CN111155189B - Preparation method of melt-spun profiled polyvinyl alcohol fiber - Google Patents
Preparation method of melt-spun profiled polyvinyl alcohol fiber Download PDFInfo
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- CN111155189B CN111155189B CN202010050165.5A CN202010050165A CN111155189B CN 111155189 B CN111155189 B CN 111155189B CN 202010050165 A CN202010050165 A CN 202010050165A CN 111155189 B CN111155189 B CN 111155189B
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- 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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/34—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated alcohols, acetals or ketals as the major constituent
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- 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
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
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- 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
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- 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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
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- 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 discloses a preparation method of melt-spun profiled polyvinyl alcohol fibers, belonging to the technical field of profiled polyvinyl alcohol fiber preparation. Which comprises the following steps: carrying out melt spinning on the modified polyvinyl alcohol powder on an extrusion-spinning device, carrying out melt extrusion, filtering and metering, then spraying out from a spinneret plate containing profiled spinneret micropores, and carrying out side-blowing cooling on the melt trickle to obtain profiled polyvinyl alcohol nascent fibers; and carrying out multi-stage drawing, wet heat drawing or dry heat drawing and heat setting on the profiled polyvinyl alcohol nascent fiber to obtain the melt-spun profiled polyvinyl alcohol fiber. The preparation method of the melt-spun profiled polyvinyl alcohol fiber realizes stable and continuous melt spinning of the polyvinyl alcohol fiber, can obtain the nascent fiber with a triangular, trilobal, quadralobal or flat wave-shaped section, successfully prepares the melt-spun profiled polyvinyl alcohol fiber which can be used for reinforcing and toughening composite materials through subsequent drawing and heat setting processes, and has high strength and good profile retention degree.
Description
Technical Field
The invention relates to the technical field of preparation of profiled polyvinyl alcohol fibers, in particular to a preparation method of melt-spun profiled polyvinyl alcohol fibers.
Background
The profiled fiber is a differential fiber with special section shape and function spun by a special method. General fibers having a circular cross section have disadvantages of a low surface gloss, a waxy feeling, easy soiling, easy pilling, no water absorption, and a low covering property. Compared with the circular cross section fiber, the chemical composition of the profiled cross section fiber is not changed, but the change of the cross section shape of the fiber endows the profiled fiber with the performance characteristics superior to that of the common chemical fiber. Such as unique gloss and stain resistance, different hand feeling and excellent pilling resistance, thicker, bulkier and plump textile fabrics and good air permeability, and the profiled fiber is a better choice for reinforcing the composite material due to larger specific surface area and larger friction coefficient. The first report on shaped fibers was triangular cross-section fibers prepared by the bulked adhesive method of dupont in 1953, and a method of manufacturing shaped fibers by separating composite fibers formed by composite spinning was proposed, and then rectangular cross-section fibers and pentagonal cross-section fibers were successively prepared. With the development of fifty years, profiled fibers have become one of the important varieties of differential fibers. At present, the preparation method of the profiled fiber comprises a profiled spinneret orifice method, a swelling adhesion method, a composite fiber separation method, an extrusion method and the like, wherein the profiled spinneret orifice method is a spinning method for processing spinneret orifices into fibers with the cross-sectional shapes similar to the required fiber cross-sectional shapes, and since Edie of 1986, after Y-shaped and eight-leaf-shaped carbon fibers are prepared by adopting a profiled spinneret plate, the manufacturing technology of a spinneret plate is rapidly developed, and the profiled spinneret orifice method becomes the most common profiled fiber spinning method. However, the shaped spinneret hole method is mainly focused on the preparation of melt-spun fibers, such as polypropylene fibers, polyethylene fibers, nylon 66 fibers, polyester fibers, and the like, due to the limitation of the spinning method. At present, in the preparation of melt-spun profiled fibers, the profile degree of the fibers is far lower than the theoretical value thereof and the profile degree retention degree is low due to the action of melt viscosity and surface tension in the spinning process. The spun profiled fiber is generally expected to obtain the fiber with small sectional area and large profile, so that the fiber has few defects and excellent mechanical property, and the unique advantages of the profiled fiber can be effectively exerted.
