CN104540987B - The flame resistant spun staple yarns made of the blend of the fiber derived from sulfonated naphthalene polyoxadiazole polymers - Google Patents

The flame resistant spun staple yarns made of the blend of the fiber derived from sulfonated naphthalene polyoxadiazole polymers Download PDF

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Publication number
CN104540987B
CN104540987B CN201380041417.6A CN201380041417A CN104540987B CN 104540987 B CN104540987 B CN 104540987B CN 201380041417 A CN201380041417 A CN 201380041417A CN 104540987 B CN104540987 B CN 104540987B
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staple fiber
fiber
staple
weight
sulfonated naphthalene
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CN104540987A (en
Inventor
P.A.布朗
J.W.陈
M.W.科布
A.塔德罗斯
J.D.特伦塔科斯塔
M.G.维恩伯格
S.R.威廉斯
R.朱
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DuPont Safety and Construction Inc
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EI Du Pont de Nemours and Co
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • 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
    • 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
    • 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
    • D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Artificial Filaments (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Woven Fabrics (AREA)

Abstract

The present invention describes a kind of flame resistant spun staple yarns, has：About 50 to about 95 parts by weight of total amount meter based on polymer fiber in yarn and textile fiber are gathered based on sulfonated naphthaleneThe textile staple fiber of the staple fiber of diazole and about 5 to about 50 parts by weight, it is described poly- based on sulfonated naphthaleneThe staple fiber of diazole includes one or both of formula (II) and (IIa) and the repetitive unit of formula (I)：Wherein Q is H or SO3M, and M is one or more cations；The textile staple fiber has the toughness of the limit oxygen index and about 2 grams per deniers or bigger of 24 or bigger.

Description

It is fire-retardant made of the blend of the fiber derived from sulfonated naphthalene polyoxadiazole polymers Spun yarn
It is described this application claims the benefit of priority for the U.S. Provisional Application 61/660115 submitted on June 15th, 2012 Provisional application, which is incorporated by reference, to be incorporated herein.
Technical field
Fabric and clothes the present invention relates to flame resistant spun staple yarns, containing these yarns and their preparation method.Yarn includes It is poly- containing sulfonated naphthaleneThe blend of the staple fiber of the polymerization of aromatic oxadiozole polymer fa.
Background technology
Be exposed to worker in flame, high temperature and/or electric arc etc. need to wear the protective garment made of heat resistance fiber and Product.Any increase of these protective article effects or these products while keeping barrier propterty comfort, durability and Any increase of stainability is welcome.
It is poly-Aromatic oxadiozole polymer fa has unique performance, and can be used in many fields, such as high-performance fiber is such as Fire resistance fibre.It is to prepare sulfonation to gather to improve flammable methodAromatic oxadiozole polymer fa.These methods have included using sulfonation list Body and rear sulfonation.Gomes et al. (US20098/0318109, US2008/0193652, US2009/0203870) makes sulphuric acid leaching One sulfonation of formation is reacted with aromatic dicarboxylic acid in phosphoric acid to gatherDiazole copolymer, then by the sulfonating polymers.It is another Method is using oleum during polymerization with the polymer obtained by sulfonation.Lee et al. (US 7,528,216 and US 7, 582,721) by making aromatic dicarboxylic acid be reacted with sulphuric acid leaching under finite quantity oleum, and sulfonated monomer (US is used 7,528,217) sulfonation is prepared randomly to gatherDiazole copolymer is made random poly-Diazole copolymer.
Therefore it needs a kind of to gather sulfonationDiazole is incorporated into the method for use in protective garment in yarn, the protective garment profit It is poly- with the sulfonation with improved performance such as anti-flammability and stainabilityThe advantageous effect of diazole fiber.
Invention content
The invention discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include based on polymer fiber and weaving in yarn About 50 to about 95 parts by weight of total amount meter of product fiber are gathered based on sulfonationThe spinning of the staple fiber of diazole and about 5 to about 50 parts by weight Fabric staple fiber, it is described poly- based on sulfonationThe staple fiber of diazole includes one or both of formula (II) and (IIa) and formula (I) Repetitive unit：
Wherein Q is H or SO3M, and M is one or more cations；The textile staple fiber has 24 or bigger The toughness of limit oxygen index and about 2 grams per deniers or bigger.
The invention also discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include based on polymer fiber and spinning in yarn The total amount meter of fabric fiber at least about 25 parts by weight are poly- based on sulfonation to about 80 parts by weightThe staple fiber of diazole and about 20 to The modacrylic fibre of about 75 parts by weight, it is described poly- based on sulfonationThe staple fiber of diazole include formula (II) and (IIa) it One or the two and formula (I) repetitive unit, wherein M be cation.
The invention also discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include based on polymer fiber and spinning in yarn About 50 to about 95 parts by weight of total amount meter of fabric fiber are gathered based on sulfonationThe staple fiber of diazole and about 5 to about 50 parts by weight High-modulus staple fiber, it is described poly- based on sulfonationThe staple fiber of diazole includes one or both of formula (II) and (IIa) and formula (I) Repetitive unit, wherein M be cation；The high-modulus staple fiber has the stretch modulus of 200 grams per deniers or bigger.
The invention also discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include based on poly- based on sulfonation in yarnTwo About 20 to about 50 parts by weight of total amount meter of the Textile material fiber of azoles are gathered based on sulfonationThe staple fiber of diazole and about 50 It is described poly- based on sulfonation to the rigid rod staple fiber of about 80 parts by weightThe staple fiber of diazole includes one of formula (II) and (IIa) Or the repetitive unit of the two and formula (I), wherein M are cation.
The invention also discloses a kind of protective garment comprising flame resistant spun staple yarns, Woven fabric, supatex fabric, band or length Silk.
Disclosed herein is a kind of method preparing spun yarn, the method includes：A) it is formed based on polymer fiber in yarn With about 50 to about 95 parts by weight of total amount meter of textile fiber based on poly-The staple fiber of diazole and about 5 to about 50 parts by weight The fibre blend of textile staple fiber, it is described based on poly-The staple fiber of diazole includes one or both of formula (II) and (IIa) And the repetitive unit of formula (I), wherein M are cation；The textile staple fiber have 24 or bigger limit oxygen index and The toughness of about 2 grams per deniers or bigger；And fibre blend b) is spun into spun yarn.
The invention also discloses a kind of method preparing spun yarn, the method includes：A) it is formed based on polymer in yarn The total amount meter of Textile material fiber at least about 25 parts by weight based on poly-The staple fiber of diazole and about 20 to about 75 weight The fibre blend of the modacrylic fibre of part, it is described based on poly-The staple fiber of diazole include formula (II) and (IIa) it One or the two and formula (1) repetitive unit, wherein M be cation；And fibre blend b) is spun into spun yarn.
The invention also discloses a kind of method preparing spun yarn, the method includes：A) it is formed based on polymer in yarn About 50 to about 95 parts by weight of total amount meter of Textile material fiber based on poly-The staple fiber of diazole and about 5 to about 50 weight The fibre blend of the high-modulus staple fiber of part, it is described based on poly-The staple fiber of diazole include one of formula (II) and (IIa) or The repetitive unit of the two and formula (I), wherein M are cation；The high-modulus staple fiber has 200 grams per deniers or bigger Stretch modulus；And fibre blend b) is spun into spun yarn.
The invention also discloses a kind of method preparing spun yarn, the method includes：A) it is formed based on polymer in yarn About 20 to about 50 parts by weight of total amount meter of Textile material fiber based on poly-The staple fiber of diazole and about 50 to about 80 weights The fibre blend of the rigid rod staple fiber of part is measured, it is described based on poly-The staple fiber of diazole includes one of formula (II) and (IIa) Or the repetitive unit of the two and formula (I), wherein M are cation；And fibre blend b) is spun into spun yarn.
Specific implementation mode
The invention discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include：
About 50 to about 95 parts by weight of total amount meter based on polymer fiber in yarn and textile fiber are gathered based on sulfonation The textile staple fiber of the staple fiber of diazole and about 5 to about 50 parts by weight, it is described poly- based on sulfonationThe staple fiber of diazole includes The repetitive unit of one or both of formula (II) and (IIa) and formula (I)：
Wherein Q is H or SO3M, and M is one or more cations；
The textile staple fiber has the toughness of the limit oxygen index and about 2 grams per deniers or bigger of 24 or bigger.
In one embodiment, poly- based on sulfonated naphthaleneThe content of the staple fiber of diazole be about 50 to about 85, or about 50 to About 75, or about 60 to about 85, or about 70 to about 80 parts by weight, and the content of high-modulus staple fiber is about 15 to about 50, or about 25 to about 40, or about 15 to about 40, or about 20 to about 30 parts by weight.
Suitable textile fiber includes meta-aramid fiber, Para-aromatic Aramide Fibre and polyazole fiber.
The invention also discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include based on polymer fiber and spinning in yarn The total amount meter of fabric fiber at least about 25 parts by weight are poly- based on sulfonated naphthalene to about 80 parts by weightThe staple fiber of diazole and about 20 It is described poly- based on sulfonated naphthalene to the modacrylic fibre of about 75 parts by weightThe staple fiber of diazole include formula (II) and One or both of (IIa) and the repetitive unit of formula (I), wherein M are cation.
In one embodiment, poly- based on sulfonated naphthaleneThe content of the staple fiber of diazole be about 35 to about 70, or about 50 to About 75 parts by weight, or about 45 to about 60, or about 45 to about 70 parts by weight, and the content of modacrylic fibre be about 30 to About 65, or about 25 to about 50, or about 40 to about 55, or about 30 to about 55 parts by weight.
Suitable denaturing acrylamide acid fiber includes the acrylonitrile copolymer mixed with vinylidene chloride.
