WO2017032295A1 - 一种高性能聚苯硫醚纤维构造体及其制造方法和用途 - Google Patents

一种高性能聚苯硫醚纤维构造体及其制造方法和用途 Download PDF

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Publication number
WO2017032295A1
WO2017032295A1 PCT/CN2016/096309 CN2016096309W WO2017032295A1 WO 2017032295 A1 WO2017032295 A1 WO 2017032295A1 CN 2016096309 W CN2016096309 W CN 2016096309W WO 2017032295 A1 WO2017032295 A1 WO 2017032295A1
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Prior art keywords
polyphenylene sulfide
yarn
fiber structure
pps
twist
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PCT/CN2016/096309
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English (en)
French (fr)
Inventor
石彦芳
杨丽丽
徐婕
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东丽纤维研究所（中国）有限公司
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Priority to DK16838554.0T priority Critical patent/DK3342909T3/da
Priority to CN201680042039.7A priority patent/CN107835873A/zh
Priority to ES16838554T priority patent/ES2875590T3/es
Priority to US15/754,093 priority patent/US20180251920A1/en
Priority to EP16838554.0A priority patent/EP3342909B1/en
Priority to JP2018505465A priority patent/JP6930527B2/ja
Publication of WO2017032295A1 publication Critical patent/WO2017032295A1/zh

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
    • D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/30—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the fibres or filaments
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/30—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the fibres or filaments
    • D03D15/37—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the fibres or filaments with specific cross-section or surface shape
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/41—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads with specific twist
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/573—Tensile strength
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/30—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensation products not covered by indexing codes D10B2331/02 - D10B2331/14
    • D10B2331/301—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensation products not covered by indexing codes D10B2331/02 - D10B2331/14 polyarylene sulfides, e.g. polyphenylenesulfide
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/022—Moisture-responsive characteristics hydrophylic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/04—Filters

Definitions

  • the present invention relates to a high performance polyphenylene sulfide fiber structure, a method for its manufacture and use.
  • Diaphragm cloth is the main core material of water electrolysis tank.
  • Water electrolysis hydrogen production and oxygen production equipment are widely used in military, petrochemical, steel and other manufacturing fields.
  • the main domestic alkaline water electrolysis hydrogen production equipment manufacturers still use asbestos cloth as diaphragm.
  • Asbestos itself is not poisonous. Its biggest hazard comes from its fiber. It is a very small fiber that is almost invisible to the naked eye. When these tiny fibers are released, they will float in the air for a long time and are easily inhaled by the human body. .
  • diaphragm cloth has always been the main core material of water electrolysis equipment.
  • the products will be pushed to the international market, using a new generation of non-asbestos diaphragm.
  • the replacement of asbestos diaphragm cloth by cloth has become a must.
  • diaphragm cloth made of polyphenylene sulfide fiber is being used instead of asbestos diaphragm cloth, although the problems of pollution and low airtightness are solved, but if the fiber fineness used for the woven PPS diaphragm cloth is not suitable and the single yarn and Inappropriate ratios between strand twists result in a non-uniform pore size and poor air tightness.
  • Chinese Patent Publication No. CN101372752 discloses a non-manufactured cloth made of ordinary polyphenylene sulfide fiber, which is then subjected to sulfonation treatment by 70 to 130 ° C, 90 to 98% of H 2 SO 4 for 20 to 40 minutes, and then used. Treated with 30% potassium hydroxide, and finally obtained a high temperature alkaline water electrolyzer diaphragm.
  • the liquid absorption rate of the nonwoven fabric is relatively strong, after the strong acid treatment, a large amount of valuable water resources and chemicals are consumed in the cleaning process, the cleaning time is long, and the process operation is complicated, and it is easy to The environment causes pollution. At the same time, the safety is also poor, and it is not suitable for industrial production.
  • Chinese Patent Publication No. CN103938337A discloses a high-density woven fabric made of ordinary 2.2T polyphenylene sulfide fiber, and then imparts hydrophilic properties to the polyphenylene sulfide membrane by plasma hydrophilic processing, and finally obtains high temperature resistance.
  • the alkali-resistant polyphenylene sulfide separator is inferior in airtightness of the obtained separator due to the unsuitable ratio of the single fiber fineness and the single yarn to the strand twist.
  • the PPS separator cloth processed by the plasma hydrophilic processing method has a poor hydrophilic effect and short time-effect, which makes the diaphragm unable to meet the production requirements.
  • Another example is the Chinese patent CN101195944, which discloses an asbestos-free environmentally-friendly and energy-saving diaphragm which is woven by using one, two or three kinds of polyetheretherketone fiber, polyphenylene sulfide fiber and polypropylene fiber. Woven fabric. Although the airtightness of the diaphragm cloth satisfies the standard requirements of the asbestos diaphragm, the poor performance of the above-mentioned chemical fiber is poor, and the resulting separator cloth is poor in hydrophilicity, and cannot truly meet the requirements for use.
  • An object of the present invention is to provide a high-performance polyphenylene sulfide fiber structure having higher airtightness and higher hydrophilicity.
  • Another object of the present invention is to provide a method for producing a high-performance polyphenylene sulfide fiber structure which is simple in process, energy-saving, and environmentally friendly.
  • the constitution of the present invention is as follows:
  • the polyphenylene sulfide fiber structure of the present invention is a woven fabric formed of polyphenylene sulfide fibers having a cross-sectional diameter of 0.1 to 12 ⁇ m, and the polyphenylene sulfide fiber structure has a maximum pore diameter of 20 ⁇ m or less.
  • the warp and weft yarn constituting the polyphenylene sulfide fiber structure of the above (1) is a polyphenylene sulfide spun yarn subjected to hydrophilization.
  • the polyphenylene sulfide fiber structure of the above (1) has an average pore diameter of 5 ⁇ m or less, and wherein the pores of 6 ⁇ m or less account for 90% or more of all the pores of the fiber structure.
  • the single yarn count constituting the above (1) is 21 to 60 s.
  • the yarn twist coefficient constituting the above (1) is from 180 to 350.
  • the warp twist of the polyphenylene sulfide fiber structure constituting the above (1) is equal to or greater than the twist of the weft yarn.
  • the ratio of the twist of the polyphenylene sulfide yarn to the twist of the polyphenylene sulfide single yarn in the polyphenylene sulfide fiber structure according to any one of the above (4) to (5) is 0.2 to 1.0.
  • the airtightness of the polyphenylene sulfide fiber structure constituting the above (1) is 400 mmH 2 O or more.
  • the surface resistance of the polyphenylene sulfide fiber structure constituting the above (1) is 60 m ⁇ cm 2 or less.
  • the invention has the beneficial effects that the present invention overcomes the prior art aperture non-uniformity and airtightness by using a polyphenylene sulfide fiber having a fineness of 0.1 to 12 ⁇ m and a ratio between a single yarn twist and a strand twist.
  • the low defect can make the obtained PPS woven fabric have small pore size and uniform distribution, which makes the polyphenylene sulfide fiber structure of the invention not only have the characteristics of high airtightness and good hydrophilicity, but also has a process. Simple, provincial Energy, no pollution to the environment.
  • the polyphenylene sulfide fiber structure of the present invention can be applied to a separator for an electrolysis device, a high temperature liquid filtration, and an insulating material.
  • the polyphenylene sulfide fiber structure of the present invention is a woven fabric formed of polyphenylene sulfide fibers having a cross-sectional diameter of 0.1 to 12 ⁇ m, and the polyphenylene sulfide fiber structure has a maximum pore diameter of 20 ⁇ m or less.
  • the plain weave has the most interlacing point and the highest degree of tightness, so a plain weave fabric is preferred.
  • the cross-sectional diameter of the polyphenylene sulfide fiber is less than 0.1 ⁇ m, since the fiber is too fine, the fiber may not be combed during the carding process, the single fiber is broken, the yarn formation is poor, and the neps are excessive, thereby affecting the yarn. Quality. If the yarn is used for weaving, it may cause excessive defects in the PPS fabric surface, affecting the thickness and pore diameter of the fabric, resulting in uneven pore size and thickness of the fabric, further causing poor airtightness of the fabric; if polyphenylene sulfide fiber The cross-section of the cross-section is greater than 12 ⁇ m. Since the diameter of the fiber is too thick, the single-fiber yarn is too hard to be formed into a yarn.
  • the cross-sectional diameter of the polyphenylene sulfide fiber is preferably 6-10 ⁇ m considering the comprehensive factors such as the airtightness of the PPS fabric and the hydrophilic processing effect in the post-processing process. More preferably, it is 6-8 micrometers.
  • the warp and weft yarn constituting the polyphenylene sulfide fiber structure is a hydrophilized polyphenylene sulfide spun yarn.
  • the warp and weft yarns of the polyphenylene sulfide fiber structure of the present invention all use short fiber yarns, and the spun yarns have strong cohesion between the single fibers compared with the longer fiber yarns, and the fibers are not caused by the structure of the yarn.
  • the voids increase, thereby affecting the pore size and airtight properties of the fabric.
  • the spun yarn used in the present invention may be a single yarn or a plied yarn composed of a single yarn, preferably a plied yarn.
  • hydrophilically processed polyphenylene sulfide staple fiber yarn is preferred.
  • Hydrophilization herein refers to the addition of hydrophilic groups such as hydroxyl groups, carboxyl groups, carbonate groups, sulfate groups, etc. on the surface of polyphenylene sulfide fibers by plasma, sulfonation or grafting.
