CA1170011A - High-modulus polyacrylonitrile filaments and fibers and a process for their production - Google Patents
High-modulus polyacrylonitrile filaments and fibers and a process for their productionInfo
- Publication number
- CA1170011A CA1170011A CA000382253A CA382253A CA1170011A CA 1170011 A CA1170011 A CA 1170011A CA 000382253 A CA000382253 A CA 000382253A CA 382253 A CA382253 A CA 382253A CA 1170011 A CA1170011 A CA 1170011A
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- CA
- Canada
- Prior art keywords
- filaments
- stretching
- filament
- tex
- acrylonitrile
- 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.)
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Abstract of the disclosure:
The invention relates to filaments and fibers which comprises polyacrylinitrile or acrylinitrile co-polymers with a content of acrylonitrile units of at least 70% by weight preferably 90 or 99 % by weight, and which have an initial modulus of more than 1,300 cN/tex. The initial modulus is preferably 1,400 to 2,200 cN/tex and the tensile strength is at least 50 cN/tex at elongations at break of at most 15 %.
Such filaments and fibers can be obtained by customary spinning, wet stretching, drying of -the filaments on hot drums and subsequent con-tact stretching of at least 1:1.5, the overall stretching being at least 1:9, prefer-ably 1:10 to 1:25.
The resulting products distinguish themselves, in particular, when used in industrial fields, such as, for example, for the production of filaments intended for conversion -to carbon fibers, as reinforcing fibers for organic and inorganic materials and for the production of awnings, filters and the like.
The invention relates to filaments and fibers which comprises polyacrylinitrile or acrylinitrile co-polymers with a content of acrylonitrile units of at least 70% by weight preferably 90 or 99 % by weight, and which have an initial modulus of more than 1,300 cN/tex. The initial modulus is preferably 1,400 to 2,200 cN/tex and the tensile strength is at least 50 cN/tex at elongations at break of at most 15 %.
Such filaments and fibers can be obtained by customary spinning, wet stretching, drying of -the filaments on hot drums and subsequent con-tact stretching of at least 1:1.5, the overall stretching being at least 1:9, prefer-ably 1:10 to 1:25.
The resulting products distinguish themselves, in particular, when used in industrial fields, such as, for example, for the production of filaments intended for conversion -to carbon fibers, as reinforcing fibers for organic and inorganic materials and for the production of awnings, filters and the like.
Description
~ 1 7~0 ~ ~
.
s The invention relates to filaments and fibers of polyacryloni-trile or polyacrylonitrile copolymers, which are predominan-tly buil-t up from acryloni-trile elements and which have an initial modulu~ - based on 100 % elongation - of greater than 1,300 cN/tex, process for -the production of such filaments and fibers is also described.
'It is known that polyacrylonitrile filament tow can be produced by combined wet and contac-t stretching.
10 Thus, for e~ample, a process in which the filamen-ts are dried, with free shrinkage allowed, after wet stretching to four to five times their length is claimed, for example, in ~erman Offenlegungsschrift 2,156,88l~.
~uring this drying in a heated gas at 135 to 145C, 15 experience shows that the filaments shrink by more than 30 %. Thereafter, dry stretching to at least 1.4 times their length is envisaged, As proved by -the examples of this previous literature, it is possible, under -these conditions. to obtain indivldual ~ilament s-trengths of 4.8 g/den ~-42,4 cN/tex (Example 1 f) or an initial modulus of 107.2 g/den - 946 cN/tex (Example 1 h)~
The maxim~n e~fective stretching in the exampIes was abou-t 1:6,8; effective stret;ching is to be understood as the actual s~retching effec-tive, for example, on the denier of t'rlr;~ individual filaznen-ts~ I-t can be calcul-ated from the individuaL stre-tch values, bu-t these must also be corrected by the shrink~lge during slack clrying.
7~
The texti.le values of the ~ilaments procluced according -to the previ.ous li-terature rnust still be regarded as inadequa-te for industrial fields of use.
There have t7nerefore been attempts, in par-ticular~ to increase the initial modulus of such :Cibers s-til].
further.
Thus, for example, German O~fenlegungsschrif-t
.
s The invention relates to filaments and fibers of polyacryloni-trile or polyacrylonitrile copolymers, which are predominan-tly buil-t up from acryloni-trile elements and which have an initial modulu~ - based on 100 % elongation - of greater than 1,300 cN/tex, process for -the production of such filaments and fibers is also described.