Polyvinyl alcohol (PVA) is a few high molecular materials which can be produced in a large scale by non-petroleum routes (a natural gas acetylene method and a calcium carbide acetylene method), and is increasingly important under the situation that global petroleum resources are increasingly deficient; the PVA fiber is one of the important application fields of PVA, is prepared by Herrmann and Haehnel by adopting dry spinning of PVA aqueous solution at the earliest time, and researches show that the polyvinyl alcohol fiber (PVA) has the advantages of good mechanical property, good dispersibility, acid and alkali resistance, wear resistance, light resistance, corrosion resistance, mildew resistance, good affinity with a base material interface and the like, and can be widely used as a cement reinforced anti-cracking material, a tire cord, a bulletproof fiber, geotextile, a marine culture net, a high-performance rope, a conveying belt, canvas and the like.
Due to the characteristic of polyhydroxy strong hydrogen bonds of polyvinyl alcohol (PVA) fibers, the melting point of the PVA fibers is close to the decomposition temperature, and thermoplastic processing windows do not exist, the existing spinning is mostly based on a solution method, wherein the cross section of the nascent fiber of wet spinning is waist-shaped, and the PVA fibers have obvious skin-core structures and cannot bear high-power stretching; other spinning methods such as gel spinning, boron-containing cross-linking wet spinning, dry-wet spinning, direct alcoholysis spinning of polyvinyl acetate and the like are all based on solution spinning, most of the methods adopt polyvinyl alcohol fibers (PVA) with high polymerization degree, the production cost is high, the problems of procedures and pollution such as solvent removal and the like exist, the process is complex, the energy consumption is high, and the existing solution spinning method is difficult to prepare special-shaped polyvinyl alcohol fibers with controllable cross sections, large profile degree and high profile degree maintenance.
Disclosure of Invention
The invention aims to provide a preparation method of melt-spun profiled polyvinyl alcohol fibers, which solves the problem that profiled polyvinyl alcohol fibers with controllable cross sections, large profile degree and high profile degree retention are difficult to obtain at present.
The technical scheme for solving the technical problems is as follows:
the preparation method of the melt-spun profiled polyvinyl alcohol fiber comprises the following steps:
(1) carrying out melt spinning on the modified polyvinyl alcohol powder on an extrusion-spinning device, carrying out melt extrusion, filtering and metering, then spraying out from a spinneret plate containing profiled spinneret micropores, and carrying out side-blowing cooling on the melt trickle to obtain profiled polyvinyl alcohol nascent fibers;
(2) and (3) stretching and heat setting the profiled polyvinyl alcohol nascent fiber to obtain the melt-spun profiled polyvinyl alcohol fiber.
Further, in a preferred embodiment of the present invention, the cross-section of the spinneret micro-holes in the spinneret plate in the step (1) is triangular, trilobal, quadralobal or flat wave, and the degree of profile of the spinneret micro-holes in the spinneret plate is 50-90%.
Further, in the preferred embodiment of the present invention, the profile degree of the triangular spinneret micro-holes is 50%; the profile degree of the trilobal spinning micropores and the quadralobal spinning micropores is 50-80%; the abnormal degree of the flat wave type spinneret micropores is 80-90%.
Further, in a preferred embodiment of the present invention, the equivalent diameter Dh of the profiled spinneret micro-holes of the spinneret plate, the shear rate γ of the modified polyvinyl alcohol powder melt, and the volume flow Q of the modified polyvinyl alcohol powder melt controlled by the metering pump satisfy the following relations:
in the formula: gamma is the melt shear rate of the modified polyvinyl alcohol powder with the unit of s-1(ii) a Q represents the volume flow of the modified polyvinyl alcohol powder melt and the unit is mm3/s，DhThe equivalent diameter of the irregular hole is expressed in mm; q represents the cross-sectional area of the spinning nozzle in mm2(ii) a s represents the perimeter of the spinning pores in mm; lambda represents a shape factor related to the cross section of the spinning nozzle and is constant and ranges from 6 to 8.
