CN114959936B - Oblate cross-section PBO fiber and preparation method thereof - Google Patents
Oblate cross-section PBO fiber and preparation method thereof Download PDFInfo
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- CN114959936B CN114959936B CN202210585470.3A CN202210585470A CN114959936B CN 114959936 B CN114959936 B CN 114959936B CN 202210585470 A CN202210585470 A CN 202210585470A CN 114959936 B CN114959936 B CN 114959936B
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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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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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
- D01D5/06—Wet spinning methods
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- General Chemical & Material Sciences (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses an oblate cross-section PBO fiber and a preparation method thereof, comprising the following process steps: preparing a polymer dope of polyphosphoric acid liquid crystal state solution; the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and enters a spinning component after accurate metering, and is extruded through an elliptical spinning hole, a rectangular spinning hole or a diamond spinning hole, wherein the extrusion temperature is 160-200 ℃, the extrusion spinning plate pressure is 3-7 MPa, and the polymer flow is 0.02-0.1 cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 20 cm-200 cm, the lateral blowing temperature is 25-50 ℃, the spinning speed is 50-80 m/min, and the spinning nozzle stretching ratio is 10-20; the spinning nozzle stretching ratio is 10-20; then the mixture enters a coagulating bath, the temperature of the coagulating bath is 40-50 ℃, and the residence time is 3-10S; washing and drying, winding the tows through a water washing roller, and spraying to wash out a small amount of phosphoric acid remained in the fiber and on the surface; drying, wherein the filament bundles are wound and dried by a drying roller, and the temperature of the drying roller is 100-300 ℃.
Description
Technical Field
The invention relates to the technical field of PBO fiber preparation, in particular to an oblate cross-section PBO fiber and a preparation method thereof.
Background
The PBO (Poly-p-phenylene benzobisoxazole) is a heterocyclic aromatic polymer, the molecular chain of the PBO is rigid, the solution of the PBO can be in a liquid crystal state under certain conditions, and the PBO can be spun, and the prepared PBO fiber has the special properties of high strength, high modulus, high chemical stability and high temperature resistance, and is known as a '21 st century super fiber'. In the process of spinning PBO fiber, polyphosphoric acid is generally used as a solvent, and is formed into a liquid crystal state at a certain concentration and temperature, and the liquid crystal fiber is produced and prepared by a dry-jet wet spinning process of liquid crystal spinning. The spinning solution is extruded by a spinneret plate after precise metering, is stretched by an air layer, then enters a coagulating bath for molding, and finally obtains finished fiber after subsequent steps such as washing, drying and the like. But the PBO fibers have smooth surfaces and poor interfacial properties, which also prevent some of their applications.
The PBO pulp fiber is adopted to form PBO paper through wet papermaking, wherein the length and the specific surface area of the PBO pulp determine the grabbing capacity of the pulp, and the strength and the overall performance of the finished PBO paper are determined. The PBO fiber with the oblate cross section has larger specific surface area and cortex ratio than the circular cross section, and is more easy to fibrillate the surface layer to form hairiness in the pulp processing process, so that the specific surface area of the prepared pulp is also higher. Therefore, the oblate cross-section PBO is more suitable for preparing high-performance paper materials.
The Chinese patent with the authorized bulletin number of CN1236133C and the bulletin day of 2006.01.11 discloses a PBO fiber surface modification method which is characterized by comprising the following steps: the PBO fibers are first soaked in a plastic or glass container containing a graft solution consisting of 2 to 4% by weight of an epoxy resin and 96 to 98% by weight of epichlorohydrin, and then the container is sealed and irradiated with gamma rays, and the PBO fibers are removed from the container after 20 to 30 hours of irradiation. The modification method makes the PBO preparation method more complex, and the interface performance of the modified PBO fiber is not very high. Because of the high viscosity of the PBO spinning solution and the particularity of the dry-wet spinning process, the cross section of the PBO fiber prepared at present is round, so that the PBO fiber has smooth surface and poor interface performance, and no special-shaped PBO fiber is reported at present.
