CA2195084A1 - Process for preparing polybenzazole filaments and fiber - Google Patents
Process for preparing polybenzazole filaments and fiberInfo
- Publication number
- CA2195084A1 CA2195084A1 CA 2195084 CA2195084A CA2195084A1 CA 2195084 A1 CA2195084 A1 CA 2195084A1 CA 2195084 CA2195084 CA 2195084 CA 2195084 A CA2195084 A CA 2195084A CA 2195084 A1 CA2195084 A1 CA 2195084A1
- Authority
- CA
- Canada
- Prior art keywords
- holes
- spinneret
- filaments
- center
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/26—Formation of staple fibres
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A process for the preparation of polybenzazole filaments which includes extruding filaments from a spinneret (1) having at least 100 holes, which are arranged to form an annular pattern (2) around the center of the spinneret (1), the center and at least two radial sections (3) of the spinneret (1) having no holes and an average width which is at least 3 times the minimum pitch of the holes, and drawing the filaments through a quench chamber while providing a substantially radial gas flow therein across the spinneret (1) from at least two different directions.
Description
~ .WO 96/05341 , 2 1 9 5 0 8 4 1 ~
PROCESS FOR PREPARING POLYBENZAZOLE FILAMENTSAND FIBER
Thepresentinventionrelatestoaprocessforthepreparationofpu'~L_u-u~Lù
or pul~b,~ uLlliazole filaments and fibers.
Fiberspreparedfrompu'~L._.,LuA.,.ule(PBO)and,uulJb~lLuLll~ ùle(pBT) (hereinafter referred to as PBZ or uu~b_. ~L~Lu!~ polymers) may be prepared by first extruding asolutionofpol~b~,,L~Lulepolymerinamineralacid(apolymer''dope'')throughadieor spinneret to prepare a dope filament. The dope filament is then drawn across an air gap, washed in a bath comprising water or a mixture of water and a mineral acid, and then dried. If 1û multiplefilamentsareextrudedsimultaneously,theymaythenbecombinedintoa ~,.ulLiril..",_"Lfiberbefore,during, orafterthewashingstep.
As the filaments of pulrb~, IL~Lul~ dope are extruded, the high extensional viscosityofthedope,therapid coolingofthefilaments,andthedifferencesinthecoolingrates ofthefilamentsextrudedatthecenterofthespinneretascomparedtothoseextrudedatthe edge of the spi nneret, may ca use f requent breaks i n the filam ents as they are drawn across the air gap. Although this spinning stability problem can be reduced to some extent by using a slower spinning speed, and/or having a lower hole density on the spinneret, these methods are often less than desirable from the standpoint of productivity or equipment design. Since smaller diameter filaments are more desirable than larger diameter filaments which would be 20 normallyobtainedbytheuseofaspinnerethavinglargerorifices,thespin-drawratiomay needtobeincreasedsignificantlytodrawthefilaments~urri~ LlyLuproducesmaller diameter filaments, which may also cause breaks in the filaments.
Further, although the stability of the spinning line may be improved by decreasing the number of holes per spinneret (referred to hereafter as hole density), it 25 becomesnecessarytoincreasethenumberofspinneretsperspinningheadortoincreasethespinneretsizeinorderto.u,,Li,.~vu,lyspinalargenumberoffilamentsfromasinglespinning head However, such equipment~u,,ri_u,~Liu,,, may be lessthan desirable.
U5. Patents S,294,390 and S,385,702 disclose processes for increasing the stability of a spinning line by extruding poly.,~. ~L~ILulu filaments through a partially enclosed air gap 30 whichhasgasflowingthroughittocoolthefilamentsatarelativelyuniformL~,,,u~...LuAlthoughthismethodincreasesthestabilityofthespinningline,methodsforfurther increasing the spinning stability and the number of filaments which can be extruded per spin head while maintaining a relatively stable spinning line are desirable.
Inoneaspect,thisinventionisaprocessforthepreparationofpul~L~.,L~,Lu'~
35 filaments which comprises (a) extruding the filaments from a spinneret having at least 100 holes, which are arranged to form an annular pattern around the center of the spinneret, the center and at least two rac!ial sections of the spinneret having no holes and an average width which is at least about 3 times the minimum pitch of the holes; and (b) drawing the filaments . WO96/05341 . . PCT/US95/10271 through a quench chamber while pro~iding a substantially radial gas flow therein across the spinneret from at least two different directions.
In a second aspect, this invention is a process for the preparation of polybenzazole filaments which comprises (a) extruding the filaments from a spinneret having 5 at least 100 holes, which are arranged to form an annular pattern around the center of the spinneret, the center havi ng no holes elnd a n average width which i s at l east about 3 ti mes the minimum pitch of the holes; and (b) drawing the filaments through a quench chamber while providingasubstantiallyradialgasflowthereinthroughthefilamentsfromatleasttwo directions.
It has been d i scovered thist the process of the i nventi on provi des a means to prepare p~llyL~ ,,-..!t filaments and fibers which permits their spinning from spin-dies having a relatively high orifice density, but whlile maintaining relatively stable spinning conditions The stability of the spinning conditions creates a more efficient spinning process by minimizing thenumberoflinebreaks,insurestheuniformityofthefilamentbeingdrawn,whichallows one to optimize the cooli ng conditions of the fi la ments, which may i m prove the tensi le strengthandtensilemodulusofthefilelments. Theairflow~,~"~ L;l;Lybetweenfilaments ~ ' ' '~underthespinneretisimproved,thecoolingofthestrandsandthethinning profile becomes more uniform, and the! spinning process is stabiiized by use of the process of the invention. These and other advantages will be apparent from the description which 20 follows.
Figure 1 shows an example of a spinneret hole pattern for use in the process of the first aspect of the invention, as described below. Referrinq now to Figure 1, a spinneret (1) is shown, which is part of a group of holes (2), three groups of which are separated from each other by radial sections of the spinneret (3) which do not have holes, having a width (W).
25 Figure 2 shows an example of a spinneret hole pattern useful in the process of the second aspect of the invention.
The ,J~,lyl, . ,,,. ,. ~!~ filaments used in the process of the invention may beobtainedbyspinningadopecontainingapol~ L ~.I.O.~lepolymer. Asusedherein, 'p~lyL~.ILc~ ''referstopulyL~ lAoL~ (PB0)I,~""op.,';. rs,polyL~..L..Ll,i.,L~J!e(PBT) 30 I.,,,.lup~Jl),..~.,,andrandom,sequentialorblock...~,ulJ.,,~ dpolymerofPBOandPBT.