  • the graft ratio of the hydrophilized polyphenylene sulfide yarn is 0.1 to 3%, and the graft ratio is preferably 0.5 to 3%.
  • the polyphenylene sulfide fiber structure of the present invention has a maximum pore diameter of 20 ⁇ m or less. If the maximum pore diameter of the polyphenylene sulfide fiber structure is more than 20 ⁇ m, the pore diameter of the polyphenylene sulfide fiber structure is too large, which leads to its use. In the hydrogen production facility, hydrogen and oxygen bubbles easily pass through the voids of the fiber structure, reducing the purity of the single gas. The maximum pore diameter of the polyphenylene sulfide fiber structure is 20 ⁇ m or less.
  • the polyphenylene sulfide fiber structure In order to make the pore size of the polyphenylene sulfide fiber structure uniform and the pore size distribution and concentration, the polyphenylene sulfide fiber structure is the most The large pore diameter is preferably 15 ⁇ m or less. In order to make the pore diameter of the fiber structure more uniform and the pore size distribution more concentrated and concentrated, the maximum pore diameter of the polyphenylene sulfide fiber structure is preferably 12 ⁇ m or less.
  • the polyphenylene sulfide fiber structure of the present invention has an average pore diameter of 5 ⁇ m or less, and pores of 6 ⁇ m or less account for 90% or more of all the pores of the fiber structure.
  • the average pore diameter of the polyphenylene sulfide fiber structure is controlled within the above range, the gas tightness is ensured, so that gas molecules and bubbles are difficult to pass, thereby preventing mixing of the anode side gas and the cathode side gas to ensure gas. Purity and safety.
  • the average pore diameter of the polyphenylene sulfide fiber structure is more than 5 ⁇ m, since the pore diameter of the woven fabric is too large, the woven fabric is not used for isolation when used in a hydrogen producing apparatus, and finally the purity of hydrogen and oxygen produced is low. Not required by the customer.
  • the gas generation efficiency is improved, and the purity of the generated gas is increased, the weaving conditions are optimized, the uniformity of the pore diameter is improved, and the pore diameter is improved under the premise of an average pore diameter of 5 ⁇ m or less.
  • the pores of 6 ⁇ m or less account for 90% or more, preferably 95% or more of all the pores.
  • the single yarn count of the polyphenylene sulfide woven fabric is selected to be 21 to 60 s, and the enthalpy coefficient ⁇ is 200 to 310.
  • the number of single yarns in the above range can ensure that the obtained PPS fabric has a small pore size and uniformity, high airtightness, and can also make the obtained woven fabric have a good hydrophilic processing effect in the subsequent passage. If the single yarn count is too low, the yarn is too thick, resulting in a large pore size of the woven fabric, and the airtightness of the woven fabric is small, which ultimately leads to poor purity of hydrogen and oxygen produced; if the single yarn count is too high, it is bound to be Very fine yarns are required, which can lead to difficulties in the production process.
  • the twist coefficient of the single yarn in the above range can ensure that the PPS yarn obtained is moderately fluffy, so that the woven fabric has small pore size and uniformity, high air tightness, and can also make the woven fabric hydrophilic processing in the latter stage. The effect is good.
  • the twist factor of the yarn is too small, the twist of the yarn is too low, resulting in low strength of the yarn, easy yarn breakage during weaving, and the strength of the obtained fabric becomes low; if the twist factor of the yarn is too large The twist of the yarn is too high, the gap at the interlacing point of the fabric is obvious, and the pore diameter is increased; on the other hand, the gap between the fibers inside the yarn is also small, resulting in uneven pore size of the entire woven fabric, and airtightness. reduce.
  • the yarn entanglement coefficient constituting the polyphenylene sulfide woven fabric is 180 to 350. If the twist coefficient of the yarn is too low, the twist angle of the single fiber is small, and the cohesion between the fibers is reduced, and the yarn is The strength is reduced, which leads to difficulty in weaving due to the low strength of the yarn during the weaving process; if the twist coefficient of the yarn is too high, the cohesion between the fibers is too large, the strength of the yarn is lowered, and it is easy to be in the weaving process. It is prone to small scorpions and is not easy to weave.
  • the tension of the warp yarn is larger than that of the weft yarn.
  • the structure of the fabric is tight, the pore diameter is small, and the pore diameter uniformity is good, and the polyphenylene of the present invention is preferably formed.
  • the warp yarn twist of the thioether fiber structure is greater than or equal to the twist of the weft yarn.
  • the warp twist is slightly larger, which can ensure the strength of the warp yarn, increase the aperture ratio, and facilitate the weaving.
  • the weft yarn is made of spun yarn with a slightly lower twist, and the yarn is fluffy, which can make up for the defects of increased aperture and unevenness caused by the increase of warp twist.
  • the ratio of the twist of the polyphenylene sulfide yarn of the present invention to the twist of the polyphenylene sulfide single yarn is 0.2 to 1.0, and the ratio of the yarn twist to the twist of the single yarn is within the above range to ensure uniform pore diameter of the woven fabric, and
  • the number of hydrophilic groups attached to the woven fabric during the hydrophilic processing process increases the liquid content of the woven fabric, and the water film formed on the surface layer of the woven fabric is thicker, which can effectively prevent the passage of bubbles. This increases the purity of the gas.
  • the woven fabric has a non-uniform pore size, and the low airtightness results in a non-uniform pore size of the woven fabric and a small number of hydrophilic groups attached.
  • the polyphenylene sulfide fiber structure of the present invention has an airtightness of 400 mmH 2 O or more.
  • the airtightness requirement of the diaphragm cloth in the actual water electrolysis cell can be basically satisfied.
  • the separator cloth can have excellent airtightness, ion passage efficiency, and processability of the separator cloth. If the air tightness is less than 400 mm H 2 O pressure, the basic requirements of the diaphragm cannot be met, and the purity of the generated gas is affected.
  • the surface resistance of the polyphenylene sulfide fiber structure of the present invention is 60 m ⁇ cm 2 or less, and preferably the sheet resistance is 10 m ⁇ cm 2 or less. If the sheet resistance of the polyphenylene sulfide fiber structure is more than 60 m ⁇ cm 2 , the impedance of the fabric is large, the consumption of electric energy is increased, and the production cost is also increased.
  • the polyphenylene sulfide fiber structure of the present invention has an alkali absorption rate of 70 to 200%. If the alkali absorption rate of the polyphenylene sulfide fiber structure is too low, it is difficult to form a water film or a water film too thin in the alkali solution. The passage of air bubbles cannot be effectively prevented, thereby reducing the purity of the gas; if the alkali absorption rate of the polyphenylene sulfide fiber structure is too high, the structure of the woven fabric is relatively loose, and the voids are increased, thereby affecting the performance of the separator.
  • the alkali absorption rate of the polyphenylene sulfide fiber structure of the present invention is preferably from 85 to 180%, more preferably from 100 to 160%.
  • the high-performance polyphenylene sulfide fiber structure of the invention is applied in a hydrogen production device, and the main function is that ions can pass and gas molecules cannot pass. Because the purity requirements of hydrogen and oxygen are different for different customers, the requirements for the pore size and air tightness of the fabric are different, and the type and organization of the fabric are not the same. Off, as long as the gas molecules do not penetrate each other to meet customer requirements.
  • the method for producing a high performance polyphenylene sulfide fiber structure of the present invention comprises the following steps:
  • Cotton spinning process Polyphenylene sulfide fibers with a cross-sectional diameter of 0.1-12 ⁇ m are passed through a cotton-carding-drawing-roving yarn, and the rovings are drawn to obtain a count of 20-60 s and a ⁇ coefficient ⁇ .
  • the cover factor of the woven fabric is preferably 2600 to 2800;
  • the scouring agent used YK30 12g/L, YS66 3.0g/L, YK37 2.0g/L,
  • the finished fabric is subjected to plasma or/and sulfonation hydrophilic processing to finally obtain a finished product.
  • a hydrophilic group can be attached to the surface of the PPS fiber, which can increase the wetting speed of the PPS woven fabric and also increase the liquid content of the PPS woven fabric.
  • the gas production efficiency is improved and the purity is high during use.
  • the grafting ratio of the fabric obtained by plasma or/and sulfonation hydrophilic processing may be different, and the graft ratio of the PPS woven fabric is preferably 3.0 to 8.0%.
  • the plasma hydrophilic processing method includes atmospheric pressure plasma processing and low pressure plasma processing, and the atmospheric plasma processing method includes glow discharge, silent discharge, and corona discharge, wherein the glow discharge includes a direct current and a high frequency current.
  • microwave radiation, low-pressure plasma processing gas can be oxygen, argon, nitrogen, etc., considering the possibility of processing, processing stability, processing efficiency, plasma pro
  • the water processing is preferably atmospheric pressure plasma glow DC discharge.
  • the conditions of atmospheric pressure plasma glow DC discharge are: voltage 5 ⁇ 15v, current 12-18A, and the content of oxygen element attached to the measured element content 15 ⁇ 25%. After plasma processing, small pits with irregularities on the surface of the PPS fiber are formed, which can increase the capillary effect and water absorption of the PPS woven fabric.
  • hydrophilic groups are attached to the surface layer of the PPS fiber, and the hydrophilic group is attached.