The Chinese patent with publication number of CN202865404U and publication date of 2013.04.10 discloses a PBO fiber with triangular cross section, which comprises a fiber body, wherein the cross section of the fiber body is in a triangular structure. The PBO fiber with the triangular section not only can improve the specific surface area and rigidity of the fiber, but also can make the fiber exhibit better gloss. The patent still has the following problems: in terms of technology, for PBO fiber, PBO is liquid crystal spinning, dry and wet spinning technology is adopted, and how polymer precursor extruded from a spinneret orifice can well keep the shape in an air layer and a coagulation bath layer is difficult, and no patent or article is disclosed at present, which relates to the technology for preparing profiled fiber by dry and wet spinning of PBO and the subsequent application of the profiled fiber.
Disclosure of Invention
In order to solve the technical problems, the invention provides a PBO fiber with an oblate cross section and a preparation method thereof, wherein the PBO fiber is extruded through a special-shaped spinneret orifice, and a dry-jet wet spinning method is adopted to control the cross-blowing temperature, the coagulation bath temperature and the spinning tension so as to well maintain the shape of the fiber.
The invention aims at realizing the following technical scheme:
an oblate cross-section PBO fiber, characterized in that: the linear density is 1.5D-4D.
Preferably, the PBO fiber has an oblate cross section.
Preferably, the oblate cross-section PBO fiber is used in pulp.
The preparation method of the PBO fiber with the oblate cross section is characterized by comprising the following process steps:
step A, preparing a material, namely preparing polymer spinning slurry of a polyphosphoric acid liquid crystal solution;
step B, spinning, namely conveying the degassed and filtered polymer spinning slurry to a metering pump, accurately metering the polymer spinning slurry, feeding the polymer spinning slurry into a spinning assembly, extruding the polymer spinning slurry through an elliptical spinning hole or a rectangular spinning hole or a diamond spinning hole, wherein the extruding temperature is 160-200 ℃, the extruding pressure of an extruding spinning plate is 3-7 MPa, and the polymer flow is 0.02-0.1 cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 20 cm-200 cm, the lateral blowing temperature is 25-50 ℃, the spinning speed is 50-80 m/min, and the spinning nozzle stretching ratio is 10-20; the spinning nozzle stretching ratio is 10-20; then the mixture enters a coagulating bath, the temperature of the coagulating bath is 40-50 ℃, and the residence time is 3-10S;
step C, washing and drying, winding the tows through a washing roller, and spraying to wash out a small amount of phosphoric acid remained in the fiber and on the surface; drying, wherein the filament bundles are wound and dried by a drying roller, and the temperature of the drying roller is 100-300 ℃.
Preferably, in the step A, the mass fraction of the polymer spinning slurry is 10% -15%, the intrinsic viscosity of the polymer is 18-28 dL/g, and the dynamic viscosity of the spinning slurry at 200 ℃ is 200-800 ten thousand centipoise measured by using a rotor viscometer.
Preferably, in the step B, the minor diameters of the elliptical spinning holes, the rectangular spinning holes and the diamond spinning holes are 0.1-0.2 mm, and the ratio of the major diameter to the minor diameter is 1.1-5.
Preferably, in the step B, the ratio of the long diameter to the short diameter of the elliptical spinning holes, the rectangular spinning holes and the diamond spinning holes is 1.5-3.
Preferably, the washing rollers in the step C comprise 3-10 groups of washing rollers, the rotating speed among the groups of rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, and the speed ratio of the latter group of washing rollers to the former group of washing rollers is 1.0001-1.1.
Preferably, the drying rollers in the step C comprise 2-5 groups of drying rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, and the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9900-0.9999.
Preferably, the temperature of the latter set of drying rolls in said step C is higher than the temperature of the former set of drying rolls.
The beneficial effects of this technical scheme are as follows:
1. compared with the conventional PBO fiber with a round section, the PBO fiber with the oblate section has higher specific surface area, and pulp prepared from the fiber with the same linear density has 10-20 percent of specific surface area, so that the PBO fiber with the oblate section is more suitable for preparing high-strength PBO paper.
2. The invention provides a preparation method of PBO fiber with oblate cross section, which is characterized in that extrusion is carried out through special-shaped spinneret orifices, and a dry-jet wet spinning method is adopted, so that the cross-blowing temperature, the coagulation bath temperature and the spinning tension are controlled, and the fiber shape is well maintained.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the terms "upper," "lower," "front," "rear," "left," "right," "top," "bottom," "inner," "outer," and the like indicate or are used in place of the elements or orientations to facilitate the description of the present invention, but are not intended to indicate or imply that the devices or elements so referred to must be in a particular orientation, be constructed or operated in a particular orientation, or be limited to the invention.