Further, in a preferred embodiment of the present invention, the spinneret plate has a spinneret hole equivalent diameter DhIs 0.25mm-0.6 mm.
Further, in a preferred embodiment of the present invention, the spinning temperature in the step (1) is 130 to 180 ℃; the spinning shear rate is 2000-15000 s-1(ii) a The spinning shear viscosity is 100-300 Pa.s; the spinning pressure is 10-30 MPa; the volume flow of the spinning is 70-300 mm3S; stretch ratio of spinning nozzle1-4 times; the temperature of the cross air blow is 10-70 ℃.
Further, in a preferred embodiment of the present invention, the modified polyvinyl alcohol powder is physically or chemically modified polyvinyl alcohol powder;
wherein, the step of physically modifying the polyvinyl alcohol powder comprises the following steps: compounding polyvinyl alcohol powder with auxiliary additives of polar micromolecules and low molecular weight, or compounding polyvinyl alcohol powder with high molecular compounds to prepare physically modified polyvinyl alcohol powder; polar small molecules include water or glycerol; the low molecular weight auxiliary additive comprises amide, polyoxyethylene with the molecular weight of less than 100 ten thousand or polyethylene glycol with the molecular weight of less than 20000; the polymer compound includes: starch, lignin, collagen, polyamide or polylactide;
the method for chemically modifying the polyvinyl alcohol powder comprises the following steps: copolymerizing vinyl monomer on the molecular chain of polyvinyl alcohol, or grafting acrylamide, n-butyl boric acid or phenyl boric acid on the molecular chain of polyvinyl alcohol.
Further, in a preferred embodiment of the present invention, the specific processing step of the step (2) includes: carrying out 1-3-grade wet-heat stretching or dry-heat stretching on the profiled polyvinyl alcohol nascent fiber at the temperature of 150-230 ℃, wherein the total stretching multiple is 10-20 times; and then carrying out heat setting at the temperature of 200-240 ℃, wherein the heat setting time is 0.5-5 min.
Further, in a preferred embodiment of the present invention, the melt-spun profiled polyvinyl alcohol fiber prepared in step (2) has a profile degree of 50-90%, and the variation range of the profile degree is less than or equal to 10%.
Further, in the preferred embodiment of the present invention, the strength of the melt-spun profiled polyvinyl alcohol fiber obtained in the step (2) is greater than or equal to 6 cN/dtex.
The invention has the following beneficial effects:
1. the preparation method of the melt-spun profiled polyvinyl alcohol fiber realizes stable and continuous melt spinning of the polyvinyl alcohol fiber, and can obtain the nascent fiber with a triangular, trilobal, quadralobal or flat wave-shaped section. The melt-spun profiled polyvinyl alcohol fiber which can be used for reinforcing and toughening composite materials is successfully prepared through subsequent hot stretching and hot setting processes, and has high strength, large profile degree and good profile retention degree.
2. The invention aims at the fact that the modified polyvinyl alcohol powder is spun at the temperature of 130-180 ℃, because the modified polyvinyl alcohol powder is a pseudoplastic fluid and has obvious shear thinning behavior at the same temperature, the modified polyvinyl alcohol powder is subjected to melt spinning at the temperature, the change range of the shear viscosity of the melt is small, the melt is in a stable flowing state, and the spinnability of the modified polyvinyl alcohol powder can be effectively improved.
3. The modified polyvinyl alcohol powder of the invention realizes the melt spinning of polyvinyl alcohol and also improves the stability of the spinning by physical or chemical modification. The intermolecular hydrogen bonds of the polyvinyl alcohol are destroyed through physical modification and chemical modification, the crystallinity of the polyvinyl alcohol is reduced, and the thermoplastic melt spinning of the polyvinyl alcohol can be realized.