  • the group is sulfate, carboxylate, carbonate, hydroxyl, carbonyl, etc., and the action of these hydrophilic groups can increase the water absorption speed of the PPS fiber, and can also improve the purity of hydrogen and oxygen.
  • the finalized fabric When the finalized fabric is simultaneously subjected to plasma and sulfonation processing, the finalized fabric is subjected to plasma treatment, so that the PPS yarn is physically etched, so that the concave and convex pits are formed on the surface layer of the fiber, and the specific surface area of the PPS fiber is increased; Then, the plasma-treated PPS fabric is subjected to a sulfonation treatment, which can increase the number of hydrophilic groups attached, so that the hydrophilic effect of the PPS fabric is better.
  • the PPS yarn obtained in the step (1) is subjected to at least one of plasma processing, sulfonation processing, and graft copolymerization treatment.
  • a hydrophilic polyphenylene sulfide yarn is obtained. Due to the single plasma processing, there may be poor durability, and the fabric will undergo a decrease in hydrophilic properties after scouring. In the post-processing process, the hydrophilic property is lowered due to the influence of the agent and the high temperature. Therefore, it is more preferable that the PPS yarn is subjected to sulfonation processing, or more preferably, the PPS yarn is subjected to sulfonation after plasma processing. machining.
  • the sulfonation processing method is to treat the yarn through a sulfonation treatment liquid (85 to 98% of chlorosulfonic acid or concentrated sulfuric acid) at a temperature of 80 to 120 ° C for 1 to 5 minutes, and attach a hydrophilic group to the surface layer of the PPS fiber. Sulfate and the like.
  • the plasma processing method can select atmospheric pressure plasma processing or vacuum plasma processing to form pits with irregularities on the surface, increase the capillary effect and water absorption of the PPS fiber, and connect the hydrophilic group sulfate to the surface layer of the PPS fiber. , carboxylate, carbonate, hydroxyl, carbonyl, etc., the role of these hydrophilic groups can increase the water absorption rate of PPS fiber, and can also improve the purity of hydrogen and oxygen.
  • each physical property was measured by the following method or calculated by the following formula.
  • N W warp direction density (root/inch) of the fabric
  • D W the fineness (dtex) of the warp filaments in the fabric
  • N f latitudinal density (root/inch) of the fabric
  • D f the fineness (dtex) of the latitudinal filaments in the fabric.
  • the fabric aperture was measured using a capillary flow gap gauge (PMI formula product, model: CFP-1100-AE) according to the ASTM F316-03 standard, and the working mode was set to wet-up/dry-down mode.
  • the test environment was 23 ° C, 50% RH.
  • the fabric sample was placed in a sample chamber and wetted with a silwick silicone fluid having a surface tension of 19.1 dynes/cm.
  • the bottom clamp of the sample chamber has a porous metal disk insert having a diameter of 2.54 cm and a thickness of 3.175 mm.
  • the top clamp of the sample chamber has a hole of 3.175 mm diameter, and the value of the average pore diameter of the fabric can be directly read. The average of the two measurements is taken as the final average pore size value.
  • the water absorption rate of the separator cloth before and after the hydrophilic treatment was measured according to GB/T 21655.1-2008.
  • the temperature range of the cryostat control device is -5 to 100 °C, and the temperature control deviation is ⁇ 0.05.
  • Working temperature is 60 ° C, and liquid medium is generally selected from dimethyl silicone oil.
  • Test range resistance 0.0005 milliohms to 33 ohms, voltage: 0.00001 to 120v DC voltage;
  • the water used in the lye is secondary ultra-pure deionized water.
  • Test environment a constant temperature and humidity environment with a temperature of 20 ° C and a humidity of 60% RH.
  • the sulfonated PPS woven fabric (phenolphthalein as an indicator) was titrated with a 0.1 mol/L NaOH standard solution.
  • the grafting ratio of the computer fabric was calculated according to the amount of NaOH consumed.
  • the woven fabric of 40mm*40mm size was weighed and weighed G 1 , soaked in a 30% potassium hydroxide solution and soaked for 4 hours. After hanging for half a minute, after dropping the lye droplets, G 2 was weighed to obtain an alkali absorption rate.
  • the formula for calculating the alkali absorption rate is as follows:
  • A diaphragm alkali absorption rate%
  • G 1 mass of the sample before alkali soaking
  • G 2 mass g of the sample after alkalizing.
  • a circular PPS fiber with a cross-sectional diameter of 10 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 40 s, a twist of 81 T/10 cm, and a ⁇ coefficient of 311.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 4 strands, and the warp and weft yarns are 45T/10cm, respectively.
  • the pores below 6 ⁇ m accounted for more than 94% of the total pores of the woven fabric, and the sheet resistance R was 2.2 m ⁇ cm 2 .
  • PPS fiber structures having a strength of 900 N/3 cm and 602 N/3 cm, respectively.
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • the PPS yarn obtained in Example 1 was subjected to 98% strength concentrated sulfuric acid at 90 ° C for 3 minutes to obtain a hydrophilized PPS yarn having a graft ratio of 1.8%.
  • the prepared hydrophilized PPS yarn was woven as a warp and a weft by a loom to obtain a plain weave having a warp density of 55.0/inch and a weft density of 48.7/inch, and then the obtained fabric was subjected to a fabric. Refining, washing, drying, heat setting at 180 °C, and then sulfonating the heat-set PPS woven fabric.
  • the coverage coefficient was 2520
  • the thickness was 0.63 mm
  • the maximum pore diameter was 15 ⁇ m
  • the average pore diameter was 3.0 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 95% of the total pores of the woven fabric, and the sheet resistance R was 1.3 m ⁇ cm 2 .
  • PPS fiber structures having a strength of 750 N/3 cm and 521 N/3 cm, respectively. The physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 8 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 60 s, a twist of 90 T/10 cm, and a ⁇ coefficient of 282.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 6 strands, and the warp and weft yarns are 44T/10cm, respectively.
  • the plain woven fabric with an inch density and a latitudinal density of 39.0/inch is then scoured, washed, dried, and heat set at 180 ° C, and then the heat-set PPS woven fabric is subjected to sulfonation processing.
  • the coverage coefficient was 2559
  • the thickness was 0.64 mm
  • the maximum pore diameter was 17 ⁇ m
  • the average pore diameter was 4.9 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 92% of the total pores of the woven fabric, and the sheet resistance R was 1.5 m ⁇ cm 2 .
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 8 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 40 s, a twist of 57 T/10 cm, and a twist factor of 219.
  • the PPS single yarn is spun by a winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 4 strands, and the warp and weft yarn twists are 47T/10cm, respectively.
  • the coverage coefficient was 2734
  • the thickness was 0.62 mm
  • the maximum pore diameter was 18 ⁇ m
  • the average pore diameter was 4.5 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 93% of the total pores of the woven fabric, and the sheet resistance R was 1.6 m ⁇ cm 2 .
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 9 ⁇ m was passed through a cotton-comb-sand- roving-spinning-winding-heat setting process to obtain a count of 20 s, a twist of 48 T/10 cm, and a ⁇ coefficient of 261.
  • the PPS single yarn is spun by a winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 2 strands, and the warp and weft yarn twists are 40T/10cm, respectively.
  • the prepared hydrophilized PPS yarn was woven as a warp and a weft by a loom to obtain a plain fabric having a warp density of 68.3/inch and a weft density of 45.2/inch, and then the obtained fabric was subjected to a fabric. Refining, washing, drying, heat setting at 180 °C, and then heat-setting the PPS woven fabric into sulfonation processing.
  • the coverage coefficient was 2758
  • the thickness was 0.61 mm
  • the maximum pore diameter was 19 ⁇ m
  • the average pore diameter was 3.3 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 95% of the total pores of the woven fabric, and the sheet resistance R was 2.0 m ⁇ cm 2 .
  • the PPS fiber structures having a strength of 1031 N/3 cm and 846 N/3 cm, respectively.
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 10 ⁇ m was passed through a clear-comb-sand-grain-roving-spun yarn-winding-heat setting process to obtain a count of 40 s, a twist of 81 T/10 cm, and a twist factor of 311.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 2 strands, and the warp and weft yarns are 71T/10cm, respectively.
  • the prepared hydrophilized PPS yarn was woven as a warp yarn and a weft yarn by a loom to obtain a plain woven fabric having a warp density of 88.0/inch and a latitudinal density of 64.0/inch, and then the obtained woven fabric was subjected to a woven fabric.
  • a circular PPS fiber with a cross-sectional diameter of 11 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 60 s, a twist of 90 T/10 cm, and a ⁇ coefficient of 282.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 2 strands, and the warp and weft yarns are 76T/10cm, respectively.
  • the prepared hydrophilized PPS yarn was woven as a warp yarn and a weft yarn by a loom to obtain a plain woven fabric having a warp density of 113.0 pieces/inch and a weft density of 60.0 pieces/inch, and then the obtained woven fabric was subjected to a woven fabric.
  • a circular PPS fiber with a cross-sectional diameter of 4 ⁇ m was passed through a clear-comb-sand-grain-roving-spun yarn-winding-heat setting process to obtain a count of 60 s, a twist of 90 T/10 cm, and a ⁇ coefficient of 282.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 2 strands, and the warp and weft yarns are 76T/10cm, respectively.
  • the plain fabric with a density of 65.0/inch in the latitudinal direction is scoured, washed, dried, and heat set at 180 ° C, and then the heat-set PPS woven fabric is subjected to sulfonation processing.
  • the coverage coefficient was 2497
  • the thickness was 0.30 mm
  • the maximum pore diameter was 16 ⁇ m
  • the average pore diameter was 4.2 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 90% of the total pores of the woven fabric, and the sheet resistance R was 1.4 m ⁇ cm 2 .
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 7 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 60 s, a twist of 90 T/10 cm, and a ⁇ coefficient of 282.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 4 strands, and the warp and weft yarns are 54T/10cm, respectively.
  • the plain fabric with a density of 60.0/inch in the latitudinal direction is scoured, washed, dried, and heat set at 180 ° C, and the heat-set PPS woven fabric is subjected to sulfonation processing.
  • the coverage factor was 2976
  • the thickness was 0.40 mm
  • the maximum pore diameter was 16 ⁇ m
  • the average pore diameter was 4.4 ⁇ m.
  • PPS fiber structures having a strength of 900 N/3 cm and 570 N/3 cm, respectively.
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 11 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 20 s, a twist of 56 T/10 cm, and a twist factor of 304.
  • the PPS single yarn is spun by a winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 2 strands, and the warp and weft yarns are 24T/10cm, respectively.
  • the concentrated sulfuric acid was treated for 3 minutes to obtain a hydrophilized PPS yarn having a graft ratio of 2.8%.
  • the prepared hydrophilized PPS yarn was woven as a warp yarn and a weft yarn by a loom to obtain a plain woven fabric having a warp density of 58.0/inch and a latitudinal density of 54.0/inch, and then the obtained woven fabric was subjected to a woven fabric.
  • a circular PPS fiber with a cross-sectional diameter of 8 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 20 s, a twist of 48 T/10 cm, and a twist factor of 261.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 2 strands, and the twist of the warp yarn is 40T/10cm.
  • the ⁇ coefficient is 307, the ratio of the twist of the warp yarn to the twist of the single yarn is 0.83; the twist used as the weft yarn is 36T/10cm, the twist coefficient is 277, and the ratio of the twist of the weft yarn to the twist of the single yarn is 0.75.
  • the obtained PPS yarn was treated with 98% strength concentrated sulfuric acid at 90 ° C for 3 min to obtain a hydrophilized PPS yarn having a graft ratio of 1.5%.
  • the prepared hydrophilized PPS yarn was woven as a warp and a weft by a loom to obtain a plain weave having a warp density of 68.3/inch and a weft density of 44.0/inch, and then the obtained fabric was subjected to Refining, washing, drying, heat setting at 180 °C, and then sulfonating the heat-set PPS woven fabric. Finally, the coverage coefficient was 2729, the thickness was 0.62 mm, the maximum pore diameter was 18 ⁇ m, and the average pore diameter was 2.9 ⁇ m. The pores below 6 ⁇ m accounted for more than 96% of the total pores of the woven fabric, and the sheet resistance R was 2.0 m ⁇ cm 2 . PPS fiber structures having a strength of 820 N/3 cm and 658 N/3 cm, respectively. The physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 8 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 40 s, a twist of 81 T/10 cm, and a twist factor of 311.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 2 strands, and the twist of the warp yarn is 80T/10cm.
  • the ⁇ coefficient is 435, the ratio of the twist of the warp yarn to the twist of the single yarn is 0.99; the twist used as the weft yarn is 60T/10cm, the twist coefficient is 326, and the ratio of the twist of the weft yarn to the twist of the single yarn is 0.74.
  • the obtained PPS yarn was treated with 98% strength concentrated sulfuric acid at 90 ° C for 3 min to obtain a hydrophilized PPS yarn having a graft ratio of 1.8%.
  • the prepared hydrophilized PPS yarn was woven as a warp and weft yarn by a loom to obtain a plain woven fabric having a warp density of 88.0/inch and a latitudinal density of 62.0/inch, and then the obtained woven fabric was subjected to a woven fabric. Refining, washing, drying, heat setting at 180 °C, and then sulfonating the heat-set PPS woven fabric. Finally, the coverage factor was 2577, the thickness was 0.42 mm, the maximum pore diameter was 15 ⁇ m, and the average pore diameter was 3.0 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 94% of the total pores of the woven fabric, and the sheet resistance R was 2.1 m ⁇ cm 2 .
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 6 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 60 s, a twist of 90 T/10 cm, and a ⁇ coefficient of 282.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 3 strands, and the twist of the warp yarn is 54T/10cm.
  • the ⁇ coefficient is 293, the ratio of the twist of the warp yarn to the twist of the single yarn is 0.60; the twist used as the weft yarn is 40T/10cm, the twist coefficient is 217, and the ratio of the twist of the weft yarn to the twist of the single yarn is 0.44.
  • the prepared PPS yarn was woven by a loom to obtain a plain weave having a warp density of 95.0/inch and a weft density of 68.0/inch, and then the obtained fabric was scoured, washed, dried, and 180. After heat setting at °C, the heat-set PPS woven fabric is subjected to sulfonation processing.
  • the coverage factor was 2801
  • the thickness was 0.48 mm
  • the maximum pore diameter was 12 ⁇ m
  • the average pore diameter was 2.3 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 96% of the total pores of the woven fabric, and the sheet resistance R was 1.9 m ⁇ cm 2 .
  • the PPS fiber structures having a strength of 611 N/3 cm and 457 N/3 cm, respectively.
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 10 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 20 s, a twist of 48 T/10 cm, and a ⁇ coefficient of 261.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 2 strands, and the twist of the warp yarn is 36T/10cm.
  • the twist factor is 277, the ratio of the twist of the warp yarn to the twist of the single yarn is 0.75; the twist used as the weft yarn is 40T/10cm, the twist coefficient is 307, and the ratio of the twist of the weft yarn to the twist of the single yarn is 0.83.
  • the obtained PPS yarn was treated with 98% strength concentrated sulfuric acid at 90 ° C for 3 min to obtain a hydrophilized PPS yarn having a graft ratio of 1.3%.
  • the prepared hydrophilized PPS yarn was woven as a warp yarn and a weft yarn by a loom to obtain a plain woven fabric having a warp density of 58.2/inch and a latitudinal density of 50.3/inch, and then the obtained woven fabric was subjected to a woven fabric. Refining, washing, drying, heat setting at 180 °C, and then sulfonating the heat-set PPS woven fabric. Finally, the coverage coefficient was 2637, the thickness was 0.59 mm, the maximum pore diameter was 17 ⁇ m, and the average pore diameter was 3.9 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 95% of the total pores of the woven fabric, and the sheet resistance R was 2.3 m ⁇ cm 2 .
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • the circular PPS fiber with a cross-sectional diameter of 0.8 ⁇ m was obtained through a clear-comb-sand-sand-roving-spinning-winding-heat setting process to obtain a count of 60 s, a twist of 90 T/10 cm, and a twist coefficient of
  • the PPS single yarn of 282 is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 6 strands, and the twist of the yarn is 45T/10cm.
  • the twist factor is 346, and the ratio of the twist of the yarn to the twist of the single yarn is 0.50.
  • the obtained PPS yarn was subjected to plasma processing to obtain a hydrophilized PPS yarn having a graft ratio of 0.8%.
  • the prepared hydrophilized PPS yarn was woven as a warp yarn and a weft yarn by a loom to obtain a plain woven fabric having a warp density of 65.0/inch and a latitudinal density of 51.5/inch, and then the obtained woven fabric was subjected to a woven fabric. Refining, washing, drying, heat setting at 180 ° C, and then heat-setting the PPS woven fabric for plasma processing. Finally, the coverage coefficient was 2831, the thickness was 0.63 mm, the maximum pore diameter was 15 ⁇ m, and the average pore diameter was 3.2 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 91% of the total pores of the woven fabric, and the sheet resistance R was 6.4 m ⁇ cm 2 .
  • the physical properties of the PPS fiber structure of the present invention were evaluated and referred to Table 1 below.
  • the PPS fiber structures obtained in Examples 1 to 15 can be applied to separators for electrolytic devices, high-temperature liquid filtration, and insulating materials.
  • a circular PPS fiber with a cross-sectional diameter of 13 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 20 s, a twist of 56 T/10 cm, and a twist coefficient of 304 PPS.
  • Single yarn, the obtained PPS single yarn is spun through the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands obtained is 2 strands, and the warp and weft yarn twists are 60T/10cm, respectively.
  • the PPS yarn of 461 wherein the ratio of the twist of the PPS yarn to the twist of the single yarn is 1.07, and the obtained PPS yarn is woven as a warp and a weft by a weaving machine to obtain a warp density of 67.0/inch.
  • the woven fabric with a latitudinal density of 46.0/inch is then subjected to scouring, water washing, drying, heat setting at 180 ° C, and plasma hydrophilic processing.
  • the coverage coefficient was 2746
  • the thickness was 0.50 mm
  • the maximum pore diameter was 30 ⁇ m
  • the average pore diameter was 5.2 ⁇ m.
  • the pores below 6 ⁇ m accounted for more than 80% of the total pores of the woven fabric, and the sheet resistance R was 4.8 m ⁇ cm 2 .
  • the physical properties of the PPS fiber structure were evaluated and referred to Table 1 below.
  • a circular PPS fiber with a cross-sectional diameter of 14 ⁇ m was passed through a clear-comb-sand-grain-roving-filament-winding-heat setting process to obtain a count of 20 s, a twist of 56 T/10 cm, and a twist factor of 304.