Preparation method of polyphosphoric acid liquid crystal solution
The preparation method of the polyphosphoric acid liquid crystal solution comprises the following steps that terephthalic acid is added in the steps of mixing, prepolymerization and post polymerization according to a certain proportion, and the ratio of the total molar amount of the terephthalic acid added in each step to the molar amount of the 4, 6-diaminoresorcinol hydrochloride added in the mixing step is 0.97-1.05: 1, grinding terephthalic acid to a particle size of 0.2-5 mu m, and then putting the terephthalic acid into use; the molar amount of terephthalic acid added in the mixture: step prepolymerization molar amount of terephthalic acid charged: molar amount of terephthalic acid used in polymerization after step = 5.0-8.5: 0.5 to 3.5:0.1 to 2.0; the specific process steps are as follows: mixing, degassing, namely heating polyphosphoric acid, putting the polyphosphoric acid into a mixing degassing kettle, and then putting phosphorus pentoxide, 4, 6-diaminoresorcinol hydrochloride and terephthalic acid into the mixing degassing kettle for degassing;
prepolymerizing the material obtained by degassing in the step A, and adding terephthalic acid in the prepolymerization process to obtain a prepolymer; the prepolymerization temperature is 120-150 ℃, during the prepolymerization process, the material temperature in the mixed degassing kettle is measured to be 80-120 ℃, when the viscosity is 100-300 Pa.s, terephthalic acid is added, and when the viscosity of the material in the mixed degassing kettle is measured to be 500-800 Pa.s, the prepolymerization reaction is stopped to obtain the prepolymer; measuring the dynamic viscosity of the sampled material by adopting a rotary viscometer, a falling ball viscometer or a vibrating viscometer;
post-polymerization, the pre-polymerized material and terephthalic acid are sent into a screw reactor for post-polymerization, and polymer spinning pulp is obtained.
Example 1
Preparing materials: the polymer dope was prepared by polymerizing 10% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 200 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 28 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is accurately metered and enters a spinning component to be extruded through an elliptical spinning hole, wherein the short diameter of the elliptical spinning hole is 0.1mm, the ratio of the long diameter to the short diameter is 1.1, the extrusion temperature is 160 ℃, the extrusion plate pressure is 3MPa, and the polymer flow rate is 0.02cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 20cm, the temperature of side blowing air is 25 ℃, the spinning speed is 50 m/min, and the spinning nozzle stretching ratio is 10; then 10% dilute phosphoric acid coagulating bath is put in, the coagulating bath temperature is 40 ℃, and the residence time is 3S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 3 groups of washing rollers, each group of rollers comprises 10 rollers, the rotating speeds among the rollers are equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.0001, a small amount of phosphoric acid remained inside and on the surface of the fiber is washed off through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 2 groups of drying rollers, each group of drying rollers comprises 4 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9900, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 300 ℃, and the drying tension is less than or equal to 0.2g/D.
Example 2
Preparing materials: the mass fraction of the polymer dope was 15%, the intrinsic viscosity of the polymer was 18dl/g, and the dynamic viscosity of the polymer dope was 800 ten thousand cps at 200℃using a rotor viscometer.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is precisely metered and enters a spinning component to be extruded through a rectangular spinning hole, wherein the short diameter of the rectangular spinning hole is 0.2mm, the ratio of the long diameter to the short diameter is 5, the extrusion temperature is 200 ℃, the extrusion pressure of an extrusion spinning plate is 7MPa, and the polymer flow is 0.1cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 200cm, the temperature of the cross-blowing air is 50 ℃, the spinning speed is 80 m/min, and the spinning nozzle stretching ratio is 20; then the mixture enters a 10% dilute phosphoric acid coagulating bath, the coagulating bath temperature is 50 ℃, and the residence time is 10S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 10 groups of washing rollers, each group of rollers comprises 20 rollers, the rotating speeds among the rollers are equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.1, a small amount of phosphoric acid remained inside and on the surface of the fiber is washed off through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 5 groups of drying rollers, each group of drying rollers comprises 20 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9999, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 135 ℃, the temperature of the third group of drying rollers is 190 ℃, the temperature of the fourth group of drying rollers is 245 ℃, the temperature of the fifth group of drying rollers is 300 ℃, and the drying tension is less than or equal to 0.2g/D.