P.,IJL~"L~.Ac,L~,le"~ L~.,LuLlli~Lu~andrandom~sequential~orblock~up~
polymers thereof are described, for exalmple, in " Liquid Crystalline Polymer Compositions, ProcessandProducts,"byWolfeet.al,lJ.S.Patent4,703,1û3(0ctober27,19B7); "Liquid Crystalline Polymer Compositions, Process and Products, " U.S. Patent 4,533,692 (August 6, 35 1985); " Liquid Crystalline Poly(2,6~ LULI li~LOl~) Composition, Process and Products,"
US.Patent4,533,724(August6,1985);"LiquidCrystallinePolymerCompositions,Processand Products," U.S.Patent4,533,693(August6, 1985); "TI~ OUA; ioLi.~l) StableArticulated p-Be~ and p-Benzobisthiazole Polymers" by Evers, U.S. Patent 4,539,567 ~ WO96105341 , ~r r~~~ r- 2 1 95084 PCTIUS9~110271 (Novemberl6,1982);and"MethodforMakingHeterocyclicBlockCopolymer,"byTsai,U.5.
Patent4,578,432 (March 25,1986).
The structural units present in PBZ polymer are preferably selected so that the polymer is Iyotropic liquid crystalline. Preferred monomer units are illustrated below in Formulas l-VIII. The polymer more preferably consists essentially of monomer units selected fromthoseillustratedbelow~andmostpreferablyconsistsessentiallyofcis-~uu:yb-~lLu~aL
trans-uulrv_.--u,....ul~,,ortrans-,uulrL .~utl~ !e.
, o ~/ ~ '>{ ~t cis-polybenzoxazole Poly[benzo(1,2-d:5,4-d')bisoxazole-2,6-diyl-1,4-phenylene]
2C trans-polybPn7nY~7ole Poly[benzo(1,2-d:4,5-d')bisoxazole-2,6-diyl-1,4-phenylene]
2s ~ / ~ / ~ ~ III
trans-polybenzothiazole .W096/0s341 ''~ 2 I q5084 pCT~S9~10271 N ~ ~ N ~ ~ IV
ci~-polybenzothiazole ~ , N
~ ~0 J
Poly(2,5-benzoxazole) ~ ~S ~ VI
Poly(2,5-benzothiazole) ~ ~ 0 ~ ' VII
Poly(2,6-bPn7~Y~7ole) and ~ ~ S ~ ~ VIII
Poly(2,6-benzothiazole) Suitable l,ol ;L~ polymers or copolymers and dopes can be synthesized by known procedures, such as those described in Wolfe et al., U.S. Patent 4,'i33,693 (August6,1985~;5ybertetal.,U.S.Patent4,772,678(5eptember20,1988);Harris,U.S.Patent WO 96/05341 ~ 2 1 9 5 0 8 4 PCINS95/10271 4,847,350(Julyll,1989~;andGregoryetal.,U.S PatentS,089,591(Februaryl8,199Z). In summary,suitablemonomersarereactedinasolutionofno,.uA;di-;..yanddehydratingacid (the acid solvent) under nUIIOA;IJ;L;nY atmosphere with vigorous mixing and high shear at a lel~ dLulethatisincreased instep-wiseorrampedfashionfrom nomorethanabout 120'C
toatleastabout190~C SuitablesolventsforthepreparationofP8Zpolymerdopeinclude ~ cresol s and non-oxid izi ng acids. Exam ples of suitabl e aci d sol vents i ncl ude uu, ~ ~,I ,u,uI .o. i ~ acid, methanesulfonicacid,andhighly~u.-~e"L,~'~dsulfuricacidormixturesthereof. Preferably, the solvent acid is puly~-l ~u,~.hu. ic acid or methane sulfonic acid, but is most preferably UVI~-hU~UI IUI ;C acid.
o Thepolymercul--el-L,~-Liu--inthesolventispreferablyatleastabout7percentby weight,morepreferablyatleastabout10percentbyweight,andmostpreferablyatleast aboutl4percentbyweight. Themaximum~ull~ellLldLiullislimitedbythepracticalfactorsof handling,suchaspolymersolubilityanddopeviscosity. Thepolymer.u..~e...,aLiu..normally doesnotexceed30percentbyweight,andispreferablynoyle~Lel Ll,d--about20percentby weight. Oxidation inhibitors, de-glossing agents, coloring agents, and anti-static agents may also be added to the dope.
Thesepo'yL~...a-ùle,aredirectlyorseparatelyspunbyadryjetwetspinning methodasspundopedissolved in~.u~ l,u,,ul.u.icacid. Thepul~L~...d-ul.dopeispreferably flltered by being passed through a porous plate having a number of holes with a diameter of 20 1toSmm. Next,itpreferablypassesthroughaspacecalledameltpoolformedbytheporous plate surface and the spinning no2~71e back surface, and through a woven material or unwoven fabric of metal f bers contained therein. The dope is then spun through a spinneret having a numberofholesarranged inacircular,latticeorclovershape. Thea.-.7-._ ,Lofthe spinningholesonthespinneretandtheholedensitywillaffecttheabilityofthegastoflow 25 pastthefilamentsclosertothesourceofthegasandreachthefilamentsfurtheraway.
Figure 1 showsanexampleofaspinneretwhichmaybeusedintheprocessofthe first aspect of the invention. As shown in this figure, the holes of the spinning nozzle are dividedintogroupswhichareseparatedfromeachotherbysectionsofthespinneretwhich have no spinning holes. The hole density on the spinneret in both processes of the invention is 30 preferably at least above 2.0 holes/cm', more preferably least about 4.0 holeslcm', and most preferablyatleastabout6.0holes/cm2,butispreferablylessthanaboutlO.Oholes/cm2,(based onthespinneretareacoveredbytheholes,whichisalsoreferredtohereinasthe"active"
area). In general, higher hole densities are preferred from a productivity standpoint, although astheholedensityincreases,itbecomesmoredifficulttoconductthecoolinggasthroughthe35 filaments being extruded, in a manner sufficient to cool them at a uniform rate.
In the process of the first aspect of the invention, the spinneret is constructed such thatthe holes are divided into at leasttwo groups, more preferably at leastthree groups. The numberofgroupsispreferablylessthanten,sincethespaceonthespinneretreguiredforthe _5_ ..... , . . _ . . .... .. ::: , = _ . ... , _ . . _ _ = _ _ _ _ _ =_ . _ _ = , . .
WO96/05341 ~ l! r ~ 50~4 r~ J~J~
sections which have no holes will reduce the space available on the spinneret for holes. The patterns of the divided spinning hole groups are not especially limited but are preferably radially symmetric with respect to the~ center of the spinneret. Preferably, the width of the radial section(s) and the center section of the spinneret having no holes in the processes of both 5 aspects of the invention is at least about 5 mm and less than about 50 mm, more preferably less than about 10 mm; or is preferably at least about 3 times the minimum pitch of the holes, and less than about 30 times the minimum pitch of the holes.
Figure 2 shows a spinneret which is useful in the process of the second aspect of the invention. In the second aspect of the invention, there is a space in the middle of the 10 spinneret having no holes, and the holes need not be divided into sections. One advantage of this aspect of the invention is that once the spinning conditions are optimized for a given radial width of filaments (the distance between the outside of the active area to the inside of the activearea,definedinpartbythewidthofthespaceinthemiddleofthespinneret)atagiven pitch distance, different size spinnerets having a different number of holes may be designed 5 andutilizedunder,uL,La..Li~llythesamespinningconditions,solongastheholesinthe spinneretareconfiguredtomaintainthesameradialwidth. Theterm"annularpattern"as usedhereinmeansthatthespinningholesarearrangedonthespinnerettoleaveaspaceinthe centerofthe.."a,._ 'whichhasnoholes. Figure2illustratesanannularlatticepattern.
