CN104540987A

CN104540987A - Flame resistant spun staple yarns made from blends of fibers derived from sulfonated naphthalene polyoxadiazole polymers

Info

Publication number: CN104540987A
Application number: CN201380041417.6A
Authority: CN
Inventors: 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
Original assignee: EI Du Pont de Nemours and Co
Current assignee: DuPont Safety and Construction Inc
Priority date: 2012-06-15
Filing date: 2013-06-11
Publication date: 2015-04-22
Anticipated expiration: 2033-06-11
Also published as: CN104540987B; EP2861789B1; JP6112683B2; WO2014007948A3; JP2015526601A; EP2861789A2; WO2014007948A2

Abstract

Described is a flame-resistant spun yarn having: about 50 to about 95 parts by weight of a sulfonated naphthalene polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (Ila) wherein Q is H or SO3M, and M is one or more cations; and about 5 to about 50 parts by weight of a textile staple fiber having limiting oxygen index of 24 or greater and a tenacity of about 2 grams per denier or greater, based on the total amount of the polymeric fiber and the textile fiber in the yarn.

Description

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

This application claims the benefit of priority of the U.S. Provisional Application 61/660115 submitted on June 15th, 2012, described provisional application is incorporated herein by reference in full.

Technical field

The present invention relates to flame resistant spun staple yarns, fabric containing these yarns and clothes and their preparation method.Yarn comprises and gathers containing sulfonated naphthalene the blend of the staple fibre of the polymerization of aromatic oxadiozole polymer fa.

Background technology

The protective clothing that the worker be exposed in flame, high temperature and/or electric arc etc. needs dress to be made up of heat resistance fiber and goods.Any increase of these protective article effects, or any increase of these goods comfortableness, durability and stainability while keeping barrier propterty are all welcome.

Poly- aromatic oxadiozole polymer fa has unique performance, and can be used in many fields, such as high-performance fiber such as fire resistance fibre.Improving flammable method is that preparation sulfonation gathers aromatic oxadiozole polymer fa.These methods have comprised use sulfonated monomer and rear sulfonation.The people such as Gomes (US20098/0318109, US2008/0193652, US2009/0203870) make sulphuric acid leaching and aromatic dicarboxylic acid react in phosphoric acid formation one sulfonation gather diazole copolymer, subsequently by described sulfonating polymers.Another kind method is between polymerization period, use fuming sulphuric acid with the polymer obtained by sulfonation.The people such as Lee (US 7,528,216 and US 7,582,721) by making aromatic dicarboxylic acid and sulphuric acid leaching react under finite quantity fuming sulphuric acid, and it is random poly-to use sulfonated monomer (US 7,528,217) to prepare sulfonation diazole copolymer, obtained random poly- diazole copolymer.

Therefore one is needed sulfonation to be gathered diazole is incorporated into the method for use in protective clothing in yarn, and described protective clothing utilizes the sulfonation with the performance such as anti-flammability and stainability of improvement to gather the beneficial effect of diazole fiber.

Summary of the invention

The invention discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises total amount about 50 the gathering based on sulfonation to about 95 weight portions based on polymer fiber in yarn and textile fiber the textiles staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION; Described textiles staple fibre has limited oxygen index and about 2 grams/DENIER or the larger toughness of 24 or larger.

The invention also discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises total amount based on polymer fiber in yarn and textile fiber at least about 25 weight portions gathering based on sulfonation to about 80 weight portions the modacrylic fibre of the staple fibre of diazole and about 20 to about 75 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION.

The invention also discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises total amount about 50 the gathering based on sulfonation to about 95 weight portions based on polymer fiber in yarn and textile fiber the high-modulus staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION; Described high-modulus staple fibre has 200 grams/DENIER or larger stretch modulus.

The invention also discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises and gathers based on sulfonation based in yarn total amount about 20 the gathering based on sulfonation to about 50 weight portions of the Textile material fiber of diazole the rigid rod staple fibre of the staple fibre of diazole and about 50 to about 80 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION.

The invention also discloses a kind of protective clothing, Woven fabric, supatex fabric, band or the long filament that comprise flame resistant spun staple yarns.

Disclosed herein is a kind of method preparing staple fibre yarn, described method comprises: a) formed based on polymer fiber in yarn and textile fiber total amount about 50 to about 95 weight portions based on poly- the fibre blend of the textiles staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described based on poly- the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION; Described textiles staple fibre has limited oxygen index and about 2 grams/DENIER or the larger toughness of 24 or larger; And b) fibre blend is spun into staple fibre yarn.

The invention also discloses a kind of method preparing staple fibre yarn, described method comprises: a) formed total amount based on polymer fiber in yarn and textile fiber at least about 25 weight portions based on poly- the fibre blend of the modacrylic fibre of the staple fibre of diazole and about 20 to about 75 weight portions, described based on poly- the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (1), wherein M is CATION; And b) fibre blend is spun into staple fibre yarn.

The invention also discloses a kind of method preparing staple fibre yarn, described method comprises: a) formed based on polymer fiber in yarn and textile fiber total amount about 50 to about 95 weight portions based on poly- the fibre blend of the high-modulus staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described based on poly- the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION; Described high-modulus staple fibre has 200 grams/DENIER or larger stretch modulus; And b) fibre blend is spun into staple fibre yarn.

The invention also discloses a kind of method preparing staple fibre yarn, described method comprises: a) formed based on polymer fiber in yarn and textile fiber total amount about 20 to about 50 weight portions based on poly- the fibre blend of the rigid rod staple fibre of the staple fibre of diazole and about 50 to about 80 weight portions, described based on poly- the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION; And b) fibre blend is spun into staple fibre yarn.

Detailed description of the invention

The invention discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises:

Based on total amount about 50 the gathering based on sulfonation to about 95 weight portions of polymer fiber in yarn and textile fiber the textiles staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION;

Described textiles staple fibre has limited oxygen index and about 2 grams/DENIER or the larger toughness of 24 or larger.

In one embodiment, gather based on sulfonated naphthalene the content of the staple fibre of diazole is about 50 to about 85, or about 50 to about 75, or about 60 to about 85, or about 70 to about 80 weight portions, and the content of high-modulus staple fibre is about 15 to about 50, or about 25 to about 40, or about 15 to about 40, or about 20 to about 30 weight portions.

Suitable textile fiber comprises meta-aramid fiber, Para-aromatic Aramide Fibre and polyazole fiber.

The invention also discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises total amount based on polymer fiber in yarn and textile fiber at least about 25 weight portions gathering based on sulfonated naphthalene to about 80 weight portions the modacrylic fibre of the staple fibre of diazole and about 20 to about 75 weight portions, described poly-based on sulfonated naphthalene the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION.

In one embodiment, gather based on sulfonated naphthalene the content of the staple fibre of diazole is about 35 to about 70, or about 50 to about 75 weight portions, or about 45 to about 60, or about 45 to about 70 weight portions, and the content of modacrylic fibre is about 30 to about 65, or about 25 to about 50, or about 40 to about 55, or about 30 to about 55 weight portions.

Suitable denaturing acrylamide acid fiber comprises the acrylonitrile copolymer mixed with vinylidene chloride.

The invention also discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises total amount the gathering based on sulfonated naphthalene at least about 50 to about 95 weight portions based on polymer fiber in yarn and textile fiber the high-modulus staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described poly-based on sulfonated naphthalene the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION; Described high-modulus staple fibre has 200 grams/DENIER or larger stretch modulus.

Many different fibers can be used as high-modulus staple fibre, comprise Para-aromatic Aramide Fibre, polyazole fiber, carbon fiber and their mixture.In certain embodiments, Para-aromatic Aramide Fibre can be used as high-modulus staple fibre in the blend.So-called aromatic polyamides refers to the polyamide that the acid amides (-CONH-) of wherein at least 85% connects base and is directly connected with two aromatic rings.Additive can be used together with aromatic polyamides, and in fact find, can be blended by other polymeric material and aromatic polyamides reaching 10 % by weight, or can copolymer be used, described copolymer has other diamines of the alternative aromatic polyamides diamines of nearly 10%, or nearly 10% other diacid chloride of alternative aromatic polyamides diacid chloride.In certain embodiments, preferred para-aramid is poly-(poly P phenylene diamine terephthalamide).The method preparing available Para-aromatic Aramide Fibre is generally disclosed in such as United States Patent (USP) 3,869,430; 3,869,429; With 3,767, in 756.This type of aromatic polyamides organic fiber various forms of is with trade name know respectively by the E.I.duPont de Nemours and Company of Wilmington, Delaware; Sell with the Teijin of Japan, Ltd.And the fiber based on copolymerization (to phenylene/3,4 '-diphenyl ether terephthalate amine) is defined as Para-aromatic Aramide Fibre as used herein.This fibrid of a kind of commercially available acquisition is called as fiber, derives from Teijin equally, Ltd.

