CN112663153B

CN112663153B - Porous moisture-permeable warm-keeping antistatic polyester fiber and preparation method thereof

Info

Publication number: CN112663153B
Application number: CN202011528084.8A
Authority: CN
Inventors: 赵金广; 吴立平; 王雨生; 倪凤军; 郭建洋; 赵慧娟
Original assignee: Jiangsu Deli Chemical Fiber Co Ltd
Current assignee: Jiangsu Deli Chemical Fiber Co Ltd
Priority date: 2020-12-22
Filing date: 2020-12-22
Publication date: 2022-05-24
Anticipated expiration: 2040-12-22
Also published as: CN112663153A

Abstract

The invention relates to a porous moisture-permeable warm-keeping antistatic polyester fiber and a preparation method thereof, wherein the raw material is antistatic modified polyester, and the process flow comprises a spinning DIO component filtering process and a cooling process; the spinning DIO component is a double-channel device; the cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt passes through a slow cooling zone, and enters a filter element in an annular blowing box for annular blowing cooling and then for side blowing cooling; the filter element in the circular blowing box is formed by sequentially sleeving an outer cylinder, a secondary inner cylinder and an inner cylinder; the upper end and the lower end between the outer cylinder and the inner cylinder are sealed by a high-temperature-resistant silica gel pad with a cap, and the outer cylinder and the secondary outer cylinder are fixed by a plurality of stainless steel support bars; two perforated plates which are parallel to each other and vertical to the spinneret plate surface are arranged in a filter element in the circular blowing box, and the two perforated plates are used for separating tows extruded from two areas on the spinneret plate; the final prepared fiber has high hollowness and good evenness.

Description

Porous moisture-permeable warm-keeping antistatic polyester fiber and preparation method thereof

Technical Field

The invention belongs to the technical field of functional polyester fibers, and particularly relates to a porous moisture-permeable warm-keeping antistatic polyester fiber and a preparation method thereof.

Background

The polyester fiber as the first large variety of chemical fiber has many excellent properties, such as high strength, good elasticity, weak acid and alkali resistance, wear resistance, fatigue resistance and the like, and is widely applied to clothing, home textile decoration, other industrial fields and the like. In recent years, with the continuous and rapid increase of Chinese economy and the continuous improvement of the consumption level of people, the demand on differentiation and functionality of polyester fibers is higher and higher, and the differentiation fibers of terylene are mainly expressed by various forms, performances and functions. The product is widely applied in the market at present, and mainly comprises the varieties of superfine denier, moisture absorption and sweat releasing, water resistance and moisture permeability, hollow heat preservation, antistatic property, electric conduction, ultraviolet resistance and the like. The development of differential varieties and the improvement of the added value of products so as to improve the economic benefit of enterprises are of great importance to the influence of the whole chemical fiber industry. On the whole, the polyester fiber industry in China also has great development potential, and product differentiation is the development direction of future polyester fibers.

The generation of porous moisture-permeable, warm-keeping and antistatic polyester fibers further promotes the development of fiber differentiation. The porous moisture-permeable warm-keeping antistatic polyester fiber adopts a plurality of special-shaped spinneret orifices, the requirements on a filament cooling and oiling device are higher, in the prior art, a circular air blowing cooling process is adopted, when two bundles of filaments in one filter element are cooled, process air is interfered with each other, filament cooling is easily uneven, and the filter element is easy to deform; as shown in fig. 7-8, the oiling of the oil nozzle and the guiding of the yarn guide hook 11 are separately performed in the oiling device in the prior art, the number of times of friction between the strand silk and the yarn guide ceramic piece is increased, a large part of monofilaments are not in direct contact (contact point 10) oiling agent when the yarn bundle is oiled in the oil nozzle, the overlapped part of the yarn bundle is more, static electricity is not completely eliminated, the shaking of the yarn bundle can be increased, uneven oiling is caused, the evenness of the yarn is poor, the hollowness is influenced, the influence on production and post-processing is huge, the product quality is reduced, the prepared fiber is poor in moisture permeability and heat preservation performance, static electricity resistance is difficult to maintain, and the like, so that a great deal of adverse influence is brought to the clothing woven in the subsequent process.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a porous moisture-permeable, warm-keeping and antistatic polyester fiber and a preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a preparation method of porous moisture-permeable warm-keeping antistatic polyester fiber adopts antistatic modified polyester as a raw material, the process flow comprises a spinning DIO component filtering process and a cooling process, the spinning DIO component is a double-channel device, two channels for filtering melt are arranged in a spindle component, two filter chambers respectively correspond to two areas on a spinneret plate, and two bundles of filaments are extruded by one spinneret plate;

the cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area, then enters a filter element in a circular blowing box for circular blowing cooling to keep higher hollowness, and then is subjected to side blowing cooling; the invention provides a cooling mode, and two-part cooling modes, namely circular blowing and side blowing, are adopted in the melt spinning process, so that the cooling uniformity of the strand silk is greatly improved;

the filter element in the circular blowing box is in a hollow cylindrical shape and is formed by sequentially sleeving an outer cylinder, a secondary inner cylinder and an inner cylinder; the outer cylinder is made of a stainless steel perforated plate, and the secondary outer cylinder, the secondary inner cylinder and the inner cylinder are made of 400-mesh stainless steel filter screens; the upper end and the lower end between the outer cylinder and the inner cylinder are sealed by a high-temperature-resistant silica gel pad with a cap, and the outer cylinder and the secondary outer cylinder are fixed by a plurality of stainless steel support bars; the filter elements are arranged in the circular blowing box side by side, fixed by a 3mm aluminum plate and connected with the bottom of the component through a sealing gasket; compared with the prior art, the stainless steel support bars are additionally arranged between the outer cylinder and the secondary outer cylinder in the filter element, the upper end and the lower end between the outer cylinder and the inner cylinder are sealed by the high-temperature-resistant silica gel pads with the caps, the filter element is not easy to deform, the upper end and the lower end have good sealing performance, circular blowing air is rectified by the stainless steel perforated plate of the outer cylinder and then uniformly blown to strand silk running in the filter element, the running stability of the strand silk is ensured, and the evenness of the strand silk is good;

A perforated plate vertical to the surface of the spinneret plate is arranged in the filter element in the circular blowing box, and one perforated plate can also be formed by longitudinally arranging two perforated plates, and the longitudinal distance between the two perforated plates is 2 mm; for separating the strands extruded from the two zones on the spinneret; the setting of perforated plate for two bundles of silk in the filter core are when cooling, and mutual interference is little, and the strand silk moves stably in the filter core, prevents to spout spun nascent fibre cooling inequality among the micropore, influences the hollowness.

As a preferable technical scheme:

according to the preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber, the length of the slow cooling area is 5-20 mm; the relative humidity of cooling air cooled by circular blowing is 80-90%, the air temperature is 15-19 ℃, and the air speed is 0.6-0.9 m/s; the height of the side-blown air chamber is 500-900 mm, the relative humidity of the cooling air is 60-80%, the air temperature is 19-21 ℃, and the air speed is 0.4-0.6 m/s; the length of a filter element in the circular blowing box is 100-200 mm, the distance between the outer cylinder and the secondary outer cylinder is 2-5 mm, and the distance between two adjacent cylinders in the secondary outer cylinder, the secondary inner cylinder and the inner cylinder is 0 mm.

The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber comprises the following process flows of oiling and guiding;

The oiling guide wire adopts a spiral full-contact type micropore oiling device;

the spiral full-contact type micropore oiling device comprises an oil pipe, a quick plug, a metal connecting rod and a spiral porcelain piece structure which are connected in sequence; the metal connecting rod is arranged on the spinning position oil frame; a first hollow channel is arranged in the metal connecting rod, a second hollow channel is arranged in the spiral porcelain piece structure, and the second hollow channel is communicated with the first hollow channel; the spiral part of the spiral porcelain piece structure forms a wire passing channel, one side of the spiral part close to the wire passing channel is a slope surface, an oil outlet and a plurality of layers of annular oil sumps are arranged on the slope surface, the oil outlet is positioned above the oil sumps, and the oil sumps are distributed around the wire passing channel; the oil outlet is communicated with the second hollow channel; the annular oil collecting groove is of a corrugated annular structure; preferably, the spiral porcelain piece structure and the metal connecting rod are integrated components; when oiling the guide wire, the spinning oil enters the second hollow channel through the oil pipe, the quick insertion and the first hollow channel, then reaches the position of the yarn passing channel, and is oiled for 360 degrees in a full-contact manner on the tows through the oil outlet and the oil collecting groove.

