WO2015120810A1 - 一种基于芳香族聚酰胺和聚芳砜的共混纤维、纱线、织物、制品及其制备方法 - Google Patents

一种基于芳香族聚酰胺和聚芳砜的共混纤维、纱线、织物、制品及其制备方法 Download PDF

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WO2015120810A1
WO2015120810A1 PCT/CN2015/072962 CN2015072962W WO2015120810A1 WO 2015120810 A1 WO2015120810 A1 WO 2015120810A1 CN 2015072962 W CN2015072962 W CN 2015072962W WO 2015120810 A1 WO2015120810 A1 WO 2015120810A1
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fiber
fibers
weight
organic solvent
stretching
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PCT/CN2015/072962
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English (en)
French (fr)
Inventor
汪晓峰
陈晟晖
吴佳
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上海特安纶纤维有限公司
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Publication of WO2015120810A1 publication Critical patent/WO2015120810A1/zh

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D02G3/047—Blended or other yarns or threads containing components made from different materials including aramid fibres
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
    • D01F6/765—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products from polyarylene sulfides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
    • 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

Definitions

  • Aromatic polyamides are generally widely used as fibers for industrial fibers and special clothing due to their excellent heat resistance.
  • the aramid fibers of the prior art have poor alkali resistance and have low strength retention when used under alkaline conditions.
  • CN1656630A provides a nonwoven fabric for an alkaline battery separator and a method for producing the same.
  • the dicarboxylic acid component containing 60 mol% or more of the dicarboxylic acid component is an aromatic dicarboxylic acid component
  • 60 mol% or more of the diamine component is a diamine component of a fatty acid alkylene diamine having 6 to 12 carbon atoms.
  • a nonwoven fabric for an alkaline battery film of a semi-aromatic polyamide fiber or an ethylene-vinyl alcohol copolymer fiber still cannot improve the alkali resistance of the aramid fiber, but only improves the alkali resistance of the fabric.
  • polyarylsulfone has good alkali resistance and temperature resistance, but polyarylsulfone generally cannot be made into fibers alone.
  • blends with aramid polymers are also only concerned with shaped articles (as disclosed in CN102782018A), not fibers, and there is no explicit mention in the literature of aramid and polyarylsulfone. Mixed.
  • the aromatic polyamide is phthaloyl p-phenylenediamine, m-phenylene isophthalamide, polysulfone amide, polyparabenzamide.
  • the strength retention rate of the immersion in a 10% NaOH solution at 85 ° C for 5 hours is 70% or more, preferably 80% or more, more preferably 85% or more.
  • it has a strength of 2.5 cN/dtex or more, preferably 2.5-3.5 cN/dtex, more preferably 2.8-3.2 cN/dtex.
  • it has a glass transition temperature of 280 ° C or higher, preferably a glass transition temperature of 300 ° C or higher, more preferably 340 ° C or higher, and most preferably 350 ° C or higher.
  • the invention further relates to a method of preparing a blended fiber based on an aromatic polyamide and a polyarylsulfone, comprising the steps of:
  • the weight ratio of the aromatic polyamide to the polyarylsulfone added in the step (i) is from 50 to 98:2 to 50, preferably from 60 to 95:5 to 40, more preferably from 70 to 90:10 to 30, most Preferably 80-85: 15-20.
  • the mass percentage concentration of the polymer in the spinning solution in step (i) is from 5 to 30% by weight, more preferably from 10 to 22% by weight, most preferably from 12 to 20% by weight.
  • the coagulation bath of the solidification filament forming step comprises a polar organic solvent and a metal halide; preferably, the polar organic solvent is contained in an amount of 40 to 70% by weight, and the metal halide is contained in an amount of 0 to 10% by weight.
  • the stretching bath in the stretching step comprises a polar organic solvent and a metal halide; preferably, the content of the polar organic solvent is 5 to 65 wt%, and the content of the metal halide is 0 to 10 wt%.
  • the organic solvent in the coagulation bath and the stretching bath may be independently selected from N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylmethyl. a mixture of one or more of amide (DMF), dimethyl sulfoxide, hexamethylphosphoric triamide (HMPA), N, N, N', N'-tetramethylurea (TMU), and
  • NMP N-methylpyrrolidone
  • DMAc N,N-dimethylacetamide
  • HMPA hexamethylphosphoric triamide
  • TNU hexamethylphosphoric triamide
  • TNU hexamethylphosphoric triamide
  • TNU hexamethylphosphoric triamide
  • TNU hex
  • the metal halide in the coagulation bath and the stretching bath may be independently selected from one or more of calcium chloride, magnesium chloride, aluminum chloride, calcium bromide, magnesium bromide, and aluminum bromide.
  • the mixture, and the metal halide in the coagulation bath and the stretching bath may be the same or different.
  • the invention also relates to a yarn comprising the fibers.
  • the yarn further comprises a selected from the group consisting of polyaryletherketone, aramid, high molecular weight polyethylene, polyphenylene sulfide, polyetheretherketone, polyetherimide, polyaroyl. a fiber obtained by mixing one or more of imine, polybenzimidazole, polybenzoxazole, polyphenylene sulfone, polydiphenyl ether sulfone, polyphenylene, polyimide sulfone .
  • the invention also relates to a fabric comprising the fibers.
  • the fabric is a woven, knitted or nonwoven structure.
  • the fabric further comprises glass fiber, asbestos fiber, polybenzoxazole fiber, polybenzimidazole fiber, polybenzoxazole fiber, poly(arylene ether fiber) and aramid fiber, carbon fiber, PTFE fiber, One of boron fiber, metal fiber, ceramic fiber, calcium silicate fiber, silicon carbide fiber, metal puff, polyacrylonitrile fiber, aramid fiber, phenolic resin or a mixture thereof.
  • the invention also relates to a protective garment comprising the fibers.
  • the invention also relates to a laminate comprising the fibers.
  • a blend spinning solution of an aromatic polyamide and a polyarylsulfone is prepared by adding an aromatic polyamide or a polyarylsulfone to an organic solvent, wherein the concentration of the polymer in the spinning solution is 5-30% by weight;
  • the weight ratio of the polyamide to the polyarylsulfone is from 60 to 98: 2 to 40, even if the resulting fiber contains 60 to 98% by weight of the aromatic polyamide, and 2 to 40% by weight of the polyarylsulfone.
  • the obtained blended fibers based on aromatic polyamide and polyarylsulfone can not only maintain the temperature resistance and mechanical properties of the aramid fiber, but also have better alkali resistance than the aramid fiber.