Example 3
Preparing materials: the polymer dope was prepared by polymerizing 13% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 300 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 23 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is accurately metered and enters a spinning component to be extruded through diamond spinning holes, wherein the short diameter of the diamond spinning holes is 0.15mm, the ratio of the long diameter to the short diameter is 3, the extrusion temperature is 180 ℃, the extrusion pressure of an extrusion spinning plate is 5MPa, and the polymer flow rate is 0.06cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 110cm, the side blowing temperature is 35 ℃, the spinning speed is 65 m/min, and the spinning nozzle stretching ratio is 15; then the mixture enters a 10% dilute phosphoric acid coagulating bath with the coagulating bath temperature of 45 ℃ and the residence time of 7S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 6 groups of washing rollers, each group of rollers comprises 15 rollers, the rotating speed between the rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.06, a small amount of phosphoric acid remained in the fiber and on the surface is washed through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 4 groups of drying rollers, each group of drying rollers comprises 7 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9950, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 150 ℃, the temperature of the third group of drying rollers is 220 ℃, and the temperature of the fourth group of drying rollers is 300 ℃, so that the drying tension is less than or equal to 0.2g/D.
Example 4
Preparing materials: the polymer dope was prepared by polymerizing 13% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 300 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 23 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is accurately metered and enters a spinning assembly to be extruded through a rectangular spinning hole, wherein the short diameter of the rectangular spinning hole is 0.15mm, the ratio of the long diameter to the short diameter is 1.5, the extrusion temperature is 180 ℃, the extrusion spinning plate pressure is 5MPa, and the polymer flow is 0.06cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 110cm, the side blowing temperature is 35 ℃, the spinning speed is 65 m/min, and the spinning nozzle stretching ratio is 15; then the mixture enters a 10% dilute phosphoric acid coagulating bath with the coagulating bath temperature of 45 ℃ and the residence time of 7S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 6 groups of washing rollers, each group of rollers comprises 15 rollers, the rotating speed between the rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.06, a small amount of phosphoric acid remained in the fiber and on the surface is washed through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 4 groups of drying rollers, each group of drying rollers comprises 7 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9950, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 150 ℃, the temperature of the third group of drying rollers is 220 ℃, and the temperature of the fourth group of drying rollers is 300 ℃, so that the drying tension is less than or equal to 0.2g/D.
Comparative example 1
Preparing materials: the polymer dope was prepared by polymerizing 10% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 200 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 28 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is accurately metered and enters a spinning component to be extruded through an elliptical spinning hole, wherein the diameter of the elliptical spinning hole is 0.1mm, the ratio of the long diameter to the short diameter is 6, the extrusion temperature is 160 ℃, the extrusion pressure of an extrusion spinning plate is 3MPa, and the polymer flow rate is 0.02cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 20cm, the temperature of side blowing air is 25 ℃, the spinning speed is 50 m/min, and the spinning nozzle stretching ratio is 10; then 10% dilute phosphoric acid coagulating bath is put in, the coagulating bath temperature is 40 ℃, and the residence time is 3S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 3 groups of washing rollers, each group of rollers comprises 10 rollers, the rotating speeds among the rollers are equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.0001, a small amount of phosphoric acid remained inside and on the surface of the fiber is washed off through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 2 groups of drying rollers, each group of drying rollers comprises 4 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9900, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 300 ℃, and the drying tension is less than or equal to 0.2g/D.
Comparative example 2
Preparing materials: the polymer dope was prepared by polymerizing 10% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 200 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 28 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is accurately metered and enters a spinning component to be extruded through an elliptical spinning hole, wherein the diameter of the elliptical spinning hole is 0.1mm, the ratio of the long diameter to the short diameter is 1.05, the extrusion temperature is 160 ℃, the extrusion plate pressure is 3MPa, and the polymer flow rate is 0.02cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 20cm, the temperature of side blowing air is 25 ℃, the spinning speed is 50 m/min, and the spinning nozzle stretching ratio is 10; then 10% dilute phosphoric acid coagulating bath is put in, the coagulating bath temperature is 40 ℃, and the residence time is 3S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 3 groups of washing rollers, each group of rollers comprises 10 rollers, the rotating speeds among the rollers are equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.0001, a small amount of phosphoric acid remained inside and on the surface of the fiber is washed off through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 2 groups of drying rollers, each group of drying rollers comprises 4 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9900, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 300 ℃, and the drying tension is less than or equal to 0.2g/D.