The invention also discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include based on polymer fiber and spinning in yarn At least about 50 to about 95 parts by weight of total amount meter of fabric fiber are gathered based on sulfonated naphthaleneThe staple fiber of diazole and about 5 to about 50 weights The high-modulus staple fiber of part is measured, it is described poly- based on sulfonated naphthaleneThe staple fiber of diazole includes one or both of formula (II) and (IIa) And the repetitive unit of formula (I), wherein M are cation；The high-modulus staple fiber has the drawing of 200 grams per deniers or bigger Stretch modulus.
In one embodiment, poly- based on sulfonated naphthaleneThe content of the staple fiber of diazole be about 50 to about 85, or about 50 to About 75, or about 60 to about 85, or about 70 to about 80 parts by weight, and the content of high-modulus staple fiber is about 15 to about 50, or about 25 to about 40, or about 15 to about 40, or about 20 to about 30 parts by weight.
Many different fibers can be used as high-modulus staple fiber, including Para-aromatic Aramide Fibre, polyazole fiber, carbon fiber Dimension and their mixture.In some embodiments, Para-aromatic Aramide Fibre can be used as Gao Mo in the blend Measure staple fiber.So-called aromatic polyamides refers to that wherein at least 85% amide (- CONH-) linker is directly connected with two aromatic rings Polyamide.Additive can be used together with aromatic polyamides, and it has in fact been found that can by up to 10 weight % its Its polymeric material is blended with aromatic polyamides or usable copolymer, and the copolymer has up to 10% replacement aromatics Other diamines of polyamide diamines, or up to 10% replacement aromatic polyamides diacid chloride other diacid chlorides.In some implementations In example, preferred para-aramid is poly- (poly P phenylene diamine terephthalamide).It is fine to prepare available para-aramid The method of dimension is generally disclosed in such as United States Patent (USP) 3,869,430；3,869,429；In 3,767,756.It is various forms of this Class aromatic polyamides organic fiber is with trade nameKnowRespectively by Wilmington, Delaware's E.I.du Pont de Nemours and Company；It is sold with the Teijin of Japan, Ltd.Moreover, based on copolymerization (to Asia Phenyl/3,4 '-diphenyl ether terephthalate amine) fiber be defined as Para-aromatic Aramide Fibre as used herein.It is a kind of This commercially available fiber is referred to asFiber equally derives from Teijin, Ltd.
In some embodiments, polyazole fiber can be used as high-modulus staple fiber in the blend.For example, suitable poly- Azoles includes polybenzoxazole, polypyridine and azoles etc., and can be homopolymer or copolymer.Additive can be used together with polyazole, And by weight, at most up to 10% other polymeric materials can be blended with polyazole.Also workable copolymer has up to Other monomers of 10% or more replacement polyazole monomer.Suitable polyazole homopolymer and copolymer can be by known method systems , such as United States Patent (USP) 4,533,693 (authorizing Wolfe et al., on August 6th, 1985), 4,703,103 (authorize Wolfe et al., On October 27th, 1987), 5,089,591 (authorize Gregory et al., on 2 18th, 1992), 4,772,678 (authorize Sybert Et al., on September 20th, 1988), 4,847,350 (authorizing Harris et al., on August 11st, 1992) and 5,276,128 (authorize Those of Rosenberg et al., on January 4th, 1994) described in.
In some embodiments, preferred polybenzoxazole be polybenzimidazoles, polybenzothiozole and polyphenyl simultaneouslyAzoles.If The polybenzoxazole is polybenzimidazoles, then its preferably poly- ([5,5 '-bis- -1H- benzimidazoles] -2,2 '-diyls -1,3- Asia Phenyl), it is known as PBI.It is preferably polyphenyl and dithiazole, and it is more if the polybenzoxazole is polybenzothiozole Preferably poly- (benzo [1,2-d：4,5-d '] dithiazole -2,6- diyl-Isosorbide-5-Nitrae-phenylene), it is known as PBT.If the polyphenyl And azoles be polyphenyl simultaneouslyAzoles, then it is preferably polyphenyl and twoAzoles, and its more preferably poly- (benzo [1,2-d：4,5-d '] TwoAzoles -2,6- diyl-Isosorbide-5-Nitrae-phenylene), it is known as PBO.
In some embodiments, preferred polypyridine and azoles are rigid rod polyphosphazene polymer pyrido diazole, including poly- (pyridine And diimidazole), poly- (pyrido dithiazole) and poly- (pyrido twoAzoles).Preferred poly- (pyrido twoAzoles) it is poly- (Isosorbide-5-Nitrae- (2,5- dihydroxy) phenylene -2,6- pyrido [2,3-d：5,6-d '] diimidazole, it is known as PIPD.Suitable polypyridine and two Azoles can be made by known method, such as United States Patent (USP) 5, those of described in 674,969.High modulus carbon fiber is that this field is ripe Know, and commercially available carbon fiber includes deriving from Toho Tenax America, Inc'sFiber.
In some preferred embodiments, high-modulus staple fiber has the limit oxygen index (LOI) of 24 or bigger, this refers to High-modulus staple fiber or only the fabric made of high-modulus staple fiber will not maintain flame to burn in air.It is preferred at some Embodiment in, the high-modulus staple fiber have at least 26 or bigger LOI.
In some embodiments, the high-modulus staple fiber has at least 5 grams per deniers (4.5 gram/dtex) or bigger Fracture toughness.In certain other embodiments, the high-modulus staple fiber is at least 10 grams per deniers (9 gram/dtex) or more Big fracture toughness.Be added more high tenacity high-modulus staple fiber additional intensity can be provided to the spun yarn, this will make by The intensity and durability of final fabric and clothing made from the spun yarn are improved.Moreover, in some cases, according to altogether Mixed percentage, it is believed that the additional toughness provided from the high-modulus staple fiber to the spun yarn can be knitted made from the yarn Amplified in object and clothes, causes to obtain the toughness improvement than the bigger in the spun yarn in the fabric.
The invention also discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include based on polymer fiber and spinning in yarn At least about 20 to about 50 parts by weight of total amount meter of fabric fiber are gathered based on sulfonated naphthaleneThe staple fiber of diazole and about 50 to about 80 The rigid rod staple fiber of parts by weight, it is described poly- based on sulfonated naphthaleneThe staple fiber of diazole includes one of formula (II) and (IIa) or two The repetitive unit of person and formula (I), wherein M are cation.
In one embodiment, poly- based on sulfonated naphthaleneThe content of the staple fiber of diazole be about 30 to about 40, or about 35 to About 40, or about 30 to about 50, or about 20 to 40 parts by weight, and the content of rigid rod staple fiber is about 60 to about 70, or about 60 To about 65, or about 50 to about 70, or about 60 to about 80 parts by weight.
For this paper purposes, " rigid rod fibers " refer to the rigid rod virtue by being known as Rigid spacer segment with this field Fiber made from race's polymer；These rigid rod fibers also form fibril under abrasion or abrasion.The Rigid spacer usually wraps Containing another annular unit or functional group's end group, such as-NH- ,-CO- ,-O- ,-COO- ,-N=N- and/or-CH=CH-.Generally These rigid rod polymers have the aryl of height para-orientation, and have high stretching die by the fiber of these polymers Amount.Under abrasion or abrasion, rigid rod fibers are easy to fibrillation；That is, they form the structure with central fiber handle, wherein fine Silk extends from the fiber handle.The fiber handle is generally cylindricality, and a diameter of 4 to 50 microns, and the fibril for institute The connected hairy unit of fiber handle is stated, diameter is only the one of several microns or several microns points of zero, and 10 to 100 microns long.
It can be used different fibers as rigid rod staple fiber.In some embodiments, Para-aromatic Aramide Fibre can It is used as rigid rod staple fiber in the blend.So-called " aromatic polyamides " refers to wherein at least 85% amide (- CONH-) The polyamide that linker is directly connected with two aromatic rings.Additive can be used together with aromatic polyamides, and actually It was found that other polymeric materials of up to 10 weight % can be blended with aromatic polyamides or usable copolymer, the copolymerization Replacement aromatic polyamides diacid chloride of the object with the up to 10% other diamines for substituting aromatic polyamides diamines, or up to 10% Other diacid chlorides.In some embodiments, preferred para-aramid is poly- (poly P phenylene diamine terephthalamide).It prepares The method of available Para-aromatic Aramide Fibre is generally disclosed in such as United States Patent (USP) 3,869,430；3,869,429；With 3, In 767,756.Various forms of such aromatic polyamides organic fibers are with trade nameWithRespectively by The E.I.du Pont de Nemours and Company of wilmington, Delaware；With the Teijin of Japan, Ltd goes out It sells.Moreover, the fiber based on copolymerization (to phenylene/3,4 '-diphenyl ether terephthalate amine) be defined as it is as used herein right Position aramid fibre.A kind of this commercially available fiber is referred to asFiber equally derives from Teijin, Ltd。
In some embodiments, polyazole fiber can be used as rigid rod fibers in the blend.For example, suitable polyazole Including polybenzoxazole, polypyridine and azoles etc., and can be homopolymer or copolymer.Additive can be used together with polyazole, and And by weight, at most up to 10% other polymeric materials can be blended with polyazole.Also workable copolymer has up to Other monomers of 10% or more replacement polyazole monomer.Suitable polyazole homopolymer and copolymer can be by known method systems , such as United States Patent (USP) 4,533,693 (authorizing wolfe et al., on August 6th, 1985), 4,703,103 (authorize Wolfe et al., On October 27th, 1987), 5,089,591 (authorize Gregory et al., on 2 18th, 1992), 4,772,678 (authorize Sybert Et al., on September 20th, 1988), 4,847,350 (authorizing Harris et al., on August 11st, 1992) and 5,276,128 (authorize Those of Rosenberg et al., on January 4th, 1994) described in.