  • aromatic polyamide in the present invention means a synthetic polymer material having a sufficiently high molecular weight to form fibers, and is mainly characterized by the following cyclic structural units:
  • each of R 1 is hydrogen or a lower alkane
  • Ar 1 and Ar 2 may be the same or different, and may be an unsubstituted or substituted divalent aryl group, these divalent
  • the linking bond of the aryl group to other groups is mainly arranged in a meta or para position, and the hydrogen on the divalent aryl group may be independently substituted or unsubstituted by one or more of the following substituents. Including halogen, C1-C4 alkyl, C1-C4 alkoxy, phenyl, acyloxy, nitro, dialkylamino, thioalkyl, carboxy, sulfonyl, carbonyl alkoxy. Among them, terephthaloyl p-phenylenediamine (PPTA) and m-phenylene isophthalamide (PMIA) are preferred.
  • PPTA terephthaloyl p-phenylenediamine
  • PMIA m-phenylene
  • aromatic polyamide in the present invention is also understood to mean that Ar 1 and Ar 2 in the macromolecular chain may be the same or different and have the following structure:
  • X and Y are independently selected from the group consisting of -O-, -CH 2 -, -CO-, -CO 2 -, -S-, -SO 2 -, -C(CH 3 ) 2 -, and X and Y may be The same or different. Among them, polysulfone amide is preferred.
  • a and B may represent an optionally substituted aromatic group.
  • the aromatic group consists of 6 to 40 carbon atoms, preferably 6 to 21 carbon atoms, i.e. contains one or more optional aryl groups, wherein the aryl group can optionally contain heteroatoms. These aryl groups are optionally substituted by a linear or branched or alicyclic C1-C5 group or a halogen atom.
  • the aryl group can be linked via a carbon bond or via a hetero atom as a linking group.
  • the polyarylsulfone is polyphenylsulfone.
  • the organic solvent is preferably a polar organic solvent, which may be an amide-based organic solvent, a urea-based organic solvent, or a mixture thereof, preferably from N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc). , N,N-dimethylformamide (DMF), dimethyl sulfoxide, hexamethylphosphoric triamide (HMPA), N, N, N', N'-tetramethylurea (TMU) One or more mixtures.
  • NMP N-methylpyrrolidone
  • DMAc N,N-dimethylacetamide
  • DMF N,N-dimethylformamide
  • HMPA hexamethylphosphoric triamide
  • TNU hexamethylphosphoric triamide
  • the aromatic polyamide and polyarylsulfone are added in an amount of from 50 to 98:2 to 50, preferably from 60 to 95:5 to 40, more preferably from 70 to 90:10 to 30, most preferably from 80 to 85:15. -20.
  • the mass percentage concentration of the polymer in the spinning solution is from 5 to 30% by weight, more preferably from 10 to 22% by weight, most preferably from 12 to 20% by weight, in order to obtain excellent fiber characteristics. If the concentration of the finally obtained polymer is less than 5% by weight, the viscosity is too low to form a fiber. If the concentration of the polymer in the spinning solution is increased, the viscosity of the spinning solution is also increased. However, if the concentration of the polymer is too high, the spinning solution may be unstable, causing problems such as gelation or precipitation of the polymer.
  • the spinning solution containing the copolymer in the present invention can be spun into a yarn by any method.
  • wet spinning is a preferred spinning method.
  • the spinning method is well known in the art and is described in CN1683431A, CN101784710A, US5536408, CN101235552A. It is preferably produced by, for example, spinning, solidification, stretching, water washing, drying, hot stretching, crimping, and cutting, which are described below.
  • the spinning device is not particularly limited, and a conventionally known wet spinning device can be used. Further, the number of spinning holes for the spinning spout is as long as the wet spinning can be stably performed.
  • the arrangement state, the hole shape, and the like are not particularly limited. For example, a porous spinning nozzle for fibers having a number of holes of 500 to 30,000 and a spinning aperture of 0.05 to 0.15 mm can be used.
  • the nascent fibers ejected through the orifice are solidified in a coagulation bath containing an organic solvent and a metal halide. If a plurality of filaments are extruded at the same time, they can form a multifilament before, during or after the solidification step.
  • the coagulation bath contains a polar organic solvent and a metal halide.
  • the content of the polar organic solvent is from 0 to 70% by weight, and the content of the metal halide is from 0 to 10% by weight.
  • the organic solvent used in the step (i) of preparing the fiber and the solidification and stretching of the fiber in the present invention is a polar organic solvent, that is, a solvent as a proton acceptor, for example, preferably from N-methylpyrrolidone (NMP), N,N-Dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide, hexamethylphosphoric triamide (HMPA), N, N, N', N One or more mixtures of '-tetramethylurea (TMU).
  • NMP N-methylpyrrolidone
  • DMAc N,N-Dimethylacetamide
  • DMF N,N-dimethylformamide
  • HMPA hexamethylphosphoric triamide
  • TNU hexamethylphosphoric triamide
  • the metal halide used in the fiber coagulation bath and stretching in the present invention may be a halogenated metal salt or a halogenated alkaline earth metal salt, such as a chloride or bromine salt of calcium, magnesium, aluminum, etc., that is, calcium chloride, magnesium chloride, Aluminum chloride, calcium bromide, magnesium bromide, aluminum bromide, and the like. It is possible to add only one inorganic salt or two or more inorganic salts. These metal halides may be the same or different in the fiber coagulation bath and the stretching bath.
  • the fibers or multifilaments are wrapped around the winding device. If necessary, the filaments can be cut to obtain short fibers.
  • the fibers of the present invention may additionally include, but are not limited to, a component selected from the group consisting of heat stabilizers, antistatic agents, extenders, organic and/or inorganic pigments (such as TiO 2 , carbon black), and acid acceptors (such as magnesium oxide), stabilizers, metal oxides (such as zinc oxide), metal sulfides (such as zinc sulfide), metal carboxylates (such as alkaline earth metals and excessive metal stearates), antioxidants, flame retardants , smoke suppressant, particulate filler, nucleating agent (such as talc), mica, kaolin, or a mixture of two or more of the above.
  • the weight of the above ingredients, based on the total weight of the fibers is preferably from 0 to 30% by weight, more preferably from 0 to 25% by weight, most preferably from 0 to 20% by weight.
  • the fibers of the present invention are not limited to the above methods and systems.
  • it is also an alternative to use a solvent to dissolve the polymeric material to make the fiber prior to spinning.
  • the fiber of the present invention can also be produced by a spunbonding method, a meltblowing method, or the like.
  • the fibers of the present invention can have a very wide range of diameters depending on the production requirements, and the number average diameter is usually from 1 nm to 100 ⁇ m.
  • the nanoscale fibers may have a diameter of, for example, 2, 5, 10, 20, 50, 100 or 200 nm; the micron-sized fibers may have a diameter of 2, 5, 10, 20, 50 or 100 ⁇ m.