In certain embodiments, polyazole fiber can be used as high-modulus staple fibre in the blend.Such as, suitable polyazole comprises polybenzoxazole, polypyridine azoles etc., and can be homopolymers or copolymer.Additive can use together with polyazole, and by weight, at most nearly other polymeric material of 10% can be blended with polyazole.Also spendable copolymer has other monomer of the alternative polyazole monomer of nearly 10% or more.Suitable polyazole homopolymers and copolymer can be obtained by known method, such as United States Patent (USP) 4,533,693 (authorize the people such as Wolfe, on August 6th, 1985), 4,703,103 (authorizing the people such as Wolfe, on October 27th, 1987), 5,089,591 (authorizing the people such as Gregory, on February 18th, 1992), 4,772,678 (authorize the people such as Sybert, on September 20th, 1988), 4,847,350 (authorize the people such as Harris, on August 11st, 1992) and 5, those described in 276,128 (authorizing the people such as Rosenberg, on January 4th, 1994).

In certain embodiments, preferred polybenzoxazole be polybenzimidazoles, polybenzothiozole and polyphenyl also azoles.If described polybenzoxazole is polybenzimidazoles, then it is preferably poly-([5,5 '-bis--1H-benzimidazole]-2,2 '-two base-1,3-phenylene), and it is called PBI.If described polybenzoxazole is polybenzothiozole, then it is preferably polyphenyl and dithiazole, and it is more preferably poly-(benzo [1,2-d:4,5-d '] dithiazole-2,6-bis-bases-Isosorbide-5-Nitrae-phenylene), and it is called PBT.If described polybenzoxazole be polyphenyl also azoles, then it is preferably polyphenyl two azoles, and it is more preferably poly-(benzo [1,2-d:4,5-d '] two azoles-2,6-bis-bases-Isosorbide-5-Nitrae-phenylene), it is called PBO.

In certain embodiments, preferred polypyridine azoles is rigid rod polyphosphazene polymer pyrido diazole, comprises poly-(pyrido diimidazole), poly-(pyrido dithiazole) and gathers (pyrido two azoles).Preferred poly-(pyrido two azoles) in order to gather, (Isosorbide-5-Nitrae-(2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d:5,6-d '] diimidazole, it is called PIPD.Suitable polypyridine diazole can be obtained by known method, such as United States Patent (USP) 5, and 674, those described in 969.High modulus carbon fiber is well known in the art, and the carbon fiber of commercially available acquisition comprises and derives from Toho Tenax America, Inc's fiber.

In some preferred embodiments, high-modulus staple fibre has the limited oxygen index (LOI) of 24 or larger, and this refers to that high-modulus staple fibre or the fabric be only made up of high-modulus staple fibre can not maintain flame and burn in atmosphere.In some preferred embodiments, described high-modulus staple fibre has the LOI of at least 26 or larger.

In certain embodiments, described high-modulus staple fibre has at least 5 grams/DENIER (4.5 gram/dtex) or larger fracture toughness.In some other embodiment, described high-modulus staple fibre has at least 10 grams/DENIER (9 gram/dtex) or larger fracture toughness.The high-modulus staple fibre adding more high tenacity can provide extra intensity to described staple fibre yarn, and the intensity and durability that make final fabric and the clothing obtained by described staple fibre yarn are improved by this.And, in some cases, according to blended percentage, it is believed that the additional toughness provided to described staple fibre yarn by described high-modulus staple fibre can be amplified in the fabric obtained by described yarn and clothes, cause and obtain than toughness larger in described staple fibre yarn improvement in described fabric.

The invention also discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises total amount the gathering based on sulfonated naphthalene at least about 20 to about 50 weight portions based on polymer fiber in yarn and textile fiber the rigid rod staple fibre of the staple fibre of diazole and about 50 to about 80 weight portions, described poly-based on sulfonated naphthalene the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION.

In one embodiment, gather based on sulfonated naphthalene the content of the staple fibre of diazole is about 30 to about 40, or about 35 to about 40, or about 30 to about 50, or about 20 to 40 weight portions, and the content of rigid rod staple fibre is about 60 to about 70, or about 60 to about 65, or about 50 to about 70, or about 60 to about 80 weight portions.

With regard to this paper object, " rigid rod fibers " refers to and is called by having this area the fiber that the rigid rod aromatic polymer of Rigid spacer fragment is obtained; These rigid rod fibers also form fibril under abrasion or wearing and tearing.Described Rigid spacer comprises another kind of annular unit or functional group's end group, such as-NH-,-CO-,-O-,-COO-,-N=N-and/or-CH=CH-usually.These rigid rod polymer general have the aryl of height para-orientation, and have high stretch modulus by the fiber of these polymers.Under wearing and tearing or abrasion, rigid rod fibers is easy to fibrillation; That is, they form the structure with central fiber handle, and wherein fibril extends from described fiber handle.Described fiber handle is generally cylindricality, and diameter is 4 to 50 microns, and described fibril is the hair-like unit be connected with described fiber handle, and diameter is only zero point several microns or several microns/mono-, and long 10 to 100 microns.

Different fibers can be used as rigid rod staple fibre.In certain embodiments, Para-aromatic Aramide Fibre can be used as rigid rod staple fibre in the blend.So-called " aromatic polyamides " refers to the polyamide that the acid amides (-CONH-) of wherein at least 85% connects base and is directly connected with two aromatic rings.Additive can be used together with aromatic polyamides, and in fact find, can be blended by other polymeric material and aromatic polyamides reaching 10 % by weight, or can copolymer be used, described copolymer has other diamines of the alternative aromatic polyamides diamines of nearly 10%, or nearly 10% other diacid chloride of alternative aromatic polyamides diacid chloride.In certain embodiments, preferred para-aramid is poly-(poly P phenylene diamine terephthalamide).The method preparing available Para-aromatic Aramide Fibre is generally disclosed in such as United States Patent (USP) 3,869,430; 3,869,429; With 3,767, in 756.This type of aromatic polyamides organic fiber various forms of is with trade name with respectively by the E.I.du Pont de Nemours and Company of wilmington, Delaware; Sell with the Teijin of Japan, Ltd.And the fiber based on copolymerization (to phenylene/3,4 '-diphenyl ether terephthalate amine) is defined as Para-aromatic Aramide Fibre as used herein.This fibrid of a kind of commercially available acquisition is called as fiber, derives from Teijin equally, Ltd.

In certain embodiments, polyazole fiber can be used as rigid rod fibers in the blend.Such as, suitable polyazole comprises polybenzoxazole, polypyridine azoles etc., and can be homopolymers or copolymer.Additive can use together with polyazole, and by weight, at most nearly other polymeric material of 10% can be blended with polyazole.Also spendable copolymer has other monomer of the alternative polyazole monomer of nearly 10% or more.Suitable polyazole homopolymers and copolymer can be obtained by known method, such as United States Patent (USP) 4,533,693 (authorize the people such as wolfe, on August 6th, 1985), 4,703,103 (authorizing the people such as Wolfe, on October 27th, 1987), 5,089,591 (authorizing the people such as Gregory, on February 18th, 1992), 4,772,678 (authorize the people such as Sybert, on September 20th, 1988), 4,847,350 (authorize the people such as Harris, on August 11st, 1992) and 5, those described in 276,128 (authorizing the people such as Rosenberg, on January 4th, 1994).

In certain embodiments, preferred polypyridine azoles is rigid rod polyphosphazene polymer pyrido diazole, comprises poly-(pyrido diimidazole), poly-(pyrido dithiazole) and gathers (pyrido two azoles).Preferred poly-(pyrido two azoles) in order to gather, (Isosorbide-5-Nitrae-(2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d:5,6-d '] diimidazole, it is called PIPD.Suitable polypyridine diazole can be obtained by known method, such as United States Patent (USP) 5, and 674, those described in 969.

In certain embodiments, described staple fibre yarn also comprises the rigid rod staple fibre with the limited oxygen index (LOI) being 21 or larger, and this refers to that rigid rod staple fibre or the fabric only obtained by rigid rod staple fibre can not maintain flame and burn in atmosphere.In some preferred embodiments, described rigid rod staple fibre has the LOI of at least 26 or larger.