4. The profiled fiber after multistage drawing still keeps a perfect profiled section, the profile degree of the section is controllable, the profiled polyvinyl alcohol fiber is always in a drawing and tightening state at high temperature in the subsequent hot drawing process, the forced orientation movement of a polyvinyl alcohol molecular chain is more than the random thermal movement of a high molecular chain segment, therefore, the section of the fiber shrinks synchronously under the surface tension, the rounding trend is small, and the characteristic shape of the profiled polyvinyl alcohol fiber is hardly influenced in the treatment process after the primary fiber is hot drawn.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic cross-sectional view of a spinneret plate according to the present invention;
FIG. 2 is a schematic view of the structural distribution of shaped spinning micro-holes of a spinneret plate according to the present invention;
FIG. 3 is a schematic cross-sectional view of a shaped orifice of a spinneret plate according to the present invention;
FIG. 4 is an electron micrograph of a melt-spun profiled polyvinyl alcohol fiber made according to example 1 of the present invention;
FIG. 5 is an electron micrograph of a melt-spun profiled polyvinyl alcohol fiber made according to example 2 of the present invention;
FIG. 6 is an electron micrograph of a melt-spun profiled polyvinyl alcohol fiber made according to example 3 of the present invention;
FIG. 7 is an electron micrograph of a melt-spun profiled polyvinyl alcohol fiber made in example 4 of the present invention.
In the figure, 1-spinneret plate body; 2-spinneret guide holes; 3-special-shaped spinneret micropores; 4-straight hole flow guide section.
Detailed Description
The principles and features of the present invention are described below in conjunction with the embodiments and the accompanying drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. Referring to fig. 1 and 2, the profile spinneret adopted in the present invention includes: the spinneret plate body 1, the both ends of spinneret plate body 1 are seted up correspondingly and are spouted guide hole 2 and a plurality of dysmorphism and spout a micropore 3, spout the center that guide hole 2 and dysmorphism spout a micropore 3 and set up with coaxial. A straight hole flow guide section 4 is arranged in the spinneret plate body 1, the pipe diameter of the straight hole flow guide section 4 is 2mm, the straight hole flow guide section 4 enables the spinneret guide holes 2 to be communicated with special-shaped spinneret micropores 3, the special-shaped spinneret micropores 3 are uniformly distributed on the spinneret plate body 1 in an annular mode by taking the center of the spinneret plate body 1 as a concentric circle, and the number of the special-shaped spinneret micropores 3 can be 16 holes, 24 holes or 30 holes. Wherein, 16 holes are uniformly distributed single rings, and the diameter of each single ring is 32 mm; the 24 holes are respectively divided into an 8-hole inner ring and a 16-hole outer ring, the diameter of the inner ring is 20mm, and the diameter of the outer ring is 32 mm; the 30 holes are respectively divided into a 10-hole inner ring and a 20-hole outer ring, the diameter of the inner ring is 10mm, and the diameter of the outer ring is 32 mm.
Referring to fig. 3, the cross section of the special-shaped spinning micro-holes 3 is triangular, trilobal, quadralobal or flat wave, when the cross section is triangular and the triangle is equilateral, the special-shaped spinning micro-holes are triangular spinning micro-holes with a special-shape degree of 50%; when the cross section is a trilobal type or a quadralobal type, the shape of the trilobal type or the quadralobal type is adjustable, and the blades are uniformly arranged, the special-shaped spinneret micropores are trilobal type or quadralobal type spinneret micropores, and the special-shaped degree is 50-80%; when the section is flat wave shape, the flat wave shape is in a shape like a straight line, and the upper end face and the lower end face of the flat wave shape are provided with semicircular arc repeating units with the same size and number, the special-shaped spinning micropores are flat wave-shaped spinning micropores, and the special-shaped degree is 80-90%.
The spinneret plate containing the anisotropic spinneret micropores is processed according to the specification, and the processing technology of the spinneret plate belongs to the prior art. The invention also comprises an extrusion-spinning device, and a discharge port of the extrusion-spinning device is provided with the spinneret plate containing the anisotropic spinneret micropores.