  • the fibers of the present invention can have different cross-sectional shapes such as circular, elliptical, star-shaped, core-shell, and the like.
  • the fibers of the present invention have a strength of 2.5 CN/dtex or more, preferably 2.5-3.5 CN/dtex, more preferably 2.8-3.2 CN/dtex.
  • the invention also relates to a yarn comprising the fibers of the invention.
  • the yarn further comprises a material selected from the group consisting of polyaryletherketone, aramid, high molecular weight polyethylene, polyphenylene sulfide, polyetheretherketone, polyetherimide, polyaryleneimide, polybenzoate
  • a fiber obtained by mixing one or more of imidazole, polybenzoxazole, polyphenylene sulfone, polydiphenyl ether sulfone, polyphenylene, and polyimide sulfone.
  • the yarn is blended from the fiber comprising the above polymer and the fiber of the present invention in any ratio.
  • Fabric as used in the present invention includes any woven, knitted or nonwoven structure.
  • woven is meant any fabric weave, such as plain weave, satin weave, twill weave, and the like.
  • knit is meant any structure prepared by entanglement or interdigitation of one or more warp, fiber or multifilament yarns.
  • nonwoven is meant fiber networks, felts, and the like.
  • the fabric may further comprise other conventional ingredients of the fabric, such as glass fibers, asbestos fibers, polybenzazole fibers, polybenzimidazole fibers, polybenzoxazole fibers, in addition to the fibers of the present invention, Polyarylene ether fibers and aramid fibers, carbon fibers, PTFE fibers, boron fibers, metal fibers, ceramic fibers (such as silicon nitride, talc-glass fibers), calcium silicate fibers (such as calcium silica microfibers), silicon carbide fibers, Metal puffs and mixtures thereof, polyacrylonitrile fibers, aramid fibers or phenolic resins.
  • other conventional ingredients of the fabric such as glass fibers, asbestos fibers, polybenzazole fibers, polybenzimidazole fibers, polybenzoxazole fibers, in addition to the fibers of the present invention, Polyarylene ether fibers and aramid fibers, carbon fibers, PTFE fibers, boron fibers, metal fibers, ceramic fibers
  • the fibers of the present invention can also be used to make articles such as filter mats, laminates, composites, and the like.
  • the fibers of the present invention can be formed into filter mats that can be used in filtration devices that can be used in a variety of applications including, but not limited to, industrial use.
  • Factory filtration equipment such as power plants, coal-fired power plants, cement plants.
  • the fibers of the present invention may be chopped to obtain short fibers, pulp particles or short fibers, etc., which are mixed in a certain ratio and dispersed in water to form a fiber paper.
  • This fiber paper has excellent properties.
  • the prepreg may be formed by hot-pressing with a calender, impregnating the thermosetting epoxy resin varnish, and combining the prepreg layers to obtain a laminate containing the fibers of the present invention.
  • the laminate can be used as a circuit board, and for this purpose, a laminate structure for a circuit board excellent in electrical insulation performance can be provided.
  • the washed and dried viscometer was placed vertically in a 25 ⁇ 0.1 ° C thermostat, and then the pure solvent (98% sulfuric acid) which had been kept warm (25 ⁇ 0.1 ° C) for 15 minutes was filtered into the viscometer with a 1 # sand core funnel.
  • the capillary diameter is 1.0 to 1.1 mm
  • the solvent flow rate t0 (second) is measured, and it is repeated three times, the difference is not more than 0.5 second, and the arithmetic mean is taken.
  • Test instrument Rotating viscometer test temperature: 50 ° C
  • Test methods can be selected: traditional glass transition temperature, measured by differential scanning calorimetry (DSC); or dynamic glass transition, measured by dynamic thermomechanical analysis (DMA).
  • DSC differential scanning calorimetry
  • DMA dynamic thermomechanical analysis
  • the alkali resistance was characterized by the fiber breaking strength retention rate before and after the treatment with the alkali solution.
  • the fibers were immersed in a 10% strength NaOH solution at 85 ° C for 5 hours to test the breaking strength of the fibers before and after the lye treatment.
  • Polysulfone amide (relative viscosity 3.1) and polyphenylsulfone (relative viscosity 2.4) were dissolved in N,N-dimethylformamide at a mass ratio of 95:5, and finally, by stirring, 5% by mass.
  • Spinning solution The spinning solution is metered by a metering pump, filtered by a filter, and sprayed from a spinneret into a coagulation bath.
  • the spinneret has a number of spinning holes of 500 holes and a spinning aperture of 0.05 mm.
  • the spinning speed was 30 m/min, and then subjected to solidification, stretching bath, water washing, drying, hot stretching, and crimping to obtain a finished fiber.
  • Polysulfone amide (relative viscosity 2.4) and polyphenylsulfone (relative viscosity 1.9) were dissolved in N-methylpyrrolidone in a weight ratio of 60:40, and finally kneaded to a spinning solution having a mass percentage of 10%.
  • the spinning solution is metered by a metering pump, filtered by a filter, and sprayed from a spinneret into a coagulation bath.
  • the spinneret has a number of spinning holes of 800 holes, a spinning aperture of 0.075 mm, a spinning speed of 20 m/min, and further solidification, stretching bath, water washing, drying, hot stretching, and crimping to obtain a finished fiber.
  • Polysulfone amide (relative viscosity 2.0) and polyphenylsulfone (relative viscosity 1.9) were dissolved in N-methylpyrrolidone in a weight ratio of 70:30, blended by a twin-screw extruder, and finally configured to have a mass percentage of 20 % spinning solution.
  • the spinning solution is metered by a metering pump, filtered by a filter, and sprayed from a spinneret into a coagulation bath.
  • the spinneret has a spinning hole number of 30,000 holes, a spinning aperture of 0.075 mm, a spinning speed of 5 m/min, and is subjected to solidification, stretching bath, water washing, drying, hot stretching, and crimping to obtain a finished fiber.
  • Polysulfone amide (relative viscosity 1.9) and polyphenylsulfone (relative viscosity 1.9) were dissolved in N-methylpyrrolidone in a weight ratio of 80:20, blended by a twin-screw extruder, and finally configured to have a mass percentage of 30. % spinning solution.
  • the spinning solution is metered by a metering pump, filtered by a filter, and sprayed from a spinneret into a coagulation bath.
  • the spinneret has a spinning hole number of 30,000 holes, a spinning aperture of 0.075 mm, a spinning speed of 5 m/min, and is subjected to solidification, stretching bath, water washing, drying, hot stretching, and crimping to obtain a finished fiber.
  • the spinneret has a spinning hole number of 30,000 holes, a spinning aperture of 0.075 mm, a spinning speed of 5 m/min, and is subjected to solidification, stretching bath, water washing, drying, hot stretching, and crimping to obtain a finished fiber.
