CN108085771B - Spinning process of polyester liquid crystal fibers - Google Patents
Spinning process of polyester liquid crystal fibers Download PDFInfo
- Publication number
- CN108085771B CN108085771B CN201711337994.6A CN201711337994A CN108085771B CN 108085771 B CN108085771 B CN 108085771B CN 201711337994 A CN201711337994 A CN 201711337994A CN 108085771 B CN108085771 B CN 108085771B
- Authority
- CN
- China
- Prior art keywords
- heat treatment
- temperature
- fiber
- liquid crystal
- solid
- 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
- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01D5/08—Melt 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a spinning process of polyester liquid crystal fibers, which comprises the steps of pretreating polyester resin through solid-phase polymerization, vacuumizing, melting by a screw extruder, metering a melt pump, forcibly filtering, spinning a component, cooling and crystallizing silk strands, winding and doffing to form primary silk, and performing heat treatment on the primary silk to obtain the polyester liquid crystal fibers containing nano-scale inorganic oxide powder. The product polymer of the invention adopts aromatic polyester synthesized by solid-phase polycondensation, simultaneously the polymer chain of the solid-phase polymerized polyester polymer is a linear rigid chain, after the high-temperature heat treatment of the nascent fiber, the polyester liquid crystal molecular chain in the fiber is in a highly ordered arrangement structure, and stronger interaction exists among molecules, and particularly after the nascent fiber is properly mixed with nano-grade materials, the elastic strength and the modulus of the fiber are improved, thereby endowing the fiber with special performance characteristics, and leading the fiber to be more suitable for severe environment.
Description
Technical Field
The invention belongs to the technical field of high-performance fiber production, relates to a spinning process of thermotropic liquid crystal fibers based on polyester compounds, and more particularly relates to a spinning process of solid-phase polymerized polyester liquid crystal fibers.
Technical Field
In the early 60's of the 20 th century, para-aminobenzoyl chloride was used as a raw material by DuPont in the United states to prepare para-substituted wholly aromatic amide Polymers (PAB) through low-temperature polycondensation, and the finding that the PAB can generate liquid crystal polymers with excellent spinnability led to the appearance of high-temperature-resistant, high-strength and high-modulus lyotropic liquid crystal fiber products such as kevlar series commodities. However, the lyotropic liquid crystal fiber adopts solution spinning, so that the spinning process is relatively complex, and the problem of solvent recovery exists at the same time. Thermotropic liquid crystal fibers have therefore attracted much interest to researchers in various countries.
13-43473494 discloses solid-phase polymerized polyester and filament, mainly describing the synthesis process of high polymer, and only introducing the preparation of filament that the melt is drawn into fiber with fineness of 0.5tex under the protection of inert gas, the heat treatment process is 2h at 200 ℃ and 7h at 200-304 ℃, the melt spinning at 250-450 ℃, preferably 300-400 ℃ is described in US 4503005A, and the heat treatment is 0.5-30 h at 100-350 ℃. U.S. Pat. No. 3, 4743416,78,78 describes a melt spinning process of solid state polymerized polyester fibers by controlling the extrusion pressure at 3kg/fcm through a nozzle2Or above, to promote better orientation of the fibers and to impart higher strength and modulus to the fibers. Although the above reports on the production method of the solid-phase polymerized polyester fiber have been made early, knots are generated in the molten state due to the solid-phase polymerized polyesterThe crystal and melt cooling solidification time is particularly short, so that it is difficult to impart a high degree of orientation to the fibers in a short time, and thus the desired strength which should be provided to the rigid structure cannot be obtained by the above simple melt spinning heat treatment process.
In Chinese patent number: CN 201110283218.9 discloses an aromatic copolyester liquid crystal fiber and a preparation method thereof, wherein the preparation process comprises the working procedures of raw material pretreatment, drying, melt spinning, post-treatment and the like. After spinning, the nascent fiber is treated by stable heating inert gas containing nonionic substances, and the fiber is pretreated by heating and soaking of inorganic halogen salt solution and then is subjected to heat treatment.
In the spinning process of the liquid crystal fiber, certain oiling agent is needed, and simultaneously, due to the molecular weight problem of the liquid crystal polyester resin, the melt-spun fiber is possibly bonded, so that the subsequent fiber heat treatment is difficult, the oiling agent on the surface of the fiber needs to be treated, the process flow is relatively lengthened, and meanwhile, other chemical substances are needed to be used for treatment, so that the production cost is increased.
In Chinese patent: CN201280015765.1 describes a liquid crystal polyester fiber and a method for producing the same
The method comprises applying inorganic particles (A) and a phosphoric acid compound (B) to a yarn obtained by melt spinning a liquid crystal polyester, and then carrying out solid phase polymerization. A mesh fabric made of the liquid crystal polyester fiber. Thus, there are provided a liquid crystal polyester fiber which is reduced in the deposition (scum) in the weaving step, is reduced in the variation in running tension, and is excellent in the step passability and product yield in the weaving step, a method for producing the same, and a web. In the production process flow of the fiber, the inorganic particles coated on the surface of the fiber are silicon dioxide, which mainly reduces the cohesiveness between fiber strands and between the strands and equipment such as a godet and the like in the spinning process flow, thereby improving the product yield, however, the coating of the inorganic particles has no direct relation with the improvement of the product performance.
In Chinese patent number: CN201110066323.7 introduces a drafting and shaping process of polyphenylene sulfide nascent fiber, wherein the polyphenylene sulfide nascent fiber is stretched and shaped at one time through a V-shaped interlayer heat treatment conduit which is formed by heating and connecting polyphenylene sulfide nascent fiber in series at constant temperature through heat conduction oil. The technological process of the invention is adopted to stretch and shape the polyphenylene sulfide nascent fiber at one time, which not only shortens the fiber drafting technological process, improves the working efficiency and the yield of the drafting fiber, and reduces the production cost, but also has the heat shaping temperature of 180 +/-2 ℃, but also needs to be necessarily improved because nitrogen, argon and carbon dioxide are needed to be introduced for protection in the heat treatment process of the liquid crystal polyester fiber.
Disclosure of Invention
The invention aims to provide a spinning process of polyester liquid crystal fibers, which is characterized in that on the basis of relatively large molecular weight of liquid crystal polyester resin by utilizing solid phase polymerization, a small amount of nano-scale silicon dioxide or titanium oxide powder is properly mixed in the resin, so that the strength of the aromatic polyester liquid crystal fibers is improved, the yield of the fibers is improved under the condition of not influencing the spinning and heat treatment of the liquid crystal polyester fibers, and meanwhile, the treatment process of fiber surface oiling agent is omitted, so that the production cost is reduced.