'It is known that polyacrylonitrile filament tow can be produced by combined wet and contac-t stretching.
10 Thus, for e~ample, a process in which the filamen-ts are dried, with free shrinkage allowed, after wet stretching to four to five times their length is claimed, for example, in ~erman Offenlegungsschrift 2,156,88l~.
~uring this drying in a heated gas at 135 to 145C, 15 experience shows that the filaments shrink by more than 30 %. Thereafter, dry stretching to at least 1.4 times their length is envisaged, As proved by -the examples of this previous literature, it is possible, under -these conditions. to obtain indivldual ~ilament s-trengths of 4.8 g/den ~-42,4 cN/tex (Example 1 f) or an initial modulus of 107.2 g/den - 946 cN/tex (Example 1 h)~
The maxim~n e~fective stretching in the exampIes was abou-t 1:6,8; effective stret;ching is to be understood as the actual s~retching effec-tive, for example, on the denier of t'rlr;~ individual filaznen-ts~ I-t can be calcul-ated from the individuaL stre-tch values, bu-t these must also be corrected by the shrink~lge during slack clrying.
7~
The texti.le values of the ~ilaments procluced according -to the previ.ous li-terature rnust still be regarded as inadequa-te for industrial fields of use.
There have t7nerefore been attempts, in par-ticular~ to increase the initial modulus of such :Cibers s-til].
further.
Thus, for example, German O~fenlegungsschrif-t
2,851,273 describes a process in which, direc-tly af-ter wet stretching, the filaments are s-tretched further in a "steam pressure s-~etching zone" at-temperatures from 110 to 140 C under the action of sa-turated steam under pressure. In the case of a continuous procedure, such a process is very expensive from an industrial poin-t of view~ in particular because of the sealing problems of the hot pressure chamber. The best fibers produced by this process have a strength of 12.8 g1den ~ 113 cN/-tex - a-t an elongation of 30%, and the initial modulus Of these filamen-ts is 140 g/den - 1,236 c~/tex. These values have been -taken from Example 10, in which filaments with an indlvidual denier of only 0.32 den - 0.3~ dtex , ~ere obtained.
However, these good tex-tile values are achieved only with very fine individual filament deniers~ During spinning of customary deniers according to Examples 1 -to 7 of the previous literature, -these hi.gh fiber values cannot be achieved by a long way~
A simi].ar stre,tch1.ng process a-t elevated terr,pera-tures under stearn pressure is al,so described in German Democratic Repub:l.ic Patent Speciflca-tion 135,509. The . .
best filaments (according to Ex~mple 3) ha~e a strength of 73.8 p/tex ~ 72.4 cN/tcx at 9.2 % elonga-l;ion. The nitial modulus was detel~nined as 17250 p/tex ~ 1,226 cN/-tex, In this patent specification9 i-t is expressly 5 indicated -that the quality of the spinning solution largely deterlnines -the stretching properties. Fibers with the sta-ted data can only be ob-tained if'-the spinning solu-tions ha~e been prepared from solution pol~ners, which have furthermore also been ripened at temperatures from 10 15 to 40C for at leas-t 20 to 100 hours. ~ccording to statemen-ts made by the authors, spi.nning solutions o.f precipi-tation polymers have a poorer s-tate of solution and thus- enable .only relatively low stretching factors to be applied. Filaments with relatively high inltial 15 moduli cannot be produced from precipitation pol~mers.
There was therefore still -the object of providing . filaments and fibers of polyacrylonitrile or acrylonitrile copolymers, ~Jhich have inl-tial moduli grea-ter -than 1,300 cN/tex and ~or which the production process difers 20 as little as possible ~rom the normal spinning process, : and in par-ticular does no-t require th~ use of steam stre-tching zonesor the like or any special ripening pro-. ce,s,s for -the spin dope, or -the use of par-ticular solution polymers~
I-t has now bee-n ~ound~ surprisingly, that it is possible to produce filaments and fibers with such proper-ties by a spinning process whicn is :;ndustrially si.mple and can be carried ou-t on conven-tio-nal units, by which means i-t was possible -to spin fi.].amen-t.s and fibers with 5 -- .
considerably be-tter properties than are described in -the li-terature both from spinning solutions of precipi- ~
tatioll pol~ners and from spinning solutions vf solu-tion polymers. The filamen-ts according -to the invention 5 have an initial modulus of over 1,300 cN/tex in -the customary denier range (about 1.5 to about 15 d-tex).