Comparative example 3
Preparing materials: the mass fraction of the polymer dope was 15%, the intrinsic viscosity of the polymer was 18dl/g, and the dynamic viscosity of the polymer dope was 800 ten thousand cps at 200℃using a rotor viscometer.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is precisely metered and enters a spinning component to be extruded through a rectangular spinning hole, wherein the short diameter of the rectangular spinning hole is 0.2mm, the ratio of the long diameter to the short diameter is 5, the extrusion temperature is 200 ℃, the extrusion pressure of an extrusion spinning plate is 7MPa, and the polymer flow is 0.1cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 10cm, the temperature of side blowing air is 20 ℃, the spinning speed is 80 m/min, and the spinning nozzle stretching ratio is 20; then the mixture enters a 10% dilute phosphoric acid coagulating bath, the coagulating bath temperature is 50 ℃, and the residence time is 10S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 10 groups of washing rollers, each group of rollers comprises 20 rollers, the rotating speeds among the rollers are equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.1, a small amount of phosphoric acid remained inside and on the surface of the fiber is washed off through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 5 groups of drying rollers, each group of drying rollers comprises 20 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9999, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 135 ℃, the temperature of the third group of drying rollers is 190 ℃, the temperature of the fourth group of drying rollers is 245 ℃, the temperature of the fifth group of drying rollers is 300 ℃, and the drying tension is less than or equal to 0.2g/D.
Comparative example 4
Preparing materials: the mass fraction of the polymer dope was 15%, the intrinsic viscosity of the polymer was 18dl/g, and the dynamic viscosity of the polymer dope was 800 ten thousand cps at 200℃using a rotor viscometer.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is precisely metered and enters a spinning component to be extruded through a rectangular spinning hole, wherein the short diameter of the rectangular spinning hole is 0.2mm, the ratio of the long diameter to the short diameter is 5, the extrusion temperature is 200 ℃, the extrusion pressure of an extrusion spinning plate is 7MPa, and the polymer flow is 0.1cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 210cm, the temperature of side blowing air is 55 ℃, the spinning speed is 80 m/min, and the spinning nozzle stretching ratio is 20; then the mixture enters a 10% dilute phosphoric acid coagulating bath, the coagulating bath temperature is 50 ℃, and the residence time is 10S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 10 groups of washing rollers, each group of rollers comprises 20 rollers, the rotating speeds among the rollers are equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.1, a small amount of phosphoric acid remained inside and on the surface of the fiber is washed off through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 5 groups of drying rollers, each group of drying rollers comprises 20 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9999, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 135 ℃, the temperature of the third group of drying rollers is 190 ℃, the temperature of the fourth group of drying rollers is 245 ℃, the temperature of the fifth group of drying rollers is 300 ℃, and the drying tension is less than or equal to 0.2g/D.
Comparative example 5
Preparing materials: the polymer dope was prepared by polymerizing 13% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 300 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 23 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is accurately metered and enters a spinning component to be extruded through diamond spinning holes, wherein the short diameter of the diamond spinning holes is 0.15mm, the ratio of the long diameter to the short diameter is 3, the extrusion temperature is 180 ℃, the extrusion pressure of an extrusion spinning plate is 5MPa, and the polymer flow rate is 0.15cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 110cm, the side blowing temperature is 35 ℃, the spinning speed is 65 m/min, and the spinning nozzle stretching ratio is 15; then the mixture enters a 10% dilute phosphoric acid coagulating bath with the coagulating bath temperature of 45 ℃ and the residence time of 7S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 6 groups of washing rollers, each group of rollers comprises 15 rollers, the rotating speed between the rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.06, a small amount of phosphoric acid remained in the fiber and on the surface is washed through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 4 groups of drying rollers, each group of drying rollers comprises 7 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9950, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 150 ℃, the temperature of the third group of drying rollers is 220 ℃, and the temperature of the fourth group of drying rollers is 300 ℃, so that the drying tension is less than or equal to 0.2g/D.