In some embodiments, preferred polybenzoxazole be polybenzimidazoles, polybenzothiozole and polyphenyl simultaneouslyAzoles.If The polybenzoxazole is polybenzimidazoles, then its preferably poly- ([5,5 '-bis- -1H- benzimidazoles] -2,2 '-diyls -1,3- Asia Phenyl), it is known as PBI.It is preferably polyphenyl and dithiazole, and it is more if the polybenzoxazole is polybenzothiozole Preferably poly- (benzo [1,2-d：4,5-d '] dithiazole -2,6- diyl-Isosorbide-5-Nitrae-phenylene), it is known as PBT.If the polyphenyl And azoles be polyphenyl simultaneouslyAzoles, then it is preferably polyphenyl and twoAzoles, and its more preferably poly- (benzo [1,2-d：4,5-d '] TwoAzoles -2,6- diyl-Isosorbide-5-Nitrae-phenylene), it is known as PBO.
In some embodiments, preferred polypyridine and azoles are rigid rod polyphosphazene polymer pyrido diazole, including poly- (pyridine And diimidazole), poly- (pyrido dithiazole) and poly- (pyrido twoAzoles).Preferred poly- (pyrido twoAzoles) it is poly- (Isosorbide-5-Nitrae- (2,5- dihydroxy) phenylene -2,6- pyrido [2,3-d：5,6-d '] diimidazole, it is known as PIPD.Suitable polypyridine and two Azoles can be made by known method, such as United States Patent (USP) 5, those of described in 674,969.
In some embodiments, the spun yarn also includes with the rigidity for 21 or the limit oxygen index (LOI) of bigger Stick staple fiber, this refers to rigid rod staple fiber or only the fabric made from rigid rod staple fiber will not maintain flame in air Burning.In some preferred embodiments, the rigid rod staple fiber has the LOI of at least 26 or bigger.
In some embodiments, the rigid rod staple fiber has at least 5 grams per deniers (4.5 gram/dtex) or bigger Fracture toughness.In certain other embodiments, the rigid rod staple fiber is at least 10 grams per deniers (9 gram/dtex) or more Big fracture toughness.Be added more high tenacity rigid rod staple fiber additional intensity can be provided to the spun yarn, this will make by The intensity and durability of final fabric and clothing made from the spun yarn are improved.Moreover, in some cases, it is believed that by The additional toughness that rigid rod staple fiber is provided to the spun yarn can be amplified in fabric and clothing made from the yarn, Cause to obtain the toughness improvement than the bigger in the spun yarn in the fabric.
The invention also discloses a kind of flame resistant spun staple yarns, the flame resistant spun staple yarns include based on polymer fiber and spinning in yarn At least about 50 to about 95 parts by weight of total amount meter of fabric fiber are gathered based on sulfonated naphthaleneThe staple fiber of diazole and about 5 to about 50 weights The textile staple fiber of part is measured, it is described poly- based on sulfonated naphthaleneThe staple fiber of diazole includes one or both of formula (II) and (IIa) And the repetitive unit of formula (I), wherein M are cation；The textile staple fiber have 21 or bigger limit oxygen index and The toughness of about 4 grams per deniers or bigger.
In one embodiment, poly- based on sulfonated naphthaleneThe content of the staple fiber of diazole be about 50 to about 85, or about 50 to About 75, or about 60 to about 85, or about 70 to about 80 parts by weight, and the content of high-modulus staple fiber is about 15 to about 50, or about 25 to about 40, or about 15 to about 40, or about 20 to about 30 parts by weight.
In flame resistant spun staple yarns disclosed herein, M is usually the cation of monovalence, such as H, Li, Na, K or NH4. It is poly- to be based on sulfonated naphthalene in some embodimentsThe total amount meter of the staple fiber of diazole, the content of formula (1) are about 5 moles of % to about 50 moles of %, or about 5 moles of % to about 40 moles of %, or about 10 moles of % to about 30 moles of %, and formula (II) and (IIa) it One or the content of the two be about 50 moles of % to about 95 moles of %, or about 60 moles of % to about 95 moles of %, or about 70 moles of % To about 90 moles of %.In other embodiments, it is rubbed using about 60 moles of % to about 95 moles of %, or about 70 moles of % to about 90 The formula (II) of your %；And use the formula (IIa) of about 0 mole of % to about 30 moles of %, or about 0 mole of % to about 20 moles of %. Also in other embodiments, formula (II) is not present or formula (IIa) is not present.
M can be transformed into another M at any time before or after spinning or formation moulded products.When M is H, polymer can It is neutralized by being contacted with salt, the salt such as, but not limited to sodium bicarbonate, sodium hydroxide, cesium hydroxide, lithium hydroxide, hydrogen-oxygen Change potassium or potassium carbonate.Can ion exchange and/or neutralization be carried out by any method as known in the art.
It is poly- based on sulfonated naphthaleneThe staple fiber of diazole also may include the repetitive unit of other parts on polymer chain.These Repetitive unit may include one or both of formula (III) and formula (IIIa)：
Wherein M is one or more cations.
It is poly- based on sulfonated naphthaleneThe staple fiber of diazole can have the sulfur-bearing of at least about 2 weight %, 4 weight % or 6 weight % Amount.Sulfur content can be improved by sulfonated monomer before polymerization or sulfonated polymer.
Polymer disclosed herein can be prepared by any method as known in the art or technique.A kind of suitable side Method includes the following steps：
A. by hydrazine, oleum, 2,6- naphthalene dicarboxylic acids (NDA), optionally 4,4 '-oxygroups bis- (benzoic acid) (OBBA) and One or both of terephthalic acid (TPA) and M-phthalic acid are mixed to form reaction mixture, and wherein the addition of oleum is with hydrazine Molal quantity is calculated as at least about 4 molar equivalent SO3；And
B., reaction mixture is heated to about to 100 DEG C to about 180 DEG C of temperature, until sulfonation and copolymerization is madeDiazole polymerize Object.
Other monomers also are present in the reaction mixture.
It is poly- that methods described herein can prepare sulfonationDiazole copolymer, the copolymer include at least about 2 weight %, 4 weights Measure the sulfur content of % or 6 weight %.It can be by wherein by NDA and/or OBBA or one of terephthalic acid (TPA) and M-phthalic acid Or the additional process steps of the two further sulfonation before polymerization, and/or by will wherein gatherDiazole is copolymerized produce The processing step of object sulfonation improves sulfur content.This sulfonation can be by known in the art adversely in any side of final product Method carries out, and is such as contacted with oleum, sulfuric acid or other sulfonated reagents.
Hydrazine can be used directly, or be used in the form of solid hydrazonium salt.A kind of suitable solid salt is sulphuric acid leaching [N2H5] HSO4, it is also known as hydrazine sulfate.
Oleum (Oleum) is also known as oleum (fuming sulfuric acid), disulfuric acid or coke Sulfuric acid refers to having various sulfur trioxide (SO3) composition sulfuric acid solution.Usually using about 15% or 18% to about 30%, or About 22% oleum, this refers to SO3Weight % in sulfuric acid.The addition of oleum is calculated as at least about with hydrazine molal quantity 4 molar equivalents, or at least about 5 molar equivalents SO3。
Reagent dosage depends on desired repetitive unit percentage in final polymer.With total dosage of dicarboxylic acids Meter, the dosages of 2,6- naphthalene dicarboxylic acids are about 1 mole of % to less than about 100 mole of %, or about 5 moles of % to about 50 moles of %, or About 5 moles of % to about 30 moles of %, and the dosage of one or both of terephthalic acid (TPA) and M-phthalic acid be about 1 mole of % or Less than about 100 moles %, or about 50 moles of % to about 99 moles of %, or about 70 moles of % to about 95 moles of %.In another reality It applies in example, the content of OBBA is about 1 mole of % to about 30 moles of %, or about 2 moles of % to about 20 moles of %.In another implementation In example, the terephthalic acid (TPA) of about 50 moles of % to about 95 moles of %, or about 80 moles of % to about 90 moles of % are used；And it uses About 0 mole of % to about 30 moles of %, or about 0 mole of % to about 20 moles of % M-phthalic acid.In another embodiment, right Phthalic acid is not present or M-phthalic acid is not present.The hydrazine of various ratios can be used, but usually using about 1: 1 molar ratio Dicarboxylic acids：Hydrazine.
Ingredient can combine in any order, but usually first be thoroughly mixed together solid constituent, then with smoke Sulfuric acid mixes.In one embodiment, oleum is added in a step；It is added with an aliquot.In another embodiment In, it can be before other dicarboxylic acids and hydrazine be added, by oleum and NDA and optionally OBBA is mixed.Then Mixture is sufficiently mixed by stirring or other agitating devices, until fully dissolving, typically at least five minutes.This dissolving can be Room temperature is to carrying out at most about 100 DEG C.
In one embodiment, it the described method comprises the following steps：
1) hydrazine or its salt, NDA and optionally OBBA and one or both of terephthalic acid (TPA) and M-phthalic acid are mixed To form premix；
2) premix is stirred at least 5 minutes；And
3) by at least about SO of 5 molar equivalents in terms of the molal quantity of hydrazine3Oleum be added in premix with shape At reaction mixture.
After dissolving, make mixture reaction until forming enough polymer.Usually at about 100 DEG C to about 180 DEG C, or about Polymerisation is carried out at least about 0.5 hour at a temperature of 120 DEG C to about 140 DEG C.It can keep or increase during reaction or rank liter The temperature.Temperature can be used for controlling the type of sulfonation repetitive unit in amount of sulfonation and final polymer.Such as, if it is desired to More sulfonation and/or closed loop repetitive unit, then should increase temperature, usually to greater than about 120 DEG C.If it is desire to less sulfonation And/or closed loop repetitive unit, then temperature answer relatively low, generally less than about 100 DEG C.