In certain embodiments, described rigid rod staple fibre has at least 5 grams/DENIER (4.5 gram/dtex) or larger fracture toughness.In some other embodiment, described rigid rod staple fibre has at least 10 grams/DENIER (9 gram/dtex) or larger fracture toughness.The rigid rod staple fibre adding more high tenacity can provide extra intensity to described staple fibre yarn, and the intensity and durability that make final fabric and the clothing obtained by described staple fibre yarn are improved by this.And, in some cases, it is believed that the additional toughness provided to described staple fibre yarn by rigid rod staple fibre can be amplified in the fabric obtained by described yarn and clothing, cause and obtain than toughness larger in described staple fibre yarn improvement in described fabric.

The invention also discloses a kind of flame resistant spun staple yarns, described flame resistant spun staple yarns comprises total amount the gathering based on sulfonated naphthalene at least about 50 to about 95 weight portions based on polymer fiber in yarn and textile fiber the textiles staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described poly-based on sulfonated naphthalene the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I), wherein M is CATION; Described textiles staple fibre has limited oxygen index and about 4 grams/DENIER or the larger toughness of 21 or larger.

In flame resistant spun staple yarns disclosed herein, M is generally the CATION of monovalence, such as H, Li, Na, K or NH ₄.In certain embodiments, to gather based on sulfonated naphthalene the total amount of the staple fibre of diazole, the content of formula (1) is about 5 % by mole to about 50 % by mole, or about 5 % by mole to about 40 % by mole, or about 10 % by mole to about 30 % by mole, and the content of formula (II) and (IIa) one or both of is about 50 % by mole to about 95 % by mole, or about 60 % by mole to about 95 % by mole, or about 70 % by mole to about 90 % by mole.In other embodiments, use about 60 % by mole to about 95 % by mole, or the formula (II) of about 70 % by mole to about 90 % by mole; And use about 0 % by mole to about 30 % by mole, or the formula (IIa) of about 0 % by mole to about 20 % by mole.Also in other embodiments, formula (II) does not exist or formula (IIa) does not exist.

M before or after spinning or forming moulded products, can be transformed into another M at any time.When M is H, polymer neutralizes by contacting with salt, and described salt is such as, but not limited to sodium bicarbonate, NaOH, cesium hydroxide, lithium hydroxide, potassium hydroxide or potash.Ion-exchange and/or neutralization can be carried out by any method as known in the art.

Gather based on sulfonated naphthalene the staple fibre of diazole also can comprise the repetitive of other parts on polymer chain.These repetitives can comprise formula (III) and formula (IIIa) one or both of:

Wherein M is one or more CATION.

Gather based on sulfonated naphthalene the staple fibre of diazole can have the sulfur content at least about 2 % by weight, 4 % by weight or 6 % by weight.Sulfur content is by sulfonated monomer before polymerization, or sulfonated polymer improves.

Polymer disclosed herein can be prepared by any method as known in the art or technique.A kind of suitable method comprises the following steps:

A. by hydrazine, fuming sulphuric acid, 2,6-naphthalene dicarboxylic acids (NDA), optionally 4, two (benzoic acid) (OBBA) of 4 '-oxygen base and terephthalic acid (TPA) and M-phthalic acid one or both of mixing are with forming reactions mixture, and wherein the addition of fuming sulphuric acid is at least about 4 molar equivalent SO with hydrazine molar basis ₃; And

B. reactant mixture is heated to the temperature of about 100 DEG C to about 180 DEG C, until obtained sulfonation and copolymerization aromatic oxadiozole polymer fa.

Other monomer also can be present in described reactant mixture.

Methods described herein can be prepared sulfonation and gather diazole copolymer, described copolymer comprises the sulfur content at least about 2 % by weight, 4 % by weight or 6 % by weight.By wherein by NDA and/or OBBA, or the additional process steps of terephthalic acid (TPA) and M-phthalic acid one or both of sulfonation further before polymerization, and/or by wherein gathering the processing step of diazole copolymer products sulfonation improves sulfur content.This sulfonation is adversely carried out in any method of end product by known in the art, such as contacts with fuming sulphuric acid, sulfuric acid or other sulfonated reagent.

Hydrazine can directly use, or uses with solid hydrazonium salt form.A kind of suitable solid salt is sulphuric acid leaching [N ₂h ₅] HSO ₄, it is also called as hydrazine sulfate.

Fuming sulphuric acid (Oleum) is also called as fuming sulphuric acid (fuming sulfuric acid), disulfuric acid or pyrosulfuric acid, refers to have various sulfur trioxide (SO ₃) sulfuric acid solution that forms.Usual use about 15% or 18% is to about 30%, or about 22% fuming sulphuric acid, and this refers to SO ₃in sulfuric acid % by weight.The addition of fuming sulphuric acid is at least about 4 molar equivalents with hydrazine molar basis, or at least about the SO of 5 molar equivalents ₃.

Reagent dosage depends on repetitive percentage desired in final polymer.With total gauge of dicarboxylic acids, 2, the consumption of 6-naphthalene dicarboxylic acids is for about 1 % by mole to being less than about 100 % by mole, or about 5 % by mole to about 50 % by mole, or about 5 % by mole to about 30 % by mole, and the consumption of terephthalic acid (TPA) and M-phthalic acid one or both of is about 1 % by mole or is less than about 100 % by mole, or about 50 % by mole to about 99 % by mole, or about 70 % by mole to about 95 % by mole.In another embodiment, the content of OBBA is about 1 % by mole to about 30 % by mole, or about 2 % by mole to about 20 % by mole.In another embodiment, use about 50 % by mole to about 95 % by mole, or the terephthalic acid (TPA) of about 80 % by mole to about 90 % by mole; And use about 0 % by mole to about 30 % by mole, or the M-phthalic acid of about 0 % by mole to about 20 % by mole.In another embodiment, terephthalic acid (TPA) does not exist, or M-phthalic acid does not exist.The hydrazine of various ratio can be used, but usually use the dicarboxylic acids of about 1: 1 mol ratio: hydrazine.

Composition can any sequential combination, but is usually first fully mixed by solid constituent, then mixes with fuming sulphuric acid.In one embodiment, a step adds fuming sulphuric acid; Namely add with an aliquot.In another embodiment, can before adding other dicarboxylic acids and hydrazine, by fuming sulphuric acid and NDA and optionally OBBA mix.Then by stirring or other agitating device, mixture is fully mixed, until fully dissolve, at least five minutes usually.This dissolving can be carried out at room temperature extremely at the most about 100 DEG C.

In one embodiment, said method comprising the steps of:

1) by hydrazine or its salt, NDA and optionally OBBA and terephthalic acid (TPA) and M-phthalic acid one or both of mixing to form premix;

2) premix is stirred at least 5 minutes; And

3) by with the SO of the molar basis of hydrazine at least about 5 molar equivalents ₃fuming sulphuric acid join in premix with forming reactions mixture.

After dissolving, mixture is reacted until form enough polymer.Usually at about 100 DEG C to about 180 DEG C, or at the temperature of about 120 DEG C to about 140 DEG C, polymerisation was carried out at least about 0.5 hour.Can keep or raise between the stage of reaction or rank rise described temperature.Temperature can be used for the type controlling sulfonation repetitive in amount of sulfonation and final polymer.Such as, if expect more sulfonation and/or closed loop repetitive, then answer raised temperature, usually to being greater than about 120 DEG C.If expect less sulfonation and/or closed loop repetitive, then temperature should be lower, is usually less than about 100 DEG C.

The sulfonated naphthalene obtained by method disclosed above is gathered aromatic oxadiozole polymer fa can formation moulded products before or after in and, H CATION is substituted by another kind of CATION, is generally monovalent cation such as Li, Na, K or NH ₄.This gathers by making sulfonated naphthalene aromatic oxadiozole polymer fa contact neutralizer or other ion-exchanger carry out, and described neutralizer is generally basic salt such as sodium bicarbonate.

The invention also discloses the sulfonation and copolymerization obtained by methods described herein aromatic oxadiozole polymer fa, and by its obtained moulded products and fiber.