Comparative example 6
Preparing materials: the polymer dope was prepared by polymerizing 13% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 300 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 23 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is precisely metered and enters a spinning component to be extruded through diamond spinning holes, wherein the short diameter of the diamond spinning holes is 0.15mm, the ratio of the long diameter to the short diameter is 3, the extrusion temperature is 180 ℃, the extrusion pressure of an extrusion spinning plate is 5MPa, and the polymer flow is 0.01cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 110cm, the side blowing temperature is 35 ℃, the spinning speed is 65 m/min, and the spinning nozzle stretching ratio is 15; then the mixture enters a 10% dilute phosphoric acid coagulating bath with the coagulating bath temperature of 45 ℃ and the residence time of 7S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 6 groups of washing rollers, each group of rollers comprises 15 rollers, the rotating speed between the rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.06, a small amount of phosphoric acid remained in the fiber and on the surface is washed through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 4 groups of drying rollers, each group of drying rollers comprises 7 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9950, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 150 ℃, the temperature of the third group of drying rollers is 220 ℃, and the temperature of the fourth group of drying rollers is 300 ℃, so that the drying tension is less than or equal to 0.2g/D.
Comparative example 7
Preparing materials: the polymer dope was prepared by polymerizing 13% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 300 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 23 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and enters a spinning assembly after accurate metering, and is extruded through a circular spinning hole, wherein the diameter of the circular spinning hole is 0.15mm, the extrusion temperature is 180 ℃, the extrusion plate pressure is 5MPa, and the polymer flow is 0.06cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 110cm, the side blowing temperature is 35 ℃, the spinning speed is 65 m/min, and the spinning nozzle stretching ratio is 15; then the mixture enters a 10% dilute phosphoric acid coagulating bath with the coagulating bath temperature of 45 ℃ and the residence time of 7S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 6 groups of washing rollers, each group of rollers comprises 15 rollers, the rotating speed between the rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.06, a small amount of phosphoric acid remained in the fiber and on the surface is washed through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 4 groups of drying rollers, each group of drying rollers comprises 7 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9950, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 150 ℃, the temperature of the third group of drying rollers is 220 ℃, and the temperature of the fourth group of drying rollers is 300 ℃, so that the drying tension is less than or equal to 0.2g/D.
Comparative example 8
Preparing materials: the polymer dope was prepared by polymerizing 13% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 300 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 23 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is accurately metered and enters a spinning assembly to be extruded through a rectangular spinning hole, wherein the short diameter of the rectangular spinning hole is 0.15mm, the ratio of the long diameter to the short diameter is 1.5, the extrusion temperature is 180 ℃, the extrusion spinning plate pressure is 5MPa, and the polymer flow is 0.06cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 110cm, the side blowing temperature is 35 ℃, the spinning speed is 65 m/min, and the spinning nozzle stretching ratio is 15; then 10% dilute phosphoric acid coagulating bath is put in, the coagulating bath temperature is 35 ℃, and the residence time is 2S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 6 groups of washing rollers, each group of rollers comprises 15 rollers, the rotating speed between the rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.06, a small amount of phosphoric acid remained in the fiber and on the surface is washed through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 4 groups of drying rollers, each group of drying rollers comprises 7 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9950, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 150 ℃, the temperature of the third group of drying rollers is 220 ℃, and the temperature of the fourth group of drying rollers is 300 ℃, so that the drying tension is less than or equal to 0.2g/D.
Comparative example 9
Preparing materials: the polymer dope was prepared by polymerizing 13% by mass of a liquid crystalline solution of polyphosphoric acid having a dynamic viscosity of 300 ten thousand centipoise at 200℃as measured by a rotor viscometer, with a polymer intrinsic viscosity of 23 dl/g.
Spinning: the polymer spinning slurry after degassing and filtering is conveyed to a metering pump, and is precisely metered and enters a spinning component to be extruded through a rectangular spinning hole, wherein the short diameter of the rectangular spinning hole is 1.5mm, the ratio of the long diameter to the short diameter is 1.5, the extrusion temperature is 180 ℃, the extrusion spinning plate pressure is 5MPa, and the polymer flow is 0.06cc/min in a single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 110cm, the side blowing temperature is 35 ℃, the spinning speed is 65 m/min, and the spinning nozzle stretching ratio is 15; then the mixture enters a 10% dilute phosphoric acid coagulating bath with the coagulating bath temperature of 55 ℃ and the residence time of 12S.