Sulfonated naphthalene is gathered made from method disclosed aboveAromatic oxadiozole polymer fa can before forming moulded products or it After neutralize so that H cations are substituted by another cation, usually monovalent cation such as Li, Na, K or NH4.This passes through Keep sulfonated naphthalene poly-Aromatic oxadiozole polymer fa contacts neutralizer or other ion-exchangers to carry out, and the neutralizer is usually basic salt Such as sodium bicarbonate.
The invention also discloses the sulfonation and copolymerizations made from methods described hereinAromatic oxadiozole polymer fa, and made from it Moulded products and fiber.
Polymer as described herein can form moulded products, such as film, fine strip body, for the fiber of floccule and for spinning The fiber that fabric uses, and it is used for protective garment, Woven fabric, supatex fabric, paper wood, band or filament.It can be via solution Spinning is spun into fiber using solution of the polymer in polymerization solvent, or the solution in another polymer solvent. Fibre spinning can be realized by multi-holed jet via dry-spinning silk, wet spinning silk or dry-jet wet-spinning silk (being also known as air gap spinning), To generate multifilament or tow known in the art.
Moulded products as described herein include extrusion or blow mold or film, moulding article etc..Film can be by any known Technique is made, and will such as spin liquid and is cast on flat surfaces, will spin liquid and is extruded through extruder to form film, or squeezes out and blow Modeling spins liquid film to form extrusion-blown modling film.The typical process that liquid film squeezes out is spun to include and be used for the similar method of those of fiber, Wherein solution enters air gap by spinning head or mold, subsequently enters coagulating bath.Description is spun liquid film extrusion and is orientated more detailed Feelings are found in Pierini et al. (United States Patent (USP) 5,367,042)；Chenevey(4,898,924)；Harvey et al. (4,939, 235)；In Harvey et al. (4,963,428).The liquid film usually obtained that spins is preferably more than about 250 mils (6.35mm) thickness, And its more preferably up to about 100 mil (2.54mm) is thick.
" fiber " is defined as the relatively flexible substance with high aspect ratio on the cross-sectional area perpendicular to its length Unit.Herein, term " fiber " is used interchangeably with term " long filament " or " warp thread " or " continuous filament yarn ".Long filament described herein Cross section can be any shape, such as circle or beans shape, but usually be typically round, and generally substantially solid and non- Hollow.Fiber in spinning to packaging on spool is referred to as continuous fiber.Fiber can be cut into short length, referred to as staple fiber. Fiber can be cut into smaller length, referred to as floccule.Yarn, multifilament or tow include plurality of fibers.Yarn can be tangled and/or Plying.
Any method can be used, by solution spun fiber, however, wet spinning and air gap spinning are most well known.In Wet-spinning In silk, spinning head directly extrudes fiber in the liquid of coagulating bath, and usually submerges or be placed on coagulating bath by spinning head Lower face.In air gap spinning (being also known as " dry-spray " wet spinning sometimes), spinning head is first within the very short duration Fiber is expressed into gas such as air, fiber is introduced into liquid coagulating bath immediately after.It is coagulated in general, spinning head is located at Admittedly bathing surface, " air gap " is generated between spinneret surface and coagulating bath surface.The general arrangement of spinning head and bath foam is this Known to field, United States Patent (USP) 3,227,793；3,414,645；3,767,756；With the description of the drawings pair in 5,667,743 In such spinning process of high-strength polymer.
" dry-spinning " refer to by the way that solution is squeezed into the hot cell with gas atmosphere, to remove solvent, leaves solid filament, And the method for preparing long filament.The solution include in a solvent formed fiber polymer, with continuous flow be extruded through one or Multiple spinneret orifices are so that polymer molecule is orientated.This is different from " wet spinning " or " air gap spinning ", and wherein polymer solution is extruded To in liquid precipitation or condensed medium with regenerated polymer long filament.In other words, in dry-spinning, gas is main solvent extraction Medium, and in wet spinning, liquid is main solvent extraction medium.It, then can after solid filament is formed in dry spinning With liquid handling long filament, to cool down long filament or washing long filament, further to extract remaining solvent.
Then on demand, using multifilament after routine techniques processing spinning or the fiber in tow, the fiber is neutralized, Washing, dry or heat treatment, are made stable and available fiber.The fiber formed by polymer described herein can be used for a variety of answer In.They are colourless or colourless to white, however impurity may cause to change colour, and are particularly used as fire resistance fibre, Because the polymer has about 24 or a higher, or about 26 or higher, or about 28 or bigger limit oxygen index.
In one embodiment, the spinning head with 5-50 hole can be used, by 5 to 25 weight % polymer concentration ranges Interior sulfuric acid solution spinning fibre, the hole have 0.003 " or 0.008 " diameter.The volume flow of spinning solution is usually 0.3-2mL/min.Then fiber is directly extruded in coagulating bath, the coagulating bath fills room temperature or high temperature or is less than environment temperature The solution of degree, the solution include sulfuric acid, saturated salt solution or the alkaline aqueous solution of 0-70 weight %.
Number, size, shape and the configuration in hole are alterable, to obtain desired fiber product.No matter previously whether lead to Non-condensable fluid layer is crossed, the spinning liquid of extrusion is added in coagulating bath.Non-condensable fluid layer is generally air, but can be any Other inert gases are not the liquid for spinning liquid coagulator.
Fiber and/or film may include common additives, such as dyestuff, pigment, antioxidant, matting agent, antistatic agent and Ultra-violet stabilizer, the additive are added into spinning solution, spin in liquid or coagulating bath, or are applied in spinning duration or later It overlays on fiber.Fiber will show good stainability, especially to the dye of positive ion.
Alkalinity or the dye of positive ion are water-soluble and are dissociated into anion and dye cation.Cation is to polymer Sulfonic acid group in masterbatch has strong affinity, and forming salt.
The sulfonation made from method disclosed above gathersDiazole copolymer can be before or after forming moulded products It neutralizes so that H cations are substituted by another cation, usually monovalent cation such as Li, Na, K or NH4.This is by making Sulfonation is poly-Diazole copolymer contacts neutralizer or other ion-exchangers to carry out, the neutralizer be usually basic salt such as Sodium bicarbonate.
When compared with long filament, as used herein, term " staple fiber " refers to the fiber for being cut into the desired length or being pulled off, Or naturally occurring fiber or fiber obtained, the fiber have the length of low-ratio with perpendicular to the transversal of the length direction Area width ratio.Artificial staple fiber obtained is cut into or is made suitable for adding on cotton, wool or worsted yarn spinning equipment The length of work processing.The staple fiber can be with (a) substantial uniform length, (b) change or random length, or (c) A part of staple fiber has substantial uniform length, and the staple fiber in other parts has different length, by the portion Staple fiber in point mixes to form substantial uniform distribution.
In some embodiments, suitable staple fiber has about 0.25 centimetre (0.1 inch) to about 30 centimetres (12 inches) Length.In some embodiments, the length of staple fiber is about 1cm (0.39in) to about 20cm (8in).It is preferred real at some It applies in example, the staple fiber made from staple process has the staple length of about 1cm (0.39in) to about 6cm (2.4in).
The staple fiber can be made by any method.For example, rotor or cutting machine can be used by continuous fibers straight in staple fiber It cuts and obtains, obtain straight (i.e. not curled) staple fiber, or can also be along staple length by the volume with saw tooth crimp The cutting of bent continuous fiber and obtain, crimp (or repeated flex) frequency be preferably more than 8 curlings/centimetre.
Staple fiber can also be formed by breaking continuous fiber, described to obtain the staple fiber with deformed part Deformed part is used as curling.Tension fracture type staple fiber can be made by being broken a bundle or a branch of continuous filament yarn during stretch break operation , the stretch break operation has the fracture zone of one or more distance to a declared goal, to form the coma randomly changed, the fibre Dimension group has the average cut length that can be controlled via fracture zone adjusting.
Traditional long fibre and staple fiber ring spinning process well known in the art can be used that spun yarn is made by staple fiber.Just For staple fiber, the cotton system spinning fiber lengths of generally use about 1.9 to 5.7cm (0.75in to 2.25in).With regard to long fine For dimension, the spinning or woolen system fiber of generally use most about 16.5cm (6.5in).However, this is not limited to ring ingot Spinning, because jet-impingement spinning, open-end-spinning and many other classes that staple fiber is transformed into available yarn also can be used The spinning method for genuine of type spins the yarn.
Stretch-broken tow also can be used directly at method by breaking directly obtained spun yarn.It is formed by traditional stretch-break method Yarn in staple fiber usually with length long at most about 18cm (7in).However for example, by PCT Patent Application WO Method described in 0077283, it is at most about 50cm (20in) that the spun yarn made from stretch-break method, which can also have maximum length, Staple fiber.Tension fracture type staple fiber is not usually required to crimp, because stretch-break method imparts a degree of volume to the fiber It is bent.
Staple fiber can also be formed by breaking continuous fiber, described to obtain the staple fiber with deformed part Deformed part is used as curling.Tension fracture type staple fiber can be made by being broken a bundle or a branch of continuous filament yarn during stretch break operation , the stretch break operation has the fracture zone of one or more distance to a declared goal, to form the coma randomly changed, the fibre Dimension group has the average cut length that can be controlled via fracture zone adjusting.
Term continuous filament yarn refers to having small diameter and soft longer than length those of specified by staple fiber of its length Tough fiber.The multifilament of continuous filament fibers and continuous filament yarn can be made by method well-known to those having ordinary skill in the art.