Polymer as herein described can form moulded products, such as film, fine strip body, for the fiber of floccule and the fiber that uses for textiles, and for protective clothing, Woven fabric, supatex fabric, paper wood, band or filament.It via solution-polymerized SBR, can use the solution of polymer in polymerization solvent, or the solution in another kind of polymer solvent, is spun into fiber.Via dry-spinning silk, wet spinning silk or dry-jet wet-spinning silk (being also called as air gap spinning), fibre spinning can be realized by multi-holed jet, to generate multifilament known in the art or tow.

Moulded products as described herein comprises to be extruded or blow mold or film, moulding article etc.Film can be obtained by any already known processes, such as will spin liquid and be cast on flat surfaces, will spin liquid and be extruded through extruder to form film, or extrudes and blowing spins liquid film to form extrusion-blown modling film.Spin the typical process that liquid film extrudes to comprise and those the similar methods for fiber, wherein solution enters air gap by spinning head or mould, enters coagulating bath subsequently.Describe and spin liquid film and extrude and be found in the people such as Pierini (United States Patent (USP) 5,367,042) with more details of orientation; Chenevey (4,898,924); The people such as Harvey (4,939,235); With in the people (4,963,428) such as Harvey.It is usually obtained that to spin liquid film thick preferably more than about 250 mils (6.35mm), and it more preferably about 100 mils (2.54mm) are thick at the most.

" fiber " is defined as perpendicular to the relatively pliable and tough urstoff cross-sectional area of its length with high aspect ratio.Herein, term " fiber " exchanges with term " long filament " or " warp thread " or " continuous filament yarn " and uses.The cross section of long filament described herein can be any shape, such as circular or beans shape, but is generally circular usually, and is solid substantially and non-hollow usually.Fiber in spinning to packaging on bobbin is called continuous fibers.Fiber can be cut into short length, is called staple fibre.Fiber can be cut into less length, is called floccule.Yarn, multifilament or tow comprise plurality of fibers.Yarn can be tangled and/or be pooled capital.

Can adopt any method, by solution spun fiber, but wet spinning and air gap spinning are known most.In wet spinning, fiber is directly expressed in the liquid of coagulating bath by spinning head, and usually by spinning head submergence or be placed on coagulating bath lower face.In air gap spinning (being sometimes also called " dry-spray " wet spinning), first fiber is expressed in gas such as air by spinning head within the very short duration, is then incorporated in liquid coagulating bath by fiber immediately.Usually, spinning head is positioned at coagulating bath surface, produces " air gap " between spinning head face and coagulating bath surface.The general layout of spinning head and body lotion is well known in the art, United States Patent (USP) 3,227,793; 3,414,645; 3,767,756; With 5,667, this type of spinning process illustrated for high-strength polymer in 743.

" dry-spinning " refer to by solution is squeezed into there is gas atmosphere hot cell in, to remove solvent, leave solid filament, and prepare the method for long filament.Described solution comprises the polymer forming fiber in a solvent, is extruded through one or more spinneret orifice to make polymer molecule orientation with Continuous Flow.This is different from " wet spinning " or " air gap spinning ", and wherein polymer solution is expressed 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.In dry spinning, after solid filament is formed, liquid handling long filament can be used subsequently, to cool long filament or washing long filament, to extract remaining solvent further.

Then on demand, the fiber in multifilament after routine techniques process spinning or tow is adopted, with by described fiber neutralization, washing, dry or heat treatment, obtained stable and available fiber.The fiber formed by polymer described herein can be used in multiple application.They are colourless, or colourless extremely white, but impurity may cause variable color, and especially can be used as fire resistance fibre, because described polymer has about 24 or higher, or about 26 or higher, or the limited oxygen index of about 28 or larger.

In one embodiment, can adopt the spinning head with 5-50 hole, by the sulfuric acid solution spinning fibre in 5 to 25 % by weight polymer concentration range, described hole has 0.003 " or 0.008 " diameter.The volume flow of spinning solution is generally 0.3-2mL/min.Then be directly expressed in coagulating bath by fiber, room temperature or high temperature or the solution lower than environment temperature are filled in described coagulating bath, and described solution comprises the sulfuric acid of 0-70 % by weight, saturated salt solution or alkaline aqueous solution.

The number in hole, size, shape and configuration alterable, to obtain desired fiber product.No matter previously whether passed through non-condensable fluid layer, the liquid that spins extruded was joined in coagulating bath.Non-condensable fluid layer is generally air, but can be other inert gas any or be not the liquid spinning liquid coagulating agent.

Fiber and/or film can comprise common additives, such as dyestuff, pigment, antioxidant, matting agent, antistatic additive and ultra-violet stabilizer, described additive is added into spinning solution, spins in liquid or coagulating bath, or at spinning duration or be applied to afterwards on fiber.Fiber will show good stainability, especially to cation dyes.

Alkalescence or cation dyes are water miscible and are dissociated into anion and dye cation.CATION has strong affinity to the sulfonic acid group in polymer master batch, and forms salt.

The sulfonation obtained by method disclosed above gathers diazole copolymer can formation moulded products before or after in and, H CATION is substituted by another kind of CATION, is generally monovalent cation such as Li, Na, K or NH ₄.This gathers by making sulfonation diazole copolymer contact neutralizer or other ion-exchanger carry out, and described neutralizer is generally basic salt such as sodium bicarbonate.

When comparing with long filament, as used herein, term " staple fibre " refers to the fiber being cut into Len req or being pulled off, or naturally occurring fiber or obtained fiber, and described fiber has the length of low ratio and the cross-sectional area width ratio perpendicular to this length direction.Manually obtained staple fibre is cut into or is made the length being suitable for processing process on cotton, wool or worsted yarn spinning equipment.Described staple fibre can have (a) substantial uniform length, (b) that change or random length, or (c) a part of staple fibre has substantial uniform length, and the staple fibre in other parts has different length, the staple fibre in described part is mixed and forms substantial uniform distribution.

In certain embodiments, suitable staple fibre has the length of about 0.25 centimetre (0.1 inch) to about 30 centimetres (12 inches).In certain embodiments, the length of staple fibre is about 1cm (0.39in) to about 20cm (8in).In some preferred embodiments, the staple fibre obtained by staple process has the staple length of about 1cm (0.39in) to about 6cm (2.4in).

Described staple fibre can be obtained by any method.Such as, staple fibre can adopt rotor or cutting machine are cut by continuous fibers straight and obtain, obtain straight (namely unconvoluted) staple fibre, or also can along staple length by have saw tooth crimp crimped continuous fibers cut and obtain, curling (or repeated flex) frequency preferably more than 8 curling/centimetre.

Staple fibre is also formed by being broken by continuous fibers, thus obtains the staple fibre with crushed element, and described crushed element is used as curling.Tension fracture type staple fibre obtains by making a bundle or the fracture of a branch of continuous filament yarn during stretch break operation, described stretch break operation has the fracture zone of one or more distance to a declared goal, thus forming the fibrous mass of random change, described fibrous mass has and can regulate via fracture zone the average cut length controlled.

Traditional long fiber well known in the art and staple fibre ring spinning process can be used to obtain staple fibre yarn by staple fibre.With regard to staple fibre, usually adopt the cotton system spinning fiber lengths of about 1.9 to 5.7cm (0.75in to 2.25in).With regard to long fiber, usually adopt the spinning or woolen system fiber of about 16.5cm (6.5in) at most.But this is not intended to be limited to ring spinning, because jet-impingement spinning, open-end-spinning also can be adopted and staple fibre is transformed into and can spins described yarn with the spinning method for genuine of other types many of yarn.

The direct slivering method of stretch-broken tow also can be adopted by breaking directly obtained staple fibre yarn.Staple fibre in the yarn formed by traditional stretch-break method has the length that about 18cm (7in) is long at the most usually.But by the such as method described in PCT patent application WO 0077283, the staple fibre yarn obtained by stretch-break method also can have the staple fibre that maximum length is about 50cm (20in) at the most.Tension fracture type staple fibre does not need curling usually because stretch-break method to impart to a certain degree to described fiber curling.

Term continuous filament yarn refers to have small diameter and its length flexible fiber longer than those length specified by staple fibre.The multifilament of continuous filament fibers and continuous filament yarn obtains by method well-known to those having ordinary skill in the art.