  • Polysulfone amide (relative viscosity 2.0) and polyphenylsulfone (relative viscosity 1.9) were dissolved in N,N-dimethylformamide at a weight ratio of 98:2, and finally kneaded to a mass ratio of 18%.
  • Spinning solution The spinning solution is metered by a metering pump, filtered by a filter, and sprayed from a spinneret into a coagulation bath.
  • the spinneret has a spinning hole number of 30,000 holes, a spinning aperture of 0.075 mm, a spinning speed of 5 m/min, and is subjected to solidification, stretching bath, water washing, drying, hot stretching, and crimping to obtain a finished fiber.
  • a polysulfone amide (relative viscosity 3.1) was dissolved in N-methylpyrrolidone to prepare a spinning solution, and the content of polysulfone amide in the spinning solution was 5%.
  • the spinning process was the same as in Example 1.
  • a polysulfone amide (relative viscosity 2.4) was dissolved in N,N-dimethylacetamide to prepare a spinning solution, and the content of polysulfone amide in the spinning solution was 10%.
  • the spinning process was the same as in Example 2.
  • the m-phenylene isophthalamide (relative viscosity 2.4) was dissolved in N,N-dimethylformamide to prepare a spinning solution, and the content of the intermediate solution of m-phenylene isophthalamide was 20%. .
  • the spinning process was the same as in Example 3.

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  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
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Abstract

本发明涉及一种耐高温和耐碱性的纤维，所述纤维中包含含砜基而不含酰胺基团的芳香族聚合物（A）与含砜基和酰胺基团的芳香族聚合物（B）。本发明所述的纤维具有良好的耐碱性能和耐高温性能，能够广泛应用于耐热防护领域中。本发明还涉及该纤维的制备方法，包含该纤维的纱线、织物和制品。

Description

一种基于芳香族聚酰胺和聚芳砜的共混纤维、纱线、织物、制品及其制备方法 技术领域
本发明涉及一种基于芳香族聚酰胺和聚芳砜的共混纤维，包含所述纤维的纱线、织物、制品及其制备方法、该纤维具有优异的耐碱性能和耐高温性能，能够广泛应用于耐热防护领域中。
背景技术
芳香族聚酰胺通常由于其优异的耐热性能而广泛被用作工业用纤维和特殊衣料用纤维等。但现有技术中的芳香族聚酰胺纤维耐碱性能差，在碱性条件下使用时，强度保持率低。
现有技术中对于芳香族聚酰胺纤维耐碱性的改进通常在于对芳香族聚酰胺的分子结构上改进，如加入取代基。CN1212259A提供了一种耐碱及耐氧化腐蚀能力强的磺化聚芳酰胺。具体是在聚芳酰胺分子的部分或全部氮原子上接有烷基磺酸侧链，它是利用酰胺键上的活性氢与γ-丙磺酸内酯或2-溴乙基磺酸钠反应，在聚酰胺分子上接枝磺酸基侧链。分子中的磺酸钠基团的离子导电性和吸湿性可改善电池隔膜的导电及吸碱性。这种对分子结构的改性方式通常需要严格控制化学反应条件才能够达到，
现有技术中对于芳香族聚酰胺纤维耐碱性的另一改进方式是，在制备无纺布时，加入另一种耐碱性纤维，以提高无纺布整体的耐碱性。CN1656630A提供了一种碱性电池隔膜用无纺布及其制造方法。具体是包含有二羧酸成分的60mol％以上为芳香族二羧酸成分的二羧酸成分及二胺成分的60mol％以上为碳数6-12的脂肪酸烷撑二胺的二胺成分构成的半芳香族聚酰胺纤维、乙烯-乙烯醇共聚体纤维的碱性电池膜用无纺布。但这种方式仍然无法改进芳香族聚酰胺纤维的耐碱性，而只能对织物的耐碱性能有所改进。
在现有技术中，聚芳砜具有良好的耐碱性和耐温性，但聚芳砜通常不能单独做纤维。且与芳香族聚酰胺聚合物的共混物也仅仅只涉及成型制品(如CN102782018A中所公开的)，而非纤维，并且该文献中也没有明确提及将芳香族聚酰胺与聚芳砜共混。
本发明旨在提供一种更加方便，操作性更强的提高芳香族聚酰胺纤维耐碱性的方法，并且同时保持纤维的耐温性和力学性能。
发明内容
本发明的目的是提供一种基于芳香族聚酰胺和聚芳砜的共混纤维，所述纤维中包含40-98wt％的芳香族聚酰胺，2-60wt％的聚芳砜，所述芳香族聚酰胺和聚芳砜是混合的。
