CN104846473B - A kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), yarn, fabric, goods and preparation method thereof - Google Patents

A kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), yarn, fabric, goods and preparation method thereof Download PDF

Info

Publication number
CN104846473B
CN104846473B CN201410051598.7A CN201410051598A CN104846473B CN 104846473 B CN104846473 B CN 104846473B CN 201410051598 A CN201410051598 A CN 201410051598A CN 104846473 B CN104846473 B CN 104846473B
Authority
CN
China
Prior art keywords
fiber
polyarylsulfone
pas
spinning
aromatic polyamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410051598.7A
Other languages
Chinese (zh)
Other versions
CN104846473A (en
Inventor
汪晓峰
陈晟晖
吴佳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongfang New Materials Co ltd
Original Assignee
Shanghai Tanlon Fiber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Tanlon Fiber Co Ltd filed Critical Shanghai Tanlon Fiber Co Ltd
Priority to CN201410051598.7A priority Critical patent/CN104846473B/en
Priority to PCT/CN2015/072962 priority patent/WO2015120810A1/en
Publication of CN104846473A publication Critical patent/CN104846473A/en
Application granted granted Critical
Publication of CN104846473B publication Critical patent/CN104846473B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Abstract

The present invention relates to a kind of high temperature resistant and alkali-proof fiber, in described fiber, comprise containing sulfuryl the not aromatic polymer of phosphinylidyne-containing amine group (A) and the aromatic polymer (B) that contains sulfuryl and amide group. Fiber of the present invention has good alkaline resistance properties and resistance to elevated temperatures, can be widely used in heat-resisting protection field. The invention still further relates to the preparation method of this fiber, the yarn, fabric and the goods that comprise this fiber.