Multiple different fiber can be used as textiles staple fibre.In certain embodiments, aramid fibre can be used as textiles staple fibre in the blend.In some preferred embodiments, meta-aramid fiber can be used as textiles staple fibre in the blend.So-called aromatic polyamides refers to the polyamide that the acid amides (-CONH-) of wherein at least 85% connects base and is directly connected with two aromatic rings.Meta-aramid is that between comprising in polymer chain, position configuration or position orientation connect a class polyamide of base.At present, meta-aramid fiber can trade name purchased from E.I.duPont de Nemours (Wilmington, Delaware).Additive can be used together with aromatic polyamides, and in fact find, can be blended by other polymeric material and aromatic polyamides reaching 10 % by weight, or can copolymer be used, described copolymer has other diamines of the diamines of the alternative aromatic polyamides of nearly 10%, or nearly 10% other diacid chloride of diacid chloride of alternative aromatic polyamides.In certain embodiments, preferred meta-aramid fiber is poly-(mpd-i) (MPD-I).Any method can be adopted, spin this fiber by dry-spinning or wet spinning; United States Patent (USP) 3,063,966 and 5,667,743 is illustrations of methods availalbe.

In certain embodiments, Para-aromatic Aramide Fibre can be used as textiles staple fibre, in the blend to increase flame resistant intensity and to reduce heat-shrinkable.At present, Para-aromatic Aramide Fibre can trade name purchased from E.I.du Pont de Nemours (Wilmington, Delaware), and can trade name purchased from Teijin Ltd. (Tokyo, Japan).With regard to object of the present invention, Teijin Ltd. (Tokyo, Japan) can be derived from, be made up of copolymerization (to benzene/3,4 ' diphenyl ester paraphenylene terephthalamide) fiber is regarded as Para-aromatic Aramide Fibre.

In certain embodiments, polyazole fiber type can be used as textile fiber in the blend.Such as, suitable polyazole comprises polybenzoxazole, polypyridine azoles etc., and can be homopolymers or copolymer.Additive can use together with polyazole, and by weight, at most nearly other polymeric material of 10% can be blended with polyazole.Also spendable copolymer has other monomer of the alternative polyazole monomer of nearly 10% or more.Suitable polyazole homopolymers and copolymer can be obtained by known method, such as United States Patent (USP) 4,533,693 (authorize the people such as Wolfe, on August 6th, 1985), 4,703,103 (authorizing the people such as Wolfe, on October 27th, 1987), 5,089,591 (authorizing the people such as Gregory, on February 18th, 1992), 4,772,678 (authorize the people such as Sybert, on September 20th, 1988), 4,847,350 (authorize the people such as Harris, on August 11st, 1992) and 5, those described in 276,128 (authorizing the people such as Rosenberg, on January 4th, 1994).

In certain embodiments, preferred polyphenyl azoles be polybenzimidazoles, polybenzothiozole and polyphenyl also azoles.If described polybenzoxazole is polybenzimidazoles, then it is preferably poly-([5,5 '-bis--1H-benzimidazole]-2,2 '-two base-1,3-phenylene), and it is called PBI.If described polyphenyl azoles is polybenzothiozole, then it is preferably polyphenyl double thiazole, and it is more preferably, and poly-(benzo [1,2-d:4,5-d '] double thiazole-2,6-bis-bases-Isosorbide-5-Nitrae-benzene, it is called PBT.If described polybenzoxazole be polyphenyl also azoles, then it is preferably polyphenyl two azoles, and it is more preferably poly-(benzo [1,2-d:4,5-d '] two azoles-2,6-bis-bases-Isosorbide-5-Nitrae-phenylene), it is called PBO.In certain embodiments, preferred polypyridine azoles is rigid rod polypyridine and diazole, comprises poly-(pyrido diimidazole), poly-(pyrido dithiazole) and gathers (pyrido two azoles).Preferred poly-(pyrido two azoles) in order to gather, (Isosorbide-5-Nitrae-(2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d:5,6-d '] diimidazole, it is called PBI.Suitable polypyridine diazole can be obtained by known method, such as United States Patent (USP) 5, and 674, those described in 969.

In certain embodiments, modified acrylic fibre can be used.The modified acrylic fibre be preferred in the present invention is the copolymer that acrylonitrile and vinylidene chloride combine.In addition, described copolymer also can comprise one or more antimony oxides to improve fire line.This type of available modified acrylic fibre includes but not limited to as United States Patent (USP) 3,193, the fiber with 2 % by weight antimony trioxides disclosed in 602, as United States Patent (USP) 3,748, in 302 disclosed be at least 2 % by weight by content and be preferably not more than 8 % by weight the obtained fiber of various antimony oxides, and as United States Patent (USP) 5,208,105 & 5,506, the fiber with 8 to 40 % by weight antimonials disclosed in 042.Preferred modified acrylic fibre can be commercially available from Kaneka Corporation (Japan) in a variety of forms, and some does not comprise antimony oxide, and other such as Protex C it is said comprise 10 to 15 % by weight those compounds.

In some preferred embodiments, polytype staple fibre can be used as staple fiber blends to be existed.So-called fiber blends refers to two or more staple fibre type combinations by any way.Preferably, staple fiber blends is " intimate blend ", and this refers to that the various staple fibres in blend form relatively uniform fibre blend.In certain embodiments, the staple fibre of two or more type before spinning yarn or when blended, make various staple fibre be evenly distributed in short yarn intrafascicular.

Fabric can be obtained by staple fibre yarn, and can include but not limited to Woven fabric or knit goods.General Fabric Design and structure are well-known to those having ordinary skill in the art.So-called " weaving " fabric refer to usually formed on loom by being interlaced with one another warp thread or longitudinal yarn and weft yarn or crosswise yam and produce the fabric of any weaving textile (such as plain weave, the crowfoot are knitted, square plain weave, satin weave, twill-weave etc.).It is believed that plain weave and twill weave are the braided fabrics the most often used in business, and be preferred in many embodiments.

So-called " knitting " fabric refers to the fabric usually by using pin the interconnection of yarn circle to be formed.In many cases, be obtained knit goods, yarn is transformed in the knitting machine of fabric by staple fibre yarn feeding.If needed, many warp thread or yarn of pooling capital or not pooling capital can be provided in knitting machine; That is, use routine techniques a branch of yarn or a branch of folded yarn to be sent in knitting machine simultaneously and to be knitted into fabric, or be directly knitted into clothing goods such as gloves.In certain embodiments, wish by one or more other short yarn or continuous filament yarn yarn are sent into one or more staple fibre yarns with fibre compact blend simultaneously, thus add to functional in knit goods.Adjustable knitting tightness is to meet any concrete needs.In such as single jersey and pile knit fabric decorative pattern, found the very effective combination of the performance of protective clothes.

Some especially can embodiment in, described staple fibre yarn can be used for preparation anti-flammability clothes.In certain embodiments, described clothes have the armored fabric that one deck is made up of staple fibre yarn substantially.These type of exemplary clothes comprise company's trousers shirt and the coveralls of fire fighter or army personnel.This type of suit is generally used for covering on outside fire fighter's clothes, and enters into certain region with extinguishing forest fire for parachute jumping.Trousers, shirt, gloves, oversleeve etc. that other clothes can be worn under can being included in the such as chemical processing industry or industrial electric/electric power environmental that extreme heat event may occur.In some preferred embodiments, described fabric has the arc resistance of every square centimeter every ounce every square yard, at least 0.8 card.

In one embodiment, gathered based on sulfonated naphthalene by obtained the staple fibre of diazole and the intimate blend of textiles staple fibre form the fibre blend of described fiber.If needed, the uniform short fibre mixture combination on the other hand of other staple fibre can be made.Blendedly to realize by many methods known in the art, comprise and many continuous filament yarn line cylinders are placed on creel, and the long filament simultaneously cutting two or more type is to form the method for cutting staple fiber blends; Or relate to the different staple fibre bundle of shredding, the then method of shredding and blended various fiber in opener, blender and carding machine; Or form various staple fibre, then it is processed further to form mixture, in carding machine, such as form the method for fibre blend bar.Other method of preparation tight fibers blend is also possible, as long as various types of different fiber is distributed in whole blend relatively uniformly.If form yarn by blend, so yarn also has relatively uniform short fibre mixture.In general, in most preferred embodiment, by independent staple fibre shredding or the normal degree being separated to obtained Useful fabrics in fiber process, the fiber knot because the bad shredding of staple fibre causes or fiber joint and other major defect are existed with the amount can not damaging final fabric quality.

In a preferred method, intimate staple fiber blend is obtained as follows: first the staple fibre and other staple fibre any (if expecting to obtain additional function) that derive from out bundle are mixed.Then carding machine is used to be shaped to by fiber blends rectangular.Usually in fiber industry, use carding machine to carry out defibre, adjustment fiber, and delivered to by fibre delivery without significantly twisting in the continuous strand of Loosely coupled fiber, it is commonly called the carded sliver.Usually through but not limited to two-step stretch method, the carded sliver is processed ripe bar.