  • the PPS single yarn is spun by the winding-and-yarn-twisting-heat setting cotton spinning process, and the number of strands is 4 strands, and the warp and weft yarns are 40T/10cm respectively.
  • the pores below 6 ⁇ m accounted for more than 40% of the total pores of the woven fabric, and the sheet resistance R was 3.4 m ⁇ cm 2 .
  • the physical properties of the PPS fiber structure were evaluated and referred to Table 1 below.

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Abstract

一种高性能聚苯硫醚纤维构造体及其制造方法和用途，该聚苯硫醚纤维构造体是由横截面直径为0.1～12μm的聚苯硫醚纤维形成的机织物，该聚苯硫醚纤维构造体的最大孔径为20μm以下。所述聚苯硫醚纤维构造体具有气密性高、亲水性好的特点，还具有工艺简单、节省能源、对环境无污染的特点，可应用于隔膜、高温液体过滤、绝缘材料中。

Description

一种高性能聚苯硫醚纤维构造体及其制造方法和用途 技术领域
本发明涉及一种高性能聚苯硫醚纤维构造体及其制造方法和用途。
背景技术
隔膜布是水电解槽的主要核心材料，水电解制氢、制氧设备又广泛用于军事、石化、钢铁等制造领域，目前国内主要的碱性水电解制氢设备厂家仍然使用石棉布作为隔膜。但是，随着工业化进程的推进和技术进步，在生产实践过程中，人们逐渐认识到石棉隔膜存在一些问题。石棉本身并无毒害，它的最大危害来自于它的纤维，这是一种非常细小、肉眼几乎看不见的纤维，当这些细小的纤维释放以后，会长时间浮游于空气中，容易被人体吸入。因此，国际社会都会加大对新型隔膜材料的研发力度，在我国隔膜布一直是水电解设备的主要核心材料，为适应日益激烈的国际竞争，把产品推向国际市场，用新一代非石棉隔膜布取代石棉隔膜布已势在必得。目前，正在采用聚苯硫醚纤维制得的隔膜布来代替石棉隔膜布，虽然解决了污染、气密性低等问题，但如果由于织造的PPS隔膜布使用的纤维纤度不合适以及单纱与股线捻度之间的配比不恰当，就会导致制得的隔膜的孔径大小不均一、气密性不好。
如中国公开专利CN101372752公开了一种采用普通聚苯硫醚纤维制成的非制造布，然后通过70～130℃，90～98％的H2SO4进行磺化处理20～40分钟，再用30％的氢氧化钾处理，最后得到耐高温碱性水电解槽隔膜。在该发明中，由于非织造布的吸液率相对较强，经过强酸处理后，在清洗过程中需要消耗大量宝贵的水资源和化学药品，清洗时间也较长，且工艺操作复杂，易对环境造成污染。同时安全性也差，不宜进行工业化生产。
如中国公开专利CN103938337A公开了一种采用普通2.2T聚苯硫醚纤维制成的高密机织布，然后通过等离子体亲水加工的方法赋予聚苯硫醚隔膜的亲水性能，最后得到耐高温耐碱的聚苯硫醚隔膜，该发明由于使用的单纤维纤度及单纱与股线捻度之间的配比不适当，导致制得的隔膜的气密性不好。除此之外，由于采用 等离子体亲水加工方法加工的PPS隔膜布，亲水效果不太好、而且时效性短，导致该隔膜无法真正满足生产的需要。
又如中国公开专利CN101195944公开了一种无石棉环保节能型隔膜，其采用以聚醚醚酮纤维、聚苯硫醚纤维、聚丙烯纤维中的一种、两种或三种为原料织造而成的机织物。虽然该隔膜布的气密性满足了石棉隔膜的标准要求，但由于上述化学纤维的吸水性差，导致制得的隔膜布亲水性差，无法真正满足使用要求。
发明内容
本发明的目的在于提供一种气密性更高、亲水性更好的高性能聚苯硫醚纤维构造体。
本发明的另一目的在于提供一种工艺简单、省能源、对环境无污染的高性能聚苯硫醚纤维构造体的制造方法。
为了达到上述目的，本发明的构成如下：
(1)本发明的聚苯硫醚纤维构造体是由横截面直径为0.1～12μm的聚苯硫醚纤维形成的机织物，该聚苯硫醚纤维构造体的最大孔径为20μm以下。
(2)构成上述(1)的聚苯硫醚纤维构造体的经纬纱为经过亲水化加工的聚苯硫醚短纤纱。
(3)上述(1)的聚苯硫醚纤维构造体的平均孔径为5μm以下，其中6μm以下的孔占纤维构造体全部孔的90％以上。
(4)构成上述(1)的的单纱支数为21～60s。
(5)构成上述(1)的纱线捻系数为180～350。
(6)构成上述(1)的聚苯硫醚纤维构造体的经纱捻度大于等于纬纱的捻度。
(7)上述(4)～(5)中任一项的的聚苯硫醚纤维构造体中聚苯硫醚纱线的捻度与聚苯硫醚单纱的捻度的比值为0.2～1.0。
(8)构成上述(1)的聚苯硫醚纤维构造体的气密性在400mmH2O以上。
(9)构成上述(1)的聚苯硫醚纤维构造体的面电阻为60mΩ.cm2以下。
本发明的有益效果是：本发明由于使用细度为0.1～12μm的聚苯硫醚纤维、以及单纱捻度与股线捻度之间的比值适当，克服了现有技术的孔径不均一、气密性低的缺陷，可以使制得的PPS机织物的孔径小且分布均匀，这就使得本发明的聚苯硫醚纤维构造体不仅具有气密性高、亲水性好的特点，还具有工艺简单、省 能源、对环境无污染的特点。本发明聚苯硫醚纤维构造体可应用于电解装置用隔膜、高温液体过滤、绝缘材料中。
具体实施方式
本发明聚苯硫醚纤维构造体是由横截面直径为0.1～12μm的聚苯硫醚纤维形成的机织物，该聚苯硫醚纤维构造体的最大孔径为20μm以下。在所有的织物组织中，平纹织物的交织点最多,紧密度最大，所以优选平纹机织物。如果聚苯硫醚纤维的横截面直径小于0.1μm，由于纤维太细，在梳理过程中会出现纤维梳理不开，单纤维断裂，出现成纱不良，棉结过多的现象，从而影响纱线的品质。如果用该纱线进行织造，有可能使得PPS布面的疵点过多，影响织物的厚度、孔径，从而致使织物的孔径、厚度不均匀，进一步造成织物的气密性差；如果聚苯硫醚纤维的横截面直经大于12μm，由于纤维的直径过粗，单纤维纱线过硬，不易成纱，另外纱线过粗也会带来织造困难，还会导致所得织物的孔径变大，织物的气密性变差，最终导致制备的氢气、氧气纯度不好；考虑到PPS织物气密性以及后加工过程中的亲水加工效果等综合因素，聚苯硫醚纤维的横截面直径优选6～10μm，更优选6～8μm。
构成该聚苯硫醚纤维构造体的经纬纱为经过亲水化加工的聚苯硫醚短纤纱。本发明的聚苯硫醚纤维构造体的经纬纱线均采用短纤维纱线，相比较长纤维纱线，短纤纱具有单纤维间抱合性强，不会因纱线的构造造成纤维之间的空隙增加，从而影响织物的孔径和气密性能。本发明中使用的短纤纱可以是单纱，也可以是有单纱构成的合股纱，优选合股纱线。为了保证聚苯硫醚纤维构造体具有优良的亲水性能，优选经过亲水加工过的聚苯硫醚短纤纱线。这里的亲水化是指通过等离子体、磺化或者接枝的方法增加聚苯硫醚纤维表面的亲水基团，如羟基，羧基，碳酸根，硫酸根基团等。经亲水化处理的聚苯硫醚纱线的接枝率为0.1～3％，接枝率优选为0.5～3％。
本发明的聚苯硫醚纤维构造体的最大孔径为20μm以下，如果聚苯硫醚纤维构造体的最大孔径大于20μm的话，则聚苯硫醚纤维构造体的孔径过大，就会导致其使用在制氢设备中时，氢气、氧气气泡易穿过纤维构造体的空隙，降低了单一气体的纯度。聚苯硫醚纤维构造体的最大孔径为20μm以下，为了使聚苯硫醚纤维构造体的孔径均一、孔径的尺寸分布聚集、集中，聚苯硫醚纤维构造体的最 大孔径优选15μm以下，为了使得纤维构造体的孔径更均一、孔径的尺寸分布更聚集、更集中，聚苯硫醚纤维构造体的最大孔径优选12μm以下。
本发明聚苯硫醚纤维构造体的平均孔径为5μm以下，其中6μm以下的孔占纤维构造体全部孔的90％以上。聚苯硫醚纤维构造体的平均孔径控制在上述范围内的话，就能保证气密性高，这样气体分子、气泡就难于通过，从而阻止阳极侧气体和阴极侧气体的混合,以保证气体的纯度且安全性好。若聚苯硫醚纤维构造体的平均孔径大于5μm，由于机织物的孔径过大，机织物在制氢设备中使用时，起不到隔离的作用，最终导致制备的氢气、氧气纯度低，达不到客户的使用要求。为了保证本发明机织物的气密性使用要求，同时提高气体的发生效率，并提高生成气体的纯度，在平均孔径5μm以下范围内的前提下，优化织造条件，提高孔径的均匀性，使孔径在6μm以下的孔占全部孔的90％以上，优选95％以上。
构成聚苯硫醚机织物的单纱支数选为21～60s、捻系数α为200～310。单纱的支数在上述范围可以保证所制得的PPS织物孔径小且均一、气密性高，还可以使所得机织物在后道的亲水加工效果好。如果单纱支数过低的话，纱线太粗，导致机织物的孔径大，机织物的气密性小，最终导致制备的氢气、氧气纯度不好；如果单纱支数过高的话，势必需要很细的纱线，这样就会导致生产过程困难。另外，单纱的捻系数在上述范围内可以保证所制得的PPS纱线蓬松感适中，使得机织物的孔径小且均一、气密性高，还可以使得机织物在后道的亲水加工效果好。如果纱线的捻系数过小的话，纱线的捻度太低，导致纱线的强力低，织造时易断纱，制得的织物的强力就会变低；如果纱线的捻系数过大的话，纱线的捻度太高，织物的交织点处空隙明显，孔径增大；另一方面，纱线内部纤维间的空隙也会变小，从而导致整个机织物的孔径大小不均一，气密性降低。
构成所述聚苯硫醚机织物的纱线捻系数为180～350，若纱线的捻系数过低的话，则导致单纤维的捻回角小，纤维间的抱合力减小，纱线的强度降低，导致在织造过程中由于纱线的强力低，难以织造；若纱线的捻系数过高的话，则导致纤维间的抱合力过大，纱线的强力降低，且容易在织造过程中易出现小辫子，不易织造。
织造上机时，经纱受到的张力比纬纱引纬张力大，为了保证聚苯硫醚织物的织造效率，使得织物的构造紧密，孔径小且孔径均匀性好，优选构成本发明聚苯 硫醚纤维构造体的经纱捻度大于等于纬纱的捻度。经纱捻度略大，可以保证经纱的强度，提高开口率，利于织造。纬纱选用略低捻度的短纤纱，纱线蓬松，可以弥补因经纱捻度提高带来的孔径增大和不匀的缺陷。
本发明的聚苯硫醚纱线的捻度与聚苯硫醚单纱的捻度的比值为0.2～1.0，纱线捻度与单纱捻度的比值在上述范围内可以保证机织物的孔径均一，还可以使得机织物在亲水加工过程中，接上的亲水基团数目多，就会使机织物的含液率增加，在机织物表层形成的水膜较厚，可以有效地阻止气泡穿过，使得气体纯度增加。如果聚苯硫醚纱线的捻度与单纱捻度的比值过小的话，纱线的捻度势必就会降低，导致聚苯硫醚纱线的强度低，制得的聚苯硫醚机织物的强力就会变低，从而就会导致机织物容易被穿破；如果聚苯硫醚的纱线捻度与单纱捻度的比值过大的话，会导致纱线内部纤维间的空隙变小，从而导致整个机织物的孔径大小不均一，气密性低下导致机织物的孔径不均一，而且使得接上去的亲水基团数目少。