Description

A kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), yarn, fabric, goods and preparation method thereof
Technical field
The present invention relates to a kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), the yarn that comprises described fiber,Fabric, goods and preparation method thereof, this fiber have excellent alkaline resistance properties and resistance to elevated temperatures, can be widely used in heat-resistingIn protection field.
Background technology
Aromatic polyamide is extensively used as industrial fibre and special dress material due to its excellent heat resistance conventionallyWith fiber etc. But aromatic polyamide fibre alkaline resistance properties of the prior art is poor, while use under alkali condition, Strength retentionRate is low.
In prior art, for aromatic polyamide fibre, alkali-proof improvement is dividing aromatic polyamide conventionallyIn minor structure, improve, as add substituting group. CN1212259A provides a kind of sulfonation alkaline-resisting and that resistance to oxidation corrosive power is strong poly-Virtue acid amides. Specifically on the part or all of nitrogen-atoms of Nomex molecule, be connected to alkyl sulfonic acid side chain, it is to utilize acid amidesReactive hydrogen on key reacts with γ-propane sultone or 2-bromoethyl sodium sulfonate, grafting sulfonic group side chain on polyamide molecule.The ionic conductivity of the sodium group in molecule and hygroscopicity can be improved the conduction of battery diaphragm and inhale alkalescence. This to moleculeThe modification mode of structure needs the strict chemical reaction condition of controlling to reach conventionally,
In prior art, for alkali-proof another improved procedure of aromatic polyamide fibre be, in the time preparing nonwoven,Add another kind of alkali resistance fiber, to improve the alkali resistance of nonwoven entirety. CN1656630A provide a kind of alkaline battery everyNonwoven and manufacture method thereof for film. The 60mol% that specifically includes dicarboxylic acids composition is aromatic dicarboxylic acid composition aboveThe 60mol% of dicarboxylic acids composition and two amine components be above two amine components of the aliphatic acid alkylene diamine of carbon number 6-12 form halfThe alkaline battery film nonwoven of aromatic polyamide fibre, ethylene-vinyl alcohol EVA fiber. But this mode still cannotImprove the alkali resistance of aromatic polyamide fibre, and can only improve to some extent to the alkaline resistance properties of fabric.
In the prior art, polyarylsulfone (PAS) has good alkali resistance and temperature tolerance, but polyarylsulfone (PAS) can not do separately fibre conventionallyDimension. And also only relate to moulded products (as disclosed in CN102782018A with the blend of aromatic polyamide polymer), but not fiber, and also clearly do not mention aromatic polyamide and polyarylsulfone (PAS) blend in the document.
The present invention aims to provide a kind of convenient, the alkali-proof side of raising aromatic polyamide fibre that operability is strongerMethod, and keep temperature tolerance and the mechanical property of fiber simultaneously.
Summary of the invention
The object of this invention is to provide a kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), in described fiber, wrapContaining the aromatic polyamide of 40-98wt%, the polyarylsulfone (PAS) of 2-60wt%, described aromatic polyamide and polyarylsulfone (PAS) mix.
Preferably, described aromatic polyamide is phenyl-diformyl p-phenylenediamine (PPD), mpd-i, polysulfones acylAmine, poly(p-benzamide).
Preferably, its strength retention soaking 5 hours at 85 DEG C in 10% NaOH solution is more than 70%, preferablyMore than 80%, more preferably more than 85%.
Preferably, it has intensity more than 2.5cN/dtex, preferably 2.5-3.5cN/dtex, more preferably 2.8-3.2cN/dtex。
Preferably, it has 280 DEG C of above vitrification points, preferably 300 DEG C of above vitrification points, more preferablyMore than 340 DEG C, most preferably more than 350 DEG C.
Preferably, it is long filament or short fiber.
The invention still further relates to a kind of method of preparing the blended fiber based on aromatic polyamide and polyarylsulfone (PAS), comprise followingStep:
(i) aromatic polyamide and polyarylsulfone (PAS) condensate are dissolved in organic solvent, are uniformly mixed, be mixed with 5-The spinning solution of 30wt%;
(ii) described spinning solution is spun into fiber.
Preferably, the described organic solvent of step in is (i) selected from 1-METHYLPYRROLIDONE (NMP), N, N-dimethyl acetylAmine (DMAc), DMF (DMF), methyl-sulfoxide, HMPA (HMPA), N, N, N ', N '-tetramethylThe mixture of one or more in urea (TMU).
Preferably, step (i) in the weight ratio adding of aromatic polyamide and polyarylsulfone (PAS) be 50-98:2-50, preferably60-95:5-40, more preferably 70-90:10-30, most preferably 80-85:15-20.
Preferably, step (i) in spinning solution the mass percent concentration of polymer be 5-30wt%, more preferably 10-22wt%, most preferably 12-20wt%.
Preferably, the step that step is prepared fiber in (ii) comprises: spinning and be frozen into silk, stretch, washing, dry, hotStretching, curling, cut-out.
Preferably, described in, be frozen in the coagulating bath of a step and comprise polar organic solvent, metal halide; Preferably,The content of polar organic solvent is 40-70wt%, and the content of metal halide is 0-10wt%.
Preferably, in described stretching step, stretch bath comprises polar organic solvent, metal halide; Preferably, polarity hasThe content of machine solvent is 5-65wt%, and the content of metal halide is 0-10wt%.
Preferably, the organic solvent in described coagulating bath and stretch bath can be independently selected from 1-METHYLPYRROLIDONE(NMP), DMA (DMAc), DMF (DMF), methyl-sulfoxide, HMPA(HMPA), N, N, N ', the mixture of one or more in N '-tetramethylurea (TMU), and described coagulating bath and described in drawThe polar organic solvent of stretching in bath can be the same or different.
Preferably, the metal halide in described coagulating bath and stretch bath can be independently selected from calcium chloride, magnesium chloride, chlorineThe mixture of one or more in change aluminium, calcium bromide, magnesium bromide, aluminium bromide, and described coagulating bath and described stretch bathIn metal halide can be the same or different.
The invention still further relates to a kind of yarn that comprises described fiber.
In some embodiments, in described yarn, also contain by being selected from PAEK, aromatic polyamides, high-molecular-weight polyEthene, polyphenylene sulfide, polyether-ether-ketone, PEI, poly-fragrant acid imide, polybenzimidazoles, polyphenyl Malignant azoles, polyphenyleneThe fiber that the mixing of one or more in sulfone, poly biphenyl ether sulfone, polyphenylene, polyimide sulfones makes.
The invention still further relates to a kind of fabric that comprises described fiber.
In some embodiments, fabric is woven, knitting or non-woven structure.
In some embodiments, described fabric also contains glass fibre, asbestos fibre, polybenzoxazole fiber, polyphenyl alsoImidazoles fiber, polybenzoxazoles fiber, polyarylether fiber and aramid fiber, carbon fiber, PTFE fiber, boron fibre, metallic fiber,Ceramic fibre, ca silicate fibre, silicon carbide fibre, metal puff, polyacrylonitrile fibre, aromatic polyamide fibre, phenolsA kind of or its mixture in resin.
The invention still further relates to a kind of protective clothes that comprises described fiber.
The invention still further relates to a kind of filter felt that comprises described fiber.
The invention still further relates to a kind of layered product that comprises described fiber.