The invention adopts the design of a plurality of special-shaped spinneret micropores, is sensitive to the oil nozzle and the thread guide porcelain piece, if the oil nozzle of the oiling device in the prior art and the thread guide hook are separately guided and are a one-hole one-groove type oiling device, namely one oil outlet and one oil collecting tank, the friction times of the strand silk and the guide wire porcelain piece are increased, the strand silk overlapping part is more in the oil nozzle, a great part of monofilaments are not directly contacted with an oiling agent during oiling, the oiling is uneven, the evenness of the strand silk is poor, and the hollowness is influenced, the spiral full-contact type micropore oiling device is adopted in the invention, the strand oiling and the guide wire are integrated to oil and wet the strand silk, meanwhile, the oiling device with a spiral structure is adopted, the tows contact the oil outlet of the porcelain body by 360 degrees in the fiber passing channel to oil in all directions without dead angles, and the tows only contact the oil agent reflowing from the wave crest in the oil collecting tank in the fiber passing channel. The problem of porous silk have some monofilament at traditional glib oiling in-process and do not directly contact the finish, the silk bundle stack is more in oil outlet part, cause the oil uneven, influence the product quality is solved, and the number of times of the strand silk of surface polygon and the friction of seal wire porcelain spare have been reduced, spinning tension has been reduced, the homogeneity and the tension stability of oiling have greatly been improved, and then it is little to have guaranteed the structural difference between the fibre, and the cavity degree is high, has improved fibrous moisture permeability cold-proof antistatic properties.

The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber adopts the one-hole multi-groove oiling device, namely, the oil outlet and the oil collecting grooves are arranged. The length of the metal connecting rod is 3-4 cm, the diameter of the first hollow channel is 3-5 mm, the diameter of the second hollow channel is 3-5 mm, the aperture of the oil outlet is 0.3-0.5 mm, the annular oil collecting grooves in the plurality of layers are 10-15 layers, the drop value of the corrugated wave crests and the wave troughs is 0.003-0.05 mm, and the aperture of the wire passing channel is 2-4 mm;

the oiling agent adopted by the oiling guide wire comprises 2.5-10% of alpha-hydrogen-omega-hydroxy poly (oxy-1, 2-ethanediyl) mono- (10-16 alkyl ether potassium phosphate) and 2.5-10% of alpha-octadecenoyl-omega-octadecenoyloxy polyethylene oxide; the invention designs the oiling agent according to the characteristic of larger fiber surface area.

In the preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber, the spinning micropores on the spinneret plate are formed by two opposite W shapes

The spinning micropores adopt a structure of combining two opposite W shapes, the design of four curvature angles can form hollow fibers with fine grooves during spinning, the shape of the fine grooves is favorable for rapid cooling of the fibers and difficult deformation, and the moisture permeability and heat retention performance of the fibers are good; the tip ends of the two opposite W-shaped slits are aligned with the blowing direction of circular blowing, so that strand silk is cooled uniformly, the hollowness of the cross section of the fiber is high, the cross section of the modified porous polyester fiber is in a hollow shape formed by rhombus, if the conventional circular blowing or side blowing cooling is adopted, the strand silk is not easy to cool, the inside and the outside are cooled unevenly, the hollowness of the cross section of the fiber is low, and the warm-keeping antistatic property cannot be ensured; the W-shaped curve angle alpha is 30-60 degrees, the four side lengths L are 0.35-0.6 mm, the slit width W1 is 0.1-0.15 mm, the distance W2 between the two opposite W-shaped slit tips is 0.05-0.08 mm, the W-shaped curve angle is arranged on the W-shaped curve angle to form a fine groove after the primary fiber is spun out of a spinning micropore, the distance between the two opposite W-shaped slit tips can determine the hollow closing degree of the prepared fiber, when the distance between the two opposite W-shaped slit tips is proper, after the melt is extruded from the spinneret micropores, the melt is expanded at the tip, the end part is bonded to form a hollow cavity, hollow fibers are formed after thinning and solidification, when the distance between the two opposite W-shaped slit tips is too large, the hollow of the fiber can not be closed, only open fiber can be spun, when the distance between the tips of the two opposite W-shaped slits is too small, the melt is extruded out of the spinneret micropores and then is quickly expanded and bonded, so that a hollow cavity cannot be formed.

According to the preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber, the antistatic modified polyester is prepared by adding the antistatic agent in the pre-polycondensation reaction stage in the polyester synthesis process, the antistatic agent is added at a specific time, the antistatic agent can be combined with a polyester macromolecular chain in an embedding manner by utilizing the stronger adsorbability of the antistatic agent, and meanwhile, an antistatic agent layer is formed on the surface of the polyester macromolecular chain to form a uniform conductive channel, so that the friction electrostatic voltage can also reach 0.15kV and have conductivity in a dry environment with the temperature lower than 20 ℃ and the relative humidity lower than 35% while the hydrophilic performance of the antistatic fiber is increased; the antistatic agent in the prior art is added in an esterification stage, and is subjected to esterification reaction (or ester exchange reaction) and polycondensation reaction to prepare antistatic polyester master batches, then a process route of bi-component sheath-core composite spinning is adopted, conventional polyester chips are used as a sheath layer structure, the antistatic polyester master batches are used as a core layer, and the antistatic polyester fiber is prepared by crystallization → drying → screw extruder melt blending. The method has complex manufacturing flow, and is easy to adhere and agglomerate if the process conditions are not well controlled in the crystallization and drying processes, so that the crystallization is not uniform, the aggregation and the uneven distribution of the antistatic master batches are generated due to large viscosity fluctuation, and the antistatic effect is influenced. The invention has simple manufacturing process, adopts melt direct spinning preparation, has small viscosity fluctuation and can form uniform conductive channels.

According to the preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber, the preparation steps of the antistatic modified polyester are as follows:

(1) preparing antistatic slurry;

mixing an antistatic agent and ethylene glycol, grinding for a period of time, and stirring for a period of time to prepare antistatic slurry; the antistatic agent is easy to generate an agglomeration effect, so that the preparation of antistatic slurry is crucial to the distribution uniformity of the antistatic slurry in polyester and fibers, and the powder slurry directly adopts an ethylene glycol solvent, so that the ethylene glycol is one of the raw materials required by the reaction and cannot cause adverse effects on products;

(2) preparing ethylene terephthalate slurry;

mixing purified terephthalic acid and ethylene glycol, and stirring and mixing for a period of time at a certain temperature to prepare ethylene glycol terephthalate slurry; the specific process is as follows: separating terephthalic acid powder with a filter at the top of a bin by circulating nitrogen, feeding the terephthalic acid into a feeding hopper by virtue of gravity, metering by a screw feeder, and feeding into a slurry mixing tank; the ethylene glycol from the ethylene glycol storage tank enters the slurry mixing tank through the delivery pump; terephthalic acid and ethylene glycol are stirred and mixed into slurry in a mixing tank through a stirrer, and the slurry is conveyed into a slurry supply tank through a slurry conveying pump;

(3) Preparing ethylene terephthalate;

reacting the ethylene terephthalate slurry prepared in the step (2) at a certain temperature and a certain pressure until the end point of the esterification reaction to prepare ethylene terephthalate; specifically, the esterification reactor is composed of a heat exchanger and a vapor separator connected in series, wherein the heat exchanger is in the form of a tube, the vapor separator is provided with a jacket and has a volume of 34m³Gas phase heating medium is introduced into both the shell pass of the heat exchanger and the jacket of the vapor separator to provide heat required by the reaction; heating the slurry from the ethylene terephthalate supply tank from bottom to top of the heat exchanger through a slurry injection nozzle by a tube array, and performing esterification reaction by controlling reaction temperature and pressure;

(4) preparing antistatic modified polyester;

firstly, mixing the ethylene terephthalate prepared in the step (3) with a catalyst and a stabilizer, then carrying out a pre-polycondensation reaction, then adding the antistatic slurry prepared in the step (1) into a pre-polycondensation reaction system, stirring at a certain stirring speed for a period of time, and finally carrying out a final polycondensation reaction to prepare antistatic modified polyester; specifically, an online viscometer is arranged on a melt conveying pipeline, the vacuum degree of a final polymerization kettle is automatically adjusted according to the melt viscosity, the purpose of controlling the melt viscosity is achieved, and the online viscosity is controlled to be 0.650-0.675.

The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber comprises the following steps that in the step (1), the antistatic agent is nano-scale zinc oxide powder; the mass ratio of the antistatic agent to the glycol is 1: 20-30; grinding for a period of time, namely grinding for 30-60 min; stirring for a period of time means stirring for 8-10 hours; the slurry is ground for a short time and stirred and dispersed for a long time, so that the damage to the powder is avoided, the distribution uniformity of the powder in the slurry is effectively improved, and the prepared slurry is uniformly dispersed and has good storage stability due to good compatibility of the powder and the glycol solvent and proper powder density;

in the step (2), the molar ratio of the purified terephthalic acid to the ethylene glycol is 1: 1.1-2.0; the certain temperature is 85-110 ℃; the period of time is 2-3 hours; a pump outlet is provided with a densimeter which can continuously measure the density of the slurry, unqualified PTA slurry is returned to the slurry mixing tank for re-preparation through a circulating pipeline, and qualified PTA slurry is conveyed to a slurry injection nozzle of an esterification kettle through a feed pump to start esterification reaction;

the addition amount of the antistatic agent in the step (1) is 0.25-0.5 wt% of the addition amount of the purified terephthalic acid in the step (2);

in the step (3), the certain temperature is 265-275 ℃; the certain pressure is 0.2-0.5 bar; the esterification reaction end point is that the distillation of esterification water reaches more than 90 percent of a theoretical value;

In the step (4), the catalyst is ethylene glycol antimony or antimony triacetate, and the addition amount of the catalyst is 0.01-0.03 wt% of the addition amount of the purified terephthalic acid in the step (2); the stabilizer is triphenyl phosphite, trimethyl phosphate or triphenyl phosphate, and the addition amount of the stabilizer is 0.01-0.03 wt% of the addition amount of the purified terephthalic acid in the step (2); the temperature of the pre-polycondensation reaction is 265-270 ℃, the pressure is below 100mbar, and the time is 30-50 min; the certain stirring speed is 2-5 revolutions per minute; the period of time is 20-40 min; the temperature of the final polycondensation reaction is 272-285 ℃, the pressure is below 10mbar, and the time is 60-100 min.