In the spinning process, the equivalent diameter Dh of the profiled spinning micropores of the spinneret plate, the shear rate gamma of the modified polyvinyl alcohol powder melt and the volume flow Q of the modified polyvinyl alcohol powder melt controlled by the metering pump satisfy the following relations:
in the formula: gamma is the melt shear rate of the modified polyvinyl alcohol powder with the unit of s-1(ii) a Q represents the volume flow of the modified polyvinyl alcohol powder melt and the unit is mm3/s，DhThe equivalent diameter of the irregular hole is expressed in mm; q represents the cross-sectional area of the spinning nozzle in mm2(ii) a s represents the perimeter of the spinning pores in mm; lambda represents a shape factor related to the cross section of the spinning micro-hole, and is a constant and ranges from 6 to 8, wherein the trilobe is 6.5, and the tetraloba is 6.63.
Example 1:
in the preparation method of the melt-spun profiled polyvinyl alcohol fiber of the embodiment, the profiled spinneret micro-holes of the spinneret plate are of a four-leaf type, and the profile degree is 50%. Which comprises the following steps:
(1) carrying out melt spinning on chemically modified polyvinyl alcohol powder on extrusion-spinning equipment, carrying out melt extrusion, filtering and metering, then spraying out from special-shaped spinning micropores, and carrying out side-blowing cooling on melt trickle to obtain special-shaped polyvinyl alcohol nascent fibers; wherein, the step of chemically modifying the polyvinyl alcohol powder comprises the following steps: vinyl monomers are copolymerized in the molecular chain of polyvinyl alcohol.
Wherein the spinning temperature is 165 ℃; the spinning shear rate is 10000s-1(ii) a The spinning shear viscosity is 300 Pa.s; the spinning pressure is 25 MPa; the volume flow of the spinning is 300mm3S; the stretch ratio of the spinneret is 2 times; the cross-blow temperature was 50 ℃. The equivalent diameter of the special-shaped spinneret micropores of the spinneret plate is 0.6 mm.
(2) Carrying out 1-stage stretching on the profiled polyvinyl alcohol nascent fiber at the temperature of 200 ℃, wherein the total stretching multiple is 15 times; and then carrying out heat setting at the temperature of 220 ℃ for 3min to obtain the melt-spun profiled polyvinyl alcohol fiber.
The melt-spun special-shaped polyvinyl alcohol fiber obtained by the embodiment has the special-shaped degree of 47 percent, the special-shaped degree is reduced by 3 percent, the strength is 7cN/dtex, and an electron microscope scanning image of the melt-spun special-shaped polyvinyl alcohol fiber is shown in 4.
Example 2:
in the preparation method of the melt-spun profiled polyvinyl alcohol fiber of the embodiment, the profiled spinneret micro-holes of the spinneret plate are of flat wave type, and the profile degree is 90%. Which comprises the following steps:
(1) carrying out melt spinning on chemically modified polyvinyl alcohol powder on extrusion-spinning equipment, carrying out melt extrusion, filtering and metering, then spraying out from special-shaped spinning micropores, and carrying out side-blowing cooling on melt trickle to obtain special-shaped polyvinyl alcohol nascent fibers; wherein, the step of chemically modifying the polyvinyl alcohol powder comprises the following steps: the molecular chain of the polyvinyl alcohol is grafted with n-butyl boric acid.
Wherein the spinning temperature is 180 ℃; the spinning shear rate is 6000s-1(ii) a The spinning shear viscosity is 200 Pa.s; the spinning pressure is 30 MPa; the volume flow of the spinning is 250mm3S; the stretch ratio of the spinneret was 4 times; the temperature of the cross-air was 70 ℃. The equivalent diameter of the special-shaped spinneret micropores of the spinneret plate is 0.4 mm.
(2) 3-stage stretching the profiled polyvinyl alcohol nascent fiber at 230 ℃, wherein the total stretching multiple is 20 times; and then carrying out heat setting at the temperature of 240 ℃ for 5min to prepare the melt-spun profiled polyvinyl alcohol fiber.