The invention still further relates to a kind of composite that comprises described fiber.
Detailed description of the invention
Can be easier to understand the present invention by the content referring to the application's detailed description of the invention, but the present invention does not limitIn described herein and/or shown in concrete grammar, conditioned disjunction parameter, and term used herein is only for to give an exampleMode is described detailed description of the invention, can not limit the claimed technical scheme of the application's claim. Hereinafter, will retouchState according to a kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS) of the present invention and preparation method thereof, and comprise thisYarn, fabric and the goods of light fibers.
Prepare the co-blended spinning solution of aromatic polyamide and polyarylsulfone (PAS)
Prepare being total to of aromatic polyamide and polyarylsulfone (PAS) by add aromatic polyamide, polyarylsulfone (PAS) in organic solventBlended ratio solution, in described spinning solution, the mass percent concentration of polymer is 5-30wt%; Wherein aromatic polyamide is with poly-The weight ratio of virtue sulfone is 60-98:2-40, though the aromatic polyamide that comprises 60-98wt% in the fiber of final gained, 2-The polyarylsulfone (PAS) of 40wt%. The blended fiber based on aromatic polyamide and polyarylsulfone (PAS) obtaining not only can keep fragrant adoptionThe heat resistance of nylon and mechanical property, can also have better alkaline resistance properties than aromatic polyamide fibre.
Term " aromatic polyamide " in the present invention refers to a kind ofly have enough HMWs can form the synthetic poly-of fiberLaminate material, and be mainly that following loop structure unit is feature:
Wherein, each R1Hydrogen or lower paraffin hydrocarbon, and Ar wherein1And Ar2Can be identical or different, andAnd can be a unsubstituted or substituted divalent aryl, the connecting key of these divalent aryls and other groups be mainTo arrange with a position or contraposition, the hydrogen on described divalent aryl can be independently by following one or more following substituting group instituteReplace or do not replace, these substituting groups comprise halogen, C1-C4 alkyl, C1-C4 alkoxyl, phenyl, acyloxy, nitro, dialkyl groupAmino, alkylthio, carboxyl, sulfonyl, carbonylic alkoxy. Wherein, preferred poly P phenylene diamine terephthalamide (PPTA), isophthalic twoFormyl m-phenylene diamine (MPD) (PMIA).
Term " aromatic polyamide " in the present invention is also appreciated that the Ar in its macromolecular chain1And Ar2Can be identicalOr different there is following structure:
Wherein, be independently selected from-O-of X, Y ,-CH2-、-CO-、-CO2-、-S-、-SO2-、-C(CH3)2-, X and Y can be phasesSame or different. Wherein, preferred polysulfonamides.
Term " polyarylsulfone (PAS) " in the present invention has following general formula I or II as repetitive:
-O-A-SO2-A-(Ⅰ)
-O-A-SO2-A-O-B-(Ⅱ)
Wherein A and B can represent the optional aromatic group replacing. This aromatic group is by 6-40 carbon atom, and preferably 6-21 carbon is formerSon composition, contains one or more optional aryl, and wherein said aryl can optionally contain hetero atom. These aryl are enough appointedSelection of land is replaced by C1-C5 group line style or branching or alicyclic or halogen atom. Described aryl can via carbon bond or viaHetero atom as linking group connects. Wherein, preferably polyarylsulfone (PAS) is PPSU.
The preferred polar organic solvent of organic solvent, can be the organic solvent based on acid amides, the organic solvent based on urea,Or their mixture, preferably from 1-METHYLPYRROLIDONE (NMP), DMA (DMAc), N, N-diformazanBase formamide (DMF), methyl-sulfoxide, HMPA (HMPA), N, N, N ', a kind of in N '-tetramethylurea (TMU) orMore than one mixture.
The addition of described aromatic polyamide and polyarylsulfone (PAS) proportionally 50-98:2-50 adds, preferably 60-95:5-40, more preferably 70-90:10-30, most preferably 80-85:15-20.
In described spinning solution, the mass percent concentration of polymer is 5-30wt%, more preferably 10-22wt%, most preferably12-20wt%, to obtain good fiber properties. If the concentration of the final polymer obtaining is less than 5wt%, viscosity tooLow, and cannot fibroblast. If the concentration of polymer increases in spinning solution, the viscosity of spinning solution also can increase thereupon so. But,If the excessive concentration of polymer, can cause spinning solution unstable, produce gelatin phenomenon or polymer and the problem such as separate out.
. the blended fiber of preparation based on aromatic polyamide and polyarylsulfone (PAS)
The spinning solution that comprises described copolymer in the present invention, can use any means to be spun into silk. Wherein wet methodSpinning is preferred spinning mode. Its this spinning process is well known in the art, CN1683431A, CN101784710A,All on the books in US5536408, CN101235552A. Preferably through spinning as described below of example and be frozen into silk, stretching, waterWash, be dried, the operation such as hot-stretch, curling, cut-out manufactures.
Be not particularly limited as device for spinning, can use known wet spinning device in the past. In addition, as long as energyEnough stable carry out wet spinning, the spinning hole count to spinning spout. Ordered state, hole shape etc. be without special restriction, for example,Can use hole count for the fiber that 500-30000 is individual, spinning aperture is 0.05-0.15mm porous spinning spout etc.
As-spun fibre through spinneret orifice ejection solidifies in the coagulating bath that contains organic solvent and metal halide. IfExtrude plurality of threads simultaneously, they can be before coagulation step, during or form afterwards multifilament. Be frozen in a step and solidifyIn bath, comprise polar organic solvent, metal halide. The content of polar organic solvent is 0-70wt%, the content of metal halideFor 0-10wt%.
After coagulating bath, fiber is stretched. Described fiber can use the stretching of wetting of stretching solution, described stretchingSolution comprises water, salt and solvent; Described salt preferable alloy halide. The content of described polar organic solvent is 5-65wt%, metalHalid content is 0-10wt%.
The step of preparing fiber in the present invention (i) in and the organic solvent that adopts when solidifying and stretching of fiber be polarityOrganic solvent, those are as the solvent of proton acceptor, for example, preferably from 1-METHYLPYRROLIDONE (NMP), N, N-dimethyl secondAcid amides (DMAc), DMF (DMF), methyl-sulfoxide, HMPA (HMPA), N, N, N ', N '-tetramethylThe mixture of one or more in base urea (TMU). These organic solvents the step of preparing fiber (i) in, coagulating bathIn, in stretch bath, can be identical can be also different.
The metal halide adopting in fiber coagulating bath and stretching in the present invention can be halo slaine or halo alkaline earthSlaine, such as villaumite or the bromine salt of calcium, magnesium, aluminium etc., i.e. calcium chloride, magnesium chloride, aluminium chloride, calcium bromide, magnesium bromide, aluminium bromideDeng. Can only add a kind of inorganic salts, also can add two or more inorganic salts. These metal halides solidify at fiberBathe and stretch bath in can be identical can be also different.
