulating bath is 2.8-3.0 min.
3. The method for preparing the wet-spun high-strength coarse denier polyvinyl alcohol fiber according to claim 1, wherein the solvent for extraction is methanol or ethanol, the temperature is 25-30 ℃, and the time is 23-24 h.
4. The method for preparing the wet-spun high-strength coarse denier polyvinyl alcohol fiber according to claim 1, wherein the wet spinning process comprises the following steps: the extrusion rate of a spinneret orifice is 4.0-4.2 ml/min, and the spinning temperature is 85-90 ℃.
5. The preparation method of the wet-spun high-strength coarse denier polyvinyl alcohol fiber according to claim 1, wherein the spinning solution is defoamed at 78-80 ℃ for 3.0-3.5 hours before wet spinning.
6. The method for preparing the wet-spun high-strength coarse-denier polyvinyl alcohol fiber according to any one of claims 1 to 5, wherein the fineness of the high-strength coarse-denier polyvinyl alcohol fiber is 19.2 to 21.1dtex, the breaking strength is 13.1 to 14.6cN/dtex, and the elastic modulus is 320 to 339 cN/dtex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010770659.0A CN112095159B (en) | 2020-08-04 | 2020-08-04 | High-strength coarse denier polyvinyl alcohol fiber spun by wet method and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010770659.0A CN112095159B (en) | 2020-08-04 | 2020-08-04 | High-strength coarse denier polyvinyl alcohol fiber spun by wet method and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112095159A CN112095159A (en) | 2020-12-18 |
| CN112095159B true CN112095159B (en) | 2022-09-16 |
Family
ID=73750242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010770659.0A Active CN112095159B (en) | 2020-08-04 | 2020-08-04 | High-strength coarse denier polyvinyl alcohol fiber spun by wet method and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112095159B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113373539B (en) * | 2021-06-29 | 2022-07-29 | 东华大学 | Preparation method and application of high-strength high-modulus polyvinyl alcohol fiber |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60126311A (en) * | 1983-12-12 | 1985-07-05 | Toray Ind Inc | Novel polyvinyl alcohol based fiber |
| JPH04240207A (en) * | 1991-01-22 | 1992-08-27 | Unitika Ltd | Polyvinyl alcoholic fiber and its production |
| JPH05239711A (en) * | 1992-02-25 | 1993-09-17 | Unitika Ltd | Dry-wet spinning process and apparatus therefor |
| JP2000136431A (en) * | 1998-11-04 | 2000-05-16 | Kuraray Co Ltd | Polyvinyl alcohol-based fiber and its production |
| JP2000273718A (en) * | 1999-03-29 | 2000-10-03 | Kuraray Co Ltd | High-speed spinning of polyvinyl alcohol-based yarn |
| CN1621584A (en) * | 2003-11-27 | 2005-06-01 | 株式会社晓星 | Crosslinked polyvinyl alcohol fiber and method for producing the same |
| CN101392412A (en) * | 2008-11-07 | 2009-03-25 | 湖南省湘维有限公司 | High strength vinylon and preparation method thereof |
| CN103031611A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工集团公司 | Polyvinyl alcohol fiber and preparation method as well as application thereof |
| CN103305955A (en) * | 2013-06-24 | 2013-09-18 | 永安市宝华林实业发展有限公司 | Preparation method of polyving akohol filament fibers |
| CN104328511A (en) * | 2014-10-08 | 2015-02-04 | 九力绳缆有限公司 | Preparation method for high-strength high-modulus polyvinyl alcohol fibers |
| CN107268105A (en) * | 2016-04-07 | 2017-10-20 | 中国石油化工集团公司 | A kind of high strength high modulus PVA fiber and its production and use |
| CN107287675A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工集团公司 | A kind of vinal and preparation method thereof |
| CN107287673A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工集团公司 | A kind of soluble thick denier PVA fibers and application thereof |
| CN111235663A (en) * | 2020-03-23 | 2020-06-05 | 浙江红雨医药用品有限公司 | Preparation method of polyvinyl alcohol fiber with high tensile property |
-
2020
- 2020-08-04 CN CN202010770659.0A patent/CN112095159B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60126311A (en) * | 1983-12-12 | 1985-07-05 | Toray Ind Inc | Novel polyvinyl alcohol based fiber |
| JPH04240207A (en) * | 1991-01-22 | 1992-08-27 | Unitika Ltd | Polyvinyl alcoholic fiber and its production |