Then adopt technology to form staple fibre yarn by ripe bar, described technology comprises conventional cotton system or the short-staple spinning processes of such as open-end-spinning and ring spinning; Or the such as Murata jet-impingement spinning of high speed gas spinning technique, wherein use air by staple fibre twisted resultant yarn.Also by using conventional woolen system, or the long fiber technique of such as combing or half combing RING SPINNING, or break spinning process to realize the formation of staple fibre yarn.No matter adopt which kind of system of processing, ring spinning is generally the method for optimizing preparing staple fibre yarn.

example

Except as otherwise noted, example all adopts following method to prepare.Reagent rate provides with mol ratio form.Fuming sulphuric acid is purchased from E.I.du Pont de Nemours and Company (Wilmington, DE).Terephthalic acid (TPA) (TA), M-phthalic acid (IA), 4,4 '-oxygen base two (benzoic acid) (OBBA), 2,6-naphthalene dicarboxylic acids (NDA), methanesulfonic acid, polyphosphoric acid and d ₆-dimethyl sulfoxide (DMSO) can purchased from Sigma- sulphuric acid leaching can purchased from Acros Organics.Sulfuric acid and sodium bicarbonate can purchased from EMDChemicals, Inc..2,6-naphthalene dicarboxylic acids (NDA) can purchased from Novolyte Technologies.

typical polymerization methods

Except as otherwise noted, each example uses typical polymerization methods, but by specified change monomer ratio.The dicarboxylic acids adding solid sulphuric acid hydrazine (0.015mol, 1 molar equivalent) and one or more totally 1 molar equivalents is added in the 100mL dry glass reactor of entrance to being equipped with glass machinery agitator, nitrogen inlet and reagent.Except as otherwise noted, dicarboxylic acids: the mol ratio of sulphuric acid leaching is 1: 1.The concrete mol ratio of often kind of dicarboxylic acids is specified in instances.In nitrogen, by solid constituent fully blended 15 minutes together.Except as otherwise noted, 18.7% fuming sulphuric acid (oleum) (fuming sulphuric acid (fumingsulfuric acid), the 18.7 % by weight free SO of 28.5g are added in solid mixture at room temperature blended to this while stirring ₃content) (4.4 mol ratio).Reactor seals completely and nothing splits leakage (comprising stirrer shaft), to prevent gas phase composition effusion still.By mixture at room temperature mechanical agitation (250RPM) some minutes.Then through ~ 30 minutes sections, mixture will be heated to 130 DEG C.Typical polymerisation is made to carry out 4 hours at 130 DEG C.During polymerisation, if the viscosity of polymeric reaction solution becomes too high, usually reduce stir speed (S.S.) or stop stirring.

In some instances, the NDA through pre-reaction is used.2,6-NDA is dissolved in 18.7% fuming sulphuric acid, and makes reaction carry out 6.5 hours at 130 DEG C.Sulphuric acid leaching and other dicarboxylic acids of ratio same as above is added to reactor.Then the mixture of sulfonation 2,6-NDA is added.Mixture comprises many solid block be not incorporated in reactant mixture.Polymerisation is made to carry out 4 hours at 130 DEG C.

conventional fibre formation method

Two kinds of methods are adopted to prepare fiber.

With sulfuric acid (95-98%) diluted polymer reactant mixture.Add enough sulfuric acid, make solution viscosity enough high, so that thin continuous flow can be added drop-wise to and comprise in the blender of water, described blender rotates with given pace, to guarantee that the fiber solidified is not opened simultaneously.To each polymerisation, determine the optimal conditions of the method.In order to coagulated fibre, rubber sheet gasket is added in blender blade top, this makes fiber to be wound and to collect.Then usually by hand fiber is rewound on vial, washes with water, be then soaked in the sodium bicarbonate of dilution, until neutralize completely.Then fiber washed with water and soak, to remove the sodium bicarbonate of any remnants.Make fiber dry at ambient conditions.In some instances, by fiber sample at room temperature high vacuum dry, with in methanesulfonic acid via size exclusion chromatography (SEC) (SEC) determining molecular weight.

By the sulfuric acid solution spinning fibre of polymer concentration in 6-9 % by weight scope.By gear pump, solution is delivered through the spinning head with 5-20 hole, described hole has the diameter of 0.003 " or 0.008 ".The volume flow of spinning solution is 0.2-2mL/min.Directly be expressed in coagulating bath by fiber, solution at room temperature is filled in described coagulating bath, and described solution is the sulfuric acid of 0-70 % by weight.The fiber leaving coagulating bath enters room temperature washing water-bath via ceramic guide.In washing bath, fiber is around two fast controlled driven roller windings, and then stretch 50-600%.Around each in these rollers, obtained three volumes usually.Filament-wound Machine is on phenolic resins core.Then in a series of interval step, in making the fiber bobbin of winding in 0.5 % by weight sodium bicarbonate or sodium hydroxide solution and, to wash in deionized water, and at room temperature air-dry.

conventional curtain coating membrane preparation method

Polymeric reaction solution sulfuric acid (95-98%) dilution, until gained viscosity makes it possible to obtain uniform film on a glass.This viscosity is less than the viscosity needed for coagulated fibre usually.Polymer and glass plate are immersed in water-bath to make film solidify.Wash the film solidified with water, be then soaked in the sodium bicarbonate of dilution, until neutralize completely.Then film washed with water and soak, to remove the sodium bicarbonate of any remnants.Film is repeatedly suppressed between paper handkerchief, until touch up substantially dry with pressure in various degree.Then film is placed between aluminium foil, and suppresses 5 minutes under 10,0001b.By gained film at room temperature high vacuum dry 24 hours.

lOI measures

Limited oxygen index (LOI) is the minimum oxygen concentration in the oxygen and nitrogen mixture represented with percent by volume, and described mixture just can maintain the flaming combustion of material under initial room-temperature under ASTM G125/D2863 condition.The ASTM method (ASTM D 2863) improved is adopted to measure LOI, with can screening sample fast.Film is arranged on sample holder, described sample holder is inserted in LOI equipment, and covers with cloche.Oxygen content in digital control cloche.Make film contacts flame, and increase the oxygen content in cloche, until sample combustion.The time point of candle shape burning can be maintained, measure the LOI of any designated samples.

example 1-93

(1) comparative example fuming sulphuric acid replaces with polyphosphoric acid, and sulfuric acid replaces with phosphoric acid

(2) comparative example.Reaction temperature is increased to 140 DEG C, instead of as described in conventional method 130 DEG C.Other specifications all are identical.

(3) comparative example.Reaction temperature is increased to 150 DEG C, instead of as described in conventional method 130 DEG C.Other specifications all are identical.

(4) comparative example.Reaction temperature is increased to 160 DEG C, instead of as described in conventional method 130 DEG C.Other specifications all are identical.

(5) (sulfonation) 2,6-NDA through pre-reaction is used.

(6) M-phthalic acid: IA.Use 5 molar equivalent fuming sulphuric acids.

example 24

the checking of 2,6-naphthalene dicarboxylic acids sulfonation

2,6-naphthalene dicarboxylic acids (0.5053g, Aldrich 99%) is added in 18.7% fuming sulphuric acid of 27.9g.It is made to react 30 minutes when being stirred by bar magnet heating materials to 130 DEG C.Reactant is removed from thermal source and makes it be cooled to room temperature.Carry out ¹h NMIR spectrum and LC/MS, and show to define desired sulfonated products.Comprising trace 3-trimethyl silyl sodium propionate-d ₄as the water-d of chemical shift indicator ₂the saturated solution of middle preparation one sulfonation sulfone product.NMR probe is inserted in solution.Document compares elementary two sulfonated products of permission ¹the ownership of H resonance. ¹h ownership (in units of the ppm relative to 0.00ppm place chemical shift indicator) is shown in hereinafter.