The melt-spun special-shaped polyvinyl alcohol fiber obtained by the embodiment has the special-shaped degree of 82 percent, the special-shaped degree is reduced by 8 percent, the strength is 8cN/dtex, and an electron microscope scanning image of the melt-spun special-shaped polyvinyl alcohol fiber is shown as 5.
Example 3:
in the preparation method of the melt-spun profiled polyvinyl alcohol fiber of the embodiment, the profiled spinning micropores of the spinneret plate adopt a trilobal shape, and the profile degree is 75%. Which comprises the following steps:
(1) carrying out melt spinning on physically modified polyvinyl alcohol powder on extrusion-spinning equipment, carrying out melt extrusion, filtering and metering, then spraying out from special-shaped spinning micropores, and carrying out side-blowing cooling on melt trickle to obtain special-shaped polyvinyl alcohol nascent fibers; wherein, the step of physically modifying the polyvinyl alcohol powder comprises the following steps: mixing and compounding glycerol, starch and polyvinyl alcohol according to the mass ratio of 10:30:60 to obtain modified polyvinyl alcohol powder.
Wherein the spinning temperature is 175 ℃; the spinning shear rate is 2000s-1(ii) a The spinning shear viscosity is 150 Pa.s; the spinning pressure is 20 MPa; the volume flow of the spinning is 100mm3S; the stretch ratio of the spinneret is 2 times; the cross-blow temperature was 30 ℃. The equivalent diameter of the special-shaped spinneret micropores of the spinneret plate is 0.35 mm.
(2) Carrying out dry heat stretching on the profiled polyvinyl alcohol nascent fiber at the temperature of 175 ℃, wherein the total stretching multiple is 15 times; and then carrying out heat setting at the temperature of 220 ℃ for 2min to obtain the melt-spun profiled polyvinyl alcohol fiber.
The melt-spun special-shaped polyvinyl alcohol fiber obtained by the embodiment has the special-shaped degree of 65 percent, the special-shaped degree is reduced by 10 percent, the strength is 6cN/dtex, and an electron microscope scanning image of the melt-spun special-shaped polyvinyl alcohol fiber is shown as 6.
Example 4:
in the preparation method of the melt-spun profiled polyvinyl alcohol fiber of the embodiment, the profiled spinneret micropores of the spinneret plate are triangular, and the profile degree is 50%. Which comprises the following steps:
(1) carrying out melt spinning on physically modified polyvinyl alcohol powder on extrusion-spinning equipment, carrying out melt extrusion, filtering and metering, then spraying out from special-shaped spinning micropores, and carrying out side-blowing cooling on melt trickle to obtain special-shaped polyvinyl alcohol nascent fibers; wherein, the step of physically modifying the polyvinyl alcohol powder comprises the following steps: mixing and compounding water, amide and polyvinyl alcohol according to the mass ratio of 30:10:60 to obtain modified polyvinyl alcohol powder.
Wherein the spinning temperature is 130 ℃; the spinning shear rate was 15000s-1(ii) a The spinning shear viscosity is 100 Pa.s; the spinning pressure is 10 MPa; the volume flow rate of the spinning is 70mm3S; the stretch ratio of the spinneret is 1 time; the cross-blow temperature was 10 ℃. The equivalent diameter of the special-shaped spinneret micropores of the spinneret plate is 0.25 mm.
(2) Carrying out wet-heat stretching on the profiled polyvinyl alcohol nascent fiber at the temperature of 150 ℃, wherein the total stretching multiple is 10 times; and then carrying out heat setting at the temperature of 200 ℃ for 0.5min to prepare the melt-spun profiled polyvinyl alcohol fiber.