本发明聚苯硫醚纤维构造体的气密性在400mmH2O以上。将该聚苯硫醚纤维构造体应用于水电解槽时，在满足400mm以上H2O压力下,保持2min不透气的条件下，可以基本满足实际水电解槽中隔膜布的气密性使用要求，且同时考虑到隔膜布能具有优异的气密性、离子的通过效率以及隔膜布的加工性。如果气密性小于400mmH2O压力，无法满足隔膜基本需求，生成的气体纯度受影响。
本发明聚苯硫醚纤维构造体的面电阻为60mΩ.cm2以下，优选面电阻为10mΩ.cm2以下。如果聚苯硫醚纤维构造体的面电阻大于60mΩ.cm2的话，导致织物的阻抗大，增加电能的消耗，而且生产成本也增加。
本发明聚苯硫醚纤维构造体的吸碱率为70～200％，如果聚苯硫醚纤维构造体的吸碱率过低，则在碱液里就难于形成水膜或水膜过薄，不能有效地阻止气泡的通过，从而降低了气体的纯度；如果聚苯硫醚纤维构造体的吸碱率过高，势必导致机织物的构造比较松散，空隙增大，从而影响到隔膜的性能。考虑到聚苯硫醚纤维构造体的亲水性及构造，本发明聚苯硫醚纤维构造体的吸碱率优选85～180％，更优选100～160％。
本发明的高性能聚苯硫醚纤维构造体是应用在制氢设备中，主要作用是离子可以通过，气体分子不可以通过。由于不同客户对制的氢气、氧气的纯度要求不一样，所以对织物的孔径大小及气密性要求也不一样，这和织物的类型及组织无 关，只要气体分子间不相互穿透即可满足客户要求。
本发明的高性能聚苯硫醚纤维构造体的制造方法，包括如下步骤：
(1)棉纺工艺：将横截面直径为0.1～12μm的聚苯硫醚纤维经过开清棉-梳棉-并条-粗纱，将粗纱经过牵伸制得支数为20～60s、捻系数α为200～310的聚苯硫醚单纱，再经过络筒-并线-加捻-热定型制得股数为1～6股的聚苯硫醚纱线；
(2)织造工艺：制得的聚苯硫醚纱线经过整经-穿综-插筘-织造，制得覆盖系数为2400～2900的聚苯硫醚机织物；机织物的覆盖系数是表征织物紧密程度的参数，覆盖系数越高，织物越紧密，通气度和孔径就越小，如果平纹机织物的覆盖系数低于2400，由于织物紧度不够，导致织物的气密性低，这样机织物就难于阻挡气体的通过，从而不能保证气体的纯度以及制造过程的安全性；如果平纹机织物的覆盖系数高于2900，对织机有较高的要求，织造困难。机织物的覆盖系数优选2600～2800；
(3)后整理工艺：将制得的聚苯硫醚机织物进行精练、水洗、干燥、180～200℃下热定型；上述精练、热定型的最佳实验条件如下：
a.使用的精练剂:YK30 12g/L、YS66 3.0g/L、YK37 2.0g/L、
b.精练槽温度：1槽40～50℃、2槽70～80℃、3槽95～105℃、
c.速度：10～14m/min、
d.热定型温度：180℃～210℃、
e.热定型速度：10～14m/min；
(4)亲水化处理工艺：将定型后的织物经过等离子体或/和磺化亲水加工，最终制得成品。通过将织物进行等离子体或/和磺化亲水加工，可以在PPS纤维表面接上亲水基团，可以增加PPS机织物的润湿速度，同时还可以增加PPS机织物的含液率，使得在使用过程中，气体的生产效率提高且纯度高。经过等离子体或/和磺化亲水加工，制得织物的接枝率会有不同，优选PPS机织物的接枝率为3.0～8.0％。
上述等离子体亲水加工方法，包括常压等离子体加工、低压等离子体加工，常压等离子体加工的方法包括辉光放电、无声放电、电晕放电，其中辉光放电包括直流电流、高频电流、微波辐射，低压等离子体加工处理的气体可以为氧气、氩气、氮气等，考虑到加工的可能性、加工的稳定性、加工的效率，等离子体亲 水加工优选常压等离子体辉光直流放电，常压等离子体辉光直流放电的条件为，电压5～15v、电流12～18A、接上的氧元素的含量占所测到的元素含量的15～25％。等离子体加工后，在PPS纤维的表面有凹凸的小坑生成，这样可以增加PPS机织物的毛细效应及吸水性，除此之外，在PPS纤维的表层接上亲水基团，亲水基团为硫酸根、羧酸根、碳酸根、羟基、羰基等，接上的这些亲水基团的作用可以增加PPS纤维的吸水速度，还可以提高氢气、氧气的纯度。
当定型后的织物同时采用等离子体和磺化加工时，定型后的织物进行等离子体处理，使得PPS纱线物理刻蚀，使得在纤维的表层形成凹凸的坑，增加了PPS纤维的比表面积；然后再将等离子体处理后的PPS织物经过磺化加工处理，这样可以增加接上亲水基团的数目，使得PPS织物的亲水效果更好。
为了使制得的PPS织物具有更好的亲水效果，优选将步骤(1)中制得的PPS纱线经过等离子体加工、磺化加工、接枝共聚处理方法中的至少一种加工，制得亲水性的聚苯硫醚纱线。由于单一的等离子体加工，可能存在耐久性差，且织物经过精练后会亲水性能下降。接枝共聚的方式在后加工过程中，因药剂和高温的影响造成亲水性能下降，所以更优选PPS纱线经过磺化加工，或更优选PPS纱线在等离子体加工后，再进行磺化加工。
磺化加工的方法，是将纱线经过温度为80～120℃磺化处理液(85～98％的氯磺酸或浓硫酸)处理1～5min、在PPS纤维的表层接上亲水基团硫酸根等。等离子体加工方法可以选择常压等离子体加工或真空等离子体加工，使其表面形成凹凸的小坑，增加PPS纤维的毛细效应及吸水性，同时在PPS纤维的表层接上亲水基团硫酸根、羧酸根、碳酸根、羟基、羰基等，接上的这些亲水基团的作用可以增加PPS纤维的吸水速度，还可以提高氢气、氧气的纯度。
通过以下实施例，对本发明作进一步说明。但本发明的保护范围并不限于这些实施例。
在实施例中，各物性用以下方法测定或用以下公式计算。
【覆盖系数】
机织物的覆盖系数的计算公式如下：
Figure PCTCN2016096309-appb-000001
其中：NW：织物的经向密度(根/英寸)；
DW：织物中经向长丝的细度(dtex)；
Nf：织物的纬向密度(根/英寸)；
Df：织物中纬向长丝的细度(dtex)。
【平均孔径】
根据ASTMF316-03标准，采用毛细管流动空隙测量仪(PMI公式产品，型号：CFP-1100-AE)测量织物孔径，设定工作模式为wet-up/dry-down模式。测试环境为23℃，50％RH。将织物样品放在样品室中，用表面张力为19.1dynes/cm的斯维克酮液(silwick silicone Fluid)润湿。样品室的底部夹件具有直径2.54cm、厚度为3.175mm的多孔金属盘插件，样品室的顶部夹件具有3.175mm直径的孔洞，织物平均孔径的值可以直接读出。取两次测量的平均值为最终的平均孔径值。
【气密性】
根据中国建材行业标准JCT 211-2009“隔膜石棉布”第4.5.2项“气密性能测试”进行测定。
【吸水率】
根据GB/T21655.1-2008测定经亲水处理前后的隔膜布的吸水率。
【吸水速度】
根据JIS L1907-2010“纤维制品的吸水性试验方法”第7.1.1项“滴下法”进行测试。
【面电阻】
根据中华人民共和国电子工业行业标准SJ/T 10171.5-91碱性蓄电池隔膜面电阻的测试标准，设置的测试PPS隔膜面电阻的设备，设备的设置参数如下：
(1)低温恒温槽控制装置
a.低温恒温槽控制装置的温度范围-5～100℃，温控偏差±0.05，
(该仪器为上海庚庚仪器设备有限公司,型号为：DC0506)；
b.工作温度60℃，液体介质一般选用二甲基硅油。
(2)电池内阻测试仪
a.规格型号：AT526(常州安柏精密仪器有限公司)；
b.测试电阻准确度：0.5％、电压：0.01％；
c.测试范围：电阻0.0005毫欧～33欧、电压：0.00001～120v的直流电压；
d.内阻仪配件：1m测试探针ATL502A；1m测试线ATL502；1.8Mrs232通行
电缆ATL108；保险丝(在电源插座内)0.5A SB。
(3)测试电阻槽的设置参数
a.槽的材质:PTFE材料；
b.电极材料纯银(99.9999％)；
c.两电极间的距离：23mm；
d.PPS隔膜的面积长*宽＝4cm*2cm。
e.使用的KOH碱液：温度:60℃、质量浓度:Wt 30％。
(4)实验时使用的实验药品
a.KOH Wt 30％(氢氧化钾：优级纯)；
b.配碱液使用的水为二级超纯去离子水。
(5)测试环境:温度为20℃、湿度为60％RH的恒温恒湿环境。
【接枝率】
用0.1mol/L的NaOH标准溶液滴定磺化后的PPS机织物(酚酞作指示剂)，根据所消耗的NaOH的量计算机织物的接枝率，接枝率的计算公式如下：接枝率％＝(0.01V*108)/1000W*100％，其中：V为消耗NaOH的毫升数，W为参加滴定的磺化后PPS隔膜布的质量，108是聚苯硫醚单体的相对分子质量。
【吸碱率】
裁取40mm*40mm大小的机织物称重G1，将其浸泡在30％浓度的氢氧化钾溶液里，浸泡4小时取出。悬挂半分钟，使碱液液滴滴出后，称重G2，得到吸碱率。吸碱率的计算公式如下：
A＝(G1-G2)/G1*100％，
式中：A：隔膜吸碱率％；
G1：浸碱前试样质量g；
G2：浸碱后试样质量g。
实施例1
将横截面直径为10μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为40s、捻度为81T/10cm、捻系数为311的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为4股，经、纬纱捻度分别为45T/10cm、捻系数为346的PPS纱线，其 中PPS纱线的捻度与单纱的捻度的比值为0.56，将制得的PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为55.3根/英寸、纬向密度为48.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2510、厚度为0.64mm、最大孔径为16μm、平均孔径为3.0μm，其中6μm以下的孔占机织物全部孔的94％以上，面电阻R为2.2mΩ.cm2，经纬向强力分别为900N/3cm、602N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例2
将实施例1所制得的PPS纱线经过98％浓度的90℃的浓硫酸处理3min，得到接枝率为1.8％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为55.0根/英寸、纬向密度为48.7根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2520、厚度为0.63mm、最大孔径为15μm、平均孔径为3.0μm，其中6μm以下的孔占机织物全部孔的95％以上，面电阻R为1.3mΩ.cm2，经纬向强力分别为750N/3cm、521N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例3