Find 55.56%C, 2.95%H, 14.88%N, 17.71%O and 2.21%S in the enterprising row element analysis of the sample obtained by example 12.Whole result is shown in hereinafter:

example 25

processbearing astrocyte

Use following methods, by the polymer fiber of example 1.By the sulfuric acid solution spinning fibre that concentration is 7.2 % by weight (15mol%NDA) POD copolymer.Via gear pump, solution is delivered through the spinning head with 10 holes, described hole has 0.005 " diameter.The volume flow of spinning solution is 1.8mL/min.Directly be expressed in coagulating bath by fiber, solution at room temperature is filled in described coagulating bath, and described solution is the sulfuric acid of 56 % by weight.The fiber leaving coagulating bath enters the washing bath of the room temperature NaOH aqueous solution maintained under pH ~ 12.0 via ceramic guide.In washing bath, fiber, around two fast controlled driven roller windings, then stretches 400%.Around each roller obtained three volumes usually.Filament-wound Machine is on phenolic resins core.Then, in the step of a series of gaps, the fiber bobbin of winding to be washed in deionized water and at room temperature air-dry.

Use following methods, by the polymer fiber of example 2.By the sulfuric acid solution spinning fibre that concentration is 7.8 % by weight (20mol%NDA) POD copolymer.Via gear pump, solution is delivered through the spinning head with 20 holes, described hole has 0.005 " diameter.The volume flow of spinning solution is 1.8mL/min.Directly be expressed in coagulating bath by fiber, solution at room temperature is filled in described coagulating bath, and described solution is the sulfuric acid of 58 % by weight.The fiber leaving coagulating bath enters the washing bath of the room temperature NaOH aqueous solution maintained under pH ~ 12.0 via ceramic guide.In washing bath, fiber, around two fast controlled driven roller windings, then stretches 340%.Around each roller obtained three volumes usually.Filament-wound Machine is on phenolic resins core.Then, in the step of a series of gaps, the fiber bobbin of winding to be washed in deionized water and at room temperature air-dry.

use the dye test that carrier carries out

Following methods is used to test separately following dyestuff:

Add in the 250-ml round-bottomed flask being equipped with reflux condenser POD-NDA yarn (30-50mg) and the solution of HCS (1 0.1 % by weight solution, ~ 0.03g), benzylalcohol (1.65g) and deionized water (53.39g).Mixture is heated 15 minutes on 46 DEG C of aluminium round bottom heat blocks.Then, the solution of basic-dyeable fibre (0.003-0.005g), benzylalcohol (0.301g) and deionized water (9.80g) is added in flask.Mixture is heated 10 minutes at 46 DEG C, adds acetic acid (0.85 % by weight, 1) afterwards.Mixture is heated to 70 DEG C further, continues 15 minutes, be then heated to 100-130 DEG C, continue 60 minutes, increase hear rate and take ~ 5-10 minute.Then, solution is removed, fiber is stayed in flask.Then use deionized water (~ 70 DEG C) washing the fibre of heat, and wash by deionized water at room temperature again.Add in flask the solution of HCS (0.1 % by weight solution of 0.061g) and deionized water (50g); Then flask is heated 20 minutes at 70 DEG C.Then deionized water (~ 70 DEG C) and the deionized water at room temperature washing the fibre of heat is used successively.Fibers encapsulation is existed sPS ^tMto dry in wiping cloth.By transversal, fiber is analyzed.Image shows that each dye distribution is to fibre core.(fiber dyeed under compared with low dye concentration demonstrates dyestuff penetration to core, but there is not dyestuff around crust; The fiber dyeed under higher dye strength demonstrates uniform dyestuff penetration.)

do not use the dye test that carrier carries out

Add in the 250-ml round-bottomed flask being equipped with reflux condenser POD-NDA yarn (30-50mg) and the solution of HCS (1 0.1 % by weight solution, ~ 0.03g), benzylalcohol (1.65g) and deionized water (53.39g).Mixture is heated 15 minutes on 46 DEG C of aluminium round bottom heat blocks.Then, the solution of basic-dyeable fibre (0.003-0.005g) and deionized water (9.80g) is added in flask.Mixture is heated 10 minutes at 46 DEG C, adds acetic acid (0.85 % by weight, 1) afterwards.Mixture is heated to 70 DEG C further, continues 15 minutes, be then heated to 100-130 DEG C, continue 60 minutes, increase hear rate and take ~ 5-10 minute.Then, solution is removed, fiber is stayed in flask.Then use deionized water (~ 70 DEG C) washing the fibre of heat, and wash by deionized water at room temperature again.Add in flask the solution of HCS (0.1 % by weight solution of 0.061g) and deionized water (50g); Then flask is heated 20 minutes at 70 DEG C.Then deionized water (~ 70 DEG C) and the deionized water at room temperature washing the fibre of heat is used successively.Fibers encapsulation is existed sPS ^tMto dry in wiping cloth.By transversal, fiber is analyzed.Image shows that each dye distribution is to fibre core.(fiber dyeed under compared with low dye concentration demonstrates dyestuff penetration to core, but there is not dyestuff around crust; The fiber dyeed under higher dye strength demonstrates uniform dyestuff penetration.)

do not use the dye test that carrier carries out under desuperheat

Add in the 250-ml round-bottomed flask being equipped with reflux condenser POD-NDA yarn (30-50mg) and the solution of HCS (1 0.1 % by weight solution, ~ 0.03g), benzylalcohol (1.65g) and deionized water (53.39g).Mixture is heated 15 minutes on 46 DEG C of aluminium round bottom heat blocks.Then, the solution of basic-dyeable fibre (0.003-0.005g) and deionized water (9.80g) is added in flask.Mixture is heated 10 minutes at 46 DEG C, adds acetic acid (0.85 % by weight, 1) afterwards.Mixture is heated to 70 DEG C further, continues 15 minutes, be then heated to 25-100 DEG C, continue 60 minutes, increase hear rate and take ~ 5-10 minute.Then, solution is removed, fiber is stayed in flask.Then use deionized water (~ 70 DEG C) washing the fibre of heat, and wash by deionized water at room temperature again.Add in flask the solution of HCS (0.1 % by weight solution of 0.061g) and deionized water (50g); Then flask is heated 20 minutes at 70 DEG C.Then deionized water (~ 70 DEG C) and the deionized water at room temperature washing the fibre of heat is used successively.Fibers encapsulation is existed sPS ^tMto dry in wiping cloth.By transversal, fiber is analyzed.Image shows that each dye distribution is to fibre core.(fiber dyeed under compared with low dye concentration demonstrates dyestuff penetration to core, but there is not dyestuff around crust; The fiber dyeed under higher dye strength demonstrates uniform dyestuff penetration.)

fiber UV stability

Then POD-NDA yarn be divided into one filament and be seated to hardboard framework to be exposed to illumination completely.Hardboard framework to be placed in Xe arc chamber and according to AATCC 16E: color fastness to light standard testing continues to test for 96 hours.Long filament is regulated 18 hours under 70F and 60% humidity.

fibre property is analyzed

TEXTTECHNO Vibromat is used to measure DENIER.Sample is cut into 9cm fragment and in due course by DENIER (1den=1g/9000m) that Weight computation is suitable.This suitable DENIER is programmed in Vibromat to determine suitable counterpoise.By TEXTECHNO vibromat software determination DENIER, and replicate analysis 5-6 time.

Then use ASTM to test D3822-07 and measure physical measurement; To obtain toughness and elongation at break (maximum).Use ASTM to test D3822-07, then use 1 inch gauge to analyze for elongation at break (maximum) and toughness versus fiber.0.1 or 0.6in/min chuck speed and 500g element is used to analyze sample.Chuck speed is measured (< 8-10%, then use 0.1in/min, and > 10%, then use 0.6in/min) by %EB.Use Bluehill software to data analysis, and replicate analysis 5-6 time.

Result is hereafter illustrating:

example 27

This example illustrate flame resistant spun staple yarns and derive from the NDA-POD fiber of example 25 and there is the limited oxygen index of 24 or larger and the textiles staple fibre of about 4 grams/DENIER or larger toughness, such as with trade mark fiber is purchased from the fabric of the intimate blend of poly-(mpd-i) (MPD-I) fiber of E.I.duPont de Nemours & Company.

By the scutching cotton blending bar of the NDA-POD staple fibre of conventional cotton system system equipment preparation and fabrication 50 % by weight and the MPD-I staple fibre of 50 % by weight, and use ring spinner to be spun into have the flame resistant spun staple yarns of the twist factor of about 4.0 and the one-ply yarn size of about 21 spies (28 yarn count).Then on buncher by two these type of singles yarns, obtained anti-flammability double strand yarn, to be used as fabric warp.Use identical blend and similar method, comprise the identical twist and blending ratio, make the single thread of 24 spies (24 yarn count), and in these one-ply yarns two strands are pooled capital to be formed bifilar fire-retardant yarn and are used as fabric weft yarn.These doubled warps and doubled weft all have the toughness of the toughness being greater than bifilar 100%NDA-POD short fibre yarn obtained at similar conditions, that is, double strand yarn has the toughness of at least 3 grams/DENIER (2.7 gram/dtex).