It can be used a variety of different fibers as textile staple fiber.In some embodiments, aramid fibre can It is used as textile staple fiber in the blend.In some preferred embodiments, meta-aramid fiber can be in institute It states and is used as textile staple fiber in blend.So-called aromatic polyamides refers to wherein at least 85% amide (- CONH-) linker The polyamide being directly connected with two aromatic rings.Meta-aramid is orientated comprising meta position configuration or meta position in polymer chain A kind of polyamide of linker.Currently, meta-aramid fiber can be with trade namePurchased from E.I.du Pont De Nemours (Wilmington, Delaware).Additive can be used together with aromatic polyamides, and actually sent out It is existing, other polymeric materials of up to 10 weight % can be blended with aromatic polyamides or usable copolymer, the copolymer With up to 10% replacement aromatic polyamides diamines other diamines, or up to 10% replacement aromatic polyamides two acyls Other diacid chlorides of chlorine.In some embodiments, preferred meta-aramid fiber is poly- (phenyl-diformyl isophthalic two Amine) (MPD-I).Any method can be used, which is spinned by dry-spinning or wet spinning；United States Patent (USP) 3,063,966 and 5,667,743 It is the illustration of methods availalbe.
In some embodiments, Para-aromatic Aramide Fibre can be used as textile staple fiber in the blend, with Increase flame resistant intensity and reduces heat-shrinkable.Currently, Para-aromatic Aramide Fibre can be with trade nameIt is purchased from E.I.du Pont de Nemours (Wilmington, Delaware), and can be with trade namePurchased from Teijin Ltd. (Tokyo, Japan).For purposes of the invention, Teijin Ltd. (Tokyo, Japan) are available from, it is (right by copolymerization Benzene/3,4 ' diphenyl ester paraphenylene terephthalamides) made ofFiber is considered as Para-aromatic Aramide Fibre.
In some embodiments, polyazole fiber type can be used as textile fiber in the blend.For example, suitable poly- Azoles includes polybenzoxazole, polypyridine and azoles etc., and can be homopolymer or copolymer.Additive can be used together with polyazole, And by weight, at most up to 10% other polymeric materials can be blended with polyazole.Also workable copolymer has up to Other monomers of 10% or more replacement polyazole monomer.Suitable polyazole homopolymer and copolymer can be by known method systems , such as United States Patent (USP) 4,533,693 (authorizing Wolfe et al., on August 6th, 1985), 4,703,103 (authorize Wolfe et al., On October 27th, 1987), 5,089,591 (authorize Gregory et al., on 2 18th, 1992), 4,772,678 (authorize Sybert Et al., on September 20th, 1988), 4,847,350 (authorizing Harris et al., on August 11st, 1992) and 5,276,128 (authorize Those of Rosenberg et al., on January 4th, 1994) described in.
In some embodiments, preferred polyphenyl azoles be polybenzimidazoles, polybenzothiozole and polyphenyl simultaneouslyAzoles.If institute It is polybenzimidazoles to state polybenzoxazole, then its preferably poly- ([5,5 '-bis- -1H- benzimidazoles] -2,2 '-diyl -1,3- Asia benzene Base), it is known as PBI.It is preferably polyphenyl and double thiazole, and it is more preferably if the polyphenyl azoles is polybenzothiozole For poly- (benzo [1,2-d：4,5-d '] double thiazole -2,6- diyl-Isosorbide-5-Nitrae-benzene, it is known as PBT.If the polybenzoxazole is poly- BenzoAzoles, then it is preferably polyphenyl and twoAzoles, and its more preferably poly- (benzo [1,2-d：4,5-d '] twoAzoles -2, 6- diyls-Isosorbide-5-Nitrae-phenylene), it is known as PBO.In some embodiments, preferred polypyridine and azoles be rigid rod polypyridine simultaneously Diazole, including poly- (pyrido diimidazole), poly- (pyrido dithiazole) and poly- (pyrido twoAzoles).Preferred poly- (pyrido TwoAzoles) it is poly- (Isosorbide-5-Nitrae-(2,5- dihydroxy) phenylene -2,6- pyrido [2,3-d：5,6-d '] diimidazole, it is known as PBI. Simultaneously diazole can be made suitable polypyridine by known method, such as United States Patent (USP) 5, those of described in 674,969.
In some embodiments, modified acrylic fibre can be used.The modified polyacrylonitrile being preferred in the present invention Fiber is the copolymer that acrylonitrile is combined with vinylidene chloride.In addition, the copolymer also may include one or more antimony oxides To improve fire line.Such available modified acrylic fibre includes but not limited to as institute is public in United States Patent (USP) 3,193,602 The fiber with 2 weight % antimony trioxides opened, such as United States Patent (USP) 3, disclosed in 748,302 is at least 2 weights by content % and preferably no greater than fiber made from the various antimony oxides of 8 weight %, and such as United States Patent (USP) 5,208,105＆5 are measured, The fiber with 8 to 40 weight % antimonials disclosed in 506,042.Preferred modified acrylic fibre can be a variety of Form is commercially available from Kaneka Corporation (Japan), certain not include antimony oxide, and other such as Protex C It is said that including those of 10 to 15 weight % compounds.
In some preferred embodiments, a plurality of types of staple fibers can be used as staple fiber blends presence.So-called fiber Blend refers to two or more combinations of staple fiber type in any way.Preferably, staple fiber blends are " close total Mixed object ", this refers to that various staple fibers in blend form relatively uniform fibre blend.In some embodiments, two kinds Or more the staple fiber of type be blended prior to or just when spinning yarn so that various staple fibers are evenly distributed in staple yarn bundle In.
Fabric can be made by spun yarn, and may include but be not limited to Woven fabric or knitted fabric.General fabric is set Meter and construction are well-known to those having ordinary skill in the art.So-called " weaving " fabric refers to usually being formed on loom by each other Interweaving warp or longitudinal yarn and weft yarn or crosswise yam and generate any weaving textile (such as plain weave, the crowfoot knit, Fang Ping Knit, satin weave, twill-weave etc.) fabric.It is believed that plain weave and twill weave are braided fabrics most-often used in business, and And it is preferred in many embodiments.
So-called " knitting " fabric refers to the fabric for usually interconnecting yarn circle by using needle and being formed.In many cases, For knitted fabric is made, spun yarn is fed, yarn is transformed into the knitting machine of fabric.If desired, can be provided into knitting machine Plying or a plurality of warp thread or yarn that do not combine；That is, a branch of yarn or a branch of folded yarn are sent into knitting machine simultaneously using routine techniques In and be knitted into fabric, or directly be knitted into clothing product such as gloves.In some embodiments, it is desirable to by by a kind of or A variety of other short yarns or continuous filament yarn yarn are sent into simultaneously with one or more spun yarns with fibre compact blend, thus will Functionality is added in knitted fabric.Adjustable knitting tight ness rating is to meet any specific needs.In such as single knitting The very effective combination of the performance of protective clothes is found that in object and pile knit fabric decorative pattern.
In certain especially useful embodiments, the spun yarn can be used for preparing anti-flammability clothes.In some embodiments In, the clothes substantially have one layer of armored fabric made of spun yarn.Illustrative such clothes include fire fighter Or the company's trousers shirt and coveralls of army personnel.Such suit is used for commonly used in covering on except fire fighter's clothes Parachute jumping enters some region with fighting forest fire.Other clothes may include that the such as chemical of extreme incident heat may occur Trousers, shirt, gloves, the oversleeve etc. that can be worn under processing industry or industrial electric/electric power environmental.In some preferred embodiments In, the fabric has at least 0.8 card every ounce every square yard of arc resistance every square centimeter.
In one embodiment, by being made poly- based on sulfonated naphthaleneThe staple fiber of diazole and textile staple fiber it is close Blend forms the fibre blend of the fiber.If desired, other staple fibers uniform staple fiber in contrast can be made Mixture combines.Blending can be realized by many methods known in the art, including many continuous filament yarn spools are placed on line On pedestal, and at the same time the method for cutting the long filament of two or more types to form cutting staple fiber blends；Or it is related to Shredding difference staple fiber is tied, then shredding and the method that various fibers are blended in opener, blender and carding machine；Or it is formed Then various staple fibres are further processed to form mixture, fibre blend item is formed such as in carding machine Method.The other methods for preparing tight fibers blend are also possible, as long as various types of difference fibers are relatively evenly It is distributed in entire blend.If forming yarn by blend, yarn also has relatively uniform short fibre mixture.Generally For, in most preferred embodiment, available fabric is extremely made in individual staple fiber shredding or separation in fiber process Normal degree so that since fiber knot or fiber section caused by the bad shredding of staple fiber and other major defects are will not damage The amount of final fabric quality exists.
In a preferred method, intimate staple fiber blend is made as follows：First by derived from open the staple fiber of bundle with Any other staple fiber (if it is desire to if obtaining additional function) mixes.Then use carding machine by fiber blends It is shaped to strip.Fiber is detached using carding machine usually in fiber industry, adjusts fiber, and fiber is delivered to loosely In the continuous strand of conjugate fiber and without notable twisting, it is commonly known as the carded sliver.Usually through but not limited to two-step stretch method, The carded sliver is processed into ripe bar.
Then technology is used to form spun yarn by ripe bar, the technology includes conventional cotton system or such as open end spinning The short-staple spinning processes of yarn and ring spinning；Or high speed gas spinning technique such as Murata jet-impingements spin, wherein using air Staple fiber is twisted into.It can also be by using the long fibre of conventional woolen system, or such as combing or half combing RING SPINNING Dimension technique, or spinning process is broken to realize the formation of spun yarn.It is usually to make no matter to use which kind of system of processing, ring spinning The preferred method of standby spun yarn.
Example
Unless otherwise specified, example is all made of following method and prepares.Reagent rate is provided in the form of molar ratio.Oleum Purchased from E.I.du Pont de Nemours and Company (Wilmington, DE).Terephthalic acid (TPA) (TA), isophthalic diformazan Sour (IA), 4,4 '-oxygroups bis- (benzoic acid) (OBBA), 2,6- naphthalene dicarboxylic acids (NDA), methanesulfonic acid, polyphosphoric acid and d6Diformazan Base sulfoxide is purchased from Sigma-Sulphuric acid leaching is purchased from Acros Organics.Sulfuric acid and sodium bicarbonate are purchased from EMD Chemicals, Inc..2,6- naphthalene dicarboxylic acids (NDA) are purchased from Novolyte Technologies.