Washing and drying: the silk bundle is wound through a washing roller, the washing roller comprises 6 groups of washing rollers, each group of rollers comprises 15 rollers, the rotating speed between the rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, the speed ratio of the back group of washing rollers to the front group of washing rollers is 1.06, a small amount of phosphoric acid remained in the fiber and on the surface is washed through spraying, and the tension is less than or equal to 0.2g/D by adjusting the rotating speed ratio of the front group of washing rollers and the back group of washing rollers; and drying, wherein the filament bundles are wound and dried by drying rollers, each drying roller comprises 4 groups of drying rollers, each group of drying rollers comprises 7 rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9950, the temperature of the first group of drying rollers is 80 ℃, the temperature of the second group of drying rollers is 150 ℃, the temperature of the third group of drying rollers is 220 ℃, and the temperature of the fourth group of drying rollers is 300 ℃, so that the drying tension is less than or equal to 0.2g/D.
The test instrument is a BET specific surface area analyzer, and the specific surface area of pulp with circular section, flat circular section and 1mm of linear density with the same grinding time is compared with that of pulp with flat circular section in the table 1:
the linear densities and specific surface areas of the oblate cross-section PBO fibers prepared in examples 1 to 4 and comparative examples 1 to 9 were measured as shown in table 2:
in view of the foregoing, it will be appreciated by those skilled in the art that, after reading the present specification, various other modifications can be made in accordance with the technical scheme and concepts of the present invention without the need for creative mental efforts, and the modifications are within the scope of the present invention.
Claims (7)
1. The preparation method of the PBO fiber with the oblate cross section is characterized by comprising the following process steps:
step A, preparing a polymer spinning slurry of a polyphosphoric acid liquid crystal solution, wherein the mass fraction of the polymer spinning slurry is 10% -15%, the intrinsic viscosity of the polymer is 18-28 dL/g, and the dynamic viscosity of the spinning slurry at 200 ℃ is 200-800 ten thousand centipoise measured by a rotor viscometer;
step B, spinning, namely conveying the degassed and filtered polymer spinning slurry to a metering pump, accurately metering the polymer spinning slurry, feeding the polymer spinning slurry into a spinning assembly, extruding the polymer spinning slurry through an elliptical spinning hole or a rectangular spinning hole or a diamond spinning hole, wherein the short diameters of the elliptical spinning hole, the rectangular spinning hole and the diamond spinning hole are 0.1-0.2 mm, and the ratio of the long diameter to the short diameter is 1.1-5; the extrusion temperature is 160-200 ℃, the extrusion spinning plate pressure is 3-7 MPa, and the polymer flow is 0.02-0.1 cc/min for single hole; the polymer trickle is stretched and cooled by a slow cooling air layer, the length of the cooling air layer is 20 cm-200 cm, the lateral blowing temperature is 25-50 ℃, the spinning speed is 50-80 m/min, and the spinning nozzle stretching ratio is 10-20; then the mixture enters a coagulating bath, the temperature of the coagulating bath is 40-50 ℃, and the residence time is 3-10S;
step C, washing and drying, winding the tows through a washing roller, and spraying to wash out a small amount of phosphoric acid remained in the fiber and on the surface; drying, wherein the filament bundles are wound and dried by a drying roller, and the temperature of the drying roller is 100-300 ℃.
2. The method for preparing the oblate cross-section PBO fiber according to claim 1, wherein: and B, the ratio of the long diameter to the short diameter of the elliptical spinning holes, the rectangular spinning holes and the diamond spinning holes is 1.5-3.
3. The method for preparing the oblate cross-section PBO fiber according to claim 2, wherein: the washing rollers in the step C comprise 3-10 groups of washing rollers, the rotating speed among the groups of rollers is equal, the linear speed of the first group of washing rollers is the same as the spinning speed, and the speed ratio of the latter group of washing rollers to the former group of washing rollers is 1.0001-1.1.
4. A method of preparing oblate cross-section PBO fiber according to claim 3, characterized in that: the drying rollers in the step C comprise 2-5 groups of drying rollers, the linear speed of the first group of drying rollers is the same as that of the last group of washing rollers, and the speed ratio of the last group of drying rollers to the former group of drying rollers is 0.9900-0.9999.
5. The method for preparing the oblate cross-section PBO fiber according to claim 4, wherein: the temperature of the latter group of drying rollers in the step C is higher than that of the former group of drying rollers.
6. A process for preparing a PBO fiber of oblate cross-section according to any of claims 1 to 5, which gives a PBO fiber of oblate cross-section, characterized in that: the linear density is 1.5D-4D; the cross section of the PBO fiber is oblate.
7. Use of an oblate cross-section PBO fiber according to claim 6 in pulp.
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