After stretching, fiber is washed, the optimal way of washing can make described fiber and one or more washing bathOr washer box contact. Washing can be by immersing in bath by described fiber or completing by fiber described in water solution spray.Washer box generally includes the fully sheathed case that contains one or more rollers, wherein yarn before exiting described fully sheathed case repeatedly around alsoPassing through described roller advances. In the time that yarn is advanced around roller, can wash fluid be contacted with fiber by the mode of spraying. Scrub streamBody is collected in the bottom of washer box continuously, and discharges casing from bottom. The temperature of wash fluid is preferably higher than 40 DEG C. Also can beVapor form is used wash fluid, but uses more convenient with liquid form. Preferably, use multiple washing baths or washingCase, by the matting multistage, and controls the concentration conditions of temperature conditions and acid amides series solvent.
After washing, fiber or multifilament can be dried to remove moisture and other liquid in drier. Can use one orMultiple driers. In certain embodiments, described drier can be baking oven, hot plate, hot-rolling etc. In drier, can be nitrogenOr other non-reactive. Described drying steps under atmospheric pressure carries out conventionally. Then, if need described drying stepsAlso can under reduced pressure carry out.
After drying steps, preferably fiber is carried out to hot-stretch, heating-up temperature can reach more than 260 DEG C, preferably 280 DEG CAbove, more preferably 300 DEG C-400 DEG C. This hot-stretch step can increase the breaking ductility of fiber, and reduces fiber filamentMechanical strain performance, the modulus of raising fiber. In some embodiments, heating is multistep method. For example, in the first step,Described fiber or multifilament are heated at the temperature of 260-270 DEG C under some tension, then carry out the second heating steps, whereinFiber or multifilament are heated at the temperature of 280-290 DEG C under some tension, then carry out the 3rd heating steps, wherein by fibreDimension or multifilament heat at the temperature of 300-320 DEG C under some tension.
Finally, the winding package on coiler device by fiber or multifilament. If needed, long filament can be cut off and obtains short fiberDimension.
Fiber of the present invention also can include but not limited to be selected from following composition in addition: heat stabilizer, antistatic additive,Extender, organic and/or inorganic pigment are (as TiO2, carbon black), acid-acceptor (as magnesia), stabilizing agent, metal oxide be (as oxygenChange zinc), metal sulfide (as zinc sulphide), metal carboxylate (as the stearate of alkaline-earth metal and transition metal), anti-oxidantAgent, fire retardant, smoke suppressant, particle filler, nucleator (as talcum powder), mica, kaolin, or above-mentioned two or moreMixture. The weight of mentioned component, the gross weight based on fiber is preferably 0-30wt%, more preferably 0-25wt%, most preferably 0-20wt%。
Fiber of the present invention is not limited to method and system above. For example, before spinning, use solvent with solvent polymerizationIt is also the mode that can select that thing material is manufactured fiber. Fiber of the present invention can also adopt spun-bond process, meltblown etc. to makeStandby.
Fiber of the present invention can have very wide diameter range according to need of production, and number average diameter conventionally from 1nm extremely100 μ m. Nano level fiber for example can have 2,5,10,20,50,100 or the diameter of 200nm; Micron-sized fiber is passableThere is the diameter of 2,5,10,20,50 or 100 μ m.
Fiber of the present invention can have different shape of cross sections, as circle, ellipse, star, nucleocapsid etc.
The strength retention that fiber of the present invention soaks 5 hours at 85 DEG C in 10% NaOH solution is more than 70%.
Fiber of the present invention has intensity more than 2.5CN/dtex, preferably 2.5-3.5CN/dtex, more preferably 2.8-3.2CN/dtex。
Described fiber has 280 DEG C of above vitrification points, preferably 300 DEG C of above vitrification points, more preferably 340More than DEG C, most preferably more than 350 DEG C.
The yarn that comprises fiber of the present invention
The invention still further relates to a kind of yarn that comprises fiber of the present invention. In described yarn, also contain by be selected from PAEK,Aromatic polyamides, High molecular weight polyethylene, polyphenylene sulfide, polyether-ether-ketone, PEI, poly-fragrant acid imide, polybenzimidazoles,The mixing of one or more in polyphenyl Malignant azoles, PPSU, poly biphenyl ether sulfone, polyphenylene, polyimide sulfonesThe fiber making. Make yarn by the fiber that comprises above-mentioned polymer and fiber of the present invention with arbitrary proportion blending.
The fabric that comprises fiber of the present invention
" fabric " described in the present invention, comprises any woven, knitting or non-woven structure. So-called " woven " comprises anyWeaving textile, such as plain weave, satin weave, twill weave structure etc. So-called " knitting " comprises any by one or more warps, fiberOr the polyfilament yarn company of ring or mutually intersect and the structure prepared mutually. So-called " non-woven " comprises network of fibers, felt etc.
In other embodiments, the present invention also further relates to fabric, and fiber of the present invention is introduced into and is knittedIn thing. Described fabric comprises long filament of the present invention or short fiber. The fabric that contains fiber of the present invention is owing to having excellent heat resistanceIndustrial protection field can be widely used in. Also can be used for aviation, automobile, medicine, military affairs, safety, chemistry, medicine and smeltingStudy of the Chinese classic industry.
Described fabric can further comprise other conventional ingredient of fabric, as except fiber of the present invention, all rightComprise for example glass fibre, asbestos fibre, polybenzoxazole fiber, PBI fibre, polybenzoxazoles fiber, polyarylether fibrePeacekeeping aramid fiber, carbon fiber, PTFE fiber, boron fibre, metallic fiber, ceramic fibre are (as silicon nitride, talcum-glass fibersDimension), ca silicate fibre (as wollastonite microfibre), silicon carbide fibre, metal puff and composition thereof, polyacrylonitrile fibre,Aromatic polyamide fibre or phenolic resin.
The goods that comprise fiber of the present invention
Fiber of the present invention can also be used to be made into the goods such as filter felt, layered product, composite.
In other embodiments, fiber of the present invention can be made to filter felt, described filter felt can be appliedIn filter, described filtration is decorated can be used to multiple application, includes but not limited to the filter for industrial plant,As power plant, coal-fired power plant, cement plant.
In other embodiments, fiber of the present invention can be prescinded and obtain short fiber and paper pulp shape particle or short fiberDimension etc. is mixed with certain proportion, and it is dispersed in water, and makes fibrous paper. This fibrous paper has excellent performance. EnterOne step, can utilize calender to carry out hot pressing processing, make its heat of immersion thermoset epoxy resin varnish form prepreg, will be pre-Laminated and the moulding of impregnating, obtains the layered product that contains fiber of the present invention. This layered product can be used as circuit substrate, for this reason, and canThe circuit board use laminate structure thing of electrical insulation capability excellence is provided.
The fiber making as mentioned above, due to its excellent heat resistance and mechanical property, it has various useOn the way. For example: fiber of the present invention is prescinded to the short fiber and the resin compounded that obtain and form fibre-reinforced composite, this is compoundMaterial has excellent mechanical property and heat resistance.
Embodiment
Further illustrate the present invention with embodiment below. Various performance parameters in embodiment, surveys by the following methodFixed.