The technical scheme of the invention is as follows:
the spinning process of the polyester liquid crystal fiber adopts the pretreatment of solid-phase polymerized polyester resin, the vacuum pumping, the melting of a screw extruder, a melt metering pump, the forced filtration and the spinning assembly, the cooling and crystallization of strand silk, the winding and doffing to manufacture the nascent fiber, and the heat treatment of the nascent fiber, and the specific process conditions comprise:
(1) adding 0.1-3 wt% of nano-scale silicon dioxide or titanium oxide powder with the particle size of 3-6 nm into powdery solid-phase polymerized polyester resin, placing the powdery solid-phase polymerized polyester resin into a high-speed stirrer, stirring the powdery solid-phase polymerized polyester resin for 36-48 min at the stirring speed of 2800-3300 rpm, inputting the mixture into a single-screw extruder, and extruding and cutting the solid-phase polymerized polyester resin containing the nano-scale silicon dioxide or titanium oxide powder into resin slices with the length of 3-6 mm and the diameter of 1-2 mm under the vacuum condition;
(2) putting the resin slices obtained in the step (1) into a vacuum oven at the temperature of 160-180 ℃, wherein the vacuum degree is-0.06-0.8 Mpa, and drying for 38-48 h;
(3) directly inputting the solid-phase polymerized polyester resin slices containing the nano-scale silicon dioxide or titanium oxide powder obtained by drying in the step (2) into a double-screw extruder, respectively arranging a vacuumizing interface with the diameter of 60mm above a heating area 3, a heating area 6 and a heating area 9 of the extruder, wherein the vacuum degree is-0.06 to-0.8 Mpa, the temperature of the resin melted by the double-screw extruder is 260 to 330 ℃, the temperature is basically in a Gaussian curve shape, the solid-phase polymerized polyester resin melt containing the nano-scale silicon dioxide or titanium oxide powder is extruded by the double-screw extruder and then is input into a heat-insulating spinning box with the temperature of 310 to 330 ℃, 4 to 6 spinning assemblies are input and configured by a metering pump configured on the heat-insulating spinning box, and the solid-phase polymerized polyester resin melt containing the nano-scale silicon dioxide or titanium oxide powder is sprayed out by a spinneret plate of the spinning assemblies, blowing carbon dioxide with the temperature of 6-16 ℃ into a position 80-380 mm below a spinneret plate to quickly crystallize and cool the filaments, directly feeding the cooled filaments into a filament winding disc at the lower end, and winding the filaments into solid-phase polymerized polyester fiber primary filaments containing nano-scale silicon dioxide or titanium oxide powder; wherein the spinning speed is 800-1400 m/min; the drafting multiplying power of the polyester fiber primary yarn is 3.6-4.8; the length-diameter ratio of the twin-screw extruder is 68: 1; setting the temperature of each heating area of the double-screw extruder: the temperature of the first zone is 60-80 ℃, the temperature of the second zone is 260-275 ℃, the temperature of the third zone is 275-290 ℃, the temperature of the fourth zone is 295-305 ℃, the temperature of the fifth zone is 310-315 ℃, the temperature of the sixth zone is 325-330 ℃, the temperature of the seventh zone is 325-330 ℃, the temperature of the eighth zone is 315-320 ℃, the temperature of the ninth zone is 300-310 ℃, the temperature of the tenth zone is 290-305 ℃, the temperature of the eleventh zone is 290-300 ℃ and the temperature of the twelfth zone is 290-300 ℃;
(4) placing the primary filaments obtained in the step (3) into a heat treatment conduit with an interlayer in series, wherein the length of the primary filaments is 2x800mm, the primary filaments are connected in a V shape, the inner diameter of the heat treatment conduit with the interlayer is 60-80 mm, a godet with the diameter of Ø 200 is installed at the bottom of the V shape, and a long slit which is 8mm and facilitates feeding of fibers is cut in the axial direction of the heat treatment conduit with the interlayer in series, wherein 4 heat treatment conduits with V-shaped jackets are connected in series, high-temperature carbon dioxide with the temperature of 160-180 ℃ is input into the heat treatment conduit along the moving direction of the filaments, heat conducting oil with the temperature of 250-270 ℃ is input into the jackets of the 4 heat treatment conduits with V-shaped jackets which are connected in series initially, under the condition that the temperature is 250-270 ℃, the drafting multiplying factor of the filaments is 1.0-1.06, the heat treatment time of the filaments is 4-8 min, and the running;
(5) putting the liquid crystal polyester fiber subjected to the initial heat treatment in the step (4) into the jackets of 4-8V-shaped jacket heat treatment pipes which are connected in series, inputting heat conduction oil with the temperature of 310-330 ℃, wherein under the condition that the temperature is 310-330 ℃, the drafting multiplying power of the filament is 3.0-3.6, the heat treatment time of the filament is 4-8 min, and the running speed of the filament is 160-480 cm/min;
(6) putting the liquid crystal polyester fibers subjected to heat treatment in the step (5) into the jackets of 4V-shaped jacket heat treatment guide pipes which are connected in series, inputting heat conducting oil with the temperature of 350-370 ℃, under the condition that the temperature is 350-370 ℃, the drafting multiplying power of the filament is 3.0-3.6, the heat treatment time of the filament is 4-8 min, and the running speed of the filament is 160-480 cm/min;
(7) inputting the fibers subjected to heat treatment in the step (6) into a series heat treatment guide pipe, wherein the fibers are connected in a V shape, the length of the fibers is 2x600mm, the inner diameter of the heat treatment guide pipe is 60-80 mm, a godet with the diameter of Ø 200 is installed at the bottom of the V shape, and a long seam which is 8mm and is convenient for feeding the fibers is cut in the axial direction of the series heat treatment guide pipe, wherein 6-8V-shaped heat treatment guide pipes are connected in series, carbon dioxide with the normal-temperature water content of 0.001-0.003 wt% and the temperature of 20-30 ℃ is input into the heat treatment guide pipe along the strand moving direction, so that a polyester fiber finished product containing the solid-phase polymerization of the nano-grade inorganic oxide powder is cooled to the normal temperature in the series heat treatment guide pipe, and then the.
The invention has the beneficial effects that:
the liquid crystal polyester resin subjected to solid phase polymerization is subjected to solid phase polycondensation reaction on the basis of a small molecular polyester resin subjected to polycondensation, so that the molecular weight of the liquid crystal polyester resin is improved, although the molecular weight of the liquid crystal polyester resin is improved by a plurality of methods, the problem of wide and narrow molecular weight distribution coefficient exists in the high molecular synthesis process, when the molecular weight distribution is wide, namely the ratio of the weight average molecular weight to the number average molecular weight is large, the content of low molecular weight polymers in a high molecular material is higher than that of the low molecular weight polymers in the case of narrow molecular weight distribution coefficient, therefore, the liquid crystal polyester resin subjected to solid phase polymerization needs to be properly purified, and although the purification methods are many, the content of the low molecular weight polymers in the liquid crystal polyester resin can be reduced by vacuumizing the melt of the liquid crystal polyester resin.
As the solid phase polycondensation is a polymerization reaction on the solid surface, the molecular chain of the polymer extends towards a single direction, the high molecular weight of the solid phase polymerized polyester is further increased, and further the molecular structure is more symmetrical, so that the liquid crystal polyester resin is converted from an amorphous phase system to a crystalline phase system, the high molecular chain of the solid phase polymerized liquid crystal polyester is a linear rigid chain, and the nascent fiber spun by the resin forms a highly orderly arranged microfiber structure through high-temperature heat treatment, and strong interaction exists among the high molecular chains, so that the fiber is endowed with higher tensile strength and modulus.
The polyester liquid crystal fiber has the advantages of extremely high dimensional stability, extremely low moisture regain and excellent bending fatigue resistance and friction resistance. The solid-phase polymerized polyester liquid crystal fiber has wide application field, can be used in fishery, aviation and other industries, and is used for manufacturing optical cables, net ropes, plastic reinforced materials, parachute lines, various sports equipment, protective gloves and the like.
The invention aims to reduce the oligomer and volatile compounds in the liquid crystal polyester resin melt to the degree close to zero to the utmost extent and further improve the finished product yield of the liquid crystal polyester fiber by adjusting the molecular microstructure to a certain degree, vacuumizing the liquid crystal resin melt during the pretreatment process of raw materials and during the preparation of resin slices, wherein the purpose is to reduce the oligomer content in the melt to a certain degree, then continuously removing the oligomer and volatile substances under the vacuum condition, and further performing vacuum treatment to remove the oligomer and volatile compounds in the fiber forming process.
In the manufacturing process of the liquid crystal polyester fiber, nano-scale silicon dioxide or titanium oxide powder with a certain particle size controlled within the range of 3-6 nm is properly added, so that the strength of the liquid crystal polyester fiber is improved, and the application field of the liquid crystal polyester fiber is further expanded; the purpose of controlling the particle size of the nano-sized inorganic oxide is to prevent clogging of the spinneret holes during the spinning of the liquid crystal polyester fiber.
The spinning process of the solid-phase polymerized polyester liquid crystal fiber can use the parameter setting of the melt spinning process for reference, but is influenced by the types and impurities of resin components, and equipment and parameter setting need to be properly adjusted according to actual conditions.