Typical polymerization methods
Unless otherwise specified, each example uses typical polymerization methods, but presses specified change monomer ratio.To with It has glass machinery blender, nitrogen inlet and reagent and addition solid sulphuric acid connection in the 100mL dry glass reactors of mouth is added The dicarboxylic acids of ammonia (0.015mol, 1 molar equivalent) and one or more totally 1 molar equivalents.Unless otherwise specified, dicarboxylic acids : the molar ratio of sulphuric acid leaching is 1: 1.The specific molar ratio of each dicarboxylic acids is specified in instances.In nitrogen, by solid at It is grouped together and is fully blended 15 minutes.Unless otherwise specified, while agitating at room temperature to the solid mixture that this is blended Middle 18.7% oleum (oleum) (oleum (fuming sulfuric acid), the 18.7 weight % that 28.5g is added Free SO3Content) (4.4 molar ratio).Reaction kettle is fully sealed and without leakage (including blender axis) is split, to prevent gas phase composition Escape kettle.By mixture mechanical agitation (250RPM) several minutes at room temperature.Then it will will be mixed through~30 minutes sections Object is heated to 130 DEG C.Typical polymerisation is set to be carried out 4 hours at 130 DEG C.During polymerisation, if polymerisation The viscosity of solution becomes excessively high, usually reduces stir speed (S.S.) or stops stirring.
In some instances, using the NDA Jing Guo pre-reaction.2,6-NDA is dissolved in 18.7% oleum, and is made Reaction carries out 6.5 hours at 130 DEG C.The sulphuric acid leaching of ratio same as above and other dicarboxylic acids is added to reactor. It is subsequently added into sulfonation 2, the mixture of 6-NDA.Mixture includes the solid block that many is not incorporated into reaction mixture.Make polymerization Reaction carries out 4 hours at 130 DEG C.
Conventional fibre forming method
Fiber is prepared using two methods.
With sulfuric acid (95-98%) diluted polymer reaction mixture.Enough sulfuric acid is added so that solution viscosity is enough Height, so that thin continuous flow can be added drop-wise in the blender comprising water, the blender is rotated with given pace simultaneously, To ensure that the fiber of solidification is not opened.To each polymerisation, the optimal conditions of this method are determined.It, will for coagulated fibre Rubber sheet gasket is added at the top of blender blade, this enables fiber to be wound and collect.Then usually by hand by fiber again around It on vial, is washed with water, is then soaked in diluted sodium bicarbonate, until complete neutralization.Then by fiber water Washing and immersion, to remove the sodium bicarbonate of any remnants.Fiber is set to dry at ambient conditions.It in some instances, will be fine Sample high vacuum dry at room temperature is tieed up, to measure molecular weight via size exclusion chromatography (SEC) in methanesulfonic acid.
By sulfuric acid solution spinning fibre of the polymer concentration within the scope of 6-9 weight %.Solution is delivered by gear pump By the spinning head with 5-20 hole, the hole has the diameter of 0.003 " or 0.008 ".The volume flow of spinning solution is 0.2-2mL/min.Fiber is directly extruded in coagulating bath, solution at room temperature is filled in the coagulating bath, and the solution is 0-70 weights Measure the sulfuric acid of %.The fiber for leaving coagulating bath enters room temperature washing water-bath via ceramic guide.In washing bath, fiber surrounds The controlled driven roller winding of two speed, then stretches 50-600%.Volume three are usually made in each in these rollers.Fiber twines It is wound on phenolic resin core.Then in a series of interval steps, make the fiber spool of winding in 0.5 weight % sodium bicarbonates or It neutralizes in sodium hydroxide solution, washs in deionized water, and air-dry at room temperature.
Conventional curtain coating membrane preparation method
Polymeric reaction solution is diluted with sulfuric acid (95-98%), until gained viscosity makes it possible to obtain on a glass Uniform film.The viscosity is usually less than the viscosity needed for coagulated fibre.Polymer and glass plate are immersed in water-bath so that film Solidification.The film of solidification is washed with water, is then soaked in diluted sodium bicarbonate, until complete neutralization.Then film is washed with water It washs and impregnates, to remove the sodium bicarbonate of any remnants.The pressure of film between paper handkerchief in various degree is set to suppress repeatedly, until Touch up substantially dry.Then it between film being placed on aluminium foil, and is suppressed 5 minutes at 10,0001b.Gained film is existed High vacuum dry 24 hours at room temperature.
LOI is measured
Limit oxygen index (LOI) is the minimum oxygen concentration in the oxygen and nitrogen mixture indicated with percent by volume, described mixed The flaming combustion of material under initial room-temperature can just be maintained under the conditions of ASTM G125/D2863 by closing object.Using improved ASTM Method (ASTM D 2863) measures LOI, with being capable of quick screening sample.Film is mounted on sample holder, by the sample Clamper is inserted into LOI device, and is covered with cloche.Oxygen content in digital control cloche.Make film contacts Flame, and increase the oxygen content in cloche, until sample combustion.In the time point that can maintain candle shape burning, measure any The LOI of designated samples.
Example 1-93
(1) comparative example oleum replaces with polyphosphoric acid, and sulfuric acid replaces with phosphoric acid
(2) comparative example.Reaction temperature increases to 140 DEG C, rather than 130 DEG C as described in conventional method.It is all other Specification is identical.
(3) comparative example.Reaction temperature increases to 150 DEG C, rather than 130 DEG C as described in conventional method.It is all other Specification is identical.
(4) comparative example.Reaction temperature increases to 160 DEG C, rather than 130 DEG C as described in conventional method.It is all other Specification is identical.
(5) using (sulfonation) 2,6-NDA Jing Guo pre-reaction.
(6) M-phthalic acid：IA.Use 5 molar equivalent oleums.
Example 24
The verification of 2,6- naphthalene dicarboxylic acids sulfonation
2,6- naphthalene dicarboxylic acids (0.5053g, Aldrich 99%) is added in 18.7% oleum of 27.9g.By material Material is heated to 130 DEG C and it is made to be reacted in the case where being stirred by bar magnet 30 minutes.Reactant is removed and made from heat source It is cooled to room temperature.It carries out1H NMIR spectrum and LC/MS, and suggest the formation of desired sulfonated products.Including trace 3- trimethyl silyl sodium propionates-d4Water-d as chemical shift indicator2The middle saturation for preparing a sulfonation sulfone product is molten Liquid.NMR is popped one's head in and is inserted into solution.Document, which compares, allows primary two sulfonated products1The ownership of H resonance.1H belongs to (with opposite The ppm of chemical shift indicator is unit at 0.00ppm) it is shown in hereinafter.
It is analyzed in the enterprising row element of the sample made from example 12 and finds 55.56%C, 2.95%H, 14.88% N, 17.71%O and 2.21%S.Whole results are shown in hereinafter：
Example 25
Fiber is formed
Using following methods, by the polymer fiber of example 1.By a concentration of 7.2 weight % (15mol%NDA) POD The sulfuric acid solution spinning fibre of copolymer.Solution is delivered through the spinning head with 10 holes, the hole tool via gear pump Have 0.005 " diameter.The volume flow of spinning solution is 1.8mL/min.Fiber is directly extruded in coagulating bath, it is described solidifying Gu bath filling solution at room temperature, the solution are the sulfuric acid of 56 weight %.The fiber for leaving coagulating bath enters via ceramic guide Maintain the washing bath of the room temperature NaOH aqueous solutions under pH~12.0.In washing bath, fiber is around the controlled driven roller volume of two speed Around then stretching 400%.Volume three are usually made around each roller.Fiber is wrapped on phenolic resin core.Then at a series of In gap step, the fiber spool of winding is washed in deionized water and is air-dried at room temperature.
Using following methods, by the polymer fiber of example 2.By a concentration of 7.8 weight % (20mol%NDA) POD The sulfuric acid solution spinning fibre of copolymer.Solution is delivered through the spinning head with 20 holes, the hole tool via gear pump Have 0.005 " diameter.The volume flow of spinning solution is 1.8mL/min.Fiber is directly extruded in coagulating bath, it is described solidifying Gu bath filling solution at room temperature, the solution are the sulfuric acid of 58 weight %.The fiber for leaving coagulating bath enters via ceramic guide Maintain the washing bath of the room temperature NaOH aqueous solutions under pH~12.0.In washing bath, fiber is around the controlled driven roller volume of two speed Around then stretching 340%.Volume three are usually made around each roller.Fiber is wrapped on phenolic resin core.Then at a series of In gap step, the fiber spool of winding is washed in deionized water and is air-dried at room temperature.
The dye test carried out using carrier
Following dyestuff is individually tested using following methods：
In the 250-ml round-bottomed flasks equipped with reflux condenser be added POD-NDA yarns (30-50mg) andHCS (1 drop 0.1 weight % solution ,~0.03g), benzylalcohol (1.65g) and deionized water (53.39g) it is molten Liquid.Mixture is heated 15 minutes on 46 DEG C of aluminium round bottom heat blocks.Then, by basic dye (0.003-0.005g), benzylalcohol (0.301g) and the solution of deionized water (9.80g) are added in flask.Mixture is heated 10 minutes at 46 DEG C, is added later Acetic acid (0.85 weight %, 1 drop).Mixture is further heated to 70 DEG C, continues 15 minutes, is then heated to 100-130 DEG C, Continue 60 minutes, increases heat consumption and take~5-10 minutes.Then, solution is removed, fiber is stayed in flask.Then it is gone with heat (~70 DEG C) washing fibers of ionized water, and washed again with deionized water at room temperature.It is added into flask HCS The solution of (the 0.1 weight % solution of 0.061g) and deionized water (50g)；Then flask is heated 20 minutes at 70 DEG C.So Afterwards fiber is washed with the deionized water (~70 DEG C) of heat and deionized water at room temperature successively.Fiber is wrapped in SPSTM To dry in wiping cloth.Fiber is analyzed by transversal.Image shows each dye distribution to fibre core.(dense compared with low dye The lower fiber dyed of degree shows dyestuff penetration to core, but dyestuff is not present around crust；It is dyed under higher dye strength Fiber show uniform dyestuff penetration.)