优选的，所述芳香族聚酰胺为苯二甲酰对苯二胺、间苯二甲酰间苯二胺、聚砜酰胺、聚对苯甲酰胺。
优选的，其在10％的NaOH溶液中85℃下浸泡5小时的强度保持率是70％以上，优选80％以上，更优选85％以上。
优选的，其具有2.5cN/dtex以上的强度，优选2.5-3.5cN/dtex，更优选2.8-3.2cN/dtex。
优选的，其具有280℃以上的玻璃化温度，优选300℃以上的玻璃化温度，更优选340℃以上，最优选350℃以上。
优选的，其为长丝或短纤。
本发明还涉及一种制备基于芳香族聚酰胺和聚芳砜的共混纤维的方法，包括下列步骤：
(i)将芳香族聚酰胺和聚芳砜聚合体溶解在有机溶剂中，搅拌混合，配制成5-30wt％的纺丝溶液；
(ii)将所述纺丝溶液纺制成纤维。
优选的，步骤(i)中的所述有机溶剂选自N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲亚砜、六甲基磷酰三胺(HMPA)、N,N,N’,N’-四甲基脲(TMU)中的一种或一种以上的混合物。
优选的，步骤(i)中芳香族聚酰胺和聚芳砜的加入的重量比为50-98：2-50，优选60-95：5-40，更优选70-90：10-30，最优选80-85：15-20。
优选的，步骤(i)中纺丝溶液中聚合物的质量百分比浓度为5-30wt％，更优选10-22wt％，最优选12-20wt％。
优选的，步骤(ii)中制备纤维的步骤包括：纺丝及凝固成丝、拉伸、水洗、干燥、热拉伸、卷曲、切断。
优选的，所述凝固成丝步骤的凝固浴中包含极性有机溶剂、金属卤化物；优选的，极性有机溶剂的含量为40-70wt％，金属卤化物的含量为0-10wt％。
优选的，所述拉伸步骤中拉伸浴包含极性有机溶剂、金属卤化物；优选的，极性有机溶剂的含量为5-65wt％，金属卤化物的含量为0-10wt％。
优选的，所述凝固浴和拉伸浴中的有机溶剂可以独立地选自N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲亚砜、六甲基磷酰三胺(HMPA)、N,N,N’,N’-四甲基脲(TMU)中的一种或一种以上的混合物，且所述凝固浴和所述拉伸浴中的极性有机溶剂可以相同也可以不同。
优选的，所述凝固浴和拉伸浴中的金属卤化物可以独立地选自氯化钙、氯化镁、氯化铝、溴化钙、溴化镁、溴化铝中的一种或一种以上的混合物，且所述凝固浴和所述拉伸浴中的金属卤化物可以相同也可以不同。
本发明还涉及一种包含所述纤维的纱线。
在一些实施方式中，所述纱线中还含有由选自聚芳醚酮、芳族聚酰胺、高分子量聚乙烯、聚苯硫醚、聚醚醚酮、聚醚酰亚胺、聚芳酰亚胺、聚苯并咪唑、聚苯并悪唑、聚亚苯基砜、聚联苯醚砜、聚亚苯基、聚酰亚胺砜中的一种或一种以上的混合制得的纤维。
本发明还涉及一种包含所述纤维的织物。
在一些实施方式中，织物是机织、针织或非织造结构。
在一些实施方式中，所述织物还含有玻璃纤维、石棉纤维、聚苯并唑纤维、聚苯并咪唑纤维、聚苯并恶唑纤维、聚芳醚纤维和芳纶纤维、碳纤维、PTFE纤维、硼纤维、金属纤维、陶瓷纤维、硅酸钙纤维、碳化硅纤维、金属膨化物、聚丙烯腈纤维、芳香族聚酰胺纤维、酚类树脂中的一种或其混合物。
本发明还涉及一种包含所述纤维的防护服装。
本发明还涉及一种包含所述纤维的过滤毡。
本发明还涉及一种包含所述纤维的层压体。
本发明还涉及一种包含所述纤维的复合材料。
具体实施方式
通过参见本申请具体实施方式的内容可以更易于理解本发明，但是本发明并不限于本文所述和/或所示的具体方法、条件或参数，并且本文中所用的术语仅是为了以举例的方式描述具体实施方式，并不能限制本申请权利要求要求保护的技术方案。在下文中，将描述根据本发明的一种基于芳香族聚酰胺和聚芳砜的共混纤维及其制备方法，以及包含本发明纤维的纱线、织物及制品。
1.制备芳香族聚酰胺和聚芳砜的共混纺丝溶液
通过向有机溶剂中加入芳香族聚酰胺、聚芳砜来制备芳香族聚酰胺和聚芳砜的共混纺丝溶液，所述纺丝溶液中聚合物的质量百分比浓度为5-30wt％；其中芳香族聚酰胺与聚芳砜的重量比为60-98：2-40，即使最终所得的纤维中包含60-98wt％的芳香族聚酰胺，2-40wt％的聚芳砜。所得到的基于芳香族聚酰胺和聚芳砜的共混纤维不仅能够保持芳香族聚酰胺纤维的耐温性能和力学性能，还能够比芳香族聚酰胺纤维具有更好的耐碱性能。
本发明中的术语“芳香族聚酰胺”是指一种有足够高分子量能形成纤维的合成聚合物材料，并主要是以下循环结构单位为特征：
Figure PCTCN2015072962-appb-000001
其中，每一个R1是氢或是低级烷烃，而其中Ar1和Ar2可以是相同的或是不同的，并且可以是一个未被取代的或已被取代的二价芳基，这些二价芳基与其他基团的连接键主要是以间位或对位排列，所述二价芳基上的氢可以独立地被以下一个或多个如下的取代基所取代或不取代，这些取代基包括卤素、C1-C4烷基、C1-C4烷氧基、苯基、酰氧基、硝基、二烷基氨基、硫代烷基、羧基、磺酰基、羰基烷氧基。其中，优选对苯二甲酰对苯二胺(PPTA)、间苯二甲酰间苯二胺(PMIA)。
本发明中的术语“芳香族聚酰胺”也可以理解其大分子链中的Ar1和Ar2可以是相同的或是不同的具有如下结构：
Figure PCTCN2015072962-appb-000002
其中，X、Y独立的选自-O-、-CH2-、-CO-、-CO2-、-S-、-SO2-、-C(CH3)2-，X和Y可以是相同的或是不同的。其中，优选聚砜酰胺。
本发明中的术语“聚芳砜”具有如下通式Ⅰ或Ⅱ作为重复单元：
-O-A-SO2-A-   (Ⅰ)
-O-A-SO2-A-O-B-   (Ⅱ)
其中A和B可表示任选取代的芳族基。该芳族基由6-40个碳原子，优选6-21个碳原子组成，即含有一个或多个任选芳基，其中所述芳基能够任选地含有杂原子。这些芳基够任选地被线型或支化的或脂环族C1-C5基团或卤原子所取代。所述芳基能够经由碳键或经由作为连接基团的杂原子来连接。其中，优选聚芳砜为聚苯砜。