| JPH05239711A (en) * | 1992-02-25 | 1993-09-17 | Unitika Ltd | Dry-wet spinning process and apparatus therefor |
| JP2000136431A (en) * | 1998-11-04 | 2000-05-16 | Kuraray Co Ltd | Polyvinyl alcohol-based fiber and its production |
| JP2000273718A (en) * | 1999-03-29 | 2000-10-03 | Kuraray Co Ltd | High-speed spinning of polyvinyl alcohol-based yarn |
| CN1621584A (en) * | 2003-11-27 | 2005-06-01 | 株式会社晓星 | Crosslinked polyvinyl alcohol fiber and method for producing the same |
| CN101392412A (en) * | 2008-11-07 | 2009-03-25 | 湖南省湘维有限公司 | High strength vinylon and preparation method thereof |
| CN103031611A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工集团公司 | Polyvinyl alcohol fiber and preparation method as well as application thereof |
| CN103305955A (en) * | 2013-06-24 | 2013-09-18 | 永安市宝华林实业发展有限公司 | Preparation method of polyving akohol filament fibers |
| CN104328511A (en) * | 2014-10-08 | 2015-02-04 | 九力绳缆有限公司 | Preparation method for high-strength high-modulus polyvinyl alcohol fibers |
| CN107268105A (en) * | 2016-04-07 | 2017-10-20 | 中国石油化工集团公司 | A kind of high strength high modulus PVA fiber and its production and use |
| CN107287675A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工集团公司 | A kind of vinal and preparation method thereof |
| CN107287673A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工集团公司 | A kind of soluble thick denier PVA fibers and application thereof |
| CN111235663A (en) * | 2020-03-23 | 2020-06-05 | 浙江红雨医药用品有限公司 | Preparation method of polyvinyl alcohol fiber with high tensile property |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112095159A (en) | 2020-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9428850B2 (en) | Process of making pan-based carbon fiber | |
| EP0858522B1 (en) | Method for spinning hollow polymeric fibres | |
| EP2524980A1 (en) | Method for producing precursor fibres and carbon fibres containing lignine | |
| CN112226840B (en) | High-strength high-modulus PVA fiber and preparation method thereof | |
| WO2009039725A1 (en) | A method for producing lower size, high tenacity and high modulus polyethylene fiber | |
| CN104264264A (en) | Preparation method of high-orientation-degree polyacrylonitrile fibers | |
| CN103031611A (en) | Polyvinyl alcohol fiber and preparation method as well as application thereof | |
| CN112095159B (en) | High-strength coarse denier polyvinyl alcohol fiber spun by wet method and preparation method thereof | |
| CN1400342A (en) | Production method of high strength polyethylene fibre and fibre | |
| CN101736411A (en) | Method for preparing polyacrylonitrile spinning solution for carbon fiber | |
| CN102560700B (en) | Para-aramid fine denier fiber and preparation method thereof | |
| CN1256474C (en) | Manufacturing method of poly p phenylene diamine terephthalamide fiber | |
| CN112095170B (en) | LaCl3Cross-linked high-strength high-modulus polyvinyl alcohol fiber and preparation method thereof | |
| KR101429686B1 (en) | Process for preparing high viscosity and high intensity industrial polyester fibre | |
| CN112226851B (en) | Preparation method of polyacrylonitrile-based carbon fiber | |
| CN104233499A (en) | Preparation method of aromatic polyarmide fiber containing heterlcyclic rings | |
| Song et al. | A comparative study on properties of cellulose/antarctic krill protein composite fiber by centrifugal spinning and wet spinning | |
| Zhang et al. | Preparation and formation mechanism analysis of regenerated silk fibroin/polyvinyl alcohol blended fibers with waste silk quilt | |
| CN111206291B (en) | Ultrahigh molecular weight polyethylene oxide fiber and preparation method thereof | |
| CN106480535A (en) | A kind of method that polyformaldehyde fibre prepared by melt spinning | |
| CN111206290A (en) | Making method of beautiful sesame fiber | |
| US2621103A (en) | Production of artificial filaments and similar products from cellulose xanthogenates | |
| CN113403694B (en) | Preparation method and application of PVA high-solid-content spinning solution | |
| CN113737393B (en) | Electrostatic spinning nanofiber membrane and preparation method thereof | |
| CN113372470B (en) | Preparation method and application of hydrolysis-resistant PVA polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |