CN101218384A - Process for removing phosphorous from a fiber or yarn - Google Patents
Process for removing phosphorous from a fiber or yarn Download PDFInfo
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- CN101218384A CN101218384A CNA2006800098253A CN200680009825A CN101218384A CN 101218384 A CN101218384 A CN 101218384A CN A2006800098253 A CNA2006800098253 A CN A2006800098253A CN 200680009825 A CN200680009825 A CN 200680009825A CN 101218384 A CN101218384 A CN 101218384A
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- 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
- D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
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- 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
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- Artificial Filaments (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
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Abstract
The present invention relates to processes for removing phosphorus from a fiber or yarn.
Description
The cross reference of related application
The application requires the U. S. application No.60/665 of submission on March 28th, 2005,741 rights and interests, and it is incorporated herein by this reference in full.
Invention field
The present invention relates generally to the preparation method of polymer fiber and this fibrid.More particularly, the present invention relates to especially from the long filament (filament) that comprises polymer and spun yarn (spun yarn), to remove the method for polyphosphoric acid.
Background of invention
Many fibers be by the solution (be called " polymer spun silk stock solution (polymer dope) ") of polymer in solvent by with the polymer spun silk stock solution through die head spinning head is extruded or spinning with preparation or be spun into spinning solution (dope) long filament and prepare.Remove solvent subsequently so that fiber or yarn to be provided.In the preparation of some fiber, solvent for use is solvent acid, for example polyphosphoric acid (PPA).Different with many typical solvents, PPA part more difficult removal usually owing to its aggregation property.Hetero atom mixes and also may suppress polyphosphoric acid in the polymer and remove from fiber or yarn.If remove a large amount of PPA, the then existing method of removing polymerization PPA solvent from polymeric material need be grown the extraction temperature of wash time or raising usually.
For example, people such as Sen, US5,393,478 disclose by contacting the method for lixiviate polyphosphoric acid from polybenzoxazole (polybenzazole) spinning solution long filament with about at least 60 ℃ leaching liquor.
People such as Sen, US5,525,638 disclose a kind of from polybenzoxazole spinning solution long filament the method for eccysis polyphosphoric acid, it uses common in the approximately repeatedly washing of room temperature, slowly reduces the phosphorus concentration that is spun in the fiber, and it claims the physical property of having improved the gained polymer fiber.
The physical property of the fiber that is spun into by polyphosphoric acid requires further improvement and/or needs therefrom remove better phosphorus.According to this specification and claim, these and other objects of the present invention become more apparent.
Summary of the invention
The present invention partly relates to the method for removing polyphosphoric acid from fiber, comprises the following steps: that the fiber that will comprise polymer and polyphosphoric acid is heated at least 120 ℃ of times that reach effective hydrolysis polyphosphoric acid; With in independent step, be that 100 ℃ or lower fluid are removed the polyphosphoric acid of hydrolysis from fiber with temperature.
The present invention also part relates to the method for the polyphosphoric acid in the hydrolysis fiber, comprises that the fiber that will comprise polymer and polyphosphoric acid is heated above the step that 100 ℃ temperature reaches the time of effective hydrolysis polyphosphoric acid in less than 4.0 acid medium in the pH value.
The present invention also partly relates to the method for the polyphosphoric acid in hydrolysis polyaromatic azoles (polyareneazole) polymeric material, comprise the following steps: to provide the polymeric material that comprises polyaromatic azoles and polyphosphoric acid, wherein the polyaromatic azoles repeat unit structure of at least 50 moles of % comprises 2,5-dihydroxy-right-phenylen moiety; Polymeric material is heated to above 100 ℃ with hydrolysis at least a portion polyphosphoric acid.
The present invention also part relates to the method for removing phosphorus from the yarn that is spun into by the polymer solution that contains polyphosphoric acid, and this yarn is included as the phosphorus of about at least 1.5 weight % of yarn weight, and this method comprises to be made yarn contact with alkali and wash yarn with aqueous fluid.
The present invention also provide comprise polyaromatic azoles polymer with pendant hydroxyl groups and account for fibre weight at least 2% comprise sodium, potassium or calcium or its cationic fiber in being combined in arbitrarily.
The present invention also part relates to the cationic method of removal from polyaromatic azoles fiber, comprise the following steps: to provide and comprise polyaromatic azoles polymer with pendant hydroxyl groups and the cationic fiber of at least 2 weight %, fiber is contacted discharging partial cation at least with containing aqueous acid, and the optional fiber that washes with water.
Description of drawings
According to as detailed below, get in touch accompanying drawing as described below, can more fully understand the present invention.
Fig. 1 is the schematic diagram of polyaromatic azoles fiber autofrettage.
Exemplary describes in detail
Unless indicate separately, used following term is construed as and has following meanings in above and in the whole text disclosing.
Long filament of the present invention can be made by polyaromatic azoles polymer." polyaromatic azoles " as herein described is meant:
The polymer of the hetero-aromatic ring that condenses with adjacent aryl (Ar) with repeat unit structure (a):
Wherein N is that nitrogen-atoms and z are sulphur, oxygen or NR group, and wherein R is connected to hydrogen on the N or replacement or not substituted alkyl or aryl; Or
Two with repeat unit structure (b1 or b2) are fused to total aryl (Ar separately
1) on the polymer of hetero-aromatic ring:
Wherein N is that nitrogen-atoms and B are oxygen, sulphur or NR group, and wherein R is connected to hydrogen on the N or replacement or not substituted alkyl or aryl.Structure (a), (b1) and (b2) shown in the quantity of repeat unit structure inessential.Preferably, each polymer chain has 10 to 25,000 repetitives.Polyaromatic azoles polymer comprises polybenzoxazole polymer and/or polypyridine and azoles (polypyridazole) polymer.In certain embodiments, the polybenzoxazole polymer comprises polybenzimidazoles or polyphenyl and two imidazoles polymer.In some other embodiment, polypyridine and azoles polymer comprise polypyridobisimidazo/e /e or polypyridine and imidazoles polymer.In some preferred embodiment, polymer is polyphenyl and two imidazoles or polypyridobisimidazo/e /e type.
In (b1) and structure (b2), Y is aromatics, heteroaromatic, aliphatic group, or does not exist; Be preferably aryl; The hexa-atomic aryl of carbon atom more preferably.More preferably, the hexa-atomic aryl (Y) of carbon atom has the para-orientation key with two substituted hydroxies; More preferably 2,5-dihydroxy-right-phenylene.
In structure (a), (b1) or (b2), Ar and Ar
1Represent any aromatics or heteroaromatic group separately.Aromatics or heteroaromatic group can be to condense or the polycyclic system of non-condensed, but are preferably single hexatomic ring.More preferably, Ar or Ar
1Group is a heteroaromatic, wherein replaces one of carbon atom of this member ring systems with nitrogen-atoms, or Ar or Ar
1Can only contain carboatomic ring atom.More preferably, Ar or Ar
1Group is a heteroaromatic.