In the spinning process flow of the solid-phase polymerized polyester liquid crystal fiber, the temperature ranges of the heating areas of the extruder are as follows: the temperature of the first zone is 60-80 ℃, the temperature of the second zone is 260-275 ℃, the temperature of the third zone is 275-290 ℃, the temperature of the fourth zone is 295-305 ℃, the temperature of the fifth zone is 310-315 ℃, the temperature of the sixth zone is 325-330 ℃, the temperature of the seventh zone is 325-330 ℃, the temperature of the eighth zone is 315-320 ℃, the temperature of the ninth zone is 300-310 ℃, the temperature of the tenth zone is 290-305 ℃, the temperature of the eleventh zone is 290-300 ℃ and the temperature of the twelfth zone is 290-300 ℃, the heating curve is basically a Gaussian curve, and vacuumizing interfaces with the diameter of 60mm are respectively arranged above the 3 rd heating zone, the 6 th heating zone and the 9 th heating zone of the extruder so as to remove vaporized oligomers, volatile compounds and; all the volume pipelines need to be kept warm, the temperature of the volume pipelines is kept within the range of 30-50 ℃ above the melting point of the polyester resin, meanwhile, according to the pressure displayed by a pressure gauge arranged on a metering pump, even if the temperature of each heating area of the double-screw extruder is adjusted, when the pressure is relatively high, the temperature of each heating area of the double-screw extruder needs to be properly increased, and conversely, the temperature of each heating area of the double-screw extruder needs to be reduced, so that the pressure and the temperature of the whole spinning system and the limit of the primary yarn formed by the melt sprayed out from a spinneret plate are relatively stable, and further, the process control conditions of the subsequent heat treatment process of the primary yarn of the liquid crystal polyester fiber are relatively stable, so that the performance of the finished fiber is relatively stable, and the application of the liquid crystal polyester fiber is facilitated.
The frequency of the variable frequency motor of the metering pump is limited by the feeding amount and the linear density of fibers, and the frequency of the variable frequency motor of the metering pump is generally changed within the range of 15-60 Hz.
The pressure of the spinneret assembly is generally kept between 0.3 MPa and 1.0MPa, and the box-making temperature is also kept within the range of 30 ℃ to 40 ℃ above the melting point of the polyester resin.
The pretreatment temperature of the spinning pack before use is also kept within the range of 30-40 ℃ above the melting point of the polyester resin.
The filament crystallization solidification zone is properly adjusted according to the local air temperature and the linear density or the draft rate of the fiber, and the fiber needs to be cooled and dried according to the solidification characteristic of the polyester liquid crystal melt and the characteristics of the fiber, so that the viscosity of the fiber is reduced, and the treatment process procedure of reducing fiber oiling agent is provided.
The frequency of the frequency-variable motor of the winding machine is limited by the feeding amount of the feeding machine on one hand, the frequency of the frequency-variable motor is determined by considering the linear density limit of the produced fibers and the diameter of the godet, and generally the frequency of the frequency-variable motor of the winding machine is controlled within the range of about 100 Hz.
According to the spinning characteristics of the polyester fiber, the draft ratio of the polyester nascent fiber needs to be properly selected, and is generally within 3.6-4.8.
The present invention is influenced by the liquid crystal polyester resin, although the molecular weight of the liquid crystal polyester resin is relatively large by the solid phase polymerization, and at the same time, various properties of the fiber are satisfactory after the fiber is spun.
The invention properly mixes a small amount of nano-scale inorganic oxide powder into the solid-phase polymerized liquid crystal polyester resin, under the condition of not influencing the spinning and heat treatment of the liquid crystal polyester fiber and the arrangement sequence of polyester molecular chains in the fiber after heat treatment, after properly mixing the nano-scale inorganic oxide, on one hand, the heat treatment speed of the fiber is improved, and on the other hand, the bonding between the fiber and between the fiber and spinning process equipment is reduced, thereby not only improving the strength of the aromatic polyester liquid crystal fiber, but also improving the yield of the fiber, and simultaneously, omitting the treatment process procedure of fiber surface oil agent, and further reducing the production cost.
Because the molecular chain structure of the liquid crystal polyester resin contains a chain-link structural unit of- [ -Ar-COO- ] -in which Ar is aryl and COO is ester group, the ester group in the structural unit is hydrophilic group, if the nascent fiber of the liquid crystal polyester fiber is subjected to directional heat treatment of the molecular chain in the air, the water in the air and the ester group generate hydrophilic reaction, so that the symmetry of the chain-link structural unit of- [ -Ar-COO- ] -in is broken, the ordered arrangement of the microstructure of the finished fiber of the liquid crystal polyester fiber is reduced, and various performances of the finished fiber are reduced, therefore, in order to improve various characteristics of the fiber, the nascent fiber of the liquid crystal polyester fiber needs to be subjected to heat treatment under the protection of inert gas, it is also desirable to control the water content of these inert gases.
In addition, the carbon dioxide gas in the heat treatment process of the liquid crystal polyester fiber nascent filament needs to be recycled, the recycling process does not need to be further detailed in the process flow of the invention, meanwhile, the used carbon dioxide gas needs to be subjected to moisture content control treatment during recycling, and the process flow does not need to be further detailed in the process flow of the invention.
The invention aims to further improve the performance of the liquid crystal polyester fiber, and adopts a three-stage heat treatment process during the heat treatment of the primary yarn of the liquid crystal polyester fiber, so that the microfiber structure of the liquid crystal polyester fiber is basically formed during the initial heat treatment, meanwhile, the strength of the fiber is also improved to a certain extent, and then the orderly arrangement of the fiber is further improved under the conditions of improving the temperature and the drafting multiplying factor, thereby further improving the strength of the fiber.
The invention can also increase or decrease the number of stages of heat treatment according to the performance characteristics of the liquid crystal fiber after heat treatment so as to obtain a liquid crystal polyester fiber finished product with stable performance.
In the process flow of the invention, in order to reduce the blockage of the feed inlet of the twin-screw extruder, the inventor finds that the first heating zone of the twin-screw extruder needs to be arranged at a low temperature through hundreds of experiments so as to reduce the cohesiveness of the liquid crystal polyester resin and the screws of the twin-screw extruder, thereby being beneficial to the input of the liquid crystal polyester resin and further enabling the feeding amount of the liquid crystal polyester resin to be more stable.
Description of the drawings:
FIG. 1 shows a heat treatment process flow of polyester liquid crystal nascent fiber
FIG. 2 shows the partial performance index of the polyester liquid crystal as-spun fiber after drawing
Detailed Description
The process flow introduction of the invention is as follows:
firstly, adding nanoscale inorganic oxide in a certain mass percentage into a high-speed mixing stirrer, and uniformly mixing the nanoscale inorganic oxide with solid-phase polymerized polyester resin at a certain rotating speed; then inputting the resin into a single screw extruder with a vacuumizing interface to prepare liquid crystal polyester resin slices, then placing the resin slices into a vacuum oven to carry out drying treatment for a certain time, partially removing low-component substances and volatile substances in the chips, inputting the dried resin chips into a double-screw extruder with a vacuumizing interface to prepare liquid crystal polyester melt, inputting the melt into a spinning box body through a melt pipeline, a metering pump is arranged on the spinning box body, the liquid crystal polyester melt is input into a certain number of spinning assemblies through the metering pump and is sprayed out by the spinneret plates of the spinning assemblies, the liquid crystal polyester melt sprayed out by the spinneret plates is cooled into filaments by cooling gas blown out from the lower part of the spinning box, under the traction of a winding godet, the filament yarn is wound into polyester liquid crystal fiber primary yarn with a certain drawing ratio, the nascent fiber is then placed into a heat treatment device for heat treatment, and a polyester liquid crystal fiber finished product containing a certain mass percentage of nano-scale inorganic oxide is obtained after the heat treatment.
Brief introduction of the heat treatment process of the present invention:
referring to fig. 1: the heat conducting oil enters from the V-shaped bottom 1 of the heat treatment conduit and flows out from the V-shaped left 2 of the heat treatment conduit and is input into the heat conducting oil constant-temperature heating device. The heat conducting oil enters from the V-shaped bottom 3 of the heat treatment conduit and flows out from the V-shaped right 4 of the heat treatment conduit, and the heat conducting oil is input into the heat conducting oil constant-temperature heating device. Meanwhile, carbon dioxide gas with certain temperature is input at the position E of the fiber inlet, and the carbon dioxide gas is discharged from the position F of the V shape.
The nascent fiber of the invention is fed from the left side A of the V shape of the heat treatment conduit, passes through a godet with the diameter of Ø 40 installed at the bottom of the V shape, then comes out from the right side B of the V shape heat treatment conduit, passes through a godet with the diameter of Ø 200, is fed from the left side C of the V shape of the heat treatment conduit, passes through a godet with the diameter of Ø 40 installed at the bottom of the V shape, comes out from the right side D of the V shape heat treatment conduit, and the V shape heat treatment conduit is composed of 4 initial heat treatment process steps which are connected in series to form the fiber, then 4 final heat treatment process steps which are connected in series to form the fiber, and then 6-8 cooling process steps which are connected in series to form the heat treatment fiber, and then is wound into a cylinder after heat treatment and cooling, thus the solid phase polymerization polyester liquid crystal nascent fiber containing nano-grade inorganic oxide powder is once heat-treated into qualified finished fiber.