将横截面直径为8μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为60s、捻度为90T/10cm、捻系数为282的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为6股，经、纬纱捻度分别44T/10cm、捻系数为338的PPS纱线，其中PPS纱线的捻度与单纱的捻度的比值为0.49，将制得的PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为66.3根/英寸、纬向密度为39.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2559、厚度为0.64mm、最大孔径为17μm、平均孔径为4.9μm，其中6μm以下的孔占机织物全部孔的92％以上，面电阻R为1.5mΩ.cm2，经纬向强力分别为991N/3cm、654N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例4
将横截面直径为8μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为40s、捻度为57T/10cm、捻系数为219的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为4股，经、纬纱捻度分别为47T/10cm、捻系数为361的PPS纱线，其中PPS纱线的捻度与单纱的捻度的比值为0.82，将制得的PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为68.8根/英寸、纬向密度为43.7根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进等离子体加工。最终制得覆盖系数为2734、厚度为0.62mm、最大孔径为18μm、平均孔径为4.5μm，其中6μm以下的孔占机织物全部孔的93％以上，面电阻R为1.6mΩ.cm2，经纬向强力分别为1014N/3cm、711N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例5
将横截面直径为9μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为20s、捻度为48T/10cm、捻系数为261的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，经、纬纱捻度分别为40T/10cm、捻系数为307的PPS纱线，其中PPS纱线的捻度与单纱的捻度的比值为0.83，将制得的PPS纱线经过98％浓度的90℃的浓硫酸处理3min，得到接枝率为1.3％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为68.3根/英寸、纬向密度为45.2根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进磺化加工。最终制得覆盖系数为2758、厚度为0.61mm、最大孔径为19μm、平均孔径为3.3μm，其中6μm以下的孔占机织物全部孔的95％以上，面电阻R为2.0mΩ.cm2，经纬向强力分别为1031N/3cm、846N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例6
将横截面直径为10μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱- 络筒-热定型过程,制得支数为40s、捻度为81T/10cm、捻系数为311的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，经、纬纱捻度分别为71T/10cm、捻系数为386的PPS纱线，其中PPS纱线的捻度与单纱的捻度的比值为0.88，将制得的PPS纱线经过常压等离子体处理后，再经过85％浓度的95℃的浓硫酸处理3min，得到接枝率为2.6％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为88.0根/英寸、纬向密度为64.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物先进行等离子体加工，再进行磺化亲水加工。最终制得覆盖系数为2612、厚度为0.41mm、最大孔径为16μm、平均孔径为3.0μm，其中6μm以下的孔占机织物全部孔的94％以上，面电阻R为2.2mΩ.cm2，经纬向强力分别为900N/3cm、602N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例7
将横截面直径为11μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为60s、捻度为90T/10cm、捻系数为282的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，经、纬纱捻度分别为76T/10cm、捻系数为337的PPS纱线，其中PPS纱线的捻度与单纱的捻度的比值为0.84，将制得的PPS纱线经过通过聚脂类亲水树脂汽蒸，得到接枝率为0.6％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为113.0根/英寸、纬向密度为60.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物先进行等离子体加工后，再进行磺化加工。最终制得覆盖系数为2427、厚度为0.35mm、最大孔径为18μm、平均孔径为4.3μm，其中6μm以下的孔占机织物全部孔的91.5％以上，面电阻R为2.4mΩ.cm2，经纬向强力分别为640N/3cm、400N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例8
将横截面直径为4μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱- 络筒-热定型过程,制得支数为60s、捻度为90T/10cm、捻系数为282的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，经、纬纱捻度分别为76T/10cm、捻系数为337的PPS纱线，其中PPS纱线的捻度与单纱的捻度的比值为0.84，将制得的PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为113.0根/英寸、纬向密度为65.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2497、厚度为0.30mm、最大孔径为16μm、平均孔径为4.2μm，其中6μm以下的孔占机织物全部孔的90％以上，面电阻R为1.4mΩ.cm2，经纬向强力分别为625N/3cm、378N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例9
将横截面直径为7μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为60s、捻度为90T/10cm、捻系数为282的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为4股，经、纬纱捻度分别为54T/10cm、捻系数为339的PPS纱线，其中PPS纱线的捻度与单纱的捻度的比值为0.60，将制得的PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为90.0根/英寸、纬向密度为60.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2976、厚度为0.40mm、最大孔径为16μm、平均孔径为4.4μm，其中6μm以下的孔占机织物全部孔的91％以上，面电阻R为1.4mΩ.cm2，经纬向强力分别为900N/3cm、570N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例10
将横截面直径为11μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为20s、捻度为56T/10cm、捻系数为304的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，经、纬纱捻度分别为24T/10cm、捻系数为184的PPS纱线，其 中PPS纱线的捻度与单纱的捻度的比值为0.43，将制得的PPS纱线经过经过常压等离子体处理后，再经过85％浓度的95℃的浓硫酸处理3min，得到接枝率为2.8％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为58.0根/英寸、纬向密度为54.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2722、厚度为0.51mm、最大孔径为19μm、平均孔径为4.8μm，其中6μm以下的孔占机织物全部孔的90.5％以上，面电阻R为3.6mΩ.cm2，经纬向强力分别为780N/3cm、602N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例11
将横截面直径为8μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为20s、捻度为48T/10cm、捻系数为261的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，用作经纱的捻度为40T/10cm、捻系数为307，经纱的捻度与单纱的捻度的比值为0.83；用作纬纱的捻度为36T/10cm、捻系数为277，纬纱的捻度与单纱的捻度的比值为0.75。将制得的PPS纱线经过98％浓度的90℃的浓硫酸处理3min，得到接枝率为1.5％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为68.3根/英寸、纬向密度为44.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2729、厚度为0.62mm、最大孔径为18μm、平均孔径为2.9μm，其中6μm以下的孔占机织物全部孔的96％以上，面电阻R为2.0mΩ.cm2，经纬向强力分别为820N/3cm、658N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例12