The warp thread that ring spins and weft yarn yarn are woven into fabric on fly-shuttle loom, obtain and have 2 × 1 twill weave and 26 through × 17 latitudes/centimetre (72 through × 52 latitudes/inch) structure and about 215g/m ²(6.5oz/yd ²) nature fabric of basic weight.Then this greige twill fabric is cleaned in the hot water, and dry under low tension.Then the fabric jet dyeing that basic-dyeable fibre will be cleaned is used.Gained fabric has about 231g/m ²(7oz/yd ²) basic weight and LOI more than 28.

A part for fabric is cut into various shape, and various shape is sewn to and takes those situations in being exposed to hot dangerous matter sources fabric to be changed into monolayer composite together.

In a similar fashion, ring spinning and the fabric that is associated and clothes are made as tester by 100%NDA-POD staple fibre.

Table 2 shows the fabric of gained and the performance of clothes."+" represents the performance than those excellent performances of tester, and marks " 0 " expression tester performance, or the performance suitable with tester performance.

table 2

example 28

This example illustrate flame resistant spun staple yarns and derive from NDA-POD fiber and the modacrylic fibre of example 24, such as by Kaneka Corporation with trade mark the fabric of the intimate blend of the modacrylic fibre manufactured.

By the scutching cotton blending bar of the NDA-POD staple fibre of conventional cotton system system equipment preparation and fabrication 65 % by weight and the modacrylic staple fibre of 35 % by weight, and use ring spinner to be spun into have the flame resistant spun staple yarns of the twist factor of about 4.0 and the one-ply yarn size of about 21 spies (28 yarn count).Then on buncher by two these type of singles yarns, obtained anti-flammability double strand yarn, to be used as fabric warp.Use identical blend and similar method, and the identical twist and blending ratio, make the single thread of 24 spies (24 yarn count), and in these one-ply yarns two strands are pooled capital to be formed bifilar fire-retardant yarn and are used as fabric weft yarn.These doubled warps and doubled weft all have the toughness of the toughness being greater than bifilar 100%NDA-POD short fibre yarn obtained at similar conditions, that is, double strand yarn has the toughness of at least 3 grams/DENIER (2.7 gram/dtex).

Table 3 shows the fabric of gained and the performance of clothes."+" represents the performance than those excellent performances of tester, and marks " 0 " expression tester performance, or the performance suitable with tester performance.

table 3

example 29

This example illustrate flame resistant spun staple yarns and derive from the NDA-POD fiber of example 25 and have high-modulus, particularly, the fiber of 200 grams/DENIER or larger stretch modulus, such as with trade mark fiber is purchased from the fabric of the intimate blend of poly-(poly P phenylene diamine terephthalamide) (PPD-T) fiber of E.I.duPont de Nemours & Company.PPD-T is known as rigid rod polymer in the art.

By the scutching cotton blending bar of the NDA-POD staple fibre of conventional cotton system system equipment preparation and fabrication 85 % by weight and the PPD-T staple fibre of 15 % by weight, and use ring spinner to be spun into have the flame resistant spun staple yarns of the twist factor of about 4.0 and the one-ply yarn size of about 21 spies (28 yarn count).Use identical blend and similar method, comprise the identical twist and blending ratio, then two strands of these type of one-ply yarns are pooled capital on buncher to manufacture bifilar fire-retardant yarn and be used as fabric warp, make the single thread of 24 spies (24 yarn count), and in these one-ply yarns two strands are pooled capital to be formed bifilar fire-retardant yarn and are used as fabric weft yarn.These doubled warps and doubled weft all have the toughness of the toughness being greater than bifilar 100%NDA-POD short fibre yarn obtained at similar conditions, that is, double strand yarn has the toughness of at least 3 grams/DENIER (2.7 gram/dtex).

Table 4 shows the fabric of gained and the performance of clothes."+" represents the performance than those excellent performances of tester, and marks " 0 " expression tester performance, or the performance suitable with tester performance.

table 4

example 30

Repeat example 29, except scutching cotton blending bar comprise 40 % by weight NDA-POD staple fibre and 60 % by weight PPD-T staple fibre except.As in example 29, the fabric that ring spins and is correlated with and clothes are made as tester by 100%NDA-POD staple fibre.

Table 5 shows the fabric of gained and the performance of clothes."+" represents the performance than those excellent performances of tester, and marks " 0 " expression tester performance, or the performance suitable with tester performance.

table 5

example 31

Repeat example 29, except scutching cotton blending bar comprise 60 % by weight NDA-POD staple fibre and 40 % by weight FR artificial silk except.As in example 29, the fabric that ring spins and is correlated with and clothes are made as tester by 100%NDA-POD staple fibre.

Table 6 shows the fabric of gained and the performance of clothes."+" represents the performance than those excellent performances of tester, and marks " 0 " expression tester performance, or the performance suitable with tester performance.

table 6

Claims

1. flame resistant spun staple yarns, described flame resistant spun staple yarns comprises:

Based on total amount about 50 the gathering based on sulfonation to about 95 weight portions of polymer fiber and textile fiber in described yarn the textiles staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION;

2. comprise the protective clothing of flame resistant spun staple yarns according to claim 1, Woven fabric, supatex fabric, band or long filament.

3. flame resistant spun staple yarns, described flame resistant spun staple yarns comprises:

Based on polymer fiber and textile fiber in described yarn total amount at least about 25 weight portions to about 80 weight portions based on sulfonation gather the modacrylic fibre of the staple fibre of diazole and about 20 to about 75 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION.

4. comprise the protective clothing of flame resistant spun staple yarns according to claim 3, Woven fabric, supatex fabric, band or long filament.

5. flame resistant spun staple yarns, described flame resistant spun staple yarns comprises:

Based on total amount about 50 the gathering based on sulfonation to about 95 weight portions of polymer fiber and textile fiber in described yarn the high-modulus staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION;

Described high-modulus staple fibre has 200 grams/DENIER or larger stretch modulus.

6. comprise the protective clothing of flame resistant spun staple yarns according to claim 5, Woven fabric, supatex fabric, band or long filament.

7. flame resistant spun staple yarns, described flame resistant spun staple yarns comprises:

Gather based on sulfonation based in described yarn total amount about 20 the gathering based on sulfonation to about 50 weight portions of the Textile material fiber of diazole the rigid rod staple fibre of the staple fibre of diazole and about 50 to about 80 weight portions, described poly-based on sulfonation the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION.

8. comprise the protective clothing of flame resistant spun staple yarns according to claim 7, Woven fabric, supatex fabric, band or long filament.

9. prepare the method for staple fibre yarn, described method comprises:

A) formed based on polymer fiber and textile fiber in described yarn total amount about 50 to about 95 weight portions based on poly- the fibre blend of the textiles staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described based on poly- the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION;

Described textiles staple fibre has limited oxygen index and about 2 grams/DENIER or the larger toughness of 24 or larger; And

B) described fibre blend is spun into staple fibre yarn.

10. prepare the method for staple fibre yarn, described method comprises:

A) formed total amount based on polymer fiber and textile fiber in described yarn at least about 25 weight portions based on poly- the fibre blend of the modacrylic fibre of the staple fibre of diazole and about 20 to about 75 weight portions, described based on poly- the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION;

And

B) described fibre blend is spun into staple fibre yarn.

11. methods preparing staple fibre yarn, described method comprises:

A) formed based on polymer fiber and textile fiber in described yarn total amount about 50 to about 95 weight portions based on poly- the fibre blend of the high-modulus staple fibre of the staple fibre of diazole and about 5 to about 50 weight portions, described based on poly- the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION;

Described high-modulus staple fibre has 200 grams/DENIER or larger stretch modulus; And

B) described fibre blend is spun into staple fibre yarn.

12. methods preparing staple fibre yarn, described method comprises:

A) formed based on polymer fiber and textile fiber in described yarn total amount about 20 to about 50 weight portions based on poly- the fibre blend of the rigid rod staple fibre of the staple fibre of diazole and about 50 to about 80 weight portions, described based on poly- the repetitive of the staple fibre contained (II) of diazole and (IIa) one or both of and formula (I):

Wherein Q is H or SO ₃m, and M is one or more CATION;

And

B) described fibre blend is spun into staple fibre yarn.