有机溶剂优选极性有机溶剂，可以是基于酰胺的有机溶剂、基于尿素的有机溶剂，或者是他们的混合物，优选自N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲亚砜、六甲基磷酰三胺(HMPA)、N,N,N’,N’-四甲基脲(TMU)中的一种或一种以上的混合物。
所述芳香族聚酰胺与聚芳砜的加入量按照比例50-98：2-50加入，优选60-95：5-40，更优选70-90：10-30，最优选80-85：15-20。
所述纺丝溶液中聚合物的质量百分比浓度为5-30wt％，更优选10-22wt％，最优选12-20wt％，以便获得优良的纤维特性。如果最终获得的聚合物的浓度小于5wt％，则粘度太低，而无法成纤。如果纺丝液中聚合物的浓度增加，那么纺丝液的粘度也会随之增加。但是，如果聚合物的浓度过高，则会导致纺丝液不稳定，产生凝胶现象或者聚合物析出等问题。
2.制备基于芳香族聚酰胺和聚芳砜的共混纤维
本发明中的包含所述共聚物的纺丝溶液，可以使用任意方法纺制成丝。其中湿法纺丝是优选的纺丝方式。其该纺丝方法是本领域熟知的，在CN1683431A、CN101784710A、US5536408、CN101235552A中均有记载。优选经过例如以下说明的纺丝及凝固成丝、拉伸、水洗、干燥、热拉伸、卷曲、切断等工序而制造的。
作为纺丝装置没有特别限定，可以使用以往公知的湿法纺丝装置。另外，只要是能够稳定进行湿法纺丝，则对纺丝喷口的纺丝孔数。排列状态、孔形状等无需特别限制，例如，可以使用孔数为500-30000个、纺丝孔径为0.05-0.15mm的纤维用多孔纺丝喷口等。
经过喷丝孔喷出的初生纤维在含有有机溶剂和金属卤化物的凝固浴中凝固。如果同时挤出多根长丝，它们可以在凝固步骤之前、期间或之后形成复丝。凝固成丝步骤中凝固浴中包含极性有机溶剂、金属卤化物。极性有机溶剂的含量为0-70wt％，金属卤化物的含量为0-10wt％。
凝固浴之后，对纤维进行拉伸。所述纤维可以使用拉伸溶液进行湿拉伸，所述拉伸溶液包含水、盐和溶剂；所述盐优选金属卤化物。所述极性有机溶剂的含量为5-65wt％，金属卤化物的含量为0-10wt％。
本发明中制备纤维的步骤(i)中以及纤维凝固和拉伸时所采用的有机溶剂为极性有机溶剂，即那些作为质子受体的溶剂，例如优选自N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲亚砜、六甲基磷酰三胺(HMPA)、N,N,N’,N’-四甲基脲(TMU)中的一种或一种以上的混合物。这些有机溶剂在制备纤维的步骤(i)中、凝固浴中、拉伸浴中可以是相同的也可以是不同的。
本发明中纤维凝固浴及拉伸中采用的金属卤化物，可以是卤代金属盐或卤代碱土金属盐，例如钙、镁、铝等的氯盐或溴盐，即氯化钙、氯化镁、氯化铝、溴化钙、溴化镁、溴化铝等。可以只加入一种无机盐，也可以加入两种或更多的无机盐。这些金属卤化物在纤维凝固浴和拉伸浴中可以是相同的也可以是不同的。
拉伸之后，对纤维进行洗涤，洗涤的优选方式可使所述纤维与一个或多个洗涤浴或洗涤箱接触。洗涤可通过将所述纤维浸入浴中或者通过用水溶液喷雾所述纤维来完成。洗涤箱通常包括含有一个或多个辊的封闭箱，其中纱线在退出所述封闭箱之前多次环绕并穿越所述辊行进。当纱线环绕辊行进时，会通过喷雾的方式使洗涤流体与纤维接触。洗涤流体连续收集在洗涤箱的底部，并从底部排出箱体。洗涤流体的温度优选高于40℃。也可以是蒸汽形式来施用洗涤流体，但以液体形式使用更为方便。优选地，使用多个洗涤浴或洗涤箱，将清洗工序多阶段化，并控制温度条件和酰胺系溶剂的浓度条件。
洗涤之后，纤维或复丝可在干燥器中干燥以去除水分和其它液体。可使用一个或多个干燥器。在某些实施例中，所述干燥器可以是烘箱，热板、热辊等。干燥器中可以是氮气或其他非反应性气氛。所述干燥步骤通常在大气压下进行。然后，如果需要，所述干燥步骤也可以在减压下进行。
干燥步骤之后，优选对纤维进行热拉伸，加热温度可以达到260℃以上，优选280℃以上，更优选300℃-400℃。该热拉伸步骤可以增加纤维的断裂延伸度，并减少纤维长丝的机械应变性能，提高纤维的模量。在一些实施方式中，加热是多步方法。例如，在第一步中，将所述纤维或复丝在260-270℃的温度下在一定张力下加热，接着进行第二加热步骤，其中将纤维或复丝在280-290℃的温度下在一定张力下加热，接着进行第三加热步骤，其中将纤维或复丝在300-320℃的温度下在一定张力下加热。
最后，将纤维或复丝在卷绕装置上缠绕包装。如有需要，可以将长丝切断得到短纤维。
本发明所述的纤维也可另外包括但不限于选自下列的成分：热稳定剂、抗静电剂、增量剂、有机和/或无机颜料(如TiO2、碳黑)、吸酸剂(如氧化镁)、稳定剂、金属氧化物(如氧化锌)、金属硫化物(如硫化锌)、金属羧酸盐(如碱土金属和过度金属的硬脂酸盐)、抗氧化剂、阻燃剂、抑烟剂、颗粒填充剂、成核剂(如滑石粉)、云母、高岭土，或上述两种或两种以上的混合物。上述成分的重量，基于纤维的总重量优选为0-30wt％，更优选0-25wt％，最优选0-20wt％。
本发明的纤维并不限于上面的方法和体系。例如，在纺丝前，使用溶剂以溶解聚合物材料来制造纤维也是可以选择的方式。本发明的纤维还可以采用纺粘法、熔喷法等来制备。
本发明的纤维可以根据生产需要具有非常广的直径范围，数均直径通常从1nm至100μm。纳米级的纤维可以具有例如2、5、10、20、50、100或200nm的直径；微米级的纤维可以具有2、5、10、20、50或100μm的直径。
本发明的纤维可具有不同的横截面形状，如圆形、椭圆形、星形、核壳等。
本发明的纤维在10％的NaOH溶液中85℃下浸泡5小时的强度保持率是70％以上。
本发明所述纤维具有2.5CN/dtex以上的强度，优选2.5-3.5CN/dtex，更优选2.8-3.2CN/dtex。
所述纤维具有280℃以上的玻璃化温度，优选300℃以上的玻璃化温度，更优选340℃以上，最优选350℃以上。
3.包含本发明纤维的纱线