(a) relative viscosity of polymer
One, the processing of sample
1, smash
2, washing
3, dry (110 degree are lower to be dried 2.5 hours)
Two, test
A blank determination (timing that solvent flows out)
The viscosimeter of clean dry is vertically placed in the thermostat of 25 ± 0.1 DEG C, then will be incubated (25 ± 0.1 DEG C)The neat solvent (98% sulfuric acid) of 15 minutes is filtered (capillary diameter is 1.0～1.1mm) in viscosimeter with 1# sand core funnel, thenSurvey its solvent flow rate t0 (second), in triplicate, difference is no more than 0.5 second, gets its arithmetic mean of instantaneous value.
B Specimen Determination (concentration is 0.5%)
Accurately take 0.1250 gram of dry polymer, be placed in the volumetric flask of 25 milliliters, first add appropriate 98% dense sulphurAcid (AR), jog, can leave standstill dissolving, can be incubated if desired dissolving and (be placed in the bath temperature accelerate dissolution of 50～60 DEG C, note waterTemperature can not exceed 60 DEG C), after all dissolving, volumetric flask is placed in the thermostat of 25 ± 0.1 DEG C and keeps 15 minutes, then use98% the concentrated sulfuric acid adds to scale, and shakes up, and then filters in clean dry dark type viscometer with 1# sand core funnel, with sameMethod records solution flow rate t(second), in triplicate, difference is no more than 0.5 second, gets its arithmetic mean of instantaneous value.
C relative viscosity is calculated
Relative viscosity η r=t/t0
(b) spinning solution apparent viscosity
Tester: rotation viscometer probe temperature: 50 DEG C
Spinning solution is poured in test vessel, and controlling bath temperature is 50 DEG C, and balance some minutes is tested with thermometerWhen spinning solution temperature reaches 50 DEG C, suitable rotor is put into spinning solution, suitable rotating speed is set, start testAnd record test value.
(c) filament number
Method of testing is referring to GB/T14335
(d) fibre strength
Method of testing is referring to GB/T14337
(e) fibrous fracture percentage elongation
Method of testing is referring to GB/T14337
(f) fibrous glass temperature
Method of testing can be selected: traditional glass transition temperature, is recorded by differential scanning calorimetry (DSC); Or beDynamically glass transition, is recorded by dynamic thermal machinery analyses (DMA).
(g) alkaline resistance properties
Before and after alkaline resistance properties is processed with alkali lye, fibrous fracture strength retention characterizes.
In the NaOH solution that is 10% in concentration by fiber, at 85 DEG C, soak 5 hours, test respectively alkali lye and process front and backThe fracture strength of fiber.
Fracture strength × 100% of fiber before the fracture strength/processing of fiber after fibrous fracture strength retention=processing
Embodiment 1
Polysulfonamides (relative viscosity 3.1) and PPSU (relative viscosity 2.4) are dissolved in to N with the mass ratio of 95:5, N-In dimethyl formamide, by stirring, be finally configured to mass percent and be 5% spinning solution. By above-mentioned spinning solution through meterThe metering of amount pump, filter filter, spray into coagulating bath from spinning head. The spinning hole count of this spinning head is 500 holes, and spinning aperture is0.05mm, spinning speed is 30m/min, then through supersolidification, stretch bath, washing, dry, hot-stretch, curling, obtains finished product fibreDimension.
Embodiment 2
Polysulfonamides (relative viscosity 2.4) and PPSU (relative viscosity 1.9) are dissolved in to N-first with the weight ratio of 60:40In base pyrrolidones, by mediating, be finally configured to mass percent and be 10% spinning solution. By above-mentioned spinning solution through meterThe metering of amount pump, filter filter, spray into coagulating bath from spinning head. The spinning hole count of this spinning head is 800 holes, and spinning aperture is0.075mm, spinning speed is 20m/min, then through supersolidification, stretch bath, washing, dry, hot-stretch, curling, obtains finished product fibreDimension.
Embodiment 3
Polysulfonamides (relative viscosity 2.0) and PPSU (relative viscosity 1.9) are dissolved in to N-first with the weight ratio of 70:30In base pyrrolidones, by double screw extruder blend, be finally configured to mass percent and be 20% spinning solution. By above-mentionedSpinning solution filters, sprays into coagulating bath from spinning head through measuring pump metering, filter. The spinning hole count of this spinning head is30000 holes, spinning aperture is 0.075mm, spinning speed is 5m/min, then through supersolidification, stretch bath, washing, dry, hot-drawnStretch, curling, obtain finished fiber.
Embodiment 4
Polysulfonamides (relative viscosity 1.9) and PPSU (relative viscosity 1.9) are dissolved in to N-first with the weight ratio of 80:20In base pyrrolidones, by double screw extruder blend, be finally configured to mass percent and be 30% spinning solution. By above-mentionedSpinning solution filters, sprays into coagulating bath from spinning head through measuring pump metering, filter. The spinning hole count of this spinning head is30000 holes, spinning aperture is 0.075mm, spinning speed is 5m/min, then through supersolidification, stretch bath, washing, dry, hot-drawnStretch, curling, obtain finished fiber.
Embodiment 5
Polysulfonamides (relative viscosity 1.9) and PPSU (relative viscosity 1.9) are dissolved in to N with the weight ratio of 90:10, N-In dimethyl formamide, by double screw extruder blend, be finally configured to mass percent and be 25% spinning solution. By upperStating spinning solution filters, sprays into coagulating bath from spinning head through measuring pump metering, filter. The spinning hole count of this spinning head is30000 holes, spinning aperture is 0.075mm, spinning speed is 5m/min, then through supersolidification, stretch bath, washing, dry, hot-drawnStretch, curling, obtain finished fiber.
Embodiment 6
Polysulfonamides (relative viscosity 2.0) and PPSU (relative viscosity 1.9) are dissolved in to N with the weight ratio of 98:2, N-In dimethyl formamide, by mediating, be finally configured to mass percent and be 18% spinning solution. By above-mentioned spinning solution warpMeasuring pump metering, filter filter, spray into coagulating bath from spinning head. The spinning hole count of this spinning head is 30000 holes, spinneret orificeFootpath is 0.075mm, and spinning speed is 5m/min, then through supersolidification, stretch bath, washing, dry, hot-stretch, curling, obtains finished productFiber.
Comparative example 1
Polysulfonamides (relative viscosity 3.1) is dissolved in 1-METHYLPYRROLIDONE and makes spinning solution, in spinning solutionThe content of polysulfonamides is 5%. Spinning technique is identical with embodiment 1.
Comparative example 2
Polysulfonamides (relative viscosity 2.4) is dissolved in and in DMA, makes spinning solution, spinning solutionThe content of middle polysulfonamides is 10%. Spinning technique is identical with embodiment 2.
Comparative example 3
Mpd-i (relative viscosity 2.4) is dissolved in in DMF, to make spinning moltenLiquid, in spinning solution, the content of mpd-i is 20%. Spinning technique is identical with embodiment 3.
TableFibre property comparison
Should be clear and definite based on above embodiment, in the situation that not departing from the spirit or scope of the present invention, can be rightThe present invention carries out various improvement and becomes modification. Therefore, the invention is intended to contain based on improvement of the present invention and modification, as long as theseImprovement and modification drop on appended claim and are equal in the scope of substitute technology means.