将横截面直径为8μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为40s、捻度为81T/10cm、捻系数为311的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，用作经纱的捻度为80T/10cm、捻系数为435，经纱的捻度与单纱 的捻度的比值为0.99；用作纬纱的捻度为60T/10cm、捻系数为326，纬纱的捻度与单纱的捻度的比值为0.74。将制得的PPS纱线经过98％浓度的90℃的浓硫酸处理3min，得到接枝率为1.8％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为88.0根/英寸、纬向密度为62.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2577、厚度为0.42mm、最大孔径为15μm、平均孔径为3.0μm，其中6μm以下的孔占机织物全部孔的94％以上，面电阻R为2.1mΩ.cm2，经纬向强力分别为769N/3cm、512N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例13
将横截面直径为6μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为60s、捻度为90T/10cm、捻系数为282的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为3股，用作经纱的捻度为54T/10cm、捻系数为293，经纱的捻度与单纱的捻度的比值为0.60；用作纬纱的捻度为40T/10cm、捻系数为217，纬纱的捻度与单纱的捻度的比值为0.44。将制得的PPS纱线通过织机进行织造，制得经向密度为95.0根/英寸、纬向密度为68.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2801、厚度为0.48mm、最大孔径为12μm、平均孔径为2.3μm，其中6μm以下的孔占机织物全部孔的96％以上，面电阻R为1.9mΩ.cm2，经纬向强力分别为611N/3cm、457N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例14
将横截面直径为10μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为20s、捻度为48T/10cm、捻系数为261的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，用作经纱的捻度为36T/10cm、捻系数为277，经纱的捻度与单纱的捻度的比值为0.75；用作纬纱的捻度为40T/10cm、捻系数为307，纬纱的捻 度与单纱的捻度的比值为0.83。将制得的PPS纱线经过98％浓度的90℃的浓硫酸处理3min，得到接枝率为1.3％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为58.2根/英寸、纬向密度为50.3根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行磺化加工。最终制得覆盖系数为2637、厚度为0.59mm、最大孔径为17μm、平均孔径为3.9μm，其中6μm以下的孔占机织物全部孔的95％以上，面电阻R为2.3mΩ.cm2，经纬向强力分别为698N/3cm、856N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例15
将横截面直径为0.8μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为60s、捻度为90T/10cm、捻系数为282的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为6股，纱线的捻度为45T/10cm、捻系数为346，纱线的捻度与单纱的捻度的比值为0.50。将制得的PPS纱线经过等离子体加工，得到接枝率为0.8％的亲水化PPS纱线。将制得的亲水化PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为65.0根/英寸、纬向密度为51.5根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再将热定型后的PPS机织物进行等离子体加工。最终制得覆盖系数为2831、厚度为0.63mm、最大孔径为15μm、平均孔径为3.2μm，其中6μm以下的孔占机织物全部孔的91％以上，面电阻R为6.4mΩ.cm2，经纬向强力分别为780N/3cm、692N/3cm的PPS纤维构造体。评价本发明PPS纤维构造体的各物性，并参见下表1。
实施例1～15中制得的PPS纤维构造体可应用于电解装置用隔膜、高温液体过滤、绝缘材料中。
比较例1
将横截面直径为13μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为20s、捻度为56T/10cm、捻系数为304PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为2股，经、纬纱捻度分别为60T/10cm、捻系数为461的PPS纱线，其中PPS 纱线的捻度与单纱的捻度的比值为1.07，将制得的PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为67.0根/英寸、纬向密度为46.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再进行等离子体亲水加工。最终制得覆盖系数为2746、厚度为0.50mm、最大孔径为30μm、平均孔径为5.2μm，其中6μm以下的孔占机织物全部孔的80％以上，面电阻R为4.8mΩ.cm2，经纬向强力分别为1280N/3cm、903N/3cm的PPS纤维构造体。评价该PPS纤维构造体的各物性，并参见下表1。
比较例2
将横截面直径为14μm的圆形PPS纤维，通过清绵-梳绵-并条-粗纱-细纱-络筒-热定型过程,制得支数为20s、捻度为56T/10cm、捻系数为304的PPS单纱，将制得的PPS单纱通过络筒-并纱-加捻-热定型的棉纺工艺进行纺纱，制得的股数为4股，经、纬纱捻度分别为40T/10cm、捻系数为435的PPS纱线，其中PPS纱线的捻度与单纱的捻度的比值为0.71，将制得的PPS纱线作为经纱和纬纱通过织机进行织造，制得经向密度为45.0根/英寸、纬向密度为30.0根/英寸的平纹坯布，然后将制得的坯布进行精练、水洗、干燥、180℃下热定型，再进行等离子体亲水加工。最终制得覆盖系数为2577、厚度为0.80mm、最大孔径为40μm、平均孔径为8.3μm，其中6μm以下的孔占机织物全部孔的40％以上，面电阻R为3.4mΩ.cm2，经纬向强力分别为1691N/3cm、1319N/3cm的PPS纤维构造体。评价该PPS纤维构造体的各物性，并参见下表1。
表1
Figure PCTCN2016096309-appb-000002

Claims (12)

  1. 一种高性能聚苯硫醚纤维构造体，其特征在于：该聚苯硫醚纤维构造体是由横截面直径为0.1～12μm的聚苯硫醚纤维形成的机织物，该聚苯硫醚纤维构造体的最大孔径为20μm以下。
  2. 根据权利要求1所述的高性能聚苯硫醚纤维构造体，其特征在于：构成该聚苯硫醚纤维构造体的经纬纱为经过亲水化加工的聚苯硫醚短纤纱。
  3. 根据权利要求1所述的高性能聚苯硫醚纤维构造体，其特征在于：该聚苯硫醚纤维构造体的平均孔径为5μm以下，其中6μm以下的孔占纤维构造体全部孔的90％以上。
  4. 根据权利要求1所述的高性能聚苯硫醚纤维构造体，其特征在于：构成所述机织物的聚苯硫醚单纱支数为21～60s。
  5. 根据权利要求1所述的高性能聚苯硫醚纤维构造体，其特征在于：构成所述机织物的聚苯硫醚纱线捻系数为180～350。
  6. 根据权利要求1所述的高性能聚苯硫醚纤维构造体，其特征在于：构成该聚苯硫醚纤维构造体的经纱捻度大于等于纬纱的捻度。
  7. 根据权利要求4或5所述的高性能聚苯硫醚纤维构造体，其特征在于：所述聚苯硫醚纱线的捻度与聚苯硫醚单纱的捻度的比值为0.2～1.0。
  8. 根据权利要求1或2所述的高性能聚苯硫醚纤维构造体，其特征在于：该聚苯硫醚纤维构造体的气密性在400mmH2O以上。
  9. 根据权利要求1或2所述的高性能聚苯硫醚纤维构造体，其特征在于：该聚苯硫醚纤维构造体的面电阻为60 mΩ.cm2以下。
  10. 一种权利要求1所述的高性能聚苯硫醚纤维构造体的制造方法，其特征在于：包括如下步骤：
    (1)棉纺工艺：将横截面直径为0.1～12μm的聚苯硫醚纤维经过开清棉-梳棉-并条-粗纱，将粗纱经过牵伸制得支数为20～60s、捻系数α为200～310的聚苯硫醚单纱，再经过络筒-并线-加捻-热定型制得股数为1～6股的聚苯硫醚纱线；
    (2)织造工艺：将制得的聚苯硫醚纱线经过整经-穿综-插筘-织造，制得覆盖系数为2400～2900的聚苯硫醚机织物；
    (3)后整理工艺：将制得的聚苯硫醚机织物进行精练、水洗、干燥、180～200℃ 下热定型；
    (4)亲水化处理工艺：将定型后的织物经过等离子体或/和磺化亲水加工，最终制得成品。
  11. 根据权利要求10所述的高性能聚苯硫醚纤维构造体的制造方法，其特征在于：将步骤(1)中制得的聚苯硫醚纱线经过等离子体加工、磺化加工、接枝共聚处理方法中的至少一种加工，制得亲水性的聚苯硫醚纱线。
  12. 一种权利要求1所述的高性能聚苯硫醚纤维构造体在电解装置用隔膜、高温液体过滤、绝缘材料中的应用。
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