These values are preferably between 1,400 and 2,500 cN/
tex. The filaments and fibers wi-th -these high ini-tial moduli are particularly suitable for indus-trial fields of use, such.as, for example 9 for -the production of filaments intended for conversion to carbon fibers or as rein.forcing fibers or filaments, or, in the form of woven-fabrics, kn.it-ted fabrics or non~wovens of fi.bers or filamen-ts~ for the production of reinforced organic or - 15 inorganic materials. Other fi.elds of use which may be ~en-tioned are the production of ~ilters or fil-ter fabrics~
and their use as the substrate fabric for -the production of coated fabrics such as, for example, -the production of translucent materials, a~rnings and sails, and also for 20 the produc-ti.on of sewing yarns and -the like . The fibers and filaments can be used in crimped or tex-turized ~orm.
Excellent results~are obtained in these fields of use with fibers or filaments which have a tenacity between 1,500 and 2,500 cN/tex. The high tensile strength 25 achieved of at:leas-t 50 cN/tex, which can be associated with elongations at break o~ at most 15 %, complete.the good pattern of properties of the filamen-ts and fibers according to -the invention.
The invention is also based on a process for the . . .
, --` il170~1 ~ 6 --produc-tion of these fibcrs and filaments by a wet or dry spinning process, in which wet stretching of the spun filaments is to take place during -the washing -treatment, and the filaments are subsequently dried and then subjec-5 ted -to hot s-tre-tchin~. The process according to the invention comprises drying the filaments under tbnsion on hot. drums, if appropriate in -to~ or hank form, and then subjecting it to con-tact stretching of at least 1-1 5, in which the effective overall stre-tchin~ must be 10 at least l:9. By cont;act stretchin~ there is to be understood, in -this contex~t, stre-tching in the dry, ho-t state, for example using flat heating elemen-ts.
- The preci.pitation or solution polymers prepared by customary proce`sses can be employed as the polymeric 15 raw materials. Both homopolymers and copolymers of acrylonitrile can be used, depending on the requirement for the fields of use. It should be ensured tha-t the puri-~y of the monomers employed i.s as high as possible.
Suitable comonomers are all the unsatura-ted compounds . 20 which can be copolymerized wi-th acrylon~rile, of which the ~ollowing may be men-tioned here as examples: acryl--amid~, acrylic acid and esters thereof, vinyl esters and ethers~ such as vinyl acetate, vinyl stearate, vinyl butyl - ether and vinyl halogenoacetates 9 suGh as vinyl bromoace-t-25 ate, vinyl dichloroacetate and vinyl trichloroace-ta-t.e~
styrene, maleimide, vinyl hali.des, such asJ for example, .inyl chlori.de, vinyli.den.e chloride and vinyl bromide, and unsaturated compounds whi.ch carry su]fonate groups, and the like.
., , ' ' ~3~
Po~ymers which have relative solution viscosi-ties - mcasured in 0.5 % s-trength dimethylIorlnamide solutions - in the range from 1.7 to 6.0 can be employed.
Good results are achieved under economical condi-tions using polymers within a viscosity range f'rom abou-t 1.~5 to 3.5, and polymers within -t~e viscosi-ty range frorn 2.5 to 3.5 give particularly good resul-ts.
The polymers employed should preferably contain a-t least 90 % o~ acrylonitrile ~mits. Particularly good tex'tile ~alues are achieved with polymers ~^Jhich are built up ~rom acrylonitrile units to -the exten-t of a-t least 99 %.
The solution condi-tions for the preparation of the spinning solutions should be chosen such that spin-ning so]u-tions which are as far as possible homogeneous and free from gel par-ticles are ob-tained. Light scattering measuremcnts using a laser as the ligh-t source are particularly suitable for checking -the quality of the spinning solution. Only high-cluality spinning solu-tions ~/hich exhibit very low ligh-t scat-tering values make possible the high stretchings required according to -the invention. The spinning solvtions can be run either con-tinuously or discontinuously~ Inorganic or organic additives, such as, f'or example, delus-tering agen-ts, stabilizers, ~lameproofing additives and the like, c~n be incorporated into the spinning solu-tionO
The splnning process according to the invention is dis-tinguished by a high effec-tive overall stre-tching o~ at leas-t l:9~ As alreac1y nlen-tioned above, in .