Claims (20)

1. a blended fiber that comprises aromatic polyamide and polyarylsulfone (PAS), is characterized in that, wherein comprises the poly-of 60-98wt%Sulfonamide, the polyarylsulfone (PAS) of 2-40wt%; The strength retention that described fiber soaks 5 hours at 85 DEG C in 10% NaOH solution isMore than 70%.
2. the strength retention that fiber according to claim 1 soaks 5 hours at 85 DEG C in 10% NaOH solution isMore than 80%.
3. fiber according to claim 1, the strength retention soaking 5 hours at 85 DEG C in 10% NaOH solution isMore than 85%.
4. according to the fiber described in claim 1-3 any one, it has intensity more than 2.5cN/dtex.
5. according to the fiber described in claim 1-3 any one, it has the intensity of 2.5-3.5cN/dtex.
6. according to the fiber described in claim 1-3 any one, it has the intensity of 2.8-3.2cN/dtex.
7. according to the fiber described in claim 1-3 any one, it has 280 DEG C of above vitrification points.
8. according to the fiber described in claim 1-3 any one, it has 300 DEG C of above vitrification points.
9. according to the fiber described in claim 1-3 any one, it has 340 DEG C of above vitrification points.
10. according to the fiber described in claim 1-3 any one, it has 350 DEG C of above vitrification points.
11. according to the fiber described in claim 1-3 any one, and it is long filament or short fiber.
Prepare the method for fiber described in claim 1-11 any one, comprise the steps: (i) by aromatic series polyamides for 12. 1 kindsAmine and polyarylsulfone (PAS) condensate are dissolved in organic solvent, are uniformly mixed, and are mixed with the spinning solution of 5-30wt%;
(ii) described spinning solution is spun into fiber.
13. methods according to claim 11, the described organic solvent of step in is (i) selected from 1-METHYLPYRROLIDONE(NMP), DMA (DMAc), DMF (DMF), methyl-sulfoxide, HMPA(HMPA), N, N, N ', the mixture of one or more in N '-tetramethylurea (TMU).
14. according to the method described in claim 12 or 13, step (i) in the weight adding of aromatic polyamide and polyarylsulfone (PAS)Than being 50-98:2-50.
15. according to the method described in claim 12 or 13, step (i) in the weight adding of aromatic polyamide and polyarylsulfone (PAS)Than being 60-95:5-40.
16. according to the method described in claim 12 or 13, step (i) in the weight adding of aromatic polyamide and polyarylsulfone (PAS)Than being 70-90:10-30.
17. according to the method described in claim 12 or 13, step (i) in the weight adding of aromatic polyamide and polyarylsulfone (PAS)Than being 80-85:15-20.
18. according to the method described in claim 12 or 13, step (i) in the mass percent concentration of polymer in spinning solutionFor 5-30wt%.
19. according to the method described in claim 12 or 13, step (i) in the mass percent concentration of polymer in spinning solutionFor 10-22wt%.
20. according to the method described in claim 12 or 13, step (i) in the mass percent concentration of polymer in spinning solutionFor 12-20wt%.
CN201410051598.7A 2014-02-14 2014-02-14 A kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), yarn, fabric, goods and preparation method thereof Active CN104846473B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201410051598.7A CN104846473B (en) 2014-02-14 2014-02-14 A kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), yarn, fabric, goods and preparation method thereof
PCT/CN2015/072962 WO2015120810A1 (en) 2014-02-14 2015-02-13 Aromatic polyamide and polyarylsulfone based blended fibre, yarn, fabric, and products, and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410051598.7A CN104846473B (en) 2014-02-14 2014-02-14 A kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), yarn, fabric, goods and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104846473A CN104846473A (en) 2015-08-19
CN104846473B true CN104846473B (en) 2016-05-25