The dye test carried out without using carrier
In the 250-ml round-bottomed flasks equipped with reflux condenser be added POD-NDA yarns (30-50mg) andHCS (1 drop 0.1 weight % solution ,~0.03g), benzylalcohol (1.65g) and deionized water (53.39g) it is molten Liquid.Mixture is heated 15 minutes on 46 DEG C of aluminium round bottom heat blocks.Then, by basic dye (0.003-0.005g) and go from The solution of sub- water (9.80g) is added in flask.Mixture is heated 10 minutes at 46 DEG C, acetic acid (0.85 weight is added later Measure %, 1 drop).Mixture is further heated to 70 DEG C, continues 15 minutes, is then heated to 100-130 DEG C, continues 60 minutes, Increase heat consumption and takes~5-10 minutes.Then, solution is removed, fiber is stayed in flask.Then the deionized water (~70 of heat is used DEG C) washing fiber, and washed again with deionized water at room temperature.It is added into flask(the 0.1 of 0.061g HCS Weight % solution) and deionized water (50g) solution；Then flask is heated 20 minutes at 70 DEG C.Then heat is used successively Deionized water (~70 DEG C) and deionized water at room temperature wash fiber.Fiber is wrapped in SPSTMTo dry in wiping cloth It is dry.Fiber is analyzed by transversal.Image shows each dye distribution to fibre core.It (is dyed under relatively low dye strength Fiber shows dyestuff penetration to core, but dyestuff is not present around crust；The fiber dyed under higher dye strength is shown Go out uniform dyestuff penetration.)
The dye test carried out under desuperheat without using carrier
In the 250-ml round-bottomed flasks equipped with reflux condenser be added POD-NDA yarns (30-50mg) andHCS (1 drop 0.1 weight % solution ,~0.03g), benzylalcohol (1.65g) and deionized water (53.39g) it is molten Liquid.Mixture is heated 15 minutes on 46 DEG C of aluminium round bottom heat blocks.Then, by basic dye (0.003-0.005g) and go from The solution of sub- water (9.80g) is added in flask.Mixture is heated 10 minutes at 46 DEG C, acetic acid (0.85 weight is added later Measure %, 1 drop).Mixture is further heated to 70 DEG C, continues 15 minutes, is then heated to 25-100 DEG C, continues 60 minutes, Increase heat consumption and takes~5-10 minutes.Then, solution is removed, fiber is stayed in flask.Then the deionized water (~70 of heat is used DEG C) washing fiber, and washed again with deionized water at room temperature.It is added into flask(the 0.1 of 0.061g HCS Weight % solution) and deionized water (50g) solution；Then flask is heated 20 minutes at 70 DEG C.Then heat is used successively Deionized water (~70 DEG C) and deionized water at room temperature wash fiber.Fiber is wrapped in SPSTMTo dry in wiping cloth It is dry.Fiber is analyzed by transversal.Image shows each dye distribution to fibre core.It (is dyed under relatively low dye strength Fiber shows dyestuff penetration to core, but dyestuff is not present around crust；The fiber dyed under higher dye strength is shown Go out uniform dyestuff penetration.)
Fiber UV stability
Then POD-NDA yarns are divided into one filament and are seated to cardboard plate framework to be completely exposed to illumination.It will be hard Paperboard frame is placed into Xe arc chambers and according to AATCC 16E：Color fastness to light standard testing continues to be tested for 96 hours. Long filament is adjusted 18 hours at 70F and 60% humidity.
Fibre property is analyzed
Danier is measured using TEXTTECHNO Vibromat.Sample is cut into 9cm segments and is passed through in due course Weight calculates danier (1den=1g/9000m) appropriate.The danier appropriate is programmed into Vibromat suitable to determine When counterpoise.Danier is determined by TEXTECHNO vibromat softwares, and replicate analysis 5-6 times.
Then ASTM tests D3822-07 is used to measure physical measurement；To obtain toughness and elongation at break (maximum value). D3822-07 is tested using ASTM, then 1 inch gauge is used to be carried out for elongation at break (maximum value) and toughness versus fiber Analysis.Sample is analyzed using 0.1 or 0.6in/min chuck speeds and 500g elements.Chuck speed is surveyed by %EB Fixed (＜ 8-10% then use 0.1in/min, ＞ 10%, then use 0.6in/min).Using Bluehill softwares to data into Row analysis, and replicate analysis 5-6 times.
As a result it shows below：
Example 27
This example illustrate flame resistant spun staple yarns and the NDA-POD fibers derived from example 25 with 24 or bigger the limit The textile staple fiber of oxygen index (OI) and the toughness of about 4 grams per deniers or bigger, such as with trade markFiber is purchased from The intimate blend of poly- (mpd-i) (MPD-I) fiber of E.I.duPont de Nemours＆Company Fabric.
The MPD-I of the NDA-POD staple fibers and 50 weight % of 50 weight % is prepared and processed by conventional cotton system system equipment The blended item of scutching cotton of staple fiber, and be spun into about 4.0 twist factor and about 21 special (28 cotton yarn branch using ring spinner Number) one-ply yarn size flame resistant spun staple yarns.Then it is bifilar that anti-flammability is made in two such singles yarns on buncher Yarn, for use as fabric warp.Using identical blend and similar method, including the identical twist and blending ratio, to be made The single thread of 24 special (24 yarn counts), and two strands in these one-ply yarns are combineeed to form bifilar fire-retardant yarn as fabric latitude Yarn.These doubled warps and doubled weft all have more than bifilar 100%NDA-POD staple fibers obtained at similar conditions The toughness of the toughness of yarn, that is, double strand yarn has the toughness of at least 3 grams per deniers (2.7 gram/dtex).
The warp thread and weft yarn yarn that ring is spun are weaved on fly-shuttle loom into fabric, and obtaining has 2 × 1 twill weaves and 26 warp × 17 Latitude/centimetre (72 warps × 52 latitudes/inch) construction and about 215g/m2(6.5oz/yd2) base weight nature fabric.Then in hot water Middle scouring greige twill fabric, and dry under low tension.Then it uses basic dye to spray the fabric cleaned to contaminate Color.Gained fabric has about 231g/m2(7oz/yd2) base weight and LOI more than 28.
A part for fabric is cut into variously-shaped, and variously-shaped is sewn to together so that fabric is converted to single layer Protective garment is for exposure to those of hot danger source situation.
In a similar way, ring spinning and associated fabric and clothes are made as by 100%NDA-POD staple fibers Reference material.
Table 2 shows the performance of the fabric and clothes of gained."+" indicates the performance that those have excellent performance than reference material, and Mark " 0 " indicate control physical performance, or with compare the comparable performance of physical performance.
Table 2
Example 28
This example illustrate flame resistant spun staple yarns and NDA-POD fibers and modacrylic fibre derived from example 24, Such as by Kaneka Corporation with trade markThe intimate blend of the modacrylic fibre of manufacture Fabric.
The denaturation for preparing and processing the NDA-POD staple fibers and 35 weight % of 65 weight % by conventional cotton system system equipment gathers The blended item of scutching cotton of acrylic staple fibers, and be spun into about 4.0 twist factor and about 21 special (28 cottons using ring spinner Yarn count) one-ply yarn size flame resistant spun staple yarns.Then it is double that anti-flammability is made in two such singles yarns on buncher Stock yarn, for use as fabric warp.Using identical blend and similar method and the identical twist and blending ratio, it is made The single thread of 24 special (24 yarn counts), and two strands in these one-ply yarns are combineeed to form bifilar fire-retardant yarn as fabric latitude Yarn.These doubled warps and doubled weft all have more than bifilar 100%NDA-POD staple fibers obtained at similar conditions The toughness of the toughness of yarn, that is, double strand yarn has the toughness of at least 3 grams per deniers (2.7 gram/dtex).
The warp thread and weft yarn yarn that ring is spun are weaved on fly-shuttle loom into fabric, and obtaining has 2 × 1 twill weaves and 26 warp × 17 Latitude/centimetre (72 warps × 52 latitudes/inch) construction and about 215g/m2(6.5oz/yd2) base weight nature fabric.Then in hot water Middle scouring greige twill fabric, and dry under low tension.Then it uses basic dye to spray the fabric cleaned to contaminate Color.Gained fabric has about 231g/m2(7oz/yd2) base weight and LOI more than 28.
A part for fabric is cut into variously-shaped, and variously-shaped is sewn to together so that fabric is converted to single layer Protective garment is for exposure to those of hot danger source situation.
In a similar way, ring spinning and associated fabric and clothes are made as by 100%NDA-POD staple fibers Reference material.
Table 3 shows the performance of the fabric and clothes of gained."+" indicates the performance that those have excellent performance than reference material, and Mark " 0 " indicate control physical performance, or with compare the comparable performance of physical performance.
Table 3
Example 29
This example illustrate flame resistant spun staple yarns and the NDA-POD fibers derived from example 25 with have high-modulus, specifically, The fiber of the stretch modulus of 200 grams per deniers or bigger, such as with trade markFiber is purchased from E.I.duPont de The fabric of the intimate blend of poly- (poly P phenylene diamine terephthalamide) (PPD-T) fiber of Nemours＆Company.PPD-T exists It is known that rigid rod polymer is used as in this field.