The process of the present invention is further described in detail below with reference to examples.
Example 1
Adding 0.1 wt% of nano-scale silicon dioxide powder with the particle size of 6nm into powdery solid-phase polymerized polyester resin, placing the powdery solid-phase polymerized polyester resin into a high-speed stirrer, stirring the powdery solid-phase polymerized polyester resin for 36min at the stirring speed of 3300rpm, inputting the mixture into a single-screw extruder, and extruding and cutting the solid-phase polymerized polyester resin containing the nano-scale silicon dioxide or titanium oxide powder into resin slices with the length of 6mm and the diameter of 2mm under the vacuum condition; placing the obtained resin slices into a vacuum oven at the temperature of 180 ℃, wherein the vacuum degree is-0.8 Mpa, and drying for 38 hours; the obtained solid-phase polymerization polyester resin slice containing the nano-scale silicon dioxide or titanium oxide powder is directly input into a double-screw extruder, vacuumizing interfaces with the diameter of 60mm are respectively arranged above a heating area 3, a heating area 6 and a heating area 9 of the extruder, the vacuum degree of the vacuumizing interfaces is-0.8 Mpa, the temperature of the double-screw extruder for melting resin is set within the range of 260-330 ℃, and the length-diameter ratio of the double-screw extruder is 68: 1; setting the temperature of each heating area of the double-screw extruder: a first zone of 60 ℃, a second zone of 260 ℃, a third zone of 275 ℃, a fourth zone of 295 ℃, a fifth zone of 310 ℃, a sixth zone of 325 ℃, a seventh zone of 325 ℃, an eighth zone of 315 ℃, a ninth zone of 300 ℃, a tenth zone of 295 ℃, an eleventh zone of 290 ℃ and a twelfth zone of 290 ℃; the temperature setting is basically in a Gaussian curve shape, the polyester resin melt containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder is extruded by a double-screw extruder and then is input into a heat-preservation spinning box with the temperature of 330 ℃, a metering pump arranged on the spinning box is input and configured with 6 spinning assemblies, the polyester resin melt containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder is sprayed out by a spinning plate of the spinning assemblies, carbon dioxide with the temperature of 6 ℃ is blown into the position 80mm below the spinning plate, the filaments are rapidly crystallized and cooled, and the cooled filaments are directly input into a filament winding disc at the lower end to be wound into the polyester fiber nascent filaments containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder; wherein the spinning speed is 800 m/min; the draft ratio of the polyester fiber raw filament was 4.8.
Putting the obtained nascent fiber into a heat treatment conduit with a series interlayer, wherein the length of the nascent fiber is 2x800mm and the nascent fiber is connected in a V shape, the inner diameter of the heat treatment conduit with the interlayer is 60mm, a yarn guide disc with the diameter of Ø 200 is arranged at the bottom of the V shape, and simultaneously, a long seam which is 8mm and is convenient for feeding the fiber is cut in the axial direction of the heat treatment conduit with the series interlayer, wherein 4 heat treatment conduits with the V-shaped jackets are connected in series, high-temperature carbon dioxide with the temperature of 180 ℃ is input into the heat treatment conduit along the moving direction of the strand silk, heat conducting oil with the temperature of 270 ℃ is input into the jackets of the 4 heat treatment conduits with the V shape in series initially, under the condition that the temperature is 270 ℃, the magnification of the strand silk is 1.06, the heat treatment time of the strand silk is 8min, and the;
placing the liquid crystal polyester fiber subjected to initial heat treatment into the jackets of 4V-shaped jacket heat treatment conduits connected in series, inputting heat conduction oil with the temperature of 310 ℃, and under the condition that the temperature is 310 ℃, the drafting multiplying factor of filament is 3.0; the heat treatment time of the strand silk is 4min, and the running speed of the strand silk is 160 cm/min;
placing the heat-treated liquid crystal polyester fiber into the jackets of 4V-shaped jacket heat treatment conduits which are connected in series, inputting heat conduction oil with the temperature of 350 ℃, and under the condition that the temperature is 350 ℃, the drafting multiplying power of the filament is 3.0; the heat treatment time of the strand silk is 4min, and the running speed of the strand silk is 160 cm/min;
inputting the heat-treated fibers into a series heat treatment guide pipe, wherein the length of the heat-treated fibers is 2x600mm, the heat-treated fibers are connected in a V shape, the inner diameter of the heat treatment guide pipe is 60mm, a wire guide disc with the diameter of Ø 200 is installed at the bottom of the V shape, a long seam which is 8mm and is convenient for feeding the fibers is cut in the axial direction of the series heat treatment guide pipe, the 6V-shaped heat treatment guide pipes are connected in series, carbon dioxide with the normal-temperature water content of 0.001 wt% and the temperature of 30 ℃ is input into the heat treatment guide pipe along the moving direction of the strand silk, so that the solid-phase polymerized polyester fiber finished product containing the nano-grade inorganic oxide powder is cooled to the normal temperature in the series heat treatment guide pipe.
The performance characteristics of the obtained liquid crystal polyester finished fiber are shown in FIG. 2.
Example 2
Adding 3 wt% of nano-scale silicon dioxide powder with the particle size of 3nm into powdery solid-phase polymerized polyester resin, placing the powdery solid-phase polymerized polyester resin into a high-speed stirrer, stirring the powdery solid-phase polymerized polyester resin for 48min at the stirring speed of 3300rpm, inputting the mixture into a single-screw extruder, and extruding and cutting the solid-phase polymerized polyester resin containing the nano-scale silicon dioxide or titanium oxide powder into resin slices with the length of 3mm and the diameter of 1mm under the vacuum condition; placing the obtained resin slices into a vacuum oven at 160 ℃, wherein the vacuum degree is-0.06 Mpa, and drying for 48 hours; the obtained solid-phase polymerization polyester resin slice containing the nano-scale silicon dioxide or titanium oxide powder is directly input into a double-screw extruder, vacuumizing interfaces with the diameter of 60mm are respectively arranged above a heating area 3, a heating area 6 and a heating area 9 of the extruder, the vacuum degree of the vacuumizing interfaces is-0.06 MPa, the temperature of the double-screw extruder for melting resin is set within the range of 260-330 ℃, and the length-diameter ratio of the double-screw extruder is 68: 1; setting the temperature of each heating area of the double-screw extruder: a first zone of 80 ℃, a second zone of 275 ℃, a third zone of 290 ℃, a fourth zone of 305 ℃, a fifth zone of 315 ℃, a sixth zone of 330 ℃, a seventh zone of 330 ℃, an eighth zone of 320 ℃, a ninth zone of 310 ℃, a tenth zone of 305 ℃, an eleventh zone of 300 ℃ and a twelfth zone of 300 ℃; the temperature setting is basically in a Gaussian curve shape, the solid-phase polymerized polyester resin melt containing nano-scale silicon dioxide or titanium oxide powder is extruded by a double-screw extruder and then is input into a heat-preservation spinning box with the temperature of 310 ℃, 4 spinning assemblies are input and configured by a metering pump configured on the spinning box, the solid-phase polymerized polyester resin melt containing the nano-scale silicon dioxide or titanium oxide powder is sprayed out by a spinning plate of the spinning assemblies, carbon dioxide with the temperature of 16 ℃ is blown into the position 380mm below the spinning plate to rapidly crystallize and cool the filaments, and the cooled filaments are directly input into a winding disc at the lower end of the filaments to be wound into solid-phase polymerized polyester fiber nascent filaments containing the nano-scale silicon dioxide or titanium oxide powder; wherein the spinning speed is 1400 m/min; the drafting multiplying power is 3.6;
putting the obtained nascent fiber into a heat treatment conduit with a series interlayer, wherein the length of the nascent fiber is 2x800mm and the nascent fiber is connected in a V shape, the inner diameter of the heat treatment conduit with the interlayer is 80mm, a godet with the diameter of Ø 200 is arranged at the bottom of the V shape, simultaneously, a long seam which is 8mm and is convenient for feeding the fiber is cut along the axial direction of the heat treatment conduit with the series interlayer, wherein 4 heat treatment conduits with the V-shaped jackets are connected in series, high-temperature carbon dioxide with the temperature of 180 ℃ is input into the heat treatment conduit along the moving direction of the strand silk, heat conducting oil with the temperature of 250 ℃ is input into the jackets of the 4 heat treatment conduits with the V shape which are connected in series initially, under the condition that the temperature is 250 ℃, the magnification of the strand silk is 1.0, the heat treatment time of the strand silk is 4min, and;
placing the liquid crystal polyester fiber subjected to initial heat treatment into the jackets of 4V-shaped jacket heat treatment conduits connected in series, inputting heat conduction oil with the temperature of 330 ℃, and under the condition that the temperature is 330 ℃, the drafting multiplying factor of filament is 3.6; the heat treatment time of the strand silk is 4min, and the running speed of the strand silk is 480 cm/min;
placing the heat-treated liquid crystal polyester fiber into the jackets of 4V-shaped jacket heat treatment conduits which are connected in series, inputting heat conduction oil with the temperature of 370 ℃, and under the condition that the temperature is 370 ℃, the drafting multiplying factor of filament is 3.6; the heat treatment time of the strand silk is 4min, and the running speed of the strand silk is 480 cm/min;
inputting the heat-treated fibers into a series heat treatment guide pipe, wherein the length of the heat-treated fibers is 2x600mm, the heat-treated fibers are connected in a V shape, the inner diameter of the heat treatment guide pipe is 80mm, a wire guide disc with the diameter of Ø 200 is installed at the bottom of the V shape, a long seam which is 8mm and is convenient for feeding the fibers is cut in the axial direction of the series heat treatment guide pipe, 8V-shaped heat treatment guide pipes are connected in series, carbon dioxide with the normal-temperature water content of 0.003 wt% and the temperature of 30 ℃ is input into the heat treatment guide pipe along the strand silk moving direction, so that a solid-phase polymerized polyester fiber finished product containing nano-grade inorganic oxide powder is cooled to the normal temperature in the series heat treatment guide pipe, and then the solid.
The performance characteristics of the obtained liquid crystal polyester finished fiber are shown in FIG. 2.
Comparative example 1
Inputting the powdery solid-phase polymerized polyester resin into a single-screw extruder, and extruding and cutting the solid-phase polymerized polyester resin into resin slices with the length of 6mm and the diameter of 2mm under the condition of vacuumizing; placing the obtained resin slices into a vacuum oven at the temperature of 180 ℃, wherein the vacuum degree is-0.8 Mpa, and drying for 38 hours; the obtained solid-phase polymerization polyester resin slice containing the nano-scale silicon dioxide or titanium oxide powder is directly input into a double-screw extruder, vacuumizing interfaces with the diameter of 60mm are respectively arranged above a heating area 3, a heating area 6 and a heating area 9 of the extruder, the vacuum degree of the vacuumizing interfaces is-0.06 to-0.8 Mpa, the temperature of the double-screw extruder for melting resin is set within the range of 260 to 330 ℃, and the length-diameter ratio of the double-screw extruder is 68: 1; setting the temperature of each heating area of the double-screw extruder: a first zone of 80 ℃, a second zone of 275 ℃, a third zone of 290 ℃, a fourth zone of 305 ℃, a fifth zone of 315 ℃, a sixth zone of 330 ℃, a seventh zone of 330 ℃, an eighth zone of 320 ℃, a ninth zone of 310 ℃, a tenth zone of 305 ℃, an eleventh zone of 300 ℃ and a twelfth zone of 300 ℃; the temperature setting is basically in a Gaussian curve shape, the solid-phase polymerized polyester resin melt containing nano-scale silicon dioxide or titanium oxide powder is extruded by a double-screw extruder and then is input into a heat-preservation spinning box with the temperature of 330 ℃, a metering pump arranged on the spinning box is input and configured with 6 spinning assemblies, the solid-phase polymerized polyester resin melt containing the nano-scale silicon dioxide or titanium oxide powder is blown out by a spinning plate of the spinning assemblies, carbon dioxide with the temperature of 16 ℃ is blown into the position 380mm below the spinning plate to rapidly crystallize and cool the filaments, and the cooled filaments are directly input into a filament winding disc at the lower end to be wound into solid-phase polymerized polyester fiber nascent filaments containing the nano-scale silicon dioxide or titanium oxide powder; wherein the spinning speed is 1400 m/min; the drafting multiplying power is 4.8;
putting the obtained nascent fiber into a heat treatment conduit with a series interlayer, wherein the length of the nascent fiber is 2x800mm and the nascent fiber is connected in a V shape, the inner diameter of the heat treatment conduit with the interlayer is 80mm, a yarn guide disc with the diameter of Ø 200 is arranged at the bottom of the V shape, and simultaneously, a long seam which is 8mm and is convenient for feeding the fiber is cut in the axial direction of the heat treatment conduit with the series interlayer, wherein 4 heat treatment conduits with the V-shaped jackets are connected in series, high-temperature carbon dioxide with the temperature of 180 ℃ is input into the heat treatment conduit along the moving direction of the strand silk, heat conducting oil with the temperature of 270 ℃ is input into the jackets of the 4 heat treatment conduits with the V shape which are connected in series initially, under the condition that the temperature is 270 ℃, the magnification of the strand silk is 1.06, the heat treatment time of the strand silk is 4 min;
placing the liquid crystal polyester fiber subjected to initial heat treatment into the jackets of 4V-shaped jacket heat treatment conduits connected in series, inputting heat conduction oil with the temperature of 330 ℃, and under the condition that the temperature is 330 ℃, the drafting multiplying factor of filament is 3.6; the heat treatment time of the strand silk is 4min, and the running speed of the strand silk is 480 cm/min;
placing the heat-treated liquid crystal polyester fiber into the jackets of 4V-shaped jacket heat treatment conduits which are connected in series, inputting heat conduction oil with the temperature of 370 ℃, and under the condition that the temperature is 370 ℃, the drafting multiplying factor of filament is 3.6; the heat treatment time of the strand silk is 8min, and the running speed of the strand silk is 480 cm/min;
inputting the heat-treated fibers into a series heat treatment guide pipe, wherein the length of the heat-treated fibers is 2x600mm, the heat-treated fibers are connected in a V shape, the inner diameter of the heat treatment guide pipe is 80mm, a wire guide disc with the diameter of Ø 200 is installed at the bottom of the V shape, a long seam which is 8mm and is convenient for feeding the fibers is cut in the axial direction of the series heat treatment guide pipe, 8V-shaped heat treatment guide pipes are connected in series, carbon dioxide with the normal-temperature water content of 0.003 wt% and the temperature of 30 ℃ is input into the heat treatment guide pipe along the strand silk moving direction, so that a solid-phase polymerized polyester fiber finished product containing nano-grade inorganic oxide powder is cooled to the normal temperature in the series heat treatment guide pipe, and then the solid.
The performance characteristics of the obtained liquid crystal polyester finished fiber are shown in FIG. 2.