The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber comprises the following specific process flows: conveying the antistatic modified polyester melt to a spinning box → metering by a melt metering pump → filtering by a spinning DIO assembly → extruding by a spinneret orifice → cooling → oiling and guiding filament → winding and forming;

the specific process of conveying the antistatic modified polyester melt to a spinning manifold comprises the following steps: firstly, filtering mechanical impurity particles with the diameter larger than 15-20 microns from an antistatic modified polyester melt by a melt filter, wherein the filter has the function of homogenizing the melt, then conveying the filtered antistatic modified polyester melt to a booster pump through a conveying pipeline with a static mixer arranged therein to increase the pressure, finally adjusting the temperature of the antistatic modified polyester melt to 283-286 ℃ by a melt heat exchanger, conveying the antistatic modified polyester melt to a spinning manifold with the temperature of 288-292 ℃ through a melt pipeline with the temperature of 284-288 ℃, and setting the temperature of the melt pipeline at 284-288 ℃ so as to reduce the degradation of the antistatic modified polyester melt in the pipeline; the static mixer is in an annular interchange shape, so that the antistatic modified polyester melt is fully mixed, the internal temperature of the antistatic modified polyester melt is ensured to be uniform, and the edge speed and the central speed of the antistatic modified polyester melt flowing in a pipeline can be consistent so as to avoid the degradation of the antistatic modified polyester melt in the pipeline;

The initial pressure of the spinning DIO component filtration is more than or equal to 150 Bar;

all spinneret orifices are arranged in a concentric circle shape and are symmetrically distributed in two areas on the spinneret plate, the spinneret guide holes in each area are arranged in a half-moon shape (the half-moon shape is half of a round moon), and the spinneret micropores and the spinneret guide holes are arranged correspondingly;

the specific process of winding and forming comprises the following steps: the oiled filament bundle enters a spinning channel to a pre-network, is drafted and shaped by a hot roller, and is wound and formed after passing through a main network; the technological parameters of the winding forming are as follows: the pre-network pressure is 0.05-0.08 MPa, the main network pressure is 0.30-0.38 MPa, the speed of a drawing roller is 2500-3000 m/min, the temperature is 78-85 ℃, the speed of a shaping roller is 3800-4400 m/min, the temperature is 118-122 ℃, the winding speed is 3700-4300 m/min, and the contact pressure of a winding head is 220-250N.

The invention also provides the porous moisture-permeable warm-keeping antistatic polyester fiber prepared by the preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber, wherein the number of monofilaments in one bundle of filaments is more than or equal to 72; cross section of monofilament

Shape (half of the cross section is rhombic hollow); the antistatic polyester fiber mainly comprises a polyester fiber matrix and an antistatic agent dispersed in the polyester fiber matrix, wherein the antistatic agent is combined with a polyester molecular chain in an inlaying mode;

Porous moisture-permeable warm-keeping antistatic polyester fiberThe filament number is 0.3-1.5 dtex, the breaking strength is more than or equal to 3.6cN/dtex, the elongation at break is 32 +/-4%, the deviation rate of linear density is less than or equal to 1.0%, the CV value of the breaking strength is less than or equal to 4.5%, the CV value of the elongation at break is less than or equal to 9.0%, the CV value of the yarn evenness unevenness is less than or equal to 2.0%, the oil content is 1.1 +/-0.2%, the hollowness is 25-35%, the moisture regain is 0.85-1.15%, and the resistivity is 3 multiplied by 10⁷～6×10⁷Ω·cm。

The polyester fiber raw material of the invention is antistatic modified polyester, mainly through the porous number, melt spinning, monofilament cross-sectional half appear rhombic hollow method to prepare, capillary phenomenon that the surface of fiber produced forms the fine groove to produce while being polygonal can make the sweat absorb moisture rapidly in the superficial layer of skin and sweat through the wicking, diffusion and transmission function, and transmit and diffuse to the surface of the cloth, even in the humid environment, can keep clothes dry and comfortable and pleasant, in addition, the special hollow fiber cross-section, the empty part has the function of obstructing the circulation of air, prevent the invasion of cold air, and add the nanometer material of antistatic in the production, can give the fiber to have moisture permeable and warm keeping and antistatic performance combination. The product can be widely applied to thermal underwear, high-collar sports wear, various outer garments, sleeping bag lining and the like.

Has the advantages that:

(1) the spinning DIO component is a double-channel device, two channels for filtering melt are arranged in a spindle component, two filtering chambers respectively correspond to two areas on a spinneret plate, two bundles of filaments are extruded by one spinneret plate, and spinneret micropores on the spinneret plate are formed by two opposite W shapes

The polyester fiber with hollow section formed by rhombus can be prepared by the shape structure, and the moisture permeability and the heat retention performance are more excellent;

(2) all spinneret orifices on the spinneret plate are arranged in a concentric circle shape and symmetrically distributed in two areas on the spinneret plate, and the spinneret orifices in each area are arranged in a half-moon shape, so that compared with the spinneret orifices arranged in a circular shape, the spinneret plate is more beneficial to cooling inner layer tows by circular blowing and improving the hollowness of fibers;

(3) in the melt spinning process, two cooling modes, namely circular blowing and side blowing, are adopted, nascent fibers are extruded through a spinneret orifice and then pass through a slow cooling area of 5-20 mm, and enter a filter element in a circular blowing box for rapid cooling forming, so that high hollowness is kept, and the fibers are subjected to primary cooling and then are subjected to slow cooling through side blowing, so that the hollowness of the fibers is improved;

(4) the porous moisture-permeable warm-keeping antistatic polyester fiber prepared by the invention is made of antistatic modified polyester, and when the antistatic agent and PET macromolecules are in mosaic distribution, an antistatic agent layer is formed on the surface of a macromolecule chain to form a conducting layer channel, so that the antistatic fiber has conducting property while the moisture permeability of the hollow fiber is improved;

(5) The antistatic modified polyester prepared by the invention has the advantages that due to the addition of the antistatic agent, the flexibility of a molecular chain is increased, the entropy change Delta S is increased, the viscosity of a melt is reduced, the spinning preparation performance is favorably improved, and meanwhile, the antistatic modified polyester can be used as a nucleating agent, the crystallization of polyester fibers is promoted, the solidification speed of the fibers is increased, the shape-preserving effect of the fibers is further improved, and the excellent performance of the polyester fibers is maintained;

(6) the porous moisture-permeable warm-keeping antistatic polyester fiber prepared by the invention has the advantages of light weight, warm keeping, high moisture absorption, cotton touch, softness, comfort and antistatic effect, and can be widely applied to warm-keeping underwear, high-collar sportswear, various outer garments, sleeping bag lining cloth and the like.

Drawings

FIG. 1 is a distribution diagram of the spinning orifices in a spinneret;

FIG. 2 is a distribution diagram of spinneret plate holes on a spinneret plate;

FIG. 3 is a schematic view of the shape of the spinneret micro-holes;

FIG. 4 is a schematic representation of a cross-section of a fiber;

FIG. 5 is a schematic structural diagram of a spiral full-contact type micropore oiling device;

FIG. 6 is a schematic view of the porcelain piece spiral structure of FIG. 5;

FIG. 7 is a schematic diagram of a prior art oiling device;

FIG. 8 is a schematic view of a prior art guidewire hook;

the device comprises an oil pipe 1, a quick plug 2, a metal connecting rod 3, a first hollow channel 4, a second hollow channel 5, a wire passing channel 6, a spiral ceramic part structure 7, an oil outlet hole 8, an oil collecting groove 9, a strand silk and oil nozzle contact point 10 and a yarn guide hook 11.

Detailed Description

The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

The spinning DIO components in the embodiments 1-6 are dual-channel devices, two channels for filtering melts are arranged in one spindle component, two filter chambers respectively correspond to two areas on a spinneret plate, and two bundles of filaments are extruded by one spinneret plate; as shown in fig. 1 to 3, all the spinneret orifices are arranged in concentric circles and symmetrically distributed in two areas on the spinneret plate; the spinneret pores on the spinneret are formed by two opposite W shapes

A shape structure; the two opposite W-shaped slit tips are aligned with the blowing direction of the circular blowing air; the W-shaped curve angle alpha is 30-60 degrees, the four side lengths L are 0.35-0.6 mm, the slit width W1 is 0.1-0.15 mm, and the distance W2 between the tips of two opposite W-shaped slits is 0.05-0.08 mm; the specific parameters in the various examples are not exactly the same, as shown in the following table.

Parameter(s)	Unit	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
								W curvature angle a	°	60	35	30	50	30	40
Side length L	mm	0.35	0.45	0.60	0.40	0.50	0.55
								Slit width W1	mm	0.1	0.12	0.15	0.11	0.13	0.14
W2	mm	0.05	0.065	0.075	0.06	0.07	0.08

The filter elements in the circular blowing box in the embodiments 1 to 6 are all in a hollow cylindrical shape, the length of each filter element is 100-200 mm, each filter element is formed by sequentially sleeving an outer cylinder, a secondary inner cylinder and an inner cylinder, the distance between the outer cylinder and the secondary outer cylinder is 2-5 mm, and the distance between two adjacent cylinders in the secondary outer cylinder, the secondary inner cylinder and the inner cylinder is 0 mm; the outer cylinder is made of a stainless steel perforated plate, and the secondary outer cylinder, the secondary inner cylinder and the inner cylinder are made of 400-mesh stainless steel filter screens; the upper end and the lower end between the outer cylinder and the inner cylinder are sealed by a high-temperature-resistant silica gel pad with a cap, and the outer cylinder and the secondary outer cylinder are fixed by a plurality of stainless steel support bars; a porous plate vertical to the surface of the spinneret plate is arranged in the filter element in the circular blowing box and is used for separating tows extruded from two areas on the spinneret plate; the specific parameters in the various examples are not exactly the same, as shown in the following table.

Parameter(s)	Unit of	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
								Length of filter element	mm	100	150	200	120	150	180
Distance between secondary cylinders	mm	2	2	2	4	5	5

The oiling guide wire in the embodiments 1-6 adopts a spiral full-contact type micropore oiling device, as shown in the figures 5-6; the spiral full-contact type micropore oiling device comprises an oil pipe 1, a quick insert 2, a metal connecting rod 3 and a spiral porcelain piece structure which are connected in sequence; the metal connecting rod is arranged on the spinning position oil rack and is 3-4 cm long; a first hollow channel 4 with the diameter of 3-5 mm is arranged in the metal connecting rod, a second hollow channel 5 with the diameter of 3-5 mm is arranged in the spiral porcelain piece structure, and the second hollow channel is communicated with the first hollow channel; a wire passing channel 6 (the aperture is 2-4 mm) is formed in the spiral part of the spiral porcelain piece structure 7, a slope surface is formed on one side of the spiral part close to the wire passing channel, multiple layers (10-15 layers) of annular oil collecting grooves (the difference value between the wave crest and the wave trough of the wave form is 0.003-0.05 mm) and oil outlet holes 8 (0.3-0.5 mm) which are in a wave form annular structure are arranged on the slope surface, a ring formed by the oil outlet holes is positioned above the oil collecting groove 9, and the oil outlet holes and the oil collecting grooves are distributed around the wire passing channel; the oil outlet is communicated with the second hollow channel. The specific parameters in the various examples are not exactly the same, as shown in the following table.

Parameter(s)	Unit of	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
								Length of metal connecting rod	cm		3	3	4	4	4	4
First hollow lane diameter	mm		3	5	4	4	5										5
								Second hollow lane diameter	mm		3	5	4	4	5	5
Bore diameter of wire passing channel	mm	2	4	4	3	4	4
								Number of ripples	Layer(s)	10	15	14	11	13	15
Crest and trough fall value	mm	0.003	0.003	0.003	0.03	0.04	0.05
								Diameter of oil outlet hole	mm	0.3	0.3	0.5	0.3	0.4	0.5

Example 1

A preparation method of porous moisture-permeable warm-keeping antistatic polyester fiber comprises the following specific process flows: conveying the antistatic modified polyester melt to a spinning box → metering by a melt metering pump → filtering by a spinning DIO assembly → extruding by a spinneret orifice → cooling → oiling and guiding filament → winding and forming; the preparation steps of the antistatic modified polyester are as follows:

(1) preparing antistatic slurry;

mixing an antistatic agent (nano-scale zinc oxide powder) and ethylene glycol in a mass ratio of 1:20, grinding for 30min, and stirring for 8h to prepare antistatic slurry;

(2) preparing ethylene terephthalate slurry;

mixing purified terephthalic acid and ethylene glycol according to a molar ratio of 1:1.2, and stirring and mixing for 2 hours at 85 ℃ to prepare ethylene glycol terephthalate slurry;

the addition amount of the antistatic agent in the step (1) is 0.25 wt% of the addition amount of the purified terephthalic acid in the step (2);

(3) preparing ethylene terephthalate;

reacting the ethylene terephthalate slurry prepared in the step (2) at 265 ℃ and 0.2bar until the distilled water of esterification reaches 90 of a theoretical value to prepare ethylene terephthalate;

(4) Preparing antistatic modified polyester;

firstly, mixing the ethylene glycol terephthalate prepared in the step (3) with a catalyst (ethylene glycol antimony, the addition amount of which is 0.015 wt% of the addition amount of the terephthalic acid in the step (2)) and a stabilizer (triphenyl phosphate, the addition amount of which is 0.01 wt% of the addition amount of the terephthalic acid in the step (2)), carrying out a pre-polycondensation reaction (the temperature is 265 ℃, the pressure is 100mbar and the time is 30min), then adding the antistatic slurry prepared in the step (1) into a pre-polycondensation reaction system, stirring at a stirring speed of 2.5 revolutions per minute for 20min, and finally carrying out a final polycondensation reaction (the temperature is 275 ℃, the pressure is 9mbar and the time is 60min) to prepare the antistatic modified polyester;

the specific process of conveying the prepared antistatic modified polyester melt to a spinning manifold comprises the following steps: firstly, filtering an antistatic modified polyester melt by a melt filter to remove mechanical impurity particles with the diameter larger than 15 mu m, then conveying the filtered antistatic modified polyester melt to a booster pump by a conveying pipeline internally provided with an annular cross-shaped static mixer to increase the pressure, finally adjusting the temperature of the antistatic modified polyester melt to 284 ℃ by a melt heat exchanger, and conveying the antistatic modified polyester melt to a spinning manifold with the temperature of 288 ℃ by a melt pipeline with the temperature of 284 ℃; the initial pressure of the spinning DIO component during filtration is 150 Bar;

The cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area with the length of 5mm, then enters a filter element in a circular blowing box to be cooled by circular blowing (the relative humidity of cooling air is 80%, the air temperature is 16 ℃, and the air speed is 0.6m/s), and then is cooled by side blowing (the height of an air chamber cooled by side blowing is 600mm, the relative humidity of cooling air is 60%, the air temperature is 19 ℃, and the air speed is 0.4 m/s);

the oiling agent adopted by the oiling guide wire comprises 2.5 percent (mass fraction) of alpha-hydro-omega-hydroxy poly (oxy-1, 2-ethanediyl) mono- (10-16 alkyl ether potassium phosphate) and 5 percent (mass fraction) of alpha-octadecenoyl-omega-octadecenoyloxy polyethylene oxide;

the specific process of winding and forming comprises the following steps: the oiled filament bundle enters a spinning channel to a pre-network, is drafted and shaped by a hot roller, and is wound and formed after passing through a main network; the technological parameters of the winding forming are as follows: the pre-network pressure, the main network pressure, the speed of the drafting roller, the temperature of the drafting roller, the speed of the setting roller, the temperature of the setting roller, the winding speed and the contact pressure of a winding head, and the specific parameter values are shown in table 1;

in the finally prepared porous moisture-permeable, warm-keeping and antistatic polyester fiber, the number of monofilaments in one bundle of filaments is shown in table 1; as shown in fig. 4, the monofilaments are in cross-section

Shaping; the antistatic polyester fiber mainly comprises a polyester fiber matrix and an antistatic agent dispersed in the polyester fiber matrix, wherein the antistatic agent is combined with a polyester molecular chain in an inlaying mode; the performance indexes of the porous moisture-permeable, warm-keeping and antistatic polyester fiber are shown in table 2.

Comparative example 1

A method for preparing porous moisture-permeable, warm-keeping and antistatic polyester fiber, which is basically the same as the method in the embodiment 1, and is different only in a cooling process, wherein the cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area (the length is the same as that of the embodiment 1), and then enters a filter element in an annular blowing box for annular blowing cooling (the relative humidity, the wind temperature and the wind speed of cooling wind are the same as those of the embodiment 1); the filter element in the circular blowing box is in a hollow cylindrical shape, the length of the filter element is the same as that of the filter element in embodiment 1, the filter element is formed by sequentially sleeving an outer cylinder, a secondary inner cylinder and an inner cylinder, the distance between the outer cylinder and the secondary outer cylinder is the same as that of embodiment 1, and the distance between two adjacent cylinders in the secondary outer cylinder, the secondary inner cylinder and the inner cylinder is 0 mm; the outer cylinder is made of a stainless steel perforated plate, and the secondary outer cylinder, the secondary inner cylinder and the inner cylinder are made of 400-mesh stainless steel filter screens; the upper end and the lower end between the outer cylinder and the inner cylinder are sealed by a high-temperature-resistant silica gel pad with a cap, and the outer cylinder and the secondary outer cylinder are fixed by a plurality of stainless steel support bars; a perforated plate is mounted in the filter element in the annular blowing box and is perpendicular to the plane of the spinneret plate, and is used for separating the filament bundles extruded from the two areas on the spinneret plate.

In the finally prepared porous moisture-permeable warm-keeping antistatic polyester fiber, the number of monofilaments in a bundle of filaments is 72, and the cross section of each monofilament is of a cross section shape

Shaping; the antistatic polyester fiber mainly comprises a polyester fiber matrix and an antistatic agent dispersed in the polyester fiber matrix, wherein the antistatic agent is combined with a polyester molecular chain in an inlaying mode; the single fiber fineness was 0.7dtex, the breaking strength was 3.60cN/dtex, the elongation at break was 28%, the linear density deviation ratio was 0.95%, the breaking strength CV value was 5.0%, the elongation at break CV value was 6.5%, the yarn evenness CV value was 2.1%, the oil content was 1.01%, the degree of hollowness was 20%, the moisture regain was 0.65%, and the resistivity was 4X 10⁷Ω·cm。

Compared with the example 1, the hollowness of the fiber of the comparative example 1 is much lower than that of the example 1, because the melt is extruded from the spinneret holes on the spinneret plate and is slowly cooled by circular blowing in the process of preparing the porous moisture-permeable warm-keeping antistatic polyester fiber, and the irregular cross section has larger specific surface area than the strand with the circular cross section, so that the strand is not uniformly cooled, the unevenness of the strand is high, and the hollowness of the fiber is small.

Comparative example 2

The method of porous moisture permeable, warm keeping and antistatic polyester fiber is basically the same as that in the embodiment 1, except that a porous plate vertical to the spinneret surface is not installed in a filter element in a circular air box in the cooling process.

In the finally prepared porous moisture-permeable warm-keeping antistatic polyester fiber, the number of monofilaments of one bundle of filaments is 72, and the cross section of each monofilament is of a cross section shape

Shaping; the antistatic polyester fiber mainly comprises a polyester fiber matrix and an antistatic agent dispersed in the polyester fiber matrix, wherein the antistatic agent is combined with a polyester molecular chain in an inlaying mode; single filament number of 0.7dtex, breaking strength of 3.75cN/dtex, elongation at break of 30%, linear densityDeviation ratio of 1.0%, breaking strength CV value of 5.5%, elongation at break CV value of 9%, yarn evenness CV value of 2.3%, oil content of 1.12%, degree of hollowness of 23%, moisture regain of 0.75%, resistivity of 5X 10⁷Ω·cm。

Compared with the embodiment 1, the hollowness of the comparative example 2 is far lower than that of the embodiment 1, and the unevenness of the fiber evenness is far higher than that of the embodiment 1, because when the two bundles of primary fibers from the DIO spinning assembly are cooled by circular blowing, turbulent flow is easily formed between the two bundles of filaments due to high process air pressure, the filaments greatly shake in the filter element to influence the cooling effect, and the prepared fiber evenness, the hollowness, the moisture regain and the heat retention performance are poor.

Comparative example 3

A method for preparing porous moisture-permeable, warm-keeping and antistatic polyester fibers, which is basically the same as that in example 1, and is different from the method only in a device for oiling and guiding yarns, wherein the device comprises an oiling device and a guiding device, the oiling device is used for oiling and wetting yarns, and the guiding device is used for changing the moving direction of the yarns; the oiling device comprises an oil pipe 1, a metal rod 3, a first hollow channel 4, an oil outlet 8, an oil collecting tank 9 and an oiling nozzle which adopt a circular oil outlet 8 and a circular oil collecting tank 9; the oil agent flows out from the oil pipe 1 to an oil outlet 8 in the oil nozzle through a first hollow channel 4 in the metal rod 3; when the strand silk passes through the oiling device, the strand silk is bunched and oiled with the contact point of the oil nozzle at a position 10 between the oil outlet 8 and the oil collecting groove 9, and after oiling is finished, the strand silk enters the channel through the yarn guide device 11.

In the finally prepared porous moisture-permeable warm-keeping antistatic polyester fiber, the number of monofilaments in a bundle of filaments is 72, and the cross section of each monofilament is of a cross section

Shaping; the antistatic polyester fiber is mainly composed of a polyester fiber matrix and an antistatic agent dispersed in the polyester fiber matrix, wherein the antistatic agent is combined with a polyester molecular chain in an embedding manner; the fineness of the single fiber was 0.7dtex, the breaking strength was 3.70cN/dtex, the elongation at break was 29%, the deviation ratio of linear density was 0.9%, the CV value of the breaking strength was 6.0%, the CV value of the elongation at break was 11%, the CV value of the yarn evenness unevenness was 2.51%, the oil content was 0.8%, the degree of hollowness was 25%, and the recoveryMoisture content of 0.80%, resistivity of 4X 10⁷Ω·cm。

Compared with the embodiment 1, the evenness of the comparative example 3 is far higher than that of the embodiment 1, and the oil content and the hollowness are far lower than those of the embodiment 1, because the oiling device adopts a hole-groove type, namely a circular oil outlet and a circular oil collecting groove, the overlapping part of the strand silk is more during oiling, only one circular backflow oil collecting groove is arranged for supplying oiling to the strand silk, the oiling uniformity and the spinning tension stability are poor, the structural difference among fibers is large, after the strand silk is drawn and shaped, the prepared fiber evenness is high, the oil content is low, the hollowness is small, the moisture regain is low, and the moisture permeability and heat insulation performance of the fiber are affected.

Comparative example 4

A method for preparing porous moisture-permeable, warm-keeping and antistatic polyester fiber is basically the same as that in example 1, except that the micropores on the spinneret plate are formed by two opposite C shapes

The shape structure, C shape external diameter is 1.3mm, and the internal diameter is 0.9mm, and the slit width is 0.11mm, and the space between two C is 0.002 mm.

In the finally prepared porous moisture-permeable warm-keeping antistatic polyester fiber, the number of monofilaments in one bundle of filaments is 72, and the cross section of each monofilament is 8-shaped; the antistatic polyester fiber mainly comprises a polyester fiber matrix and an antistatic agent dispersed in the polyester fiber matrix, wherein the antistatic agent is combined with a polyester molecular chain in an inlaying mode; the single fiber fineness was 0.7dtex, the breaking strength was 4.1cN/dtex, the elongation at break was 39%, the linear density deviation ratio was 0.95%, the breaking strength CV value was 4.0%, the elongation at break CV value was 5.5%, the yarn evenness CV value was 2.2%, the oil content was 0.95%, the degree of hollowness was 21%, the moisture regain was 0.45%, and the resistivity was 5X 10⁷Ω·cm。

The degree of hollowness and moisture regain of comparative example 4 are much lower than those of example 1 compared to example 1, because the micro-pore design on the spinneret consists of two opposite C-shapes

A shape structure in which there are only twoGaps are formed at the openings of the C-shaped structure and the C-shaped structure, and the rest parts are designed in a circular arc shape, so that compared with two opposite W-shaped structures with four curvature angles, the cooling effect of the strand silk is poor, the hollowness of the cross section of the prepared fiber is small, the moisture regain is low, and the moisture permeability and heat retention performance are poor.

Comparative example 5

The method for preparing the porous moisture-permeable warm-keeping antistatic polyester fiber is basically the same as that in example 1, and only comprises the following steps of preparing the antistatic modified polyester:

(1) preparing antistatic polyester slurry;

mixing an antistatic agent (nano-scale zinc oxide powder) and ethylene glycol in a mass ratio of 1:20, and then melting and blending to prepare polyester antistatic slurry;

(2) preparing ethylene terephthalate slurry;

the same as example 1;

(3) preparing ethylene terephthalate;

adding the polyester antistatic slurry prepared in the step (1) into the ethylene terephthalate slurry prepared in the step (2), and then performing esterification reaction (the temperature, the pressure and the termination conditions are the same as those in the example 1) to prepare ethylene terephthalate;

(4) preparing antistatic modified polyester master batch;

mixing the ethylene terephthalate prepared in the step (3) with a catalyst (the type and the adding amount of the catalyst are the same as those in the embodiment 1) and a stabilizer (the type and the adding amount of the stabilizer are the same as those in the embodiment 1), then carrying out a pre-polycondensation reaction (the temperature, the pressure and the time are the same as those in the embodiment 1), and then carrying out a final polycondensation reaction (the temperature, the pressure and the time are the same as those in the embodiment 1) to prepare the antistatic modified polyester master batch;

(5) Preparing porous moisture-permeable warm-keeping antistatic polyester fiber;

the method adopts a process route of bi-component sheath-core composite spinning, uses conventional polyester chips as a sheath structure, uses antistatic polyester master batches as a core layer, and prepares the antistatic polyester fiber through crystallization → drying → screw extruder melt blending.