" polybenzoxazole " as herein described is meant have repetitive structure (a), (b1) or (b2) polyaromatic azoles polymer, wherein Ar or Ar
1Group is the hexa-atomic aromatic ring of the list of carbon atom.Preferably, polybenzoxazole is that a class has structure (b1) or rigidity clavate polybenzoxazole (b2); More preferably has the six-membered carbon ring of having aromatic ring Ar
1Structure (b1) or rigidity clavate polybenzoxazole (b2).The preferred polybenzoxazole of this class includes but not limited to, polybenzimidazoles (B=NR), polybenzothiozole (B=S), poly-benzoxazol (B=O) and their mixture or copolymer.When polybenzoxazole was polybenzimidazoles, it is poly-(benzo [1,2-d:4,5-d '] two imidazoles-2,6-two bases-1,4-phenylene) preferably.When polybenzoxazole was polybenzothiozole, it is poly-(benzo [1,2-d:4,5-d '] double thiazole-2,6-two bases-1,4-phenylene) preferably.When polybenzoxazole is that it is poly-(the two azoles-2 of benzo [1,2-d:4,5-d '], 6-two bases-1,4-phenylene) preferably when gathering benzoxazol.
" polypyridine and azoles " as herein described is meant have repetitive structure (a), (b1) or polyaromatic azoles polymer (b2), wherein Ar or Ar
1Group is the hexa-atomic aromatic ring of list of five carbon atoms and a nitrogen-atoms.Preferably, these polypyridines and azoles are that a class has structure (b1) or (b2) rigidity clavate polypyridine and azoles, more preferably have the hexa-member heterocycle of having aromatic ring Ar
1Structure (b1) or rigidity clavate polypyridine and azoles (b2).Preferred polypyridine of this class and azoles include but not limited to polypyridobisimidazo/e /e (B=NR), polypyridine and double thiazole (B=S), polypyridine and two azoles (B=O) and their mixture or copolymer.Preferred again polypyridine and azoles are the polypyridobisimidazo/e /es (B=NR) of following array structure:
Wherein N is a nitrogen-atoms, and R is connected to hydrogen on the N or replacement or not substituted alkyl or aryl, and preferably wherein R is H, and the Y definition as above.The quantity of the unit of repetitive structure or structure representative is inessential.Preferably, each polymer chain has 10 to 25,000 repetitives.
Long filament of the present invention is by polybenzoxazole (PBZ) or polypyridine and azoles polymer manufacture.Term used herein " long filament " or " fiber " are meant and have high length-width ratio relative flexible macroscopical isotropic body of (wide be across with the width of the cross section of its length quadrature).Filament cross can have Any shape, but is generally circular.
" yarn " as herein described be meant with or not with certain distortion or interlacing degree strand (laid), many long filaments of pricking (bundled) or fitting together, thereby form can be used for for example weaving, knitting, compile the continuous strand of pigtail (plaiting) or braiding (braiding), wherein the fiber definition is as above.
" fabric " used herein is meant any weaving (woven), knitting (knitted) or non-woven (non-woven) structure." weave " and be meant any fabric weave, for example plain weave weave, the crowfoot (crowfoot) weave, basket weave (basket) weave, satin face weave, twill weave, or the like." knitting " is meant the structure of making by mutual loops (interlooping) or interweave one or more warp thread, fiber or multifilament yarn." non-woven " is meant network of fibers, comprises unidirectional fibre, felt and analog.
" coagulating bath " as herein described is meant the medium that is used to solidify the spinning solution long filament.This bath comprises liquid, normally alcohol, water, aqueous acids or other liquid, aqueous mixture.Preferably, this bath is water or phosphate aqueous solution, but this liquid can provide the water that helps the PPA hydrolysis or any material of other parts.
In some embodiments, preferred rigidity clavate polypyridine and azoles include, but not limited to polypyridobisimidazo/e /e homopolymers and copolymer, and for example United States Patent (USP) 5,674, those that describe in 969 (the authorizing people such as Sikkema on October 7th, 1997).The exemplary polypyridobisimidazo/e /e of a kind of this class is homopolymers poly-(1,4-(2, the 5-dihydroxy) phenylene-2,6-diimidazole be [4,5-b:4 ' 5 '-e] inferior pyridine radicals (pyridinylene) also).
Used polyaromatic azoles polymer can have and rigidity clavate structure, semi-rigid clavate structure or flexible wire circular structure among the present invention; The character of preferred rigidity clavate structurally associated.When this class rigid rod 1ike polymer has structure (b1) or (b2) time, it preferably has two and is fused to aryl Ar
1On azoles (azole) group.
Suitable polyaromatic azoles available among the present invention comprises homopolymers and copolymer.Can be with other polymeric material and the blending of polyaromatic azoles of maximum 25 weight %.Also can use following copolymer---wherein with nearly 25% or more other polyaromatic azoles monomer or other monomer replace the monomer of most polyaromatic azoles.Suitable polyaromatic azoles homopolymers and copolymer can be by the known procedure manufacturings, for example United States Patent (USP) 4,533,693 (authorizing people such as Wolfe on August 6th, 1985), 4,703,103 (authorizing people such as Wolfe on October 27th, 1987), 5,089,591 (authorizing people such as Gregory on February 18th, 1992), 4,772,678 (authorizing people such as Sybert on September 20th, 1988), 4,847,350 (authorizing people such as Harris on August 11st, 1992), 5,276, described in 128 (authorizing people such as Rosenberg on January 4th, 1994) and the United States Patent (USP) 5,674,969 (authorizing people such as Sikkema on October 7th, 1997) those.Also can be with the aequum blast blending in the polyaromatic azoles, for example antioxidant, lubricant, screening uv-ray agent, colouring agent and analog.
The present invention relates generally to polyaromatic azoles long filament, more specifically relates to the preparation method of polybenzoxazole (PBZ) long filament or polypyridine and azoles long filament and this class long filament.The invention further relates to yarn, fabric and the goods that contain long filament of the present invention and make the method for this class yarn, fabric and goods.
When any variable occurred surpassing one time in any composition or any formula, the definition when it occurs at every turn and its definition at another place were irrelevant.The combination of substituting group and/or variable is only just feasible when this class combination results stable compound.
Correspondingly, in certain embodiments, the present invention relates to from fiber, remove the method for polyphosphoric acid, comprise the following steps: that the fiber that will comprise polymer and polyphosphoric acid is heated at least 120 ℃ of times that reach effective hydrolysis polyphosphoric acid usually; With in independent step, be that 100 ℃ or lower fluid are removed the polyphosphoric acid of hydrolysis from fiber with temperature.In some embodiments, effectively the time of hydrolysis polyphosphoric acid mostly is about 120 seconds most.In other embodiments, the step that adds thermal fiber can comprise Convective Heating, radiation heating (radiant heating), ray heating (radiationheating), RF heating, conduction heating, Steam Heating or its any combination.In some embodiments again, polymer comprises the polyaromatic azoles; More preferably, wherein the polyaromatic azoles is polypyridine and azoles.In some other embodiment, the polyaromatic azoles is a polypyridobisimidazo/e /e; More preferably poly-(1,4-(2, the 5-dihydroxy) phenylene-2,6-diimidazole be [4,5-b:4 ' 5 '-e] inferior pyridine radicals also).In other embodiments, the polyaromatic azoles is a polybenzoxazole, more preferably polyphenyl and two azoles.In some embodiments more generally, removing the hydrolysis polyphosphoric acid comprises and uses the neutralizing treatment fiber; More preferably, before with neutralizing treatment and afterwards, wash fiber with water.Usually, must select by force, and generally include NaOH, potassium hydroxide, ammonium hydroxide, sodium bicarbonate or its any combination, preferably NaOH, potassium hydroxide or its any combination to the alkali that is enough to destroy the key between polymer and the phosphoric acid.In certain embodiments, removal hydrolysis polyphosphoric acid comprises with the neutralizing treatment fiber and uses acid elution subsequently.In other embodiments, fiber is cooled to less than 60 ℃ and the step of from fiber, removing the hydrolysis polyphosphoric acid and carries out simultaneously.In some embodiments again, the fluid that is used to remove the hydrolysis polyphosphoric acid has about 60 ℃ or lower temperature.
In the various embodiments of the method for the polyphosphoric acid that is used for hydrolysis fiber of the present invention, the fiber that will comprise polymer and polyphosphoric acid usually is heated above the time that 100 ℃ temperature reaches effective hydrolysis polyphosphoric acid in less than 4.0 acid medium in the pH value.In some embodiments, effectively the time of hydrolysis polyphosphoric acid mostly is about 120 seconds most.In other embodiments, acid medium comprises about 80 weight % phosphoric acid at most.In certain embodiments, acid medium more generally has less than 3.0, preferably less than 2.0 pH value.In certain embodiments, acid medium preferably includes temperature less than 140 ℃ boiling phosphoric acid.Although do not need to remove the polyphosphoric acid of hydrolysis from fiber, in certain embodiments, this method further comprises the step of removing the hydrolysis polyphosphoric acid from fiber.In a preferred embodiment, polymer keeps not hydrolysis substantially after the polyphosphoric acid hydrolysis.Polymer as herein described " keeps not hydrolysis substantially " and is meant that polymer property viscosity is not subjected to this method affect in essence.
In other embodiments, the present invention relates to the method for the polyphosphoric acid in the hydrolysis polyaromatic azoles polymeric material, comprise the following steps: a) to provide the polymeric material that comprises polyaromatic azoles and polyphosphoric acid, wherein the polyaromatic azoles repeat unit structure of at least 50 moles of % comprises 2,5-dihydroxy-right-phenylen moiety; And b) usually polymeric material is heated to above 100 ℃ with hydrolysis at least a portion polyphosphoric acid.More generally, this method further comprises the step of removing the hydrolysis polyphosphoric acid from polymeric material.
In other embodiments, the present invention relates to from the yarn that is spun into by the polymer solution that contains polyphosphoric acid, remove the method for phosphorus, this yarn comprises the phosphorus of about at least 1.5 weight % of yarn weight, and this method comprises to be made yarn contact with alkali and wash yarn with aqueous fluid.In certain embodiments, the phosphorus content of yarn was generally 2 to 20% of yarn weight before yarn contacted with alkali, and more generally, phosphorus content is 4 to 15% of a yarn weight.In some embodiments, yarn comprises sprinkling, coating with contacting of alkali, flows, draws (drawing), dipping or its any combination.Usually, the alkali that contacts with yarn comprises NaOH, potassium hydroxide, ammonium hydroxide, sodium bicarbonate or its any combination.In other embodiments, the aqueous fluid that is usually used in washing yarn contains acid, more generally volatile acid.The suitable non-limitative example of volatile acid comprises formic acid, acetate, propionic acid, butyric acid, isobutyric acid, pivalic acid or its any combination.Preferably, volatile acid is acetate or propionic acid.In certain embodiments, polymer comprises the polyaromatic azoles.Preferably, the polyaromatic azoles is polypyridine and azoles; Polypyridobisimidazo/e /e more preferably.Preferred in certain embodiments polyaromatic azoles is poly-(1,4-(2, the 5-dihydroxy) phenylene-2,6-diimidazole be [4,5-b:4 ' 5 '-e] inferior pyridine radicals also).In other embodiments, the polyaromatic azoles is a polybenzoxazole, more generally polyphenyl and two azoles.
In other methods of removing phosphorus from the yarn that is spun into by the polymer solution that contains polyphosphoric acid, yarn contains 0.1% the phosphorus that is less than or equal to yarn weight usually after with the aqueous fluid washing.In certain embodiments, be heated at least 120 ℃ of times that reach effective hydrolysis polyphosphoric acid, preferred about 600 seconds at most, more preferably provided yarn at most in about 120 seconds by the polyfilament yarn that comprises polymer and polyphosphoric acid that will be spun into.In certain embodiments, the alkali that is used for contacting with yarn is that sodium hydrate aqueous solution and/or aqueous cleaning solution contain acetate.In other embodiments, the duration of the step that contacts with alkali is no more than 30 seconds usually, preferred 20 seconds or shorter.Similarly, in some other embodiment, be no more than 30 seconds, preferred 20 seconds or shorter with duration of the step of aqueous fluid washing.In other embodiments, the step that contacts with alkali of yarn began before the step with aqueous fluid washing yarn.
In certain embodiments, the present invention relates to comprise polyaromatic azoles polymer with pendant hydroxyl groups and account for fibre weight at least 2% comprise sodium, potassium or calcium or its cationic fiber in being combined in arbitrarily.In some embodiments, the polyaromatic azoles is polypyridine and azoles normally, preferred polypyridobisimidazo/e /e.Preferred polypyridobisimidazo/e /e is poly-(1,4-(2, the 5-dihydroxy) phenylene-2,6-diimidazole be [4,5-b:4 ' 5 '-e] inferior pyridine radicals also).In other embodiments, the polyaromatic azoles is a polybenzoxazole, usually polyphenyl and two azoles.In certain embodiments, fiber contains 2% sodium above fibre weight usually.In other embodiments, fiber contains 3% CATION above fibre weight usually.In certain embodiments, fiber contains 3% sodium above fibre weight.
In other embodiments, the present invention relates to from polyaromatic azoles fiber, remove cationic method, comprise the following steps: a) to provide and comprise polyaromatic azoles polymer with pendant hydroxyl groups and the cationic fiber of at least 2 weight %, b) described fiber is contacted discharging at least a portion CATION with containing aqueous acid, and c) the optional fiber that washes with water.In certain embodiments, acid more generally is volatile acid.The suitable non-limitative example of volatile acid comprises formic acid, acetate, propionic acid, butyric acid, isobutyric acid, pivalic acid or its any combination; Be preferably acetate, propionic acid or its any combination.In some embodiments, the aqueous solution contains about 0.1 usually to about 10 weight % acid.In other embodiments, the CATION of removing from polyaromatic azoles fiber comprises sodium, potassium, calcium or its any combination.Fiber generally includes sprinkling, coating, flows, draws, floods or its any combination with contacting of the aqueous solution.Although contact procedure can be according to particular polymers or fiber and shorter or longer, however the at most about 30 seconds usually duration of contact procedure, preferred about 20 seconds or shorter at most.Similarly, the time of optionally washing step may be inessential, but the maximum about 30 seconds usually duration of optionally washing step, preferred about 20 seconds or shorter at most.In certain embodiments, fiber with contain that aqueous acid contacts and optional wash the step of fiber with water after, fiber contains maximum about 0.1% the CATION that accounts for fibre weight, preferably accounts for about 0.05% maximum CATION of fibre weight.In other embodiments, with before the aqueous solution contacts, fiber further comprises about at least 0.1% the phosphorus that accounts for fibre weight at fiber, is more typically in fiber and comprises about at least 1% the phosphorus that accounts for fibre weight before contacting with the aqueous solution.In other embodiments, the polyaromatic azoles is polypyridine and azoles, usually polypyridobisimidazo/e /e.In some preferred embodiment, polypyridobisimidazo/e /e is poly-(1,4-(2, the 5-dihydroxy) phenylene-2, the inferior pyridine radicals of 6-diimidazole [4,5-b:4 ' 5 '-e]).In other embodiments, the polyaromatic azoles is a polybenzoxazole, preferred polyphenyl and two azoles.
Suitable polyaromatic azoles monomer in the solution of non-oxide and dehydracetic acid under nonoxidizing atmosphere, when mixing, with progressively or oblique line (ramped) mode be increased under about at least 170 ℃ temperature and react from being no more than about 120 ℃.Polyaromatic azoles polymer can be rigid rod, semi-rigid rod or flexible coil.It is preferably the lyotropic liquid crystal polymer, and it forms liquid crystal farmland (domain) in solution when concentration surpasses critical concentration.Rigidity polyaromatic azoles polymer inherent viscosity at 30 ℃ in Loprazolam is preferably at least approximately 10dL/g, more preferably about at least 15dL/g, most preferably about at least 20dL/g.
Discuss certain embodiments of the present invention with reference to Fig. 1.In some embodiments, in sour solvent, form polymer, thereby spinning solution 2 is provided.In other embodiments, polymer is dissolved in sour solvent after forming.Arbitrary scheme all within the scope of the invention.Preferably, polymer forms in sour solvent and uses for the present invention.The spinning solution 2 that comprises polymer and polyphosphoric acid contains the polymer of enough high concentrations usually so that polymer forms acceptable long filament 6 after extruding and solidifying.When polymer was lyotropic liquid crystal, the concentration of polymer in spinning solution 2 preferably was high enough to provide fiber spinning from crystalline state stoste.The preferably about at least 7 weight % of the concentration of polymer, more preferably about at least 10 weight %, most preferably about at least 14 weight %.Usually main by practical factor, for example polymer dissolution degree and spinning solution viscosity are selected Cmax.Polymer concentration preferably is no more than 30 weight %, more preferably no more than about 20 weight %.
Polymer spun silk stock solution 2 can contain the additive of common adding, for example antioxidant, lubricant, screening uv-ray agent, colouring agent and analog.
Polymer spun silk stock solution 2 extrude by die head or spinning head 4 usually or spinning with preparation or be spun into the spinning solution long filament.Spinning head 4 preferably contains a plurality of holes.Hole number in spinning head and the arrangement thereof is of no significance for the invention, but for economic reasons, preferably makes the hole number maximization.Spinning head 4 can contain nearly 100 or 1000 or more hole, and they can be arranged with annular, grid or with any other required arrangement mode.Spinning head 4 can be by can not constituted by any material that spinning solution 2 is degraded.
Can be made by solution and be spun into fiber in many ways, still, wet spinning and " air gap " spinning are widely known by the people most.It is as known in the art being used for the spinning head of these spin processes and a general configuration of bath, United States Patent(USP) Nos. 3,227, the accompanying drawing illustration in 793,3,414,645,3,767,756 and 5,667,743 be used for this class spin processes of high-strength polymer.In " air gap " spinning, spinning head at first is expressed into gas with fiber usually, for example in the air.Use Fig. 1 so that illustration uses the method (being also referred to as " dry-spray " wet spinning sometimes) of " air gap " spinning, the spinning solution 2 that leaves spinning head 4 enters the very short duration of gap 8 between spinning head 4 and the coagulating bath 10 (so-called " air gap ", yet do not need to contain air).Gap 8 can be contained can not cause and solidifies or can be sharply and any fluid of spinning solution reaction, for example air, nitrogen, argon gas, helium or carbon dioxide.The spinning solution of extruding 6 is pulled through air gap 8 under the situation of extending or not extending, and enters the liquid coagulating bath immediately.Perhaps, fiber can " wet spinning ".In wet spinning, spinning head directly is expressed into fiber in the liquid of coagulating bath usually, and usually spinning head is flooded or is placed on the lower face of coagulating bath.Can use arbitrary spin processes that the fiber of using in the method for the invention is provided.In some embodiments of the present invention, the air gap spinning is preferred.
The spinning solution of extruding 6 is in the coagulating bath 10 of the mixture of moisture or moisture and phosphoric acid " solidifying ", and it removes spinning solution 6 in any subsequently process the obviously elongation of enough polyphosphoric acid to prevent to extrude.If extrude plurality of fibers simultaneously, they can before the coagulation step, among or be merged into polyfilament yarn afterwards.Term used herein " solidifies " and means that not necessarily the spinning solution of extruding 6 is flowing liquids and is transformed into solid phase.The spinning solution of extruding 6 can be in enough low temperature so that it did not flow substantially before entering coagulating bath 10.But coagulating bath 10 guarantees really or finishes solidifying of long filament that promptly polymer changes into solid-state substantially polymer filaments 12 from spinning solution 2.The solvent of removing in coagulation step, promptly the amount of polyphosphoric acid depends on the time of staying of spinning solution long filament in coagulating bath, the temperature and the solvent concentration therein of bath 10.
Do not wish to be limited by any particular theory of operation, the present invention is considered to part based on following discovery, if promptly residual phosphorus content is low, then keeps long-term fibre property better.Especially, this can realize by hydrolysis PPA before PPA is removed from fiber, because believe that the polyphosphoric acid that can effectively remove basic hydrolysis from fiber is to realize low-residual phosphorus.Usually, PPA is keeping basic hydrolysis under the unhydrolysed substantially condition of fiber.Although implement many patterns of the present invention is that those skilled in the art can expect after understanding the present invention, can come hydrolysis PPA easily by heated yarn or yarn before washing and/or neutralization procedure.A kind of hydrolysis method comprises the short time Convective Heating of coagulated fibre.As the alternative of Convective Heating, can in boiling water or aqueous acid, heat by the long filament that solidifies attitude (as coagulated) that will wet or yarn and implement hydrolysis.Heat treatment provides PPA hydrolysis in the TENSILE STRENGTH that fully keeps the product fiber.Heat treatment step can carry out in independent cell 14, or carries out as the initial process step before one or more follow-up washing steps in existing washing chamber 14.
In some embodiments, followingly provide hydrolysis and removal: (a) make spinning solution long filament and solution bathe or cell 14 in contact, hydrolysis PPA thus, then (b) make long filament and neutralization solution in the bath of the alkali that contains water and effective dose or cell 16, be enough in long filament in the phosphoric acid, polyphosphoric acid of sufficient quantity or its contact under condition of combination arbitrarily.
Behind the polyphosphoric acid (PPA) that links to each other with the long filament that solidifies with basic hydrolysis through processing, can come from long filament or yarn 12, to remove hydrolysis PPA by washing in one or more washing steps, thereby from long filament or yarn 12, remove the PPA of most of residual acid solvent and/or hydrolysis.The washing of long filament or yarn 12 can be by carrying out with alkali or with repeatedly carrying out washing treatment long filament or yarn 12, wherein before with alkali treatment long filament or yarn and/or wash with water afterwards.Long filament or yarn also can use acid treatment to reduce the cations in the polymer subsequently.This washing order can be by making long filament pass a series of baths and/or passing one or more washing chambers and carry out in continuity method.Fig. 1 has described a washing bath or chamber 14.The washing chamber generally includes the sealing chamber that contains one or more rollers, and long filament moved for several times and crossed (across) these rollers around these rollers before leaving this chamber., it is sprayed with cleaning solution during at long filament or yarn 12 around the roller operation.Cleaning solution is collected in this bottom, chamber continuously and therefrom discharges.
The temperature effect of cleaning solution the diffusion rate of control washing process, this makes temperature select to have actual importance.Preferably, according to the required time of staying, use 20 to 90 ℃ temperature.Cleaning solution can apply with vapor form, but more conveniently provides with liquid form.Preferably, use many washing baths or chamber.Long filament or yarn 12 time of staying in arbitrary washing bath or chamber 14 is depended on the required residual phosphorus concentration in long filament or the yarn 12, but the time of staying is preferably about 1 second to being less than about 2 minutes.In continuity method, the duration of whole washing process in preferred a plurality of washing baths and/or chamber preferably is no more than about 10 minutes, more preferably surpasses about 5 seconds to being no more than about 160 seconds.
In some embodiments, the preferred alkali that is used to remove hydrolysis PPA comprises NaOH, KOH, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, ammonia or trialkylamine, preferred tri-butylamine, or their mixture.In one embodiment, alkali is water miscible.Typical aqueous base comprises NaOH, KOH, Na
2CO
3, NaHCO
3, K
2CO
3And KHCO
3Or their mixture; Be more typically NaOH.
With after the alkali treatment fiber, this method can choose wantonly comprise make step that long filament contacts with the cleaning solution that contains water and/or acid with remove all or nearly all excessive alkali or with polymer fiber bonding or the base cations that links to each other.This cleaning solution can apply in washing bath or chamber 18.
After washing, fiber or yarn 12 can be dry to remove water and other liquid in drier 20.Temperature in the drier is generally 80 ℃ to 130 ℃.The drier time of staying is generally 5 seconds to reaching 5 minutes at a lower temperature.Can provide nitrogen or other non-reactive for drier.Can choose in thermosetting device 22 for example further processing fiber then wantonly.Further processing can be carried out in the tube furnace 22 that nitrogen purging is crossed to improve the mechanical stress of molecule in toughness and/or the release long filament.At last, long filament or yarn 12 are wound into packing on coiler device 24.Roller, pin, guider and/or tracker action 26 are suitably located so that long filament or yarn are transmitted by this process.
Moulded products as herein described comprises formed body or film, mechanograph and the analog of extruding with blowing.Film can be by the known technology manufacturing, and for example (1) to flat surfaces, extrude spinning solution forming film by extruder (2) with the spinning solution curtain coating, or (3) are with the spinning solution film is extruded or blowing is extruded with formation blown film.The typical technology that the spinning solution film is extruded comprises and those similar methods that are used for fiber that wherein solution enters air gap or fluid layer and enters coagulating bath subsequently through spinning head or die head.More details of extruding and being orientated of describing the spinning solution film can be in people such as Pierini (U.S. Patent No. 5,367,042); Chenevey (4,898,924); Find among the people (4,963,428) such as people such as Harvey (4,939,235) and Harvey.It is thick that the spinning solution film of making preferably is no more than about 250 mils (6.35 millimeters) usually, and more preferably about 100 mils (2.54 millimeters) are thick at most.
Preferably, the phosphorus content of dry long filament is more preferably less than about 4,000 ppm by weight (0.4%), most preferably less than about 2,000 ppm by weight (0.2%) less than about 5,000 ppm by weight (0.5%) behind the removal hydrolysis PPA.
The present invention also part relates to the yarns of the long filaments that comprise many basic inventions, comprises the fabric of long filament of the present invention or yarn and comprises the goods of fabric of the present invention.
Embodiment
The experiment test method
In the following example, use following method of testing.
Temperature: all temperature are all ℃ to record.
Dawn number (Denier)Measure and be the line density of the fiber that shows of the weight in grams numerical table with 9000 meters fibers according to ASTM D1577.
ToughnessMeasure and be the maximum or the breaking stress of the fiber represented with the gram/dawn according to ASTM D 885.
Elementary analysis: the elementary analysis of alkaline kation (M) and phosphorus (P) is according to the following mensuration of inductively coupled plasma (ICP) method.The sample (1-2 gram) of accurately weighing is placed in the quartz container of CEM Star6 microwave system.Add the concentrated sulfuric acid (5 milliliters) and turn to soaking.Condenser is connected on this container, and uses moderate to burn (moderate char) method digestion in sample.This method comprises sample is heated to the highest 260 ℃ all temps to burn organic material.Automatically add the nitric acid aliquot by this equipment in each stage of digestion.The final digestion product of limpid liquid is cooled to room temperature and is diluted to 50 milliliters with deionized water.Can on Perkin Elmeroptima inductively coupled plasma equipment, use the condition of manufacturer recommendation and be provided with and analyze this solution.Can be to each sample at several different wave length analyses 26 kinds of different elements altogether.For some element of for example sodium and phosphorus and so on, may need 1/10 dilution.Calibration criterion is 1 to 10ppm.
The processing and implementation example
Provide many following example with illustration each embodiment of the present invention and should not be regarded as limiting by any way the present invention.All polymer solids concentration are based on the percentage by weight and the polymer solution percentage P of monomer
2O
5Concentration is basic representation with the TD-complex compound as 1: 1 between TAP and the DHTA mole complex compound.The TD complex compound is considered to monohydrate.
In the following example, poly-([dihydroxy] is to the two imidazoles of phenylene pyrido) long filaments (be also referred to as " PIPD " in this article, show with one of its tautomeric form below) are spun into by the polymer solution that comprises 18 weight %PIPD in polyphosphoric acid.This solution is extruded from spinning head, be pulled through air gap and in water, solidify.The wet bobbin of not processing in 6 hours is freezing until further processing.
In the following example some have shown the difficulty of removing residual (gathering) phosphoric acid from the fiber that newly is spun into.For example, embodiment A has shown when not carrying out autotelic removal typical P content in the fiber.Embodiment B has shown the difficulty of using traditional washing eccysis PPA from wet yarn.Embodiment C is considered to preferred acid content than the high acid concentration limit when having shown processing PIPD fiber.Be higher than under this content in certain embodiments, fiber may begin disintegration.
Embodiment D has shown the difficulty of using traditional boiling water washing eccysis PPA from wet yarn.Embodiment E-K has shown to combine with the washing of fiber or yarn and has carried out the benefit of heat treatment step with the residual polyphosphoric acid of hydrolysis.
Embodiment A
This embodiment has shown the difficulty of using traditional washing eccysis PPA from wet yarn.Use 250 hole spinnerets with the PIPD polymer with contain 81.6 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.Make the wet yarn that solidifies attitude air-dry, analyze phosphorus then.Find that sample contains very high phosphorus content (63400ppm) and 175ppm sodium.
The PIPD yarn samples of solidifying attitude that will wet was then at room temperature soaked 5 minutes in fresh water.With yarn samples rinsing 20 seconds in fresh water, make it air-dry then, analyze phosphorus then.Find that sample contains 58500ppm phosphorus and 453ppm sodium.
The PIPD yarn samples of solidifying attitude that will wet was then soaked 5 minutes in the water of 100 ℃ of gentle boilings.Then this yarn samples at room temperature being soaked in fresh water made it air-dry in 20 seconds then.Find that sample contains 55700ppm phosphorus and 700ppm sodium.
Embodiment B
Use 250 hole spinnerets with the PIPD polymer with contain 82.5 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.Make the wet yarn that solidifies attitude gentle boiling 20 minutes in 100 ℃ water.Then with the rinsing 10 seconds in fresh water of this yarn samples, and make it air-dry.Find that sample contains 44500ppm phosphorus and 1000ppm sodium.
Embodiment C
Use 250 hole spinnerets with the PIPD polymer with contain 81.9 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.The wet PIPD yarn samples of solidifying attitude was handled 15 seconds in 80% phosphoric acid (142 ℃) of boiling, and washing is 10 seconds in 91 ℃ of water, respectively washs 10 seconds in 60 ℃ of baths of 2% caustic-alkali aqueous solution, water, 2% acetic acid aqueous solution and water then.Make sample air-dry then.Find that this sample shows long filament sticking or clinkering and has 7.44% residual phosphorus content.
Another sample of the PIPD yarn that solidifies attitude that this is wet places (180 ℃) 90% phosphoric acid of boiling.The rapid disintegration of sample.
Embodiment D
Use 250 hole spinnerets with the PIPD polymer with contain about 82.1 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.The wet yarn samples of solidifying attitude is seethed with excitement in water the various times as shown in table 1.Then with this sample 60 ℃ at water, 2 weight % caustic-alkali aqueous solutions, water, 2% acetic acid aqueous solution, further washing in the continuous bath of water then, washing is 20 seconds in each is bathed.After the drying, find that sample contains phosphorus content as shown in Table.
Table 1
| Sample | Time, minute | P(ug/g) | P(w％) |
| D-1 | 0 | 23800 | 2.38 |
| D-2 | 5 | 16200 | 1.62 |
| D-3 | 10 | 14000 | 1.4 |
| D-4 | 15 | 10700 | 1.07 |
| D-5 | 20 | 9180 | 0.918 |
| D-6 | 30 | 6380 | 0.638 |
| D-7 | 45 | 6320 | 0.632 |
| D-8 | 60 | 3920 | 0.392 |
Embodiment E
Use 250 hole spinnerets with the PIPD polymer with contain 82.5 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.Take out the wet PIPD yarn samples of solidifying attitude, at first use boiling phosphoric acid to handle through high temperature, acidic hydrolysis condition with various concentration as shown in table 2.In hydrolysis medium with shown in time and Temperature Treatment yarn samples.The washing of carrying out sample as shown in table 2 then.The combination that washing step comprises the following steps: a) in water, wash; B) in 2% sodium hydrate aqueous solution, wash; C) in water, wash; D) in 2% acetic acid aqueous solution, wash; With in water, wash.Washing is carried out with time and temperature shown in the table.When combining,, can realize being lower than the residual phosphorus content of 2 weight % by the hydrolysising condition of this fierceness with washing.
Table 2
| Project | Medium | Temperature (℃) | Time (second) | Coolant-temperature gage/time | Alkali temperature/time | Coolant-temperature gage/time | Acid temperature/time | Coolant-temperature gage/time | P | Na |
| (wt％) | ||||||||||
| 1-1 | 70％ H 3PO 4 | 130 | 60 | 100/20 | -/- | -/- | -/- | 65/20 | 4 | 0.05 |
| 1-2 | 70％ H 3PO 4 | 130 | 60 | 100/20 | 62/20 | -/- | -/- | 62/20 | 0.8 | 2.6 |
| 1-3 | 70％ H 3PO 4 | 130 | 60 | 100/20 | 62/20 | 62/20 | 62/20 | 62/20 | 0.7 | 0.21 |
| 1-4 | 60％ H 3PO 4 | 115 | 50 | 90/20 | 62/20 | -/- | -/- | 62/20 | 1.3 | 2.9 |
| 1-5 | 50％ H 3PO 4 | 110 | 60 | 100/20 | -/- | -/- | -/- | 65/20 | 2.4 | 1.3 |
| 1-6 | 50％ H 3PO 4 | 110 | 60 | 100/20 | 62/20 | -/- | -/- | 62/20 | 1.2 | 3.7 |
| 1-7 | 50％ H 3PO 4 | 110 | 60 | 100/20 | 62/20 | 62/20 | 62/20 | 62/20 | 1.6 | 0.29 |
| 1-8 | 40％ H 3PO 4 | 106 | 60 | 100/20 | 62/20 | -/- | -/- | 62/20 | 1.7 | 4.2 |
| 1-9 | 20％ H 3PO 4 | 103 | 60 | 100/20 | -/- | -/- | -/- | 65/20 | 5.6 | 0.6 |
| 1-10 | 20％ H 3PO 4 | 103 | 60 | 100/20 | 62/20 | -/- | -/- | 62/20 | 1.7 | 5.0 |
| 1-11 | 20％ H 3PO 4 | 103 | 60 | 100/20 | 62/20 | 62/20 | 62/20 | 62/20 | 0.9 | 0.15 |
| 1-12 | - | - | - | -/- | -/- | -/- | -/- | -/- | 7.0 | 0.01 |
| 1-13 | Water | 100 | 60 | 100/20 | 62/20 | -/- | -/- | 62/20 | 2.8 | 4.7 |
Embodiment F
Use 250 hole spinnerets with the PIPD polymer with contain 82.5 weight %P
2O
5Polyphosphate solution be spun into fiber.The wet PIPD yarn samples of solidifying attitude was handled 60 seconds rinsing 20 seconds in 60 ℃ of water then in atmospheric pressure vapor (100 ℃).Make sample air-dry and it is found that and contain 6.48 weight %P.With the not air-dry another kind of sample of seemingly handling at 60 ℃ in the further washing 20 seconds in the continuous bath of water then of 2 weight % sodium hydrate aqueous solutions.After drying, find that this sample contains 2.1 weight % phosphorus.
Embodiment G
Use 250 hole spinnerets with the PIPD polymer with contain 82.5 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.The wet PIPD yarn samples of solidifying attitude that so is spun into was handled 60 seconds about 58psig and 148 ℃ in saturated vapor, then in following bath 60 ℃ of washings 20 seconds: water, 2 weight % caustic-alkali aqueous solutions, water, 2% acetic acid aqueous solution, water then.After drying, find that this sample contains 0.33 weight % phosphorus.
Another sample of the wet PIPD yarn that solidifies attitude was handled 60 seconds 100psig and 165 ℃ in saturated vapor, carried out then and identical before washing step.Washing and the dry sample of crossing it is found that and contain 0.11 weight % phosphorus.
Embodiment H and I show and use the xeothermic rapid hydrolysis of carrying out.Embodiment J shows that the use steam heat is hydrolyzed.
Embodiment H
Use 100 hole spinning heads with the PIPD polymer with contain 82.1 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.The tube furnace that one foot long nitrogen purging is crossed is passed in the wet PIPD yarn stretching of solidifying attitude.Table 3 has shown the influence to washing and dried sample gained phosphorus content of tube furnace temperature and the time of staying.All samples at water, was respectively washed 20 seconds in 60 ℃ of baths of 2% sodium hydrate aqueous solution, water, 2% acetic acid aqueous solution and water then.Use the xeothermic hydrolysis of the wet yarn that solidifies attitude and subsequently shown in washing, acquisition is lower than the phosphorus content of 1 weight % under many conditions.
Table 3
| Project | Furnace temperature | The time of staying | Yarn | P | Na |
| (C) | (s) | dpf | (microgram/gram) | ||
| H-1 | 180 | 30 | 1.5 | 6690 | 807 |
| H-2 | 180 | 20 | 2 | 7880 | 643 |
| H-3 | 180 | 30 | 2 | 7370 | 384 |
| H-4 | 180 | 20 | 2 | 8800 | 439 |
| H-5 | 180 | 10 | 2 | 23600 | 698 |
| H-6 | 200 | 10 | 2 | 15600 | 503 |
| H-7 | 200 | 20 | 2 | 3210 | 605 |
| H-8 | 200 | 30 | 2 | 3650 | 454 |
| H-9 | 200 | 30 | 1.5 | 3510 | 525 |
| H-10 | 220 | 30 | 1.5 | 3310 | 484 |
| H-11 | 220 | 30 | 2 | 2450 | 524 |
| H-12 | 220 | 20 | 2 | 2310 | 395 |
| H-13 | 220 | 10 | 2 | 12500 | 374 |
| H-14 | 240 | 10 | 2 | 2910 | 294 |
| H-15 | 240 | 20 | 2 | 2500 | 210 |
Dpf is the dawn number of every long filament
Example I
Use 250 hole spinnerets with the PIPD polymer with contain 82.7 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.Described in embodiment H, the wet PIPD yarn that solidifies attitude is handled in stove continuously, but the time of staying and temperature are as shown in table 4.Current yarn samples was only handled 20 seconds at 45-50 ℃ in each following bath (water, 2% sodium hydrate aqueous solution, He Shui).Residual phosphorus and sodium value are listed in the table 3 and have shown that the pyrohydrolysis processing is to reducing the benefit of residual phosphorus content.
Table 4
| Project | Furnace temperature | The time of staying | P | Na |
| (℃) | (s) | (microgram/gram) | ||
| I-1 | 140 | 30 | 21600 | 25600 |
| I-2 | 160 | 30 | 16600 | 27300 |
| I-3 | 180 | 30 | 11000 | 20900 |
| I-4 | 200 | 30 | 5720 | 24200 |
| I-5 | 220 | 30 | 3110 | 20500 |
| I-6 | 240 | 30 | 3140 | 24500 |
| I-7 | - | - | 21200 | 39700 |
| I-8 | - | - | 21900 | 40000 |
For the phosphorus content in the fiber before definite the processing, analyze the phosphorus of the yarn of the quenching attitude of as above using that wets, and find to contain 34600ppm.After drying, find that this sample contains 63900ppm phosphorus.The percentage by weight difference of phosphorus is owing to the unnecessary liquid in the wet yarn between the yarn samples.
Embodiment J
Use 100 hole spinning heads with the PIPD polymer with contain 82.1 weight %P
2O
5The solution of polyphosphoric acid be spun into fiber.The 1 foot long tube furnace that purged with atmospheric pressure vapor is passed in the wet PIPD yarn stretching of solidifying attitude.Table 5 has shown the influence to the gained phosphorus content in washing and the dry back sample of temperature and the time of staying.With all samples at water, respectively washed 20 seconds in 60 ℃ of baths of 2% sodium hydrate aqueous solution, water, 2% acetic acid aqueous solution and water then.Under optimum condition, obtain to be lower than the phosphorus content of 1 weight % easily.