The dope fi I aments extruded through the spi nneret are cooled to a i , aLul e 2û less than the soli difying I , a LIA . ~1 of the dope by passing them through an air gap and i nto a washing bath containing a suitable washing fluid. Initially, as the filaments are extruded fromthespinneret,theypreferablypassthroughaquenchchamberwhichsurroundsthe filaments as they leave the spinneret. While the quench chamber length is optional, it is preferablylongenoughto providearelativelyconstantLc.,.~._.aLu,~atmosphereuponinitial 25 extrusi on from the spin neret such as with a fl ow of i nert gas across the fi I aments to maintain a Lt",~ Lu~from0~Cto100'Cinthequenchchamber. Oncethefilamentleavesthequench chamber, it can be exposed to atmospheric conditions until it is coagulated. The length of the quench chamber is preferably between 2 and 120 cm, but may be longer.
Thegasflowacrossthefilamentsisdirectedfromatleasttwodifferentdirections.
30 Preferably,anumberofgasjetsareuse,dtodirectthegasflowacrossradialportionsofthe filamentsfromasmanydirectionsasispractical. A!t~., luL;~-ly~ aseriesofbaffiesinsidethe quench chamber may be used to help direct gas flow therein, or a pressurized device surroundingthefilamentshavingascreenorfilter whichpermitsanevenlydistributedgas flow through the radial sections of filaments may also be utilized. The gas may originate either 35 from outside the al 1 ~ L of filame!nts, or from a source located in the middle of the al, ~ny~ L. It is believed, without intending to be bound, that a radial quench of the filaments by a gas coming from a number of directions around the filaments is highly desirable in terms of cooling all of the filaments at a uniform rate, permitting the cooling i , . .,Lu, ~ to ~ . WO 96/05341 , ~ 2 ~ 9 ~ 0 8 4 be more easily optimized for all of the filaments, and increasing the stability of the spinning line. Asthegastravelsacrossaradialportionofthea"~"~ ,.Loffilaments,itis continuously drawn downwards between the filaments. The temperature of the gas is preferably at Ieast about 30~C, more preferably at Ieast about 40~C, and most preferably at Ieast 5 about 50~C, but is preferably no greater than about 1 00~C, more preferably no greater than ~ about 90~C, and most preferabl y no greater than about 80~C.
A convenient means of washing the filaments as an initial washing step in a multi--step washing process is to run the filaments through a funnel-shaped solidifying bath, a multi--step water aspi rator, or other verti cal bath. Thereafter, the fi laments may be fu I ll, ~ . ~..,1,_1 in a bath utilizingwash rolls. Afterthefilamentsarepassedthroughthefirstwashing bath, theytraveloveratleastonedrivenroller. Themaximumspin/drawratiointheairgapwhich will ailow continuous stable spinning decreases as the filament deniers become thinner. Stable spinning of 1.5 denier filaments at a speed greater than 200 m/minutes is possible by the method of this invention. The average denier per filament (dpf) is preferably at least about 1.5, 15 andlessthanabout3~s~
The filaments are subsequently washed under conditions sufficient to preferably rem ove at I east a bout 98.0 wei ght percent of the solvent acid present in the fi laments, more preferably at least about 99 weight percent, and most preferably at least about 99.S weight percent. Suitablewashingfluidsincludeanyliquidwhichisanon-solventforthepolymer,but 20 which will dilute the acid solvent in the dope filament. Examples of washing fluids include water, methanol, acetone, and m ixtures of water and the solvent of which the ~ ulyL~ ,u! r dopeiscomprised,eitherinliquidorvaporform. Preferably,thedopeispreparedutiiizing,uul ~ ~hu~Jhu~ i. acid and the washi ng fl uid is a mixture of water and PUI~ U~ ,ufic acid.
Fu.Lh~..,,u,~,thewashingofthefilamentsmaybecarriedoutasamulti-stepprocess.
The washed filaments may be subsequently dried in a suitable drying process.
Fl.,LI,~,,,ult~itmayalsobedesirabletoapplyaspinfinishtothefilamentsbeforeorafterbeing dried, in orderto help protectthe filamentsfrom mechanical damage. To increasethe tensilemodulusofthefilament,theymaybeheat-treatedata~ Lu,egreaterthan300~C
or more preferably at a L~" I,U~ . ., Lu~ ~ greater than 450~C, but i s preferably less than 650~C.
The process of the invention is preferably carried out at a terminal velocity of at least about 2ûO m/minute, more preferably at least about 400 m/minute, and most preferably at least about 600 m/minute.
The filament utilized in the process of the invention may be combined with otherfilaments to form a mult filament fiber at any point during the process of the invention.
PROCESS FOR PREPARING POLYBENZAZOLE FILAMENTSAND FIBER
Thepresentinventionrelatestoaprocessforthepreparationofpu'~L_u-u~Lù
or pul~b,~ uLlliazole filaments and fibers.
Fiberspreparedfrompu'~L._.,LuA.,.ule(PBO)and,uulJb~lLuLll~ ùle(pBT) (hereinafter referred to as PBZ or uu~b_. ~L~Lu!~ polymers) may be prepared by first extruding asolutionofpol~b~,,L~Lulepolymerinamineralacid(apolymer''dope'')throughadieor spinneret to prepare a dope filament. The dope filament is then drawn across an air gap, washed in a bath comprising water or a mixture of water and a mineral acid, and then dried. If 1û multiplefilamentsareextrudedsimultaneously,theymaythenbecombinedintoa ~,.ulLiril..",_"Lfiberbefore,during, orafterthewashingstep.
As the filaments of pulrb~, IL~Lul~ dope are extruded, the high extensional viscosityofthedope,therapid coolingofthefilaments,andthedifferencesinthecoolingrates ofthefilamentsextrudedatthecenterofthespinneretascomparedtothoseextrudedatthe edge of the spi nneret, may ca use f requent breaks i n the filam ents as they are drawn across the air gap. Although this spinning stability problem can be reduced to some extent by using a slower spinning speed, and/or having a lower hole density on the spinneret, these methods are often less than desirable from the standpoint of productivity or equipment design. Since smaller diameter filaments are more desirable than larger diameter filaments which would be 20 normallyobtainedbytheuseofaspinnerethavinglargerorifices,thespin-drawratiomay needtobeincreasedsignificantlytodrawthefilaments~urri~ LlyLuproducesmaller diameter filaments, which may also cause breaks in the filaments.
Further, although the stability of the spinning line may be improved by decreasing the number of holes per spinneret (referred to hereafter as hole density), it 25 becomesnecessarytoincreasethenumberofspinneretsperspinningheadortoincreasethespinneretsizeinorderto.u,,Li,.~vu,lyspinalargenumberoffilamentsfromasinglespinning head However, such equipment~u,,ri_u,~Liu,,, may be lessthan desirable.
U5. Patents S,294,390 and S,385,702 disclose processes for increasing the stability of a spinning line by extruding poly.,~. ~L~ILulu filaments through a partially enclosed air gap 30 whichhasgasflowingthroughittocoolthefilamentsatarelativelyuniformL~,,,u~...LuAlthoughthismethodincreasesthestabilityofthespinningline,methodsforfurther increasing the spinning stability and the number of filaments which can be extruded per spin head while maintaining a relatively stable spinning line are desirable.
Inoneaspect,thisinventionisaprocessforthepreparationofpul~L~.,L~,Lu'~
35 filaments which comprises (a) extruding the filaments from a spinneret having at least 100 holes, which are arranged to form an annular pattern around the center of the spinneret, the center and at least two rac!ial sections of the spinneret having no holes and an average width which is at least about 3 times the minimum pitch of the holes; and (b) drawing the filaments . WO96/05341 . . PCT/US95/10271 through a quench chamber while pro~iding a substantially radial gas flow therein across the spinneret from at least two different directions.
In a second aspect, this invention is a process for the preparation of polybenzazole filaments which comprises (a) extruding the filaments from a spinneret having 5 at least 100 holes, which are arranged to form an annular pattern around the center of the spinneret, the center havi ng no holes elnd a n average width which i s at l east about 3 ti mes the minimum pitch of the holes; and (b) drawing the filaments through a quench chamber while providingasubstantiallyradialgasflowthereinthroughthefilamentsfromatleasttwo directions.
It has been d i scovered thist the process of the i nventi on provi des a means to prepare p~llyL~ ,,-..!t filaments and fibers which permits their spinning from spin-dies having a relatively high orifice density, but whlile maintaining relatively stable spinning conditions The stability of the spinning conditions creates a more efficient spinning process by minimizing thenumberoflinebreaks,insurestheuniformityofthefilamentbeingdrawn,whichallows one to optimize the cooli ng conditions of the fi la ments, which may i m prove the tensi le strengthandtensilemodulusofthefilelments. Theairflow~,~"~ L;l;Lybetweenfilaments ~ ' ' '~underthespinneretisimproved,thecoolingofthestrandsandthethinning profile becomes more uniform, and the! spinning process is stabiiized by use of the process of the invention. These and other advantages will be apparent from the description which 20 follows.
Figure 1 shows an example of a spinneret hole pattern for use in the process of the first aspect of the invention, as described below. Referrinq now to Figure 1, a spinneret (1) is shown, which is part of a group of holes (2), three groups of which are separated from each other by radial sections of the spinneret (3) which do not have holes, having a width (W).
25 Figure 2 shows an example of a spinneret hole pattern useful in the process of the second aspect of the invention.
The ,J~,lyl, . ,,,. ,. ~!~ filaments used in the process of the invention may beobtainedbyspinningadopecontainingapol~ L ~.I.O.~lepolymer. Asusedherein, 'p~lyL~.ILc~ ''referstopulyL~ lAoL~ (PB0)I,~""op.,';. rs,polyL~..L..Ll,i.,L~J!e(PBT) 30 I.,,,.lup~Jl),..~.,,andrandom,sequentialorblock...~,ulJ.,,~ dpolymerofPBOandPBT.
P.,IJL~"L~.Ac,L~,le"~ L~.,LuLlli~Lu~andrandom~sequential~orblock~up~
polymers thereof are described, for exalmple, in " Liquid Crystalline Polymer Compositions, ProcessandProducts,"byWolfeet.al,lJ.S.Patent4,703,1û3(0ctober27,19B7); "Liquid Crystalline Polymer Compositions, Process and Products, " U.S. Patent 4,533,692 (August 6, 35 1985); " Liquid Crystalline Poly(2,6~ LULI li~LOl~) Composition, Process and Products,"
US.Patent4,533,724(August6,1985);"LiquidCrystallinePolymerCompositions,Processand Products," U.S.Patent4,533,693(August6, 1985); "TI~ OUA; ioLi.~l) StableArticulated p-Be~ and p-Benzobisthiazole Polymers" by Evers, U.S. Patent 4,539,567 ~ WO96105341 , ~r r~~~ r- 2 1 95084 PCTIUS9~110271 (Novemberl6,1982);and"MethodforMakingHeterocyclicBlockCopolymer,"byTsai,U.5.
Patent4,578,432 (March 25,1986).
The structural units present in PBZ polymer are preferably selected so that the polymer is Iyotropic liquid crystalline. Preferred monomer units are illustrated below in Formulas l-VIII. The polymer more preferably consists essentially of monomer units selected fromthoseillustratedbelow~andmostpreferablyconsistsessentiallyofcis-~uu:yb-~lLu~aL
trans-uulrv_.--u,....ul~,,ortrans-,uulrL .~utl~ !e.
, o ~/ ~ '>{ ~t cis-polybenzoxazole Poly[benzo(1,2-d:5,4-d')bisoxazole-2,6-diyl-1,4-phenylene]
2C trans-polybPn7nY~7ole Poly[benzo(1,2-d:4,5-d')bisoxazole-2,6-diyl-1,4-phenylene]
2s ~ / ~ / ~ ~ III
trans-polybenzothiazole .W096/0s341 ''~ 2 I q5084 pCT~S9~10271 N ~ ~ N ~ ~ IV
ci~-polybenzothiazole ~ , N
~ ~0 J
Poly(2,5-benzoxazole) ~ ~S ~ VI
Poly(2,5-benzothiazole) ~ ~ 0 ~ ' VII
Poly(2,6-bPn7~Y~7ole) and ~ ~ S ~ ~ VIII
Poly(2,6-benzothiazole) Suitable l,ol ;L~ polymers or copolymers and dopes can be synthesized by known procedures, such as those described in Wolfe et al., U.S. Patent 4,'i33,693 (August6,1985~;5ybertetal.,U.S.Patent4,772,678(5eptember20,1988);Harris,U.S.Patent WO 96/05341 ~ 2 1 9 5 0 8 4 PCINS95/10271 4,847,350(Julyll,1989~;andGregoryetal.,U.S PatentS,089,591(Februaryl8,199Z). In summary,suitablemonomersarereactedinasolutionofno,.uA;di-;..yanddehydratingacid (the acid solvent) under nUIIOA;IJ;L;nY atmosphere with vigorous mixing and high shear at a lel~ dLulethatisincreased instep-wiseorrampedfashionfrom nomorethanabout 120'C
toatleastabout190~C SuitablesolventsforthepreparationofP8Zpolymerdopeinclude ~ cresol s and non-oxid izi ng acids. Exam ples of suitabl e aci d sol vents i ncl ude uu, ~ ~,I ,u,uI .o. i ~ acid, methanesulfonicacid,andhighly~u.-~e"L,~'~dsulfuricacidormixturesthereof. Preferably, the solvent acid is puly~-l ~u,~.hu. ic acid or methane sulfonic acid, but is most preferably UVI~-hU~UI IUI ;C acid.
o Thepolymercul--el-L,~-Liu--inthesolventispreferablyatleastabout7percentby weight,morepreferablyatleastabout10percentbyweight,andmostpreferablyatleast aboutl4percentbyweight. Themaximum~ull~ellLldLiullislimitedbythepracticalfactorsof handling,suchaspolymersolubilityanddopeviscosity. Thepolymer.u..~e...,aLiu..normally doesnotexceed30percentbyweight,andispreferablynoyle~Lel Ll,d--about20percentby weight. Oxidation inhibitors, de-glossing agents, coloring agents, and anti-static agents may also be added to the dope.
Thesepo'yL~...a-ùle,aredirectlyorseparatelyspunbyadryjetwetspinning methodasspundopedissolved in~.u~ l,u,,ul.u.icacid. Thepul~L~...d-ul.dopeispreferably flltered by being passed through a porous plate having a number of holes with a diameter of 20 1toSmm. Next,itpreferablypassesthroughaspacecalledameltpoolformedbytheporous plate surface and the spinning no2~71e back surface, and through a woven material or unwoven fabric of metal f bers contained therein. The dope is then spun through a spinneret having a numberofholesarranged inacircular,latticeorclovershape. Thea.-.7-._ ,Lofthe spinningholesonthespinneretandtheholedensitywillaffecttheabilityofthegastoflow 25 pastthefilamentsclosertothesourceofthegasandreachthefilamentsfurtheraway.
Figure 1 showsanexampleofaspinneretwhichmaybeusedintheprocessofthe first aspect of the invention. As shown in this figure, the holes of the spinning nozzle are dividedintogroupswhichareseparatedfromeachotherbysectionsofthespinneretwhich have no spinning holes. The hole density on the spinneret in both processes of the invention is 30 preferably at least above 2.0 holes/cm', more preferably least about 4.0 holeslcm', and most preferablyatleastabout6.0holes/cm2,butispreferablylessthanaboutlO.Oholes/cm2,(based onthespinneretareacoveredbytheholes,whichisalsoreferredtohereinasthe"active"
area). In general, higher hole densities are preferred from a productivity standpoint, although astheholedensityincreases,itbecomesmoredifficulttoconductthecoolinggasthroughthe35 filaments being extruded, in a manner sufficient to cool them at a uniform rate.
In the process of the first aspect of the invention, the spinneret is constructed such thatthe holes are divided into at leasttwo groups, more preferably at leastthree groups. The numberofgroupsispreferablylessthanten,sincethespaceonthespinneretreguiredforthe _5_ ..... , . . _ . . .... .. ::: , = _ . ... , _ . . _ _ = _ _ _ _ _ =_ . _ _ = , . .
WO96/05341 ~ l! r ~ 50~4 r~ J~J~
sections which have no holes will reduce the space available on the spinneret for holes. The patterns of the divided spinning hole groups are not especially limited but are preferably radially symmetric with respect to the~ center of the spinneret. Preferably, the width of the radial section(s) and the center section of the spinneret having no holes in the processes of both 5 aspects of the invention is at least about 5 mm and less than about 50 mm, more preferably less than about 10 mm; or is preferably at least about 3 times the minimum pitch of the holes, and less than about 30 times the minimum pitch of the holes.
Figure 2 shows a spinneret which is useful in the process of the second aspect of the invention. In the second aspect of the invention, there is a space in the middle of the 10 spinneret having no holes, and the holes need not be divided into sections. One advantage of this aspect of the invention is that once the spinning conditions are optimized for a given radial width of filaments (the distance between the outside of the active area to the inside of the activearea,definedinpartbythewidthofthespaceinthemiddleofthespinneret)atagiven pitch distance, different size spinnerets having a different number of holes may be designed 5 andutilizedunder,uL,La..Li~llythesamespinningconditions,solongastheholesinthe spinneretareconfiguredtomaintainthesameradialwidth. Theterm"annularpattern"as usedhereinmeansthatthespinningholesarearrangedonthespinnerettoleaveaspaceinthe centerofthe.."a,._ 'whichhasnoholes. Figure2illustratesanannularlatticepattern.
The dope fi I aments extruded through the spi nneret are cooled to a i , aLul e 2û less than the soli difying I , a LIA . ~1 of the dope by passing them through an air gap and i nto a washing bath containing a suitable washing fluid. Initially, as the filaments are extruded fromthespinneret,theypreferablypassthroughaquenchchamberwhichsurroundsthe filaments as they leave the spinneret. While the quench chamber length is optional, it is preferablylongenoughto providearelativelyconstantLc.,.~._.aLu,~atmosphereuponinitial 25 extrusi on from the spin neret such as with a fl ow of i nert gas across the fi I aments to maintain a Lt",~ Lu~from0~Cto100'Cinthequenchchamber. Oncethefilamentleavesthequench chamber, it can be exposed to atmospheric conditions until it is coagulated. The length of the quench chamber is preferably between 2 and 120 cm, but may be longer.
Thegasflowacrossthefilamentsisdirectedfromatleasttwodifferentdirections.
30 Preferably,anumberofgasjetsareuse,dtodirectthegasflowacrossradialportionsofthe filamentsfromasmanydirectionsasispractical. A!t~., luL;~-ly~ aseriesofbaffiesinsidethe quench chamber may be used to help direct gas flow therein, or a pressurized device surroundingthefilamentshavingascreenorfilter whichpermitsanevenlydistributedgas flow through the radial sections of filaments may also be utilized. The gas may originate either 35 from outside the al 1 ~ L of filame!nts, or from a source located in the middle of the al, ~ny~ L. It is believed, without intending to be bound, that a radial quench of the filaments by a gas coming from a number of directions around the filaments is highly desirable in terms of cooling all of the filaments at a uniform rate, permitting the cooling i , . .,Lu, ~ to ~ . WO 96/05341 , ~ 2 ~ 9 ~ 0 8 4 be more easily optimized for all of the filaments, and increasing the stability of the spinning line. Asthegastravelsacrossaradialportionofthea"~"~ ,.Loffilaments,itis continuously drawn downwards between the filaments. The temperature of the gas is preferably at Ieast about 30~C, more preferably at Ieast about 40~C, and most preferably at Ieast 5 about 50~C, but is preferably no greater than about 1 00~C, more preferably no greater than ~ about 90~C, and most preferabl y no greater than about 80~C.
A convenient means of washing the filaments as an initial washing step in a multi--step washing process is to run the filaments through a funnel-shaped solidifying bath, a multi--step water aspi rator, or other verti cal bath. Thereafter, the fi laments may be fu I ll, ~ . ~..,1,_1 in a bath utilizingwash rolls. Afterthefilamentsarepassedthroughthefirstwashing bath, theytraveloveratleastonedrivenroller. Themaximumspin/drawratiointheairgapwhich will ailow continuous stable spinning decreases as the filament deniers become thinner. Stable spinning of 1.5 denier filaments at a speed greater than 200 m/minutes is possible by the method of this invention. The average denier per filament (dpf) is preferably at least about 1.5, 15 andlessthanabout3~s~
The filaments are subsequently washed under conditions sufficient to preferably rem ove at I east a bout 98.0 wei ght percent of the solvent acid present in the fi laments, more preferably at least about 99 weight percent, and most preferably at least about 99.S weight percent. Suitablewashingfluidsincludeanyliquidwhichisanon-solventforthepolymer,but 20 which will dilute the acid solvent in the dope filament. Examples of washing fluids include water, methanol, acetone, and m ixtures of water and the solvent of which the ~ ulyL~ ,u! r dopeiscomprised,eitherinliquidorvaporform. Preferably,thedopeispreparedutiiizing,uul ~ ~hu~Jhu~ i. acid and the washi ng fl uid is a mixture of water and PUI~ U~ ,ufic acid.
Fu.Lh~..,,u,~,thewashingofthefilamentsmaybecarriedoutasamulti-stepprocess.
The washed filaments may be subsequently dried in a suitable drying process.
Fl.,LI,~,,,ult~itmayalsobedesirabletoapplyaspinfinishtothefilamentsbeforeorafterbeing dried, in orderto help protectthe filamentsfrom mechanical damage. To increasethe tensilemodulusofthefilament,theymaybeheat-treatedata~ Lu,egreaterthan300~C
or more preferably at a L~" I,U~ . ., Lu~ ~ greater than 450~C, but i s preferably less than 650~C.
The process of the invention is preferably carried out at a terminal velocity of at least about 2ûO m/minute, more preferably at least about 400 m/minute, and most preferably at least about 600 m/minute.
The filament utilized in the process of the invention may be combined with otherfilaments to form a mult filament fiber at any point during the process of the invention.
3 5 Preferabl y, however, the fi la ments are combi ned j ust prior to, or duri ng, the fi rst washi ng bath.
In addition, when a large number of filaments are spun simultaneously, the filaments can be -.WO96/05341 ~ . 2 t 95~84 ~ C~" ~
divided into several groups by a guide after the initial washing step, as a means to prepare morethanone".ulLiril~...._.,Lfiberfromthesamespinneret, The tensile strength of the filaments produced by the process of the invention is preferably at least about 600 Ksi (600,000 psi), and is more preferably at least about 800 Ksi.
5 Thetensilemodulusofthefilamentsproducedbytheprocessoftheinventionispreferablyat least about 20 Msi (30 x 106 psi), more preferably at least about 30 Msi.
Examples The following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. The following methods for measuring the physical 10 propertiesofthefilamentsandfibersandthespinningstabilitywereusedtoobtainthedata reported in Table 1.
Method for Measurinq the Intrinsic Viscositv Thereducedviscosityat30~Cwasobtainedbydissolvinguol~b~...aL~ into methanesulfonicacidatvarious~un~cllLlaLiull~andthen~ apulaLillytozero~oll~llLlaL
MonofilamentDenier A sample of fiber was maintained at a t~ . aLul e of 2o + 2oc and a relative humidityof65+2percentfor18hours,a90mportionofthesamplewastaken,itsweightwas measured, and the measured weightwas converted into a weight of 9000 m to obtain the fiber denier. The ' ' denier was calculated from the fiber bundle denier by dividing by 20 the number of ' ' ~ t, in the bundle.
Method for Determininq the Maximum sPin/draw ratio Thefiberstrandwastakenbyapullingroller(group)withoutcontactingitwitha washingfluid~thesaidrolleruil~ul~relelllialspeedwasincreasedbyacertainrateofincrease andthemaximumspinldrawratiowasdefinedastheratioofthemaximumspinningspeedat 25 which f iber breaking occurred (Vw) to the ejecti on I ine speed within a hol e (Vo) obta i ned from â single hole ejection amount and the hole diameter, or VwNo.
Method for evaluatinq the sPinninq stabilitv Spinningwasperforn;edataspeedof200m/minute,untilastatistically significantrateoffiberbreakagewasobtained,whichwasthenconvertedtorepresentthe 30 number of breaks over an 8 hour period.
Method for measurinq fuzz (filament breakaae~
A wound roll of washed and dried fiber was unwound at a rate of 100 m/minute, andthefuzzwascountedbyaul,uLu~ L,ictubetypefuzzdetectoruntilastatistically si gni fi cant n umber was obtai ned, which was then converted i nto a rate of filam ent breakage 35 per l O,ooo m.
MethodformeasurinatheTensileStrenclth,TensileModulus,andElonqationatBreak The averages of the tensile strength, tensile modulus, and elongation at break wereobtainedfrommca~u,c..,~.,L,atagripintervalofScm,astretchingspeedoflOOpercent -~ . WO 96/05341 ' ' 2 1 9 50 8 4 PCT/US9S
per minute and n = 30 using a Tensilon-~ machine from Orientech (Inc.) Company, in accordance with Test Method No. ~IS L 1013 (1981).
Example 1 Aportionof4,6-diamino-1,3benzenedi~.1 iil.,l~.~l,lv.ide(50.0g,0.23smol)was stirredwith200gp~,.r"1,1"~,1,u,icacid(withaphosphoruspentoxidecontentof83.3weight percent) under a nitrogen gas flow at 40'C for 12 hours. The temperature of the mixture was raised to 60~C and hydrochloric acid was removed under a reduced pressure of about 50 mm Hg. Terephthalicacid(39.0g,0.236mol)andphosphoruspentoxide(103g)wereaddedtothe above and the mixture was polymerized under a nitrogen gas flow at 60~C for 8 hours and at 10 120~C for 9 hours, at 150~C for 1 S hours; and at 180~C for 24 hours. F~lyL_. ,.ale polymer solution obtained thus was used as dope for spinning. The intrinsic viscosity of the polymer was obtainedbymixingasampleofthesolutionwithwaterinablendertoobtainawashedsample of the polymer particles. The polymer particles were redissolved in methane sulfonic acid, the viscosity was measured at 215~C and the intrinsic viscosity 11] was 30.5 dl/g.
5 Thepolymer.o.,.e.. L,alio,.ofthedopewasl4.0weightpercent,andthe ~un~e~ Li~l) of the solvent of the case of using phosphorus pentoxide as p~ u~ ic ~u..~.u~;Liw~was86.0weightpercent. Afterkneadingthedopeusingatwin-screwextruder and degassing the dope, it was transferred to the spinning head via a gear pump. It was passed throughaparticlefillerlayerofalayerwidthofSOmm(withvariedaveraqeparticlediameter20 andaverageaspectratio)composedofinorganicsubstancesatthespinninghead,passed through a dispersing plate with a multiple number of holes of a diameter of 2 mm punctured in a frame form, and then passed through a laminate layer of a rate of permeadon of particles of above 15 mm of 2.5 percent, constructed from a metal fiber fabric of a diameter of 10 mm.
The dope was spun at a ~ . a Lu, . of 160~C and an ejection rate of 64.2 25 g~mi nute by being passed through a spi nneret having a hol e density of 4.8 holes/cm2 with 284 flne holes of a hole diameter of 0.20 mm, a hole length of 0.20 m, and an entrance angle of 20 degrees, divided into groups by a section width (vV) of 8.6 mm as shown in Figure 1. The number of orifice holes was preferably at least about 500, more preferably at least about 1,000, and most preferably at I east about 2,500.