The melt-spun special-shaped polyvinyl alcohol fiber obtained by the embodiment has the special-shaped degree of 41 percent, the special-shaped degree is reduced by 9 percent, the strength is 9cN/dtex, and the electron microscope scanning image of the melt-spun special-shaped polyvinyl alcohol fiber is shown as 7.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The preparation method of the melt-spun profiled polyvinyl alcohol fiber is characterized by comprising the following steps:
(1) carrying out melt spinning on the modified polyvinyl alcohol powder on an extrusion-spinning device, carrying out melt extrusion, filtering and metering, then spraying out from a spinneret plate containing profiled spinneret micropores, and carrying out side-blowing cooling on the melt trickle to obtain profiled polyvinyl alcohol nascent fibers;
(2) after stretching and heat setting the profiled polyvinyl alcohol nascent fiber, melt-spinning profiled polyvinyl alcohol fiber is prepared;
wherein the equivalent diameter Dh of the profiled spinneret micropores of the spinneret plate, the shear rate gamma of the modified polyvinyl alcohol powder melt and the volume flow Q of the modified polyvinyl alcohol powder melt controlled by the metering pump satisfy the following relations:
in the formula: gamma is the melt shear rate of the modified polyvinyl alcohol powder with the unit of s-1(ii) a Q represents the volume flow of the modified polyvinyl alcohol powder melt and the unit is mm3/s，DhThe equivalent diameter of the irregular hole is expressed in mm; q represents the cross-sectional area of the spinning nozzle in mm2(ii) a s represents the perimeter of the spinning pores in mm; lambda represents a shape factor related to the section of the spinneret micropores, and is a constant and ranges from 6 to 8, wherein the trilobe is 6.5, and the tetraloba is 6.63;
the equivalent diameter of the special-shaped spinneret micropores of the spinneret plate is 0.25-0.6 mm;
the modified polyvinyl alcohol powder is chemically modified polyvinyl alcohol powder;
wherein, the step of chemically modifying the polyvinyl alcohol powder comprises the following steps: copolymerizing vinyl monomers on a polyvinyl alcohol molecular chain, or grafting acrylamide, n-butyl boric acid or phenyl boric acid on the polyvinyl alcohol molecular chain;
the melt-spun profiled polyvinyl alcohol fiber prepared in the step (2) has the profile degree of 50-90%, and the variation amplitude of the profile degree is less than or equal to 10%;
the strength of the melt-spun profiled polyvinyl alcohol fiber prepared in the step (2) is more than or equal to 6 cN/dtex.
2. A process for preparing a meltspun shaped polyvinyl alcohol fiber according to claim 1, wherein the cross-section of the shaped-spinning micro-holes in step (1) is triangular, trilobal, quadralobal or flat wavy, and the degree of profile of the shaped-spinning micro-holes is 50-90%.
3. A method of making meltspun shaped polyvinyl alcohol fibers as defined in claim 2, wherein the triangular spinning holes have a degree of profile of 50%; the profile degree of the trilobal spinning micropores and the quadralobal spinning micropores is 50-80%; the profile degree of the flat wave type spinneret micropores is 80-90%.
4. A method of preparing a melt-spun shaped polyvinyl alcohol fiber according to any one of claims 1 to 3, wherein the spinning temperature in step (1) is 130 to 180 ℃; the spinning shear rate is 2000-15000 s-1(ii) a The spinning shear viscosity is 100-300 Pa.s; the spinning pressure is 10-30 MPa; the volume flow of the spinning is 70-300 mm3S; the stretch ratio of the spinning nozzle is 1-4 times; the temperature of the cross air blow is 10-70 ℃.
5. A method of making meltspun shaped polyvinyl alcohol fibers as claimed in claim 1, wherein the specific processing step of step (2) comprises: carrying out 1-3-stage stretching, wet-heat stretching or dry-heat stretching on the profiled polyvinyl alcohol nascent fiber at the temperature of 150-230 ℃, wherein the total stretching multiple is 10-20 times; and then carrying out heat setting at the temperature of 200-240 ℃, wherein the heat setting time is 0.5-5 min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910973874 | 2019-10-14 | ||
| CN2019109738748 | 2019-10-14 |
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| CN111155189A CN111155189A (en) | 2020-05-15 |
| CN111155189B true CN111155189B (en) | 2022-02-18 |
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