本发明还涉及一种包含本发明纤维的纱线。所述纱线中还含有由选自聚芳醚酮、芳族聚酰胺、高分子量聚乙烯、聚苯硫醚、聚醚醚酮、聚醚酰亚胺、聚芳酰亚胺、聚苯并咪唑、聚苯并悪唑、聚亚苯基砜、聚联苯醚砜、聚亚苯基、聚酰亚胺砜中的一种或一种以上的混合制得的纤维。由包含上述聚合物的纤维与本发明的纤维以任意比例混纺制成纱线。
4.包含本发明纤维的织物
本发明中所述的“织物”，包括任何机织、针织或非织造结构。所谓“机织”包括任何织物编织，例如平纹、缎纹、斜纹编织结构等。所谓“针织”包括任何将一个或多个经线、纤维或复丝纱线相互环连或相互交叉而制备的结构。所谓“非织造”包括纤维网络、毡等。
在另一些实施方式中，本发明还进一步涉及织物，将本发明所述的纤维引入至织物中。所述织物包含本发明的长丝或短纤。含有本发明纤维的织物由于具有优异的耐热性能可以广泛地应用于工业防护领域。也可用于航空、汽车、医药、军事、安全、化学、药物和冶金学工业。
所述织物可进一步包含织物的其他的常规成分，如除了本发明的纤维外，还可以包含例如玻璃纤维、石棉纤维、聚苯并唑纤维、聚苯并咪唑纤维、聚苯并恶唑纤维、聚芳醚纤维和芳纶纤维、碳纤维、PTFE纤维、硼纤维、金属纤维、陶瓷纤维(如氮化硅、滑石-玻璃纤维)、硅酸钙纤维(如钙硅石微纤维)、碳化硅纤维、金属膨化物及其混合物、聚丙烯腈纤维、芳香族聚酰胺纤维或酚类树脂。
5.包含本发明纤维的制品
本发明的纤维还可以用来制作成过滤毡、层压体、复合材料等制品。
在另一些实施方式中，可以将本发明所述的纤维制成过滤毡，所述过滤毡可应用于过滤装置中，所述过滤装饰可被用于多种应用，包括但不限于用于工业工厂的过滤装置，如发电厂、燃煤发电厂、水泥厂。
在另一些实施方式中，可以将本发明的纤维切短得到短纤维与纸浆状粒子或短纤维等以一定比例进行混合，使其分散在水中，制成纤维纸。这种纤维纸具有优异的性能。进一步的，可以利用压延机进行热压加工，使其浸渍热固性环氧树脂清漆形成预浸渍体，将预浸渍体层合并成型，得到含有本发明纤维的层压体。该层压体可以用作电路基板，为此，可提供电绝缘性能优异的电路基板用层压体结构物。
如上所述制得的纤维，由于其优异的耐热性能和力学性能，其具有各种各样的用途。例如：将本发明的纤维切短得到的短纤维和树脂复合形成纤维增强的复合材料，该复合材料具有优异的力学性能和耐热性能。
实施例
下面，用实施例进一步说明本发明。实施例中的各项性能参数，按以下方法进行测定。
(a)聚合物的相对粘度
一、试样的处理
1、打碎
2、洗涤
3、烘干(110度下烘2.5小时)
二、测试
a空白测定(溶剂流出的时间测定)
将洗净干燥的粘度计垂直放在25±0.1℃的恒温槽中，然后将已保温(25±0.1℃)15分钟的纯溶剂(98％硫酸)用1#砂芯漏斗滤入粘度计中(毛细管直径为1.0～1.1mm)，然后测其溶剂流速t0(秒)，重复三次，差值不超过0.5秒，取其算术平均值。
b试样测定(浓度为0.5％)
精确称取干燥聚合物0.1250克，置于25毫升的容量瓶中，先加入适量的98％的浓硫酸(AR)，轻摇，可静置溶解，必要时可保温溶解(置于50～60℃的浴温中加速溶解，注意，水温不能超过60℃)，待全部溶解后，把容量瓶放在25±0.1℃的恒温槽中保持15分 钟，然后用98％的浓硫酸加至刻度，并摇匀，然后用1#砂芯漏斗滤入清洁干燥的乌式粘度计中，用同样方法测得溶液流速t(秒)，重复三次，差值不超过0.5秒，取其算术平均值。
c相对粘度计算
相对粘度ηr＝t/t0
(b)纺丝溶液表观粘度
测试仪器：旋转粘度计测试温度：50℃
将纺丝溶液倒入测试器皿中，控制水浴温度为50℃，平衡若干分钟，用温度计测试纺丝溶液温度达到50℃时，将合适的旋转转子放入纺丝溶液中，设置合适的转速，开始测试并记录测试值。
(c)单丝纤度
测试方法参见：GB/T14335
(d)纤维强度
测试方法参见：GB/T14337
(e)纤维断裂伸长率
测试方法参见：GB/T14337
(f)纤维玻璃化温度
测试方法可选择：传统的玻璃化转变温度，由差示扫描热量法(DSC)测得；或则是动态玻璃化转变，由动态热机械分析(DMA)测得。
(g)耐碱性能
耐碱性能用碱液处理前后，纤维断裂强度保持率来表征。
将纤维在浓度为10％的NaOH溶液中，在85℃下浸泡5小时，分别测试碱液处理前后纤维的断裂强度。
纤维断裂强度保持率＝处理后纤维的断裂强度/处理前纤维的断裂强度×100％
实施例1
将聚砜酰胺(相对粘度3.1)与聚苯砜(相对粘度2.4)以95：5的质量比溶解于N,N-二甲基甲酰胺中，通过搅拌，最终配置成质量百分比为5％的纺丝溶液。将上述纺丝溶液经计量泵计量、过滤器过滤、从喷丝头喷入凝固浴中。该喷丝头的纺丝孔数为500孔，纺丝孔径为0.05mm， 纺丝速度为30m/min,再经过凝固、拉伸浴、水洗、干燥、热拉伸、卷曲，得到成品纤维。
实施例2
将聚砜酰胺(相对粘度2.4)与聚苯砜(相对粘度1.9)以60：40的重量比溶解于N-甲基吡咯烷酮中，通过捏合，最终配置成质量百分比为10％的纺丝溶液。将上述纺丝溶液经计量泵计量、过滤器过滤、从喷丝头喷入凝固浴中。该喷丝头的纺丝孔数为800孔，纺丝孔径为0.075mm，纺丝速度为20m/min,再经过凝固、拉伸浴、水洗、干燥、热拉伸、卷曲，得到成品纤维。
实施例3
将聚砜酰胺(相对粘度2.0)与聚苯砜(相对粘度1.9)以70：30的重量比溶解于N-甲基吡咯烷酮中，通过双螺杆挤出机共混，最终配置成质量百分比为20％的纺丝溶液。将上述纺丝溶液经计量泵计量、过滤器过滤、从喷丝头喷入凝固浴中。该喷丝头的纺丝孔数为30000孔，纺丝孔径为0.075mm，纺丝速度为5m/min,再经过凝固、拉伸浴、水洗、干燥、热拉伸、卷曲，得到成品纤维。
实施例4
将聚砜酰胺(相对粘度1.9)与聚苯砜(相对粘度1.9)以80：20的重量比溶解于N-甲基吡咯烷酮中，通过双螺杆挤出机共混，最终配置成质量百分比为30％的纺丝溶液。将上述纺丝溶液经计量泵计量、过滤器过滤、从喷丝头喷入凝固浴中。该喷丝头的纺丝孔数为30000孔，纺丝孔径为0.075mm，纺丝速度为5m/min,再经过凝固、拉伸浴、水洗、干燥、热拉伸、卷曲，得到成品纤维。
实施例5