Family

ID=53799607

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410051598.7A Active CN104846473B (en) 2014-02-14 2014-02-14 A kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), yarn, fabric, goods and preparation method thereof

Country Status (2)

Country Link
CN (1) CN104846473B (en)
WO (1) WO2015120810A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104611839B (en) * 2015-02-13 2018-05-01 上海特安纶纤维有限公司 Nonwoven webs and preparation method comprising a kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS) and heat-resistance and flame-retardant fiber
CN107305937B (en) * 2016-04-19 2019-06-18 微宏动力系统（湖州）有限公司 A kind of aromatic polyamide composite diaphragm, preparation method and secondary cell
CN108048953B (en) * 2017-12-15 2020-12-22 浙江华峰氨纶股份有限公司 Polysulfone-polyurethane urea composite elastic fiber and preparation method thereof
CN111101221A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Sand-impregnated vinylon with excellent performance and method for preparing sand-impregnated vinylon by dry-wet spinning
CN110368822A (en) * 2019-08-09 2019-10-25 四川斯派恩新材料有限公司 A kind of high temperature resistant semi-aromatic seperation film and preparation method thereof
WO2022218972A1 (en) * 2021-04-15 2022-10-20 Teijin Aramid B.V. Process to manufacture an aramid solution
CN113684573A (en) * 2021-08-16 2021-11-23 深圳市栢迪科技有限公司 Preparation method of polyether-ether-ketone spun yarn and polyether-ether-ketone spun yarn