Example 3:
adding 2 wt% of nano-scale titanium oxide powder with the particle size of 4nm into powdery solid-phase polymerized polyester resin, placing the powdery solid-phase polymerized polyester resin into a high-speed stirrer, stirring the powdery solid-phase polymerized polyester resin for 44min at the stirring speed of 3000rpm, inputting the mixture into a single-screw extruder, and extruding and cutting the solid-phase polymerized polyester resin containing the nano-scale silicon dioxide or titanium oxide powder into resin slices with the length of 4mm and the diameter of 1.5mm under the vacuum pumping condition; placing the obtained resin slices into a vacuum oven at the temperature of 160-180 ℃, wherein the vacuum degree is-0.07 Mpa, and drying for 44 hours; the obtained solid-phase polymerization polyester resin slice containing the nano-scale silicon dioxide or titanium oxide powder is directly input into a double-screw extruder, vacuumizing interfaces with the diameter of 60mm are respectively arranged above a heating area 3, a heating area 6 and a heating area 9 of the extruder, the vacuum degree of the vacuumizing interfaces is-0.06 to-0.8 Mpa, the temperature of the double-screw extruder for melting resin is set within the range of 260 to 330 ℃, and the length-diameter ratio of the double-screw extruder is 68: 1; setting the temperature of each heating area of the double-screw extruder: a first zone of 70 ℃, a second zone of 270 ℃, a third zone of 280 ℃, a fourth zone of 300 ℃, a fifth zone of 310 ℃, a sixth zone of 328 ℃, a seventh zone of 328 ℃, an eighth zone of 318 ℃, a ninth zone of 308 ℃, a tenth zone of 303 ℃, an eleventh zone of 298 ℃ and a twelfth zone of 298 ℃; the temperature setting is basically in a Gaussian curve shape, the polyester resin melt containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder is extruded by a double-screw extruder and then is input into a thermal insulation spinning box with the temperature of 320 ℃, a metering pump arranged on the spinning box is input and configured with 6 spinning assemblies, the polyester resin melt containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder is blown out by a spinneret plate of the spinning assemblies, carbon dioxide with the temperature of 11 ℃ is blown into the position 180mm below the spinneret plate, the filaments are rapidly crystallized and cooled, and the cooled filaments are directly input into a filament winding disc at the lower end to be wound into the polyester fiber nascent filaments containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder; wherein the spinning speed is 1000 m/min; the drafting multiplying power is 4.0;
putting the obtained nascent fiber into a heat treatment conduit with a series interlayer, wherein the length of the nascent fiber is 2x800mm and the nascent fiber is connected in a V shape, the inner diameter of the heat treatment conduit with the interlayer is 70mm, a godet with the diameter of Ø 200 is arranged at the bottom of the V shape, a long seam which is 8mm and is convenient for feeding the fiber is cut along the axial direction of the heat treatment conduit with the series interlayer, 4 heat treatment conduits with the V-shaped jackets are connected in series, high-temperature carbon dioxide with the temperature of 170 ℃ is input into the heat treatment conduit along the moving direction of the strand silk, heat conducting oil with the temperature of 260 ℃ is input into the jackets of the 4 heat treatment conduits which are connected in series at first, under the condition that the temperature is 260 ℃, the magnification of the strand silk is 1.03, the heat treatment time of the strand silk is 6min, and the running speed of the strand;
placing the liquid crystal polyester fiber subjected to initial heat treatment into the jackets of 4V-shaped jacket heat treatment conduits connected in series, inputting heat conduction oil with the temperature of 320 ℃, and under the condition that the temperature is 320 ℃, the drafting multiplying factor of filament is 3.3; the heat treatment time of the strand silk is 6min, and the running speed of the strand silk is 330 cm/min;
placing the heat-treated liquid crystal polyester fiber into the jackets of 4V-shaped jacket heat treatment conduits which are connected in series, inputting heat conduction oil with the temperature of 360 ℃, and under the condition that the temperature is 360 ℃, the drafting multiplying power of the filament is 3.3; the heat treatment time of the strand silk is 6min, and the running speed of the strand silk is 330 cm/min;
inputting the heat-treated fibers into a series heat treatment guide pipe, wherein the length of the heat-treated fibers is 2x600mm, the heat treatment guide pipe is connected in a V shape, the inner diameter of the heat treatment guide pipe is 70mm, a godet with the diameter of Ø 200 is arranged at the bottom of the V shape, a long seam which is 8mm and is convenient for feeding the fibers is cut in the axial direction of the series heat treatment guide pipe, 7V-shaped heat treatment guide pipes are connected in series, and carbon dioxide with the normal temperature and the water content of 0.002 percent by weight and the temperature of 26 ℃ is input into the heat treatment guide pipe along the strand silk moving direction, so that a solid-phase polymerized polyester fiber finished product containing nano-grade inorganic oxide powder is cooled to the normal temperature in the series heat treatment guide pipe, and then;
the performance characteristics of the obtained liquid crystal polyester finished fiber are shown in FIG. 2.
Example 4
Adding 1.8 wt% of nano-scale titanium oxide powder with the particle size of 5nm into powdery solid-phase polymerized polyester resin, placing the mixture into a high-speed stirrer, stirring the mixture for 39min at the stirring speed of 3100rpm, inputting the mixture into a single-screw extruder, and extruding and cutting the solid-phase polymerized polyester resin containing the nano-scale silicon dioxide or titanium oxide powder into resin slices with the length of 4mm and the diameter of 2mm under the condition of vacuumizing; placing the obtained resin slices into a vacuum oven at 168 ℃ with the vacuum degree of-0.076 Mpa, and drying for 46 h; the obtained solid-phase polymerization polyester resin slice containing the nano-scale silicon dioxide or titanium oxide powder is directly input into a double-screw extruder, vacuumizing interfaces with the diameter of 60mm are respectively arranged above a heating area 3, a heating area 6 and a heating area 9 of the extruder, the vacuum degree of the vacuumizing interfaces is-0.076 Mpa, the temperature of the double-screw extruder for melting resin is set within the range of 260-330 ℃, and the length-diameter ratio of the double-screw extruder is 68: 1; setting the temperature of each heating area of the double-screw extruder: a first region of 75 ℃, a second region of 273 ℃, a third region of 286 ℃, a fourth region of 299 ℃, a fifth region of 313 ℃, a sixth region of 326 ℃, a seventh region of 329 ℃, an eighth region of 316 ℃, a ninth region of 306 ℃, a tenth region of 301 ℃, an eleventh region of 299 ℃ and a twelfth region of 299 ℃; the temperature setting is basically in a Gaussian curve shape, the polyester resin melt containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder is extruded by a double-screw extruder and then is input into a thermal insulation spinning box with the temperature of 326 ℃, a metering pump arranged on the spinning box is input and configured with 4 spinning assemblies, the polyester resin melt containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder is blown out by a spinneret plate of the spinning assemblies, carbon dioxide with the temperature of 13 ℃ is blown into the position 280mm below the spinneret plate, the strand silk is rapidly crystallized and cooled, and the cooled strand silk is directly input into a strand silk winding disc at the lower end to be wound into the polyester fiber primary silk containing the solid phase polymerization of the nano-silicon dioxide or titanium oxide powder; wherein the spinning speed is 1200 m/min; the drafting multiplying power is 4.3;
putting the obtained nascent fiber into a heat treatment conduit with a series interlayer, wherein the length of the nascent fiber is 2x800mm and the nascent fiber is connected in a V shape, the inner diameter of the heat treatment conduit with the interlayer is 75mm, a godet with the diameter of Ø 200 is arranged at the bottom of the V shape, simultaneously, a long seam which is 8mm and is convenient for feeding the fiber is cut along the axial direction of the heat treatment conduit with the series interlayer, wherein 4 heat treatment conduits with the V-shaped jackets are connected in series, high-temperature carbon dioxide with the temperature of 175 ℃ is input into the heat treatment conduit along the moving direction of the strand silk, heat conducting oil with the temperature of 268 ℃ is input into the jackets of the 4 heat treatment conduits with the V shape in series initially, under the condition that the temperature is 268 ℃, the strand silk magnification is 1.04, the heat treatment time of the strand silk is 7min, and the running speed of the;
putting the liquid crystal polyester fiber subjected to initial heat treatment into the jackets of 4V-shaped jacket heat treatment conduits which are connected in series, inputting heat conduction oil with the temperature of 321 ℃, and under the condition that the temperature is 321 ℃, the drafting multiplying factor of filament is 3.4; the heat treatment time of the strand silk is 7min, and the running speed of the strand silk is 430 cm/min;
placing the heat-treated liquid crystal polyester fiber into the jackets of 4V-shaped jacket heat treatment conduits which are connected in series, inputting heat-conducting oil with the temperature of 366 ℃, and under the condition that the temperature is 366 ℃, the drafting multiplying factor of the filament is 3.4; the heat treatment time of the strand silk is 7min, and the running speed of the strand silk is 430 cm/min;
inputting the heat-treated fibers into a series heat treatment guide pipe, wherein the length of the heat-treated fibers is 2x600mm, the heat-treated fibers are connected in a V shape, the inner diameter of the heat treatment guide pipe is 75mm, a wire guide disc with the diameter of Ø 200 is installed at the bottom of the V shape, a long seam which is 8mm and is convenient for feeding the fibers is cut in the axial direction of the series heat treatment guide pipe, 8V-shaped heat treatment guide pipes are connected in series, and carbon dioxide with the normal-temperature water content of 0.0023 percent by weight and the temperature of 26 ℃ is input into the heat treatment guide pipe along the moving direction of the strand silk, so that the solid-phase polymerized polyester fiber finished product containing the nano-grade inorganic oxide powder is cooled to the normal temperature in the series heat treatment guide pipe.