Finally prepared porous moisture-permeable warm-keeping antistatic polyester fiberIn the bundle of filaments, the number of the monofilaments is 72, and the cross section of the monofilaments is shaped

Shaping; the single fiber fineness was 0.7dtex, the breaking strength was 3.0cN/dtex, the elongation at break was 37%, the linear density deviation ratio was 0.9%, the breaking strength CV value was 5.0%, the elongation at break CV value was 7.0%, the yarn evenness CV value was 2.0%, the oil content was 1.05%, the degree of hollowness was 28%, the moisture regain was 1.05%, and the resistivity was 2X 10⁷Ω·cm。

Compared with the example 1, the fiber breaking strength of the comparative example 5 is much lower than that of the example 1, because the moisture-permeable, warm-keeping and antistatic polyester fiber is different from the example 1 in the preparation process flow, the antistatic master batch is prepared first, and then the polyester fiber with the skin-core layer structure is prepared by blending the antistatic master batch with the conventional polyester chip.

Example 2

(1) Preparing antistatic slurry;

mixing an antistatic agent (nano-scale zinc oxide powder) and ethylene glycol in a mass ratio of 1:25, grinding for 50min, and stirring for 9h to prepare antistatic slurry;

(2) preparing ethylene terephthalate slurry;

mixing purified terephthalic acid and ethylene glycol according to a molar ratio of 1:1.5, and stirring and mixing for 2 hours at 95 ℃ to prepare ethylene glycol terephthalate slurry;

the addition amount of the antistatic agent in the step (1) is 0.35 wt% of the addition amount of the purified terephthalic acid in the step (2);

(3) preparing ethylene terephthalate;

reacting the ethylene terephthalate slurry prepared in the step (2) at 270 ℃ and 0.28bar until the distilled water of esterification reaches 90 of a theoretical value to prepare ethylene terephthalate;

(4) preparing antistatic modified polyester;

firstly, mixing the ethylene glycol terephthalate prepared in the step (3) with a catalyst (ethylene glycol antimony, the addition amount of which is 0.02 wt% of the addition amount of the purified terephthalic acid in the step (2)) and a stabilizer (triphenyl phosphate, the addition amount of which is 0.02 wt% of the addition amount of the purified terephthalic acid in the step (2)), carrying out a pre-polycondensation reaction (the temperature is 268 ℃, the pressure is 95mbar, and the time is 40min), then adding the antistatic slurry prepared in the step (1) into a pre-polycondensation reaction system, stirring at a stirring speed of 3 revolutions per minute for 30min, and finally carrying out a final polycondensation reaction (the temperature is 280 ℃, the pressure is 8mbar, and the time is 80min) to prepare the antistatic modified polyester;

The specific process of conveying the prepared antistatic modified polyester melt to a spinning manifold comprises the following steps: firstly, filtering an antistatic modified polyester melt by a melt filter to remove mechanical impurity particles with the diameter larger than 17 mu m, then conveying the filtered antistatic modified polyester melt to a booster pump by a conveying pipeline internally provided with an annular interchange-shaped static mixer to increase the pressure, finally adjusting the temperature of the antistatic modified polyester melt to 285 ℃ by a melt heat exchanger, and conveying the antistatic modified polyester melt to a spinning manifold with the temperature of 290 ℃ by a melt pipeline with the temperature of 286 ℃; the initial pressure of the spinning DIO component during filtration is 160 Bar;

the cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area with the length of 5mm, then enters a filter element in an annular blowing box to be cooled by annular blowing (the relative humidity of cooling air is 85%, the air temperature is 17 ℃, and the air speed is 0.8m/s), and then is cooled by side blowing (the height of an air chamber cooled by side blowing is 800mm, the relative humidity of cooling air is 70%, the air temperature is 21 ℃, and the air speed is 0.5 m/s);

the oiling agent adopted by the oiling guide wire comprises 5 percent (mass fraction) of alpha-hydrogen-omega-hydroxy poly (oxy-1, 2-ethanediyl) mono- (10-16 alkyl ether potassium phosphate) and 7.5 percent (mass fraction) of alpha-octadecenoyl-omega-octadecenoyloxy polyethylene oxide;

in the finally prepared porous moisture-permeable, warm-keeping and antistatic polyester fiber, the number of monofilaments in one bundle of filaments is shown in table 1; cross section of monofilament

Example 3

(1) preparing antistatic slurry;

mixing an antistatic agent (nano-scale zinc oxide powder) and ethylene glycol in a mass ratio of 1:30, grinding for 60min, and stirring for 10h to prepare antistatic slurry;

(2) Preparing ethylene terephthalate slurry;

mixing purified terephthalic acid and ethylene glycol in a molar ratio of 1:2, and stirring and mixing for 2 hours at 110 ℃ to prepare ethylene glycol terephthalate slurry;

the addition amount of the antistatic agent in the step (1) is 0.45 wt% of the addition amount of the purified terephthalic acid in the step (2);

(3) preparing ethylene terephthalate;

reacting the ethylene terephthalate slurry prepared in the step (2) at 275 ℃ and 0.4bar until the distilled water of esterification reaches 90 of a theoretical value to prepare ethylene terephthalate;

(4) preparing antistatic modified polyester;

firstly, mixing the ethylene glycol terephthalate prepared in the step (3) with a catalyst (ethylene glycol antimony, the adding amount of which is 0.03 wt% of the adding amount of the purified terephthalic acid in the step (2)) and a stabilizer (triphenyl phosphate, the adding amount of which is 0.03 wt% of the adding amount of the purified terephthalic acid in the step (2)), carrying out a pre-polycondensation reaction (the temperature is 270 ℃, the pressure is 90mbar, and the time is 50min), then adding the antistatic slurry prepared in the step (1) into a pre-polycondensation reaction system, stirring at a stirring speed of 5 r/min for 40min, and finally carrying out a final polycondensation reaction (the temperature is 285 ℃, the pressure is 5mbar, and the time is 100min) to prepare the antistatic modified polyester;

The specific process of conveying the prepared antistatic modified polyester melt to a spinning manifold comprises the following steps: firstly, filtering an antistatic modified polyester melt by a melt filter to remove mechanical impurity particles with the diameter larger than 20 mu m, then conveying the filtered antistatic modified polyester melt to a booster pump by a conveying pipeline internally provided with an annular cross-shaped static mixer to increase the pressure, finally adjusting the temperature of the antistatic modified polyester melt to 286 ℃ by a melt heat exchanger, and conveying the antistatic modified polyester melt to a spinning manifold with the temperature of 291 ℃ by a melt pipeline with the temperature of 287 ℃; the initial pressure during the filtration of the spinning DIO component is 175 Bar;

the cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area with the length of 10mm, then enters a filter element in an annular blowing box to be cooled by annular blowing (the relative humidity of cooling air is 90%, the air temperature is 19 ℃, and the air speed is 0.9m/s), and then is cooled by side blowing (the height of an air chamber cooled by side blowing is 900mm, the relative humidity of cooling air is 80%, the air temperature is 21 ℃, and the air speed is 0.6 m/s);

the oiling agent adopted by the oiling guide wire comprises 10 percent (mass fraction) of alpha-hydrogen-omega-hydroxy poly (oxy-1, 2-ethanediyl) mono- (10-16 alkyl ether potassium phosphate) and 10 percent (mass fraction) of alpha-octadecenoyl-omega-octadecenoyloxy polyethylene oxide;

The specific process of winding and forming comprises the following steps: the oiled filament bundle enters a spinning channel to a pre-network, is drafted and shaped by a hot roller, and is wound and formed after passing through a main network; the winding forming process parameters are as follows: the pre-network pressure, the main network pressure, the speed of the drafting roller, the temperature of the drafting roller, the speed of the setting roller, the temperature of the setting roller, the winding speed and the contact pressure of a winding head, and the specific parameter values are shown in table 1;

Example 4

(1) preparing antistatic slurry;

mixing an antistatic agent (nano-scale zinc oxide powder) and ethylene glycol in a mass ratio of 1:20, grinding for 40min, and stirring for 8h to prepare antistatic slurry;

(2) Preparing ethylene terephthalate slurry;

mixing purified terephthalic acid and ethylene glycol according to a molar ratio of 1:1.1, and stirring and mixing for 3 hours at 85 ℃ to prepare ethylene glycol terephthalate slurry;

the addition amount of the antistatic agent in the step (1) is 0.28 wt% of the addition amount of the purified terephthalic acid in the step (2);

(3) preparing ethylene terephthalate;

reacting the ethylene terephthalate slurry prepared in the step (2) at 275 ℃ and 0.2bar until the distilled water of esterification reaches 95 of a theoretical value to prepare ethylene terephthalate;

(4) preparing antistatic modified polyester;

firstly, mixing the ethylene glycol terephthalate prepared in the step (3) with a catalyst (antimony triacetate, the addition amount is 0.01 wt% of the addition amount of the purified terephthalic acid in the step (2)) and a stabilizer (triphenyl phosphite, the addition amount is 0.01 wt% of the addition amount of the purified terephthalic acid in the step (2)), carrying out a pre-polycondensation reaction (the temperature is 266 ℃, the pressure is 50mbar, and the time is 35min), then adding the antistatic slurry prepared in the step (1) into a pre-polycondensation reaction system, stirring at a stirring speed of 2.5 rpm for 20min, and finally carrying out a final polycondensation reaction (the temperature is 275 ℃, the pressure is 8mbar, and the time is 60min) to prepare the antistatic modified polyester;