The spun fliaments were then guided through a quench chamber providing an air flow through the filaments from at least two directions into a funnel-shaped coagulating apparatuscirculatinga20percentaqueoussolutionofp.,1r,-1,."~,1,."icacidmaintainedata temperature of 22 1 2~C, installed 35 cm below the spinning nozzle surface. Furthermore, extractionandwashingofphosphoricacidinthefiberstrandwereperformedbyrollingthe 35 spunflberonaroiler(group)installedattheloweroutsideofthesaidextractionbathto change the running direction of the fiber strand, releasing the spinning tension by rolling the flber strand on a roller (group), while spraying water on the running flber strand by a spraying apparatusinstallednearthesaidroller. Thefiberwasthenpassedthroughahotaircirculatory g .WO 9610S341 I 2 I q 50 8 4 PCT/US9S110271 ~
dryertodecreaseitswatercontenttolessthan2.0weightpercent,andthenwoundataspeed of ZOO m/minutes. The results are shown below in Table 1.
Examples 2-1 1 Fibers were prepared using the method described in Example 1, with following 5 exceptions: For Exampies 2 and 3, the diameter of the holes in the spinneret was 0.20 mm, the hol e I ength was 0. 20 m m, the entrance angl e to the spi n ning holes was 20~C, and the hole density was 3.4 and 4.0 holeslcm2, respectively, for each example. For examples 4 and 5, the width of the sections divided into growps of spinning holes (W) was changed to 6.5 mm (Example 4), and 9.9 mm (Example 5). In Examples 6-8, the spinnerets have 2, 6, and 8 groups 10 of spinningholes,respectively. InExamples9-11,thesingleholeejectionamountwasO.69 glminute, and the ejected dope filament was cooled at the air gap area by applying a gas flow at an average flow speed of 0.7 mlsecond at a i , ., Lul .: of sS~C to 95~C The results are shown in Tables I and 11.
~ . WO96/05341 .i ' i ~ PCTIUS9~/10271 -- 2 t 9 5~B4 U~
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In addition, when a large number of filaments are spun simultaneously, the filaments can be -.WO96/05341 ~ . 2 t 95~84 ~ C~" ~
divided into several groups by a guide after the initial washing step, as a means to prepare morethanone".ulLiril~...._.,Lfiberfromthesamespinneret, The tensile strength of the filaments produced by the process of the invention is preferably at least about 600 Ksi (600,000 psi), and is more preferably at least about 800 Ksi.
5 Thetensilemodulusofthefilamentsproducedbytheprocessoftheinventionispreferablyat least about 20 Msi (30 x 106 psi), more preferably at least about 30 Msi.
Examples The following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. The following methods for measuring the physical 10 propertiesofthefilamentsandfibersandthespinningstabilitywereusedtoobtainthedata reported in Table 1.
Method for Measurinq the Intrinsic Viscositv Thereducedviscosityat30~Cwasobtainedbydissolvinguol~b~...aL~ into methanesulfonicacidatvarious~un~cllLlaLiull~andthen~ apulaLillytozero~oll~llLlaL
MonofilamentDenier A sample of fiber was maintained at a t~ . aLul e of 2o + 2oc and a relative humidityof65+2percentfor18hours,a90mportionofthesamplewastaken,itsweightwas measured, and the measured weightwas converted into a weight of 9000 m to obtain the fiber denier. The ' ' denier was calculated from the fiber bundle denier by dividing by 20 the number of ' ' ~ t, in the bundle.
Method for Determininq the Maximum sPin/draw ratio Thefiberstrandwastakenbyapullingroller(group)withoutcontactingitwitha washingfluid~thesaidrolleruil~ul~relelllialspeedwasincreasedbyacertainrateofincrease andthemaximumspinldrawratiowasdefinedastheratioofthemaximumspinningspeedat 25 which f iber breaking occurred (Vw) to the ejecti on I ine speed within a hol e (Vo) obta i ned from â single hole ejection amount and the hole diameter, or VwNo.
Method for evaluatinq the sPinninq stabilitv Spinningwasperforn;edataspeedof200m/minute,untilastatistically significantrateoffiberbreakagewasobtained,whichwasthenconvertedtorepresentthe 30 number of breaks over an 8 hour period.
Method for measurinq fuzz (filament breakaae~
A wound roll of washed and dried fiber was unwound at a rate of 100 m/minute, andthefuzzwascountedbyaul,uLu~ L,ictubetypefuzzdetectoruntilastatistically si gni fi cant n umber was obtai ned, which was then converted i nto a rate of filam ent breakage 35 per l O,ooo m.
MethodformeasurinatheTensileStrenclth,TensileModulus,andElonqationatBreak The averages of the tensile strength, tensile modulus, and elongation at break wereobtainedfrommca~u,c..,~.,L,atagripintervalofScm,astretchingspeedoflOOpercent -~ . WO 96/05341 ' ' 2 1 9 50 8 4 PCT/US9S
per minute and n = 30 using a Tensilon-~ machine from Orientech (Inc.) Company, in accordance with Test Method No. ~IS L 1013 (1981).
Example 1 Aportionof4,6-diamino-1,3benzenedi~.1 iil.,l~.~l,lv.ide(50.0g,0.23smol)was stirredwith200gp~,.r"1,1"~,1,u,icacid(withaphosphoruspentoxidecontentof83.3weight percent) under a nitrogen gas flow at 40'C for 12 hours. The temperature of the mixture was raised to 60~C and hydrochloric acid was removed under a reduced pressure of about 50 mm Hg. Terephthalicacid(39.0g,0.236mol)andphosphoruspentoxide(103g)wereaddedtothe above and the mixture was polymerized under a nitrogen gas flow at 60~C for 8 hours and at 10 120~C for 9 hours, at 150~C for 1 S hours; and at 180~C for 24 hours. F~lyL_. ,.ale polymer solution obtained thus was used as dope for spinning. The intrinsic viscosity of the polymer was obtainedbymixingasampleofthesolutionwithwaterinablendertoobtainawashedsample of the polymer particles. The polymer particles were redissolved in methane sulfonic acid, the viscosity was measured at 215~C and the intrinsic viscosity 11] was 30.5 dl/g.
5 Thepolymer.o.,.e.. L,alio,.ofthedopewasl4.0weightpercent,andthe ~un~e~ Li~l) of the solvent of the case of using phosphorus pentoxide as p~ u~ ic ~u..~.u~;Liw~was86.0weightpercent. Afterkneadingthedopeusingatwin-screwextruder and degassing the dope, it was transferred to the spinning head via a gear pump. It was passed throughaparticlefillerlayerofalayerwidthofSOmm(withvariedaveraqeparticlediameter20 andaverageaspectratio)composedofinorganicsubstancesatthespinninghead,passed through a dispersing plate with a multiple number of holes of a diameter of 2 mm punctured in a frame form, and then passed through a laminate layer of a rate of permeadon of particles of above 15 mm of 2.5 percent, constructed from a metal fiber fabric of a diameter of 10 mm.