The PPD-T of the NDA-POD staple fibers and 15 weight % of 85 weight % is prepared and processed by conventional cotton system system equipment The blended item of scutching cotton of staple fiber, and be spun into about 4.0 twist factor and about 21 special (28 cotton yarn branch using ring spinner Number) one-ply yarn size flame resistant spun staple yarns.Using identical blend and similar method, including the identical twist and blended Than two strands of such one-ply yarns are combineeed on buncher then and are used as fabric warp to manufacture bifilar fire-retardant yarn, 24 spies (24 are made Yarn count) single thread, and two strands in these one-ply yarns combineeed with formed bifilar fire-retardant yarn be used as fabric weft yarn.These Doubled warps and doubled weft all have tough more than bifilar 100%NDA-POD staple yarns obtained at similar conditions The toughness of degree, that is, double strand yarn has the toughness of at least 3 grams per deniers (2.7 gram/dtex).
The warp thread and weft yarn yarn that ring is spun are weaved on fly-shuttle loom into fabric, and obtaining has 2 × 1 twill weaves and 26 warp × 17 Latitude/centimetre (72 warps × 52 latitudes/inch) construction and about 215g/m2(6.5oz/yd2) base weight nature fabric.Then in hot water Middle scouring greige twill fabric, and dry under low tension.Then it uses basic dye to spray the fabric cleaned to contaminate Color.Gained fabric has about 231g/m2(7oz/yd2) base weight and LOI more than 28.
A part for fabric is cut into variously-shaped, and variously-shaped is sewn to together so that fabric is converted to single layer Protective garment is for exposure to those of hot danger source situation.
In a similar way, ring spinning and associated fabric and clothes are made as by 100%NDA-POD staple fibers Reference material.
Table 4 shows the performance of the fabric and clothes of gained."+" indicates the performance that those have excellent performance than reference material, and Mark " 0 " indicate control physical performance, or with compare the comparable performance of physical performance.
Table 4
Example 30
Example 29 is repeated, in addition to the blended item of scutching cotton includes the PPD-T of the NDA-POD staple fibers and 60 weight % of 40 weight % Other than staple fiber.Such as in example 29, work is made by 100%NDA-POD staple fibers in ring spinning and relevant fabric and clothes For reference material.
Table 5 shows the performance of the fabric and clothes of gained."+" indicates the performance that those have excellent performance than reference material, and Mark " 0 " indicate control physical performance, or with compare the comparable performance of physical performance.
Table 5
Example 31
Example 29 is repeated, in addition to the blended item of scutching cotton includes the FR people of the NDA-POD staple fibers and 40 weight % of 60 weight % It makes other than silk.Such as in example 29, ring spinning and relevant fabric and clothes are made as by 100%NDA-POD staple fibers Reference material.
Table 6 shows the performance of the fabric and clothes of gained."+" indicates the performance that those have excellent performance than reference material, and Mark " 0 " indicate control physical performance, or with compare the comparable performance of physical performance.
Table 6

Claims (16)

1. flame resistant spun staple yarns, the flame resistant spun staple yarns include：
50 to 95 weight of total amount meter based on staple fiber and other textile staple fibers based on sulfonated naphthalene polyoxadiazole in the yarn Other textile staple fibers of the staple fiber and 5 to 50 parts by weight based on sulfonated naphthalene polyoxadiazole of part are measured, it is described to be based on sulfonation The staple fiber of Nai polyoxadiazoles include the repetitive unit of one or both of formula (II) and (IIa) and include formula (I) repetition list Member：
Wherein Q is H or SO3M, and M is one or more cations；
Other textile staple fibers have the toughness of the limit oxygen index and 2 grams per deniers or bigger of 24 or bigger；
Wherein in terms of the total amount of the staple fiber based on sulfonated naphthalene polyoxadiazole, the content of formula (I) is 5 moles of % to 50 moles of %；And The wherein described staple fiber based on sulfonated naphthalene polyoxadiazole has at least sulfur content of 2 weight %.
2. including the protective garment or band of flame resistant spun staple yarns described in claim 1.
3. including the Woven fabric or supatex fabric of flame resistant spun staple yarns described in claim 1.
4. flame resistant spun staple yarns, the flame resistant spun staple yarns include：
Total amount meter based on staple fiber and modacrylic fibre based on sulfonated naphthalene polyoxadiazole in the yarn at least 25 weights Part is measured to the modacrylic fibre of the staple fiber and 20 to 75 parts by weight based on sulfonated naphthalene polyoxadiazole of 80 parts by weight, institute It states the repetitive unit that the staple fiber based on sulfonated naphthalene polyoxadiazole includes one or both of formula (II) and (IIa) and includes formula (I) repetitive unit：
Wherein Q is H or SO3M, and M is one or more cations；And the wherein described short fibre based on sulfonated naphthalene polyoxadiazole Dimension has at least sulfur content of 2 weight %.
5. including the protective garment or band of the flame resistant spun staple yarns described in claim 4.
6. including the Woven fabric or supatex fabric of the flame resistant spun staple yarns described in claim 4.
7. flame resistant spun staple yarns, the flame resistant spun staple yarns include：
50 to 95 parts by weight of total amount meter based on staple fiber and high-modulus staple fiber based on sulfonated naphthalene polyoxadiazole in the yarn The staple fiber and 5 to 50 parts by weight based on sulfonated naphthalene polyoxadiazole high-modulus staple fiber, it is described be based on sulfonated naphthalene Ju Evil bis- The staple fiber of azoles include the repetitive unit of one or both of formula (II) and (IIa) and include formula (I) repetitive unit：
Wherein Q is H or SO3M, and M is one or more cations；
The high-modulus staple fiber has the stretch modulus of 200 grams per deniers or bigger；And it is wherein described based on the poly- Evil of sulfonated naphthalene The staple fiber of diazole has at least sulfur content of 2 weight %.
8. including the protective garment or band of the flame resistant spun staple yarns described in claim 7.
9. including the Woven fabric or supatex fabric of the flame resistant spun staple yarns described in claim 7.
10. flame resistant spun staple yarns, the flame resistant spun staple yarns include：
20 to 50 parts by weight of total amount meter based on staple fiber and rigid rod staple fiber based on sulfonated naphthalene polyoxadiazole in the yarn The staple fiber and 50 to 80 parts by weight based on sulfonated naphthalene polyoxadiazole rigid rod staple fiber, it is described be based on sulfonated naphthalene Ju Evil bis- The staple fiber of azoles include the repetitive unit of one or both of formula (II) and (IIa) and include formula (I) repetitive unit：
Wherein Q is H or SO3M, and M is one or more cations；And the wherein described short fibre based on sulfonated naphthalene polyoxadiazole Dimension has at least sulfur content of 2 weight %.
11. including the protective garment or band of flame resistant spun staple yarns according to any one of claims 10.
12. including the Woven fabric or supatex fabric of flame resistant spun staple yarns according to any one of claims 10.
13. the method for preparing spun yarn, the method includes：
A) the total amount meter 50 based on staple fiber and other textile staple fibers based on sulfonated naphthalene polyoxadiazole in the yarn is formed Fiber to other textile staple fibers of the staple fiber and 5 to 50 parts by weight based on sulfonated naphthalene polyoxadiazole of 95 parts by weight is mixed Close object, the staple fiber based on sulfonated naphthalene polyoxadiazole include the repetitive unit of one or both of formula (II) and (IIa) and Include the repetitive unit of formula (I)：
Wherein Q is H or SO3M, and M is one or more cations；
Other textile staple fibers have the toughness of the limit oxygen index and 2 grams per deniers or bigger of 24 or bigger；And its Described in the staple fiber based on sulfonated naphthalene polyoxadiazole there is at least sulfur content of 2 weight %；And
B) fibre blend is spun into spun yarn.
14. the method for preparing spun yarn, the method includes：
A) the total amount meter based on staple fiber and modacrylic fibre based on sulfonated naphthalene polyoxadiazole in the yarn is formed extremely The fiber of the modacrylic fibre of the staple fiber and 20 to 75 parts by weight based on sulfonated naphthalene polyoxadiazole of few 25 parts by weight Mixture, repetitive unit of the staple fiber based on sulfonated naphthalene polyoxadiazole comprising one or both of formula (II) and (IIa) is simultaneously And include the repetitive unit of formula (I)：
Wherein Q is H or SO3M, and M is one or more cations；And the wherein described short fibre based on sulfonated naphthalene polyoxadiazole Dimension has at least sulfur content of 2 weight %；
And
B) fibre blend is spun into spun yarn.
15. the method for preparing spun yarn, the method includes：
A) the total amount meter 50 to 95 based on staple fiber and high-modulus staple fiber based on sulfonated naphthalene polyoxadiazole in the yarn is formed The fibre blend of the high-modulus staple fiber of the staple fiber and 5 to 50 parts by weight based on sulfonated naphthalene polyoxadiazole of parts by weight, institute It states the repetitive unit that the staple fiber based on sulfonated naphthalene polyoxadiazole includes one or both of formula (II) and (IIa) and includes formula (I) repetitive unit：
Wherein Q is H or SO3M, and M is one or more cations；
The high-modulus staple fiber has the stretch modulus of 200 grams per deniers or bigger；And it is wherein described based on the poly- Evil of sulfonated naphthalene The staple fiber of diazole has at least sulfur content of 2 weight %；And
B) fibre blend is spun into spun yarn.
16. the method for preparing spun yarn, the method includes：
A) the total amount meter 20 to 50 based on staple fiber and rigid rod staple fiber based on sulfonated naphthalene polyoxadiazole in the yarn is formed The fibre blend of the rigid rod staple fiber of the staple fiber and 50 to 80 parts by weight based on sulfonated naphthalene polyoxadiazole of parts by weight, institute It states the repetitive unit that the staple fiber based on sulfonated naphthalene polyoxadiazole includes one or both of formula (II) and (IIa) and includes formula (I) repetitive unit：
Wherein Q is H or SO3M, and M is one or more cations；And the wherein described short fibre based on sulfonated naphthalene polyoxadiazole Dimension has at least sulfur content of 2 weight %；
And
B) fibre blend is spun into spun yarn.
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