Table 5
| Project | Furnace temperature (C) | The time of staying (s) | P | Na |
| (microgram/gram) | ||||
| J-1 | 280 | 41 | 2500 | 697 |
| J-2 | 250 | 41 | 6910 | 890 |
| J-3 | 230 | 41 | 6550 | 833 |
| J-4 | 230 | 30 | 3910 | 776 |
| J-5 | 230 | 20 | 3490 | 714 |
| J-6 | 230 | 10 | 22400 | 793 |
| J-7 | 200 | 10 | 24800 | 928 |
| J-8 | 200 | 20 | 3870 | 819 |
| J-9 | 200 | 30 | 6040 | 1180 |
| J-10 | 180 | 30 | 7440 | 613 |
| J-11 | 180 | 20 | 9880 | 391 |
Embodiment K
By being included in polyphosphoric acid (82.1 weight %P
2O
5) in the polymer solution of 18 weight %PIPD be spun into the PIPD long filament.This solution is extruded from the spinning head with about 250 holes, be pulled through air gap, and in water, solidify.Wet yarn is processed and is wound on the bobbin with 61 meters/minute (200 feet per minute clocks) on 201-221 ℃ the warm-up mill that records the surface temperature operation a pair of.The yarn of having processed on hot-rolling is stone according to observations and have a clinkering of each excessive long filament.In addition, it is residual to observe unacceptable fiber on hot-rolling.Other processing details and result are presented in the table 6.Then by bobbin was respectively flooded 5 minutes in five continuous baths that are in room temperature, washing and in and the yarn on the bobbin.These baths are water in regular turn; 2% sodium hydrate aqueous solution; Water; 2% acetic acid aqueous solution; And water.Make the yarn on the bobbin air-dry then, and take out yarn samples, find that residual phosphorus content is very indefinite, for about 0.77 weight % to about 3.42 weight % phosphorus.
Table 6
| Project | Roll temperature | Tension force | Yarn | Phosphorus |
| ℃ | The dawn number | (wt％) | ||
| K-1 | 202 | 250 | 503 | 3.42 |
| K-2 | 201 | 250 | 465 | 1.77 |
| K-3 | 221 | 250 | 458 | 0.77 |
Each patent that exemplifies in this document or describe, patent application and disclosed disclosure are incorporated herein by this reference fully.
Those of skill in the art will recognize that and to make many changes and modification to the preferred embodiments of the invention, and can make this class change and modification without departing from the spirit of the invention.Therefore, claims are intended to cover the equal change of all these classes that drops in true spirit of the present invention and the scope.
Claims (20)
1. remove the method for phosphorus from the yarn that is spun into by the polymer solution that contains polyphosphoric acid, this yarn comprises the phosphorus of the about at least 1.5 weight % that account for yarn, and this method comprises to be made yarn contact with alkali and wash yarn with aqueous fluid.
2. the process of claim 1 wherein that at yarn with before alkali contacts, the phosphorus content of yarn is 2 to 20% of a yarn weight.
3. the process of claim 1 wherein that at yarn with before alkali contacts, the phosphorus content of yarn is 4 to 15% of a yarn weight.
4. the process of claim 1 wherein yarn contact with alkali comprise sprinkling, coating, flow, traction, dipping or its any combination.
5. the method for claim 4, wherein alkali comprises NaOH, potassium hydroxide, ammonium hydroxide, sodium bicarbonate or its any combination.
6. the process of claim 1 wherein that aqueous fluid contains acid.
7. the method for claim 6, wherein acid is volatile acid.
8. the method for claim 7, wherein volatile acid comprises acetate or propionic acid, or its any combination.
9. the process of claim 1 wherein that polymer comprises the polyaromatic azoles.
10. the method for claim 9, wherein the polyaromatic azoles is polypyridine and azoles.
11. the method for claim 10, wherein polypyridine and azoles are polypyridobisimidazo/e /es.
12. the method for claim 11, wherein polypyridobisimidazo/e /e be poly-(1,4-(2, the 5-dihydroxy) phenylene-2, the two imidazoles of 6-pyrido [2,3-d:5,6-d '].
13. the method for claim 9, wherein the polyaromatic azoles is polyphenyl and two azoles.
14. the process of claim 1 wherein that yarn is with containing 0.1% the phosphorus that is less than yarn weight after the aqueous fluid washing.
15. the process of claim 1 wherein to be heated at least 120 ℃ of times that reach effective hydrolysis polyphosphoric acid, yarn be provided by the multifilament yarn that is spun into that will comprise polymer and polyphosphoric acid.
16. the process of claim 1 wherein that alkali is that sodium hydrate aqueous solution and/or aqueous fluid contain acetate.
17. the process of claim 1 wherein that the duration of contact procedure is no more than 30 seconds.
18. the process of claim 1 wherein that the duration of washing step is no more than 30 seconds.
19. the process of claim 1 wherein that the step that yarn contacts with alkali began before the step with aqueous fluid washing yarn.
20. the method for claim 15, wherein effectively the time of hydrolysis polyphosphoric acid mostly is about 120 seconds most.
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| US60/665,741 | 2005-03-28 | ||
| PCT/US2006/011513 WO2006105225A1 (en) | 2005-03-28 | 2006-03-27 | Process for removing phosphorous from a fiber or yarn |
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| US7683122B2 (en) | 2005-03-28 | 2010-03-23 | E. I. Du Pont De Nemours And Company | Processes for increasing polymer inherent viscosity |
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| EP1863957B1 (en) * | 2005-03-28 | 2012-06-13 | E.I. Du Pont De Nemours And Company | Process for hydrolyzing polyphosphoric acid in a spun yarn |
| WO2006105227A1 (en) | 2005-03-28 | 2006-10-05 | E. I. Du Pont De Nemours And Company | Thermal processes for increasing polyareneazole inherent viscosities |
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| US8202965B2 (en) | 2005-03-28 | 2012-06-19 | E.I. Du Pont De Nemours And Company | Fusion free hydrolysis of polyphosphoric acid in spun multifilament yarns |
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| AU2003244069A1 (en) * | 2002-06-26 | 2004-01-19 | Toyo Boseki Kabushiki Kaisha | Highly durable polybenzazole composition, fiber and film |
| US7189346B2 (en) * | 2004-07-22 | 2007-03-13 | E. I. Du Pont De Nemours And Company | Polybenzazole fibers and processes for their preparation |
| EP1863957B1 (en) * | 2005-03-28 | 2012-06-13 | E.I. Du Pont De Nemours And Company | Process for hydrolyzing polyphosphoric acid in a spun yarn |
-
2006
- 2006-03-27 AT AT06748888T patent/ATE495287T1/en not_active IP Right Cessation
- 2006-03-27 EP EP06748888A patent/EP1863956B1/en active Active
- 2006-03-27 KR KR1020077024744A patent/KR101337734B1/en active IP Right Grant
- 2006-03-27 CN CN2006800098253A patent/CN101218384B/en active Active
- 2006-03-27 JP JP2008504320A patent/JP4769290B2/en active Active
- 2006-03-27 WO PCT/US2006/011513 patent/WO2006105225A1/en active Application Filing
- 2006-03-27 DE DE602006019564T patent/DE602006019564D1/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| DE602006019564D1 (en) | 2011-02-24 |
| CN101218384B (en) | 2010-12-08 |
| JP4769290B2 (en) | 2011-09-07 |
| ATE495287T1 (en) | 2011-01-15 |
| KR20080034829A (en) | 2008-04-22 |
| EP1863956B1 (en) | 2011-01-12 |
| EP1863956A1 (en) | 2007-12-12 |
| KR101337734B1 (en) | 2013-12-06 |
| WO2006105225A1 (en) | 2006-10-05 |
| JP2008534804A (en) | 2008-08-28 |
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