The performance characteristics of the obtained liquid crystal polyester finished fiber are shown in FIG. 2.
Comparative example 2
Adding 0.05 wt% of nano-scale titanium oxide powder with the particle size of 18nm into powdery solid-phase polymerized polyester resin, putting the powdery solid-phase polymerized polyester resin into a high-speed stirrer, stirring the powdery solid-phase polymerized polyester resin for 48min at the stirring speed of 2800rpm, inputting the mixture into a single-screw extruder, and extruding and cutting the solid-phase polymerized polyester resin containing the nano-scale silicon dioxide or titanium oxide powder into resin slices with the length of 3mm and the diameter of 1mm under the vacuum condition; placing the obtained resin slices into a vacuum oven at 160 ℃, wherein the vacuum degree is-0.06 Mpa, and drying for 48 hours; the obtained solid-phase polymerization polyester resin slice containing the nano-scale silicon dioxide or titanium oxide powder is directly input into a double-screw extruder, vacuumizing interfaces with the diameter of 60mm are respectively arranged above a heating area 3, a heating area 6 and a heating area 9 of the extruder, the vacuum degree of the vacuumizing interfaces is-0.8 Mpa, the temperature of the double-screw extruder for melting resin is set within the range of 260-330 ℃, and the length-diameter ratio of the double-screw extruder is 68: 1; setting the temperature of each heating area of the double-screw extruder: a first zone of 60 ℃, a second zone of 260 ℃, a third zone of 275 ℃, a fourth zone of 295 ℃, a fifth zone of 310 ℃, a sixth zone of 325 ℃, a seventh zone of 325 ℃, an eighth zone of 315 ℃, a ninth zone of 300 ℃, a tenth zone of 295 ℃, an eleventh zone of 290 ℃ and a twelfth zone of 290 ℃; the temperature setting is basically in a Gaussian curve shape, the solid-phase polymerized polyester resin melt containing nano-scale silicon dioxide or titanium oxide powder is extruded by a double-screw extruder and then is input into a heat-preservation spinning box with the temperature of 310 ℃, 4 spinning assemblies are input and configured by a metering pump configured on the spinning box, the solid-phase polymerized polyester resin melt containing the nano-scale silicon dioxide or titanium oxide powder is sprayed out by a spinneret plate of the spinning assemblies, carbon dioxide with the temperature of 6 ℃ is blown into the position 80mm below the spinneret plate, the strand silk is rapidly crystallized and cooled, and the cooled strand silk is directly input into a strand silk winding disc at the lower end to be wound into solid-phase polymerized polyester fiber nascent silk containing the nano-scale silicon dioxide or titanium oxide powder; wherein the spinning speed is 800 m/min; the drafting multiplying power is 3.6;
putting the obtained nascent fiber into a heat treatment conduit with a series interlayer, wherein the length of the nascent fiber is 2x800mm and the nascent fiber is connected in a V shape, the inner diameter of the heat treatment conduit with the interlayer is 60mm, a godet with the diameter of Ø 200 is arranged at the bottom of the V shape, simultaneously, a long seam which is 8mm and is convenient for feeding the fiber is cut along the axial direction of the heat treatment conduit with the series interlayer, wherein 4 heat treatment conduits with the V-shaped jackets are connected in series, high-temperature carbon dioxide with the temperature of 160 ℃ is input into the heat treatment conduit along the moving direction of the strand silk, heat conducting oil with the temperature of 250 ℃ is input into the jackets of the 4 heat treatment conduits with the V shape which are connected in series initially, under the condition that the temperature is 250 ℃, the magnification of the strand silk is 1.0, the heat treatment time of the strand silk is 8min, and;
placing the liquid crystal polyester fiber subjected to initial heat treatment into the jackets of 4V-shaped jacket heat treatment conduits connected in series, inputting heat conduction oil with the temperature of 310 ℃, and under the condition that the temperature is 310 ℃, the drafting multiplying factor of filament is 3.0; the heat treatment time of the strand silk is 8min, and the running speed of the strand silk is 160 cm/min;
placing the heat-treated liquid crystal polyester fiber into the jackets of 4V-shaped jacket heat treatment conduits which are connected in series, inputting heat conduction oil with the temperature of 350 ℃, and under the condition that the temperature is 350 ℃, the drafting multiplying power of the filament is 3.0; the heat treatment time of the strand silk is 8min, and the running speed of the strand silk is 160 cm/min;
inputting the heat-treated fibers into a series heat treatment guide pipe, wherein the length of the heat-treated fibers is 2x600mm, the heat-treated fibers are connected in a V shape, the inner diameter of the heat treatment guide pipe is 60mm, a wire guide disc with the diameter of Ø 200 is installed at the bottom of the V shape, a long seam which is 8mm and is convenient for feeding the fibers is cut in the axial direction of the series heat treatment guide pipe, the 6V-shaped heat treatment guide pipes are connected in series, carbon dioxide with the normal-temperature water content of 0.001 wt% and the temperature of 20 ℃ is input into the heat treatment guide pipe along the moving direction of the strand silk, so that the solid-phase polymerized polyester fiber finished product containing the nano-grade inorganic oxide powder is cooled to the normal temperature in the series heat treatment guide pipe.
The performance characteristics of the obtained liquid crystal polyester finished fiber are shown in FIG. 2.
Claims (2)
1. A spinning process of polyester liquid crystal fibers adopts pretreatment of solid-phase polymerized polyester resin, vacuumizing, melting by a screw extruder, melt metering pump, forced filtration, spinning assembly, strand cooling crystallization, winding and doffing to produce primary yarns, and heat treatment of the primary yarns; the method is characterized in that: the spinning process comprises the following specific steps:
(1) adding 0.1-3 wt% of nano-scale inorganic oxide powder into powdery solid-phase polymerized polyester resin, placing the powdery solid-phase polymerized polyester resin into a high-speed stirrer, stirring the powdery solid-phase polymerized polyester resin for 36-48 min at the stirring speed of 2800-3300 rpm, inputting the mixture into a single-screw extruder, and extruding and cutting the solid-phase polymerized polyester resin containing the nano-scale inorganic oxide powder into resin slices with the length of 3-6 mm and the diameter of 1-2 mm under the vacuum condition;
(2) putting the resin slices obtained in the step (1) into a vacuum oven at the temperature of 160-180 ℃, wherein the vacuum degree is-0.06-0.8 Mpa, and drying for 38-48 h;
(3) directly inputting the solid-phase polymerized polyester resin slices containing the nano-scale inorganic oxide powder obtained by drying in the step (2) into a double-screw extruder, respectively arranging a vacuumizing interface with the diameter of 60mm above a heating zone 3, a heating zone 6 and a heating zone 9 of the extruder, wherein the vacuum degree is-0.06-0.8 Mpa, the temperature of the resin melted by the double-screw extruder is 260-330 ℃, the temperature is set to be Gaussian curve-shaped, the solid-phase polymerized polyester resin melt containing the nano-scale inorganic oxide powder is input into a heat-preserving spinning box with the temperature of 310-330 ℃ after being extruded by the double-screw extruder, inputting and configuring 4-6 spinning assemblies by a metering pump configured on the heat-preserving spinning box, and after being ejected by a spinning plate of the spinning assemblies, the solid-phase polymerized polyester resin melt containing the nano-scale inorganic oxide powder is positioned 80-380 mm below the spinning plate, blowing carbon dioxide at the temperature of 6-16 ℃ to rapidly crystallize and cool the filaments, directly feeding the cooled filaments into a filament winding disc at the lower end, and winding the filaments into solid-phase polymerized polyester fiber nascent filaments containing nano-scale inorganic oxide powder; the spinning speed is 800-1400 m/min; the drafting multiplying power of the polyester fiber primary yarn is 3.6-4.8; the length-diameter ratio of the double-screw extruder is 68: 1; the temperature of each heating area of the double-screw extruder is 60-80 ℃ in a first area, 260-275 ℃ in a second area, 275-290 ℃ in a third area, 295-305 ℃ in a fourth area, 310-315 ℃ in a fifth area, 325-330 ℃ in a sixth area, 325-330 ℃ in a seventh area, 315-320 ℃ in an eighth area, 300-310 ℃ in a ninth area, 290-305 ℃ in a tenth area, 290-300 ℃ in an eleventh area and 290-300 ℃ in a twelfth area;