将聚砜酰胺(相对粘度1.9)与聚苯砜(相对粘度1.9)以90：10的重量比溶解于N,N-二甲基甲酰胺中，通过双螺杆挤出机共混，最终配置成质量百分比为25％的纺丝溶液。将上述纺丝溶液经计量泵计量、过滤器过滤、从喷丝头喷入凝固浴中。该喷丝头的纺丝孔数为30000孔，纺丝孔径为0.075mm，纺丝速度为5m/min,再经过凝固、拉伸浴、水洗、干燥、热拉伸、卷曲，得到成品纤维。
实施例6
将聚砜酰胺(相对粘度2.0)与聚苯砜(相对粘度1.9)以98：2的重量比溶解于N,N-二甲基甲酰胺中，通过捏合，最终配置成质量百分比为18％的纺丝溶液。将上述纺丝溶液经计量泵计量、过滤器过滤、从喷丝头喷入凝固浴中。该喷丝头的纺丝孔数为30000孔，纺丝孔径为0.075mm，纺丝速度为5m/min,再经过凝固、拉伸浴、水洗、干燥、热拉伸、卷曲，得到成品纤维。
对比例1
将聚砜酰胺(相对粘度3.1)溶解于N-甲基吡咯烷酮中制成纺丝溶液，纺丝溶液中聚砜酰胺的含量为5％。纺丝工艺与实施例1相同。
对比例2
将聚砜酰胺(相对粘度2.4)溶解于N,N-二甲基乙酰胺中制成纺丝溶液，纺丝溶液中聚砜酰胺的含量为10％。纺丝工艺与实施例2相同。
对比例3
将间苯二甲酰间苯二胺(相对粘度2.4)溶解于N,N-二甲基甲酰胺中制成纺丝溶液，纺丝溶液中间苯二甲酰间苯二胺的含量为20％。纺丝工艺与实施例3相同。
表1纤维性能比较
Figure PCTCN2015072962-appb-000003
基于以上实施例应该明确的是，在不脱离本发明的精神或范围的情况下，可以对本发明 进行各种改进和变变型。因此，本发明意在涵盖基于本发明的改进和变型，只要这些改进和变型落在所附的权利要求及其等同替代技术手段的范围内。

Claims (24)

  1. 一种包含芳香族聚酰胺和聚芳砜的共混纤维，其特征在于，其中含有包含60-98wt％的芳香族聚酰胺，2-40wt％的聚芳砜。
  2. 根据权利要求1所述的纤维，所述芳香族聚酰胺为苯二甲酰对苯二胺、间苯二甲酰间苯二胺、聚砜酰胺、聚对苯甲酰胺。
  3. 根据权利要求1或2所述的纤维，其在10％的NaOH溶液中85℃下浸泡5小时的强度保持率是70％以上，优选80％以上，更优选85％以上。
  4. 根据权利要求1-3任一项所述的纤维，其具有2.5cN/dtex以上的强度，优选2.5-3.5cN/dtex，更优选2.8-3.2cN/dtex。
  5. 根据权利要求1-4任一项所述的纤维，其具有280℃以上的玻璃化温度，优选300℃以上的玻璃化温度，更优选340℃以上，最优选350℃以上。
  6. 根据权利要求1-5任一项所述的纤维，其为长丝或短纤。
  7. 一种制备权利要求1-6任一项所述纤维的方法，包括如下步骤：
    (i)将芳香族聚酰胺和聚芳砜聚合体溶解在有机溶剂中，搅拌混合，配制成5-30wt％的纺丝溶液；
    (ii)将所述纺丝溶液纺制成纤维。
  8. 根据权利要求7的方法，步骤(i)中的所述有机溶剂选自N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲亚砜、六甲基磷酰三胺(HMPA)、N,N,N’,N’-四甲基脲(TMU)中的一种或一种以上的混合物。
  9. 根据权利要求7-8任一项所述的方法，步骤(i)中芳香族聚酰胺和聚芳砜的加入的重量比为50-98：2-50，优选60-95：5-40，更优选70-90：10-30，最优选80-85：15-20。
  10. 根据权利要求7-9任一项所述的方法，步骤(i)中纺丝溶液中聚合物的质量百分比浓度为5-30wt％，更优选10-22wt％，最优选12-20wt％。
  11. 根据权利要求7-10任一项所述的方法，步骤(ii)中制备纤维的步骤包括：纺丝及凝固成丝、拉伸、水洗、干燥、热拉伸、卷曲、切断。
  12. 根据权利要求11所述的方法，所述凝固成丝步骤的凝固浴中包含极性有机溶剂、金属卤化物；优选的，极性有机溶剂的含量为40-70wt％，金属卤化物的含量为0-10wt％。
  13. 根据权利要求11或12任一项所述的方法，所述拉伸步骤中拉伸浴包含极性有机溶剂、金属卤化物；优选的，极性有机溶剂的含量为5-65wt％，金属卤化物的含量为0-10wt％。
  14. 根据权利要求12或13任一项所述的方法，所述凝固浴和拉伸浴中的有机溶剂可以独立 地选自N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲亚砜、六甲基磷酰三胺(HMPA)、N,N,N’,N’-四甲基脲(TMU)中的一种或一种以上的混合物，且所述凝固浴和所述拉伸浴中的极性有机溶剂可以相同也可以不同。
  15. 根据权利要求12-14任一项所述的方法，所述凝固浴和拉伸浴中的金属卤化物可以独立地选自氯化钙、氯化镁、氯化铝、溴化钙、溴化镁、溴化铝中的一种或一种以上的混合物，且所述凝固浴和所述拉伸浴中的金属卤化物可以相同也可以不同。
  16. 一种包含权利要求1-6任一项所述纤维的纱线。
  17. 根据权利要求16所述的纱线，其中还含有由选自聚芳醚酮、芳族聚酰胺、高分子量聚乙烯、聚苯硫醚、聚醚醚酮、聚醚酰亚胺、聚芳酰亚胺、聚苯并咪唑、聚苯并悪唑、聚亚苯基砜、聚联苯醚砜、聚亚苯基、聚酰亚胺砜中的一种或一种以上的混合制得的纤维。
  18. 一种包含权利要求1-6任一项所述纤维的织物。
  19. 根据权利要求18所述的织物，所述织物是机织、针织或非织造结构。
  20. 根据权利要求18或19所述的织物，所述织物还含有玻璃纤维、石棉纤维、聚苯并唑纤维、聚苯并咪唑纤维、聚苯并恶唑纤维、聚芳醚纤维和芳纶纤维、碳纤维、PTFE纤维、硼纤维、金属纤维、陶瓷纤维、硅酸钙纤维、碳化硅纤维、金属膨化物、聚丙烯腈纤维、芳香族聚酰胺纤维、酚类树脂中的一种或其混合物。
  21. 一种包含权利要求1-6任一项所述纤维的防护服装。
  22. 一种包含权利要求1-6任一项所述纤维的过滤毡。
  23. 一种包含权利要求1-6任一项所述纤维的层压体。
  24. 一种包含权利要求1-6任一项所述纤维的复合材料。
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