The dope was spun at a ~ . a Lu, . of 160~C and an ejection rate of 64.2 25 g~mi nute by being passed through a spi nneret having a hol e density of 4.8 holes/cm2 with 284 flne holes of a hole diameter of 0.20 mm, a hole length of 0.20 m, and an entrance angle of 20 degrees, divided into groups by a section width (vV) of 8.6 mm as shown in Figure 1. The number of orifice holes was preferably at least about 500, more preferably at least about 1,000, and most preferably at I east about 2,500.
The spun fliaments were then guided through a quench chamber providing an air flow through the filaments from at least two directions into a funnel-shaped coagulating apparatuscirculatinga20percentaqueoussolutionofp.,1r,-1,."~,1,."icacidmaintainedata temperature of 22 1 2~C, installed 35 cm below the spinning nozzle surface. Furthermore, extractionandwashingofphosphoricacidinthefiberstrandwereperformedbyrollingthe 35 spunflberonaroiler(group)installedattheloweroutsideofthesaidextractionbathto change the running direction of the fiber strand, releasing the spinning tension by rolling the flber strand on a roller (group), while spraying water on the running flber strand by a spraying apparatusinstallednearthesaidroller. Thefiberwasthenpassedthroughahotaircirculatory g .WO 9610S341 I 2 I q 50 8 4 PCT/US9S110271 ~
dryertodecreaseitswatercontenttolessthan2.0weightpercent,andthenwoundataspeed of ZOO m/minutes. The results are shown below in Table 1.
Examples 2-1 1 Fibers were prepared using the method described in Example 1, with following 5 exceptions: For Exampies 2 and 3, the diameter of the holes in the spinneret was 0.20 mm, the hol e I ength was 0. 20 m m, the entrance angl e to the spi n ning holes was 20~C, and the hole density was 3.4 and 4.0 holeslcm2, respectively, for each example. For examples 4 and 5, the width of the sections divided into growps of spinning holes (W) was changed to 6.5 mm (Example 4), and 9.9 mm (Example 5). In Examples 6-8, the spinnerets have 2, 6, and 8 groups 10 of spinningholes,respectively. InExamples9-11,thesingleholeejectionamountwasO.69 glminute, and the ejected dope filament was cooled at the air gap area by applying a gas flow at an average flow speed of 0.7 mlsecond at a i , ., Lul .: of sS~C to 95~C The results are shown in Tables I and 11.
~ . WO96/05341 .i ' i ~ PCTIUS9~/10271 -- 2 t 9 5~B4 U~
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Z S Q Z C U, 8 ' Z - ' ~ b. Q~ EO EO~
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8E ~~cAJ ~E 1 ~ ~ --C~ 8E ~ K 8 C C 'C
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Claims (11)
1. A process for the preparation of polybenzazole filaments which comprises (a) extruding the filaments from a spinneret having at least 100 holes, which are arranged to form an annular pattern around the center of the spinneret, the center and at least two radial sections of the spinneret having no holes and an average width which is at least about 3 times the minimum pitch of the holes; and (b) drawing the filaments through a quench chamber while providing a substantially radial gas flow therein across the spinneret from at least two different directions.
2. The process of Claim 1 wherein the spinneret has at least 500 holes.
3. The process of Claim 1 wherein the spinneret has at least 1,000 holes.
4. The process of Claim 1 wherein the spinneret hole density is at least about 4.0 holes/cm2.
5. The process of Claim 1 wherein the spinneret hole density is at least about 6.0 holes/cm2.
6. A process for the preparation of polybenzazole filaments which comprises (a) extruding the filaments from a spinneret having at least 100 holes, which are arranged to form an annular pattern around the center of the spinneret, the center having no holes and an average width which is at least about 3 times the minimum pitch of the holes; and (b) drawing the filaments through a quench chamber while providing a substantially gas flow therein through the filaments from at least two directions.
7. The process of Claim 6 wherein the spinneret has at least 500 holes.
8. The process of Claim 6 wherein the spinneret has at least 1,000 holes.
9. The process of Claim 6 wherein the hole density is at least about 4.0 holes/cm2.
10. The process of Claim 6 wherein the hole density is at least about 6.0 holes/cm2.
11. A process for the preparation of polybenzazole filaments which comprises extruding the filaments from a spinneret having at least 100 holes, which are arranged to form an annular pattern around the center of the spinneret, the center and at least two radial sections of the spinneret having no holes and an average width which is at least about 3 times the minimum pitch of the holes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06-190635 | 1994-08-12 | ||
| JP19063594A JP3463768B2 (en) | 1994-08-12 | 1994-08-12 | Method for producing polybenzazole fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2195084A1 true CA2195084A1 (en) | 1996-02-22 |
Family
ID=16261358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2195084 Abandoned CA2195084A1 (en) | 1994-08-12 | 1995-08-10 | Process for preparing polybenzazole filaments and fiber |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0804639B1 (en) |
| JP (1) | JP3463768B2 (en) |
| CA (1) | CA2195084A1 (en) |
| DE (1) | DE69534504T2 (en) |
| ES (1) | ES2246054T3 (en) |
| WO (1) | WO1996005341A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3748014B2 (en) † | 1999-08-27 | 2006-02-22 | ユニ・チャーム株式会社 | Absorbent articles |
| CN102021664A (en) * | 2010-12-30 | 2011-04-20 | 张家港欣阳化纤有限公司 | Spinneret plate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2932851A (en) * | 1959-01-16 | 1960-04-19 | Courtaulds Inc | Spinning jet and process of using same |
| US5296185A (en) * | 1992-12-03 | 1994-03-22 | The Dow Chemical Company | Method for spinning a polybenzazole fiber |
| US5294390A (en) * | 1992-12-03 | 1994-03-15 | The Dow Chemical Company | Method for rapid spinning of a polybenzazole fiber |
-
1994
- 1994-08-12 JP JP19063594A patent/JP3463768B2/en not_active Expired - Lifetime
-
1995
- 1995-08-10 EP EP95929496A patent/EP0804639B1/en not_active Expired - Lifetime
- 1995-08-10 CA CA 2195084 patent/CA2195084A1/en not_active Abandoned
- 1995-08-10 DE DE69534504T patent/DE69534504T2/en not_active Expired - Fee Related
- 1995-08-10 ES ES95929496T patent/ES2246054T3/en not_active Expired - Lifetime
- 1995-08-10 WO PCT/US1995/010271 patent/WO1996005341A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| ES2246054T3 (en) | 2006-02-01 |
| WO1996005341A1 (en) | 1996-02-22 |
| DE69534504T2 (en) | 2006-06-29 |
| DE69534504D1 (en) | 2006-02-16 |
| EP0804639A4 (en) | 1997-11-12 |
| EP0804639B1 (en) | 2005-10-05 |
| JPH0860436A (en) | 1996-03-05 |
| EP0804639A1 (en) | 1997-11-05 |
| JP3463768B2 (en) | 2003-11-05 |
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