(4) placing the primary filaments obtained in the step (3) into a heat treatment conduit with an interlayer in series, wherein the length of the primary filaments is 2x800mm, the primary filaments are connected in a V shape, the inner diameter of the heat treatment conduit with the interlayer is 60-80 mm, a godet with the diameter of Ø 200 is installed at the bottom of the V shape, and a long slit which is 8mm and facilitates feeding of fibers is cut in the axial direction of the heat treatment conduit with the interlayer in series, wherein 4 heat treatment conduits with V-shaped jackets are connected in series, high-temperature carbon dioxide with the temperature of 160-180 ℃ is input into the heat treatment conduit along the moving direction of the filaments, heat conducting oil with the temperature of 250-270 ℃ is input into the jackets of the 4 heat treatment conduits with V-shaped jackets which are connected in series initially, under the condition that the temperature is 250-270 ℃, the drafting multiplying factor of the filaments is 1.0-1.06, the heat treatment time of the filaments is 4-8 min, and the running;
(5) putting the liquid crystal polyester fiber subjected to the initial heat treatment in the step (4) into the jackets of 4V-shaped jacket heat treatment pipes which are connected in series, inputting heat conducting oil with the temperature of 310-330 ℃, wherein under the condition that the temperature is 310-330 ℃, the drafting multiplying power of the filament is 3.0-3.6, the heat treatment time of the filament is 4-8 min, and the running speed of the filament is 160-480 cm/min;
(6) putting the liquid crystal polyester fibers subjected to heat treatment in the step (5) into the jackets of 4V-shaped jacket heat treatment guide pipes which are connected in series, inputting heat conducting oil with the temperature of 350-370 ℃, under the condition that the temperature is 350-370 ℃, the drafting multiplying power of the filament is 3.0-3.6, the heat treatment time of the filament is 4-8 min, and the running speed of the filament is 160-480 cm/min;
(7) inputting the fibers subjected to heat treatment in the step (6) into a series heat treatment guide pipe, wherein the length of the fibers is 2x600mm, the fibers are connected in a V shape, the inner diameter of the heat treatment guide pipe is 60-80 mm, a yarn guide disc with the diameter of Ø 200 is installed at the bottom of the V shape, and a long seam which is 8mm convenient for feeding the fibers is cut in the axial direction of the series heat treatment guide pipe, wherein 6-8V-shaped heat treatment guide pipes are connected in series, normal-temperature carbon dioxide with the temperature of 20-30 ℃ is input into the heat treatment guide pipe along the strand silk moving direction, so that a solid-phase polymerized polyester fiber finished product containing nano-scale inorganic oxide powder is cooled to normal temperature in the series heat treatment guide pipe, and then the polyester liquid crystal fiber;
wherein the water content of the carbon dioxide is 0.001-0.003 wt%; the nano-scale inorganic oxide powder is silicon dioxide or titanium oxide; the particle size of the nano inorganic oxide powder is 3-6 nm.
2. The spinning process of polyester liquid crystal fiber according to claim 1, characterized in that: in the heat treatment process flow of the liquid crystal fiber, a 3-stage heat treatment process can be adopted, wherein the second stage and the third stage are connected in series and are in a continuous heat treatment process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711337994.6A CN108085771B (en) | 2017-12-14 | 2017-12-14 | Spinning process of polyester liquid crystal fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711337994.6A CN108085771B (en) | 2017-12-14 | 2017-12-14 | Spinning process of polyester liquid crystal fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108085771A CN108085771A (en) | 2018-05-29 |
| CN108085771B true CN108085771B (en) | 2020-05-22 |
Family
ID=62174373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711337994.6A Active CN108085771B (en) | 2017-12-14 | 2017-12-14 | Spinning process of polyester liquid crystal fibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108085771B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139547A (en) * | 2019-12-31 | 2020-05-12 | 上海普利特化工新材料有限公司 | Preparation method of wholly aromatic liquid crystal polyester nascent fiber |
| CN114134590B (en) * | 2021-12-30 | 2023-11-03 | 浙江甬川聚嘉新材料科技有限公司 | High-performance liquid crystal polyarylester fiber and preparation method and production equipment thereof |
| CN117328154B (en) * | 2023-11-24 | 2024-03-05 | 烟台泰和新材高分子新材料研究院有限公司 | Method and equipment for continuously producing liquid crystal polyester fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622384A (en) * | 2007-02-28 | 2010-01-06 | 东丽株式会社 | Liquid crystalline polyester fiber and process for production of the same |
| CN103459684A (en) * | 2011-03-29 | 2013-12-18 | 东丽株式会社 | Liquid crystal polyester fibers and method for producing same |
| CN102677198B (en) * | 2011-03-18 | 2015-01-21 | 四川得阳工程塑料开发有限公司 | Polyphenylene sulfide (PPS) nascent fiber drafting and setting technology |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014029038A (en) * | 2012-07-31 | 2014-02-13 | Toyobo Co Ltd | Method for manufacturing a fully aromatic polyester fiber |
| JP2016089308A (en) * | 2014-11-07 | 2016-05-23 | 東レ株式会社 | Manufacturing method of liquid crystal polyester fiber |
-
2017
- 2017-12-14 CN CN201711337994.6A patent/CN108085771B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622384A (en) * | 2007-02-28 | 2010-01-06 | 东丽株式会社 | Liquid crystalline polyester fiber and process for production of the same |
| CN102677198B (en) * | 2011-03-18 | 2015-01-21 | 四川得阳工程塑料开发有限公司 | Polyphenylene sulfide (PPS) nascent fiber drafting and setting technology |
| CN103459684A (en) * | 2011-03-29 | 2013-12-18 | 东丽株式会社 | Liquid crystal polyester fibers and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108085771A (en) | 2018-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108085771B (en) | Spinning process of polyester liquid crystal fibers | |
| CN101671854B (en) | Method for producing polyester industrial yarn by one-step method | |
| JP3655577B2 (en) | Method for producing polyethylene naphthalate fiber | |
| WO2018040690A1 (en) | Different-shrinkage composite yarn and preparation method therefor | |
| CN102947494A (en) | Ultra-high strength UHMW PE fibers and products | |
| CN105862152A (en) | Production method for high-speed spinning low-stretching high-modulus low-shrinkage polyester industrial filaments | |
| CN1221690C (en) | Production method of high strength polyethylene fibre and fibre | |
| JPH03119105A (en) | Preparation of polyethylene filament | |
| US3048467A (en) | Textile fibers of polyolefins | |
| CN111235649A (en) | Process method for spinning regenerated polyester filament yarn by utilizing recycled polyester bottle flakes | |
| CN108642584B (en) | Spinning and drawing combination machine for split-fiber female yarns | |
| JP6790121B2 (en) | Porous and ultrafine polyester fibers and their manufacturing methods | |
| CN111719192A (en) | Production method and system of nylon 66 antistatic fiber | |
| CN1407145A (en) | Polyester fibre manufacture | |
| WO2005059212A1 (en) | Method for producing polyester fiber and spinning mouth piece for melt spinning | |
| CN110295402B (en) | Preparation method of polyphenylene sulfide fiber | |
| CN102330159A (en) | Industrial yarn production process | |
| CN102277631B (en) | Preparation method of differential polyolefin fibers | |
| KR101810168B1 (en) | Manufacturing method of high strength synthetic fibers using high molecular weight thermoplastic polymer and synthetic fibers with high tenacity | |
| CN212128355U (en) | Multicomponent spinning manifold | |
| CN108004617A (en) | A kind of polyether-ether-ketone/polyether sulfone composite fibre and preparation method thereof | |
| CN109722718A (en) | A kind of manufacturing method of high strength industrial silk | |
| CN114232119A (en) | Preparation method of high-orientation yarn | |
| CN111118645A (en) | Preparation method of ultrahigh-strength polyformaldehyde fiber | |
| CN216919507U (en) | Preparation system of low-cost carbon fiber |
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 |