The specific process of conveying the prepared antistatic modified polyester melt to a spinning manifold comprises the following steps: firstly, filtering an antistatic modified polyester melt by a melt filter to remove mechanical impurity particles with the diameter larger than 16 mu m, then conveying the filtered antistatic modified polyester melt to a booster pump by a conveying pipeline internally provided with an annular cross-shaped static mixer to increase the pressure, finally adjusting the temperature of the antistatic modified polyester melt to 283 ℃ by a melt heat exchanger, and conveying the antistatic modified polyester melt to a spinning manifold with the temperature of 290 ℃ by a melt pipeline with the temperature of 284 ℃; the initial pressure of the spinning DIO component during filtration is 165 Bar;

the cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area with the length of 10mm, then enters a filter element in an annular blowing box to be cooled by annular blowing (the relative humidity of cooling air is 83%, the air temperature is 16 ℃, the air speed is 0.7m/s), and then is cooled by side blowing (the height of an air chamber cooled by side blowing is 500mm, the relative humidity of cooling air is 60%, the air temperature is 19 ℃, and the air speed is 0.4 m/s);

the oiling agent adopted by the oiling guide wire comprises 3 percent (mass fraction) of alpha-hydrogen-omega-hydroxy poly (oxy-1, 2-ethanediyl) mono- (10-16 alkyl ether potassium phosphate) and 2.5 percent (mass fraction) of alpha-octadecenoyl-omega-octadecenoyloxy polyethylene oxide;

Example 5

(1) preparing antistatic slurry;

mixing an antistatic agent (nano-scale zinc oxide powder) and ethylene glycol in a mass ratio of 1:20, grinding for 50min, and stirring for 9h to prepare antistatic slurry;

(2) Preparing ethylene terephthalate slurry;

mixing purified terephthalic acid and ethylene glycol in a mass ratio of 1:1.5, and stirring and mixing for 3 hours at 95 ℃ to prepare ethylene glycol terephthalate slurry;

(3) preparing ethylene terephthalate;

reacting the ethylene terephthalate slurry prepared in the step (2) at 270 ℃ and 0.3bar until the distilled water of esterification reaches 98 of a theoretical value to prepare ethylene terephthalate;

(4) preparing antistatic modified polyester;

firstly, mixing the ethylene glycol terephthalate prepared in the step (3) with a catalyst (antimony triacetate, the addition amount is 0.02 wt% of the addition amount of the terephthalic acid in the step (2)) and a stabilizer (triphenyl phosphite, the addition amount is 0.02 wt% of the addition amount of the terephthalic acid in the step (2)), carrying out a pre-polycondensation reaction (the temperature is 269 ℃, the pressure is 60mbar, and the time is 45min), then adding the antistatic slurry prepared in the step (1) into a pre-polycondensation reaction system, stirring at a stirring speed of 3.5 revolutions per minute for 25min, and finally carrying out a final polycondensation reaction (the temperature is 280 ℃, the pressure is 5mbar, and the time is 70min) to prepare the antistatic modified polyester;

The specific process of conveying the prepared antistatic modified polyester melt to a spinning manifold comprises the following steps: firstly, filtering an antistatic modified polyester melt by a melt filter to remove mechanical impurity particles with the diameter larger than 18 mu m, then conveying the filtered antistatic modified polyester melt to a booster pump by a conveying pipeline internally provided with an annular interchange-shaped static mixer to increase the pressure, finally adjusting the temperature of the antistatic modified polyester melt to 284 ℃ by a melt heat exchanger, and conveying the antistatic modified polyester melt to a spinning manifold with the temperature of 291 ℃ by a melt pipeline with the temperature of 285 ℃; the initial pressure of the spinning DIO component during filtration is 180 Bar;

the cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area with the length of 15mm, then enters a filter element in an annular blowing box to be cooled by annular blowing (the relative humidity of cooling air is 84%, the air temperature is 18 ℃, and the air speed is 0.8m/s), and then is cooled by side blowing (the height of an air chamber cooled by side blowing is 700mm, the relative humidity of cooling air is 70%, the air temperature is 20 ℃, and the air speed is 0.5 m/s);

the oiling agent adopted by the oiling guide wire comprises 6 percent (mass fraction) of alpha-hydrogen-omega-hydroxy poly (oxy-1, 2-ethanediyl) mono- (10-16 alkyl ether potassium phosphate) and 5 percent (mass fraction) of alpha-octadecenoyl-omega-octadecenoyloxy polyethylene oxide;

Example 6

(1) preparing antistatic slurry;

(2) Preparing ethylene terephthalate slurry;

mixing purified terephthalic acid and ethylene glycol in a molar ratio of 1:2, and stirring and mixing for 3 hours at 100 ℃ to prepare ethylene glycol terephthalate slurry;

the addition amount of the antistatic agent in the step (1) is 0.5 wt% of the addition amount of the terephthalic acid in the step (2);

(3) preparing ethylene terephthalate;

reacting the ethylene terephthalate slurry prepared in the step (2) at 275 ℃ and 0.4bar until the distilled water of esterification reaches 99 of a theoretical value to prepare ethylene terephthalate;

(4) preparing antistatic modified polyester;

firstly, mixing the ethylene glycol terephthalate prepared in the step (3) with a catalyst (antimony triacetate, the addition amount is 0.03 wt% of the addition amount of the purified terephthalic acid in the step (2)) and a stabilizer (trimethyl phosphate, the addition amount is 0.03 wt% of the addition amount of the purified terephthalic acid in the step (2)), carrying out a pre-polycondensation reaction (the temperature is 270 ℃, the pressure is 70mbar, and the time is 50min), then adding the antistatic slurry prepared in the step (1) into a pre-polycondensation reaction system, stirring at a stirring speed of 4.5 revolutions per minute for 30min, and finally carrying out a final polycondensation reaction (the temperature is 285 ℃, the pressure is 4mbar, and the time is 100min) to prepare the antistatic modified polyester;

The specific process of conveying the prepared antistatic modified polyester melt to a spinning manifold comprises the following steps: firstly, filtering mechanical impurity particles with the diameter larger than 19 mu m from an antistatic modified polyester melt by a melt filter, then conveying the filtered antistatic modified polyester melt to a booster pump through a conveying pipeline provided with an annular interchange-shaped static mixer to increase the pressure, finally adjusting the temperature of the antistatic modified polyester melt to 285 ℃ by a melt heat exchanger, and conveying the antistatic modified polyester melt to a spinning manifold with the temperature of 292 ℃ through a melt pipeline with the temperature of 288 ℃; the initial pressure of the spinning DIO component during filtration is 155 Bar;

the cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area with the length of 20mm, then enters a filter element in an annular blowing box to be cooled by annular blowing (the relative humidity of cooling air is 86%, the air temperature is 19 ℃, and the air speed is 0.9m/s), and then is cooled by side blowing (the height of an air chamber cooled by side blowing is 900mm, the relative humidity of cooling air is 80%, the air temperature is 21 ℃, and the air speed is 0.6 m/s);

the oiling agent adopted by the oiling guide wire comprises 9 percent (mass fraction) of alpha-hydrogen-omega-hydroxy poly (oxy-1, 2-ethanediyl) mono- (10-16 alkyl ether potassium phosphate) and 8 percent (mass fraction) of alpha-octadecenoyl-omega-octadecenoyloxy polyethylene oxide;

TABLE 1

Examples	X	1	2	3	4	5	6
								Pre-network pressure	MPa	0.06	0.07	0.08	0.05	0.06	0.08
Main network pressure	MPa	0.35	0.36	0.38	0.36	0.35	0.38
								Speed of drafting roller	m/min	2600	2800	2800	2500	3000	2850
Temperature of the drawing roll	℃	82	80	78	84	82	78
								Speed of the sizing roller	m/min	3800	3900	3800	4100	4250	3900
Temperature of setting roll	℃	118	120	118	122	119	118
								Winding speed	m/min	4300	4000	3700	4100	4150	3800
Contact pressure of winding head	N	250	240	220	245	240	230

TABLE 2

Examples	X	1	2	3	4	5	6
								Root length of filament	Root of herbaceous plant	72	144	192	72	144	192
Fineness of single filament	dtex	0.7	0.55	0.38	1.5	0.9	0.6
								Breaking strength	cN/dtex	3.90	3.80	3.65	4.20	3.90	3.60
Elongation at break	％	30	29	28	36	34	33
								Rate of deviation of linear density	％	0.90	0.85	0.80	0.90	0.85	0.80
CV value of breaking strength	％	2.5	3.5	3.5	3	3.5	4.5
								CV value of elongation at break	％	4.4	6	7.5	4.5	6.5	8.0
Yarn evenness unevenness CV value	％	1.4	1.65	1.75	1.8	1.85	1.80
								Oil content	％	0.98	1.08	1.2	1.05	1.1	1.3
Degree of hollowness	％	29	29	31	25	30	35
								Moisture regain	％	0.95	1.05	1.15	0.85	1.0	1.05
Resistivity of	Ω·cm	3×10⁷	4×10⁷	2×10⁷	6×10⁷	5×10⁷	9×10⁶