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6610398B1 (en) * 2000-06-02 2003-08-26 Biogeneral, Inc. Haptic materials and process for preparation
CN1678776A (en) * 2002-09-04 2005-10-05 盖尔麦公司 Articles comprising fibres and/or fibrids, fibres and fibrids and production method of same
CN1772791A (en) * 2005-11-04 2006-05-17 东华大学 Solid phase polymerization process for preparing ethylene telephthalate and aromatic diamine copolymer
WO2008116837A3 (en) * 2007-03-23 2008-12-31 Solvay Advanced Polymers Llc Polymer fibers, assemblies incorporating such polymer fibers, and systems incorporating such filter assemblies

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7550216B2 (en) * 1999-03-03 2009-06-23 Foster-Miller, Inc. Composite solid polymer electrolyte membranes
US7955692B2 (en) * 2007-08-22 2011-06-07 E. I. Du Pont De Nemours And Company Protective garment comprising fibers comprising copolymers containing structures derived from a plurality of amine monomers including 4,4′ diamino diphenyl sulfone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6610398B1 (en) * 2000-06-02 2003-08-26 Biogeneral, Inc. Haptic materials and process for preparation
CN1678776A (en) * 2002-09-04 2005-10-05 盖尔麦公司 Articles comprising fibres and/or fibrids, fibres and fibrids and production method of same
CN1772791A (en) * 2005-11-04 2006-05-17 东华大学 Solid phase polymerization process for preparing ethylene telephthalate and aromatic diamine copolymer
WO2008116837A3 (en) * 2007-03-23 2008-12-31 Solvay Advanced Polymers Llc Polymer fibers, assemblies incorporating such polymer fibers, and systems incorporating such filter assemblies

Also Published As

Publication number Publication date
CN104846473A (en) 2015-08-19
WO2015120810A1 (en) 2015-08-20

Similar Documents

Publication Publication Date Title
CN104846473B (en) A kind of blended fiber based on aromatic polyamide and polyarylsulfone (PAS), yarn, fabric, goods and preparation method thereof
CN104846468B (en) A kind of fiber being made by the aromatic polymer that contains sulfuryl, yarn, fabric, goods and preparation method thereof
CN104652038B (en) Fiber type, adhesive-bonded fabric, filtering material and its manufacture method comprising the fiber is blended
CN104630957B (en) Yarn and fabric and preparation method made of a kind of blended fiber and polyphenylene sulfide fibre based on aromatic polyamide and polyarylsulfone (PAS)
RU2534767C2 (en) Fibre from completely aromatic metatype polyamide
CN104674405B (en) Blending type aramid fiber mixture and its product containing sulfuryl
EP0007632A1 (en) Aromatic polyamide composition
CN104611839A (en) Non-woven fabric comprising blend fiber based on aromatic polyamide and polyarylsulfone and high temperature resistant flame retardant fiber and preparation method
CN104674452B (en) The filtering material and its manufacture method of a kind of blending fiber type containing polyimide fiber and containing sulfuryl
JP2010255140A (en) Aramid fiber
JP3995532B2 (en) Method for producing dense meta-type wholly aromatic polyamide fiber
JP2011037984A (en) Manufacturing method for aromatic copolyamide
CN104652040B (en) A kind of filtering material and its manufacture method of the blending type aramid fibre containing containing sulfuryl and high-temperature fibre
JP4588032B2 (en) Improved process of wet spinning for salt-containing aramid polymers
JP2016196599A (en) Wholly aromatic polyamide fiber
JP2010126826A (en) Fabric for stab-proof clothes
CN101781813B (en) Aramid fiber containing fluorine and preparation method thereof
JP2020147861A (en) Para-type fully aromatic polyamide fiber, and method for producing the same
JP7315378B2 (en) Meta-type wholly aromatic polyamide fiber and method for producing the same
JP7148350B2 (en) Wholly aromatic polyamide modified cross-section fiber bundle
JP2021179028A (en) Chemical-resistant meta-type wholly aromatic polyamide fiber and method for producing the same
JP6807789B2 (en) High-strength hollow fiber
CN105133069A (en) Meta-type wholly aromatic polyarmide fiber
JP2021095663A (en) Para-type wholly aromatic polyamide fibers and method of manufacturing the same, and method of manufacturing para-type wholly aromatic polyamide resin coating liquid
JP2015200045A (en) Method for producing para-type wholly aromatic polyamide fiber

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20220120

Address after: 257300 Guangrao Binhai New Area, Dongying City, Shandong Province

Patentee after: AFCHINA CORPORATION Co.,Ltd.

Address before: 200336 room 104, South Building, No. 1488, Hongqiao Road, Changning District, Shanghai

Patentee before: SHANGHAI TANLON FIBER Co.,Ltd.

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20220608

Address after: 257000 No. 101, building 4, No. 299, Chizhou Road, Dongying Development Zone, Shandong Province

Patentee after: Zhongfang new materials Co.,Ltd.

Address before: 257300 Guangrao Binhai New Area, Dongying City, Shandong Province

Patentee before: AFCHINA CORPORATION Co.,Ltd.

TR01 Transfer of patent right