Claims

1. A porous moisture-permeable warm-keeping antistatic polyester fiber preparation method, the raw material is antistatic modified polyester, the technological process includes spinning DIO assembly filtration process, cooling process and oiling and yarn-guiding process, characterized by that, spinning DIO assembly is a double-channel device, there are two channels to filter the melt in a spindle assembly, two filter chambers correspond to two areas on the spinneret separately, a spinneret extrudes two bunches of filaments;

The cooling process comprises the following steps: after being extruded from a spinneret orifice on a spinneret plate, the antistatic modified polyester melt firstly passes through a slow cooling area, then enters a filter element in a circular blowing box for circular blowing cooling, and then is cooled by side blowing;

the filter element in the circular blowing box is in a hollow cylindrical shape and is formed by sequentially sleeving an outer cylinder, a secondary inner cylinder and an inner cylinder; the outer cylinder is made of a stainless steel perforated plate, and the secondary outer cylinder, the secondary inner cylinder and the inner cylinder are made of stainless steel filter screens; the upper end and the lower end between the outer cylinder and the inner cylinder are sealed by a high-temperature-resistant silica gel pad with a cap, and the outer cylinder and the secondary outer cylinder are fixed by a plurality of stainless steel support bars;

a porous plate vertical to the surface of the spinneret plate is arranged in the filter element in the circular blowing box and is used for separating tows extruded from two areas on the spinneret plate;

the spiral full-contact type micropore oiling device comprises an oil pipe, a quick plug, a metal connecting rod and a spiral porcelain piece structure which are sequentially connected; the metal connecting rod is arranged on the spinning position oil frame; a first hollow channel is arranged in the metal connecting rod, a second hollow channel is arranged in the spiral porcelain piece structure, and the second hollow channel is communicated with the first hollow channel; the spiral part of the spiral porcelain piece structure forms a wire passing channel, one side of the spiral part close to the wire passing channel is a slope, a plurality of layers of annular oil sumps and oil outlets are arranged on the slope, the oil outlets are positioned above the oil sumps, and the oil sumps are distributed around the wire passing channel; the oil outlet is communicated with the second hollow channel; the annular oil collecting groove is of a corrugated annular structure.

2. The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber according to claim 1, wherein the length of the slow cooling zone is 5-20 mm; the relative humidity of cooling air cooled by circular blowing is 80-90%, the air temperature is 15-19 ℃, and the air speed is 0.6-0.9 m/s; the height of the side-blown air cooling chamber is 500-900 mm, the relative humidity of the cooling air is 60-80%, the air temperature is 19-21 ℃, and the air speed is 0.4-0.6 m/s; the length of a filter element in the circular blowing box is 100-200 mm, the distance between the outer cylinder and the secondary outer cylinder is 2-5 mm, and the distance between two adjacent cylinders in the secondary outer cylinder, the secondary inner cylinder and the inner cylinder is 0 mm.

3. The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber according to claim 1, wherein the oiling device is a one-hole multi-groove device; the length of the metal connecting rod is 3-4 cm, the diameter of the first hollow channel is 3-5 mm, the diameter of the second hollow channel is 3-5 mm, the aperture of the oil outlet is 0.3-0.5 mm, the annular oil collecting grooves in the plurality of layers are 10-15 layers, the drop value of the corrugated wave crests and the wave troughs is 0.003-0.05 mm, and the aperture of the wire passing channel is 2-4 mm;

the oiling agent adopted by the oiling guide wire comprises 2.5-10% of alpha-hydrogen-omega-hydroxy poly (oxy-1, 2-ethanediyl) mono- (10-16 alkyl ether potassium phosphate) and 2.5-10% of alpha-octadecenoyl-omega-octadecenoyloxy polyethylene oxide.

4. The method for preparing the porous moisture-permeable warm-keeping antistatic polyester fiber according to any one of claims 1 to 3, wherein spinneret micropores on a spinneret plate are formed by two opposite W shapes

A shape structure; the two opposite W-shaped slit tips are aligned with the blowing direction of the circular blowing air; the W-shaped curve angle alpha is 30-60 degrees, the four side lengths L are 0.35-0.6 mm, the slit width W1 is 0.1-0.15 mm, and the distance W2 between the two opposite W-shaped slit tips is 0.05-0.08 mm.

5. The method for preparing the porous moisture-permeable warm-keeping antistatic polyester fiber as claimed in claim 4, wherein the antistatic modified polyester is prepared by adding an antistatic agent in a pre-polycondensation reaction stage in the polyester synthesis process.

6. The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber as claimed in claim 5, characterized in that the preparation steps of the antistatic modified polyester are as follows:

(1) preparing antistatic slurry;

mixing an antistatic agent and ethylene glycol, grinding for a period of time, and stirring for a period of time to prepare antistatic slurry;

(2) preparing ethylene terephthalate slurry;

mixing purified terephthalic acid and ethylene glycol, and stirring and mixing for a period of time at a certain temperature to prepare ethylene glycol terephthalate slurry;

(3) Preparing ethylene terephthalate;

reacting the ethylene terephthalate slurry prepared in the step (2) at a certain temperature and a certain pressure until the end point of the esterification reaction to prepare ethylene terephthalate;

(4) preparing antistatic modified polyester;

firstly, mixing the ethylene terephthalate prepared in the step (3) with a catalyst and a stabilizer, then carrying out a pre-polycondensation reaction, then adding the antistatic slurry prepared in the step (1) into a pre-polycondensation reaction system, stirring at a certain stirring speed for a period of time, and finally carrying out a final polycondensation reaction to prepare the antistatic modified polyester.

7. The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber according to claim 6, wherein in the step (1), the antistatic agent is nano-zinc oxide powder; the mass ratio of the antistatic agent to the ethylene glycol is 1: 20-30, and the grinding for a period of time is 30-60 min; stirring for a period of time means stirring for 8-10 hours; the addition amount of the antistatic agent in the step (1) is 0.25-0.5 wt% of the addition amount of the purified terephthalic acid in the step (2);

in the step (2), the molar ratio of terephthalic acid to ethylene glycol is 1: 1.1-2.0; the certain temperature is 85-110 ℃; the period of time is 2-3 hours;

In the step (3), the certain temperature is 265-275 ℃; the certain pressure is 0.2-0.5 bar; the end point of the esterification reaction is that the distilled water of the esterification reaches more than 90 percent of the theoretical value;

in the step (4), the catalyst is ethylene glycol antimony or antimony triacetate, and the addition amount of the catalyst is 0.01-0.03 wt% of the addition amount of the terephthalic acid in the step (2); the stabilizer is triphenyl phosphite, trimethyl phosphate or triphenyl phosphate, and the addition amount of the stabilizer is 0.01-0.03 wt% of the addition amount of the terephthalic acid in the step (2); the temperature of the pre-polycondensation reaction is 265-270 ℃, the pressure is less than 100mbar, and the time is 30-50 min; the certain stirring speed is 2-5 revolutions per minute; the period of time is 20-40 min; the temperature of the final polycondensation reaction is 272-285 ℃, the pressure is below 10mbar, and the time is 60-100 min.

8. The preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber according to claim 5, characterized in that the specific process flow is as follows: conveying the antistatic modified polyester melt to a spinning box → metering by a melt metering pump → filtering by a spinning DIO assembly → extruding by a spinneret orifice → cooling → oiling and guiding filament → winding and forming;

the specific process of conveying the antistatic modified polyester melt to a spinning manifold comprises the following steps: firstly, filtering mechanical impurity particles with the diameter larger than 15-20 microns from an antistatic modified polyester melt by a melt filter, then conveying the filtered antistatic modified polyester melt to a booster pump through a conveying pipeline with a static mixer arranged inside to increase the pressure, finally adjusting the temperature of the antistatic modified polyester melt to 283-286 ℃ by a melt heat exchanger, and conveying the antistatic modified polyester melt to a spinning manifold with the temperature of 288-292 ℃ through a melt pipeline with the temperature of 284-288 ℃; the static mixer is in an annular interchange shape;

all spinneret orifices are arranged in a concentric circle shape and symmetrically distributed in two areas on the spinneret plate;

9. The porous moisture-permeable warm-keeping antistatic polyester fiber prepared by the preparation method of the porous moisture-permeable warm-keeping antistatic polyester fiber according to claim 8, wherein the number of monofilaments in one bundle of filaments is more than or equal to 72; cross section of monofilament

Shaping; the antistatic polyester fiber mainly comprises a polyester fiber matrix and an antistatic agent dispersed in the polyester fiber matrix, wherein the antistatic agent is combined with a polyester molecular chain in an inlaying mode;

the monofilament titer of the porous moisture-permeable, warm-keeping and antistatic polyester fiber is 0.3-1.5 dtex, and the breaking strength is highThe degree is more than or equal to 3.6cN/dtex, the elongation at break is 32 +/-4%, the deviation rate of linear density is less than or equal to 1.0%, the CV value of the breaking strength is less than or equal to 4.5%, the CV value of the elongation at break is less than or equal to 9.0%, the CV value of the evenness is less than or equal to 2.0%, the oil content is 1.1 +/-0.2%, the degree of hollowness is 25-35%, the moisture regain is 0.85-1.15%, and the resistivity is 3 multiplied by 10 ⁷～6×10⁷Ω·cm。