However, these good tex-tile values are achieved only with very fine individual filament deniers~ During spinning of customary deniers according to Examples 1 -to 7 of the previous literature, -these hi.gh fiber values cannot be achieved by a long way~
A simi].ar stre,tch1.ng process a-t elevated terr,pera-tures under stearn pressure is al,so described in German Democratic Repub:l.ic Patent Speciflca-tion 135,509. The . .
best filaments (according to Ex~mple 3) ha~e a strength of 73.8 p/tex ~ 72.4 cN/tcx at 9.2 % elonga-l;ion. The nitial modulus was detel~nined as 17250 p/tex ~ 1,226 cN/-tex, In this patent specification9 i-t is expressly 5 indicated -that the quality of the spinning solution largely deterlnines -the stretching properties. Fibers with the sta-ted data can only be ob-tained if'-the spinning solu-tions ha~e been prepared from solution pol~ners, which have furthermore also been ripened at temperatures from 10 15 to 40C for at leas-t 20 to 100 hours. ~ccording to statemen-ts made by the authors, spi.nning solutions o.f precipi-tation polymers have a poorer s-tate of solution and thus- enable .only relatively low stretching factors to be applied. Filaments with relatively high inltial 15 moduli cannot be produced from precipitation pol~mers.
There was therefore still -the object of providing . filaments and fibers of polyacrylonitrile or acrylonitrile copolymers, ~Jhich have inl-tial moduli grea-ter -than 1,300 cN/tex and ~or which the production process difers 20 as little as possible ~rom the normal spinning process, : and in par-ticular does no-t require th~ use of steam stre-tching zonesor the like or any special ripening pro-. ce,s,s for -the spin dope, or -the use of par-ticular solution polymers~
I-t has now bee-n ~ound~ surprisingly, that it is possible to produce filaments and fibers with such proper-ties by a spinning process whicn is :;ndustrially si.mple and can be carried ou-t on conven-tio-nal units, by which means i-t was possible -to spin fi.].amen-t.s and fibers with 5 -- .
considerably be-tter properties than are described in -the li-terature both from spinning solutions of precipi- ~
tatioll pol~ners and from spinning solutions vf solu-tion polymers. The filamen-ts according -to the invention 5 have an initial modulus of over 1,300 cN/tex in -the customary denier range (about 1.5 to about 15 d-tex).
These values are preferably between 1,400 and 2,500 cN/
tex. The filaments and fibers wi-th -these high ini-tial moduli are particularly suitable for indus-trial fields of use, such.as, for example 9 for -the production of filaments intended for conversion to carbon fibers or as rein.forcing fibers or filaments, or, in the form of woven-fabrics, kn.it-ted fabrics or non~wovens of fi.bers or filamen-ts~ for the production of reinforced organic or - 15 inorganic materials. Other fi.elds of use which may be ~en-tioned are the production of ~ilters or fil-ter fabrics~
and their use as the substrate fabric for -the production of coated fabrics such as, for example, -the production of translucent materials, a~rnings and sails, and also for 20 the produc-ti.on of sewing yarns and -the like . The fibers and filaments can be used in crimped or tex-turized ~orm.
Excellent results~are obtained in these fields of use with fibers or filaments which have a tenacity between 1,500 and 2,500 cN/tex. The high tensile strength 25 achieved of at:leas-t 50 cN/tex, which can be associated with elongations at break o~ at most 15 %, complete.the good pattern of properties of the filamen-ts and fibers according to -the invention.
The invention is also based on a process for the . . .
, --` il170~1 ~ 6 --produc-tion of these fibcrs and filaments by a wet or dry spinning process, in which wet stretching of the spun filaments is to take place during -the washing -treatment, and the filaments are subsequently dried and then subjec-5 ted -to hot s-tre-tchin~. The process according to the invention comprises drying the filaments under tbnsion on hot. drums, if appropriate in -to~ or hank form, and then subjecting it to con-tact stretching of at least 1-1 5, in which the effective overall stre-tchin~ must be 10 at least l:9. By cont;act stretchin~ there is to be understood, in -this contex~t, stre-tching in the dry, ho-t state, for example using flat heating elemen-ts.
- The preci.pitation or solution polymers prepared by customary proce`sses can be employed as the polymeric 15 raw materials. Both homopolymers and copolymers of acrylonitrile can be used, depending on the requirement for the fields of use. It should be ensured tha-t the puri-~y of the monomers employed i.s as high as possible.
Suitable comonomers are all the unsatura-ted compounds . 20 which can be copolymerized wi-th acrylon~rile, of which the ~ollowing may be men-tioned here as examples: acryl--amid~, acrylic acid and esters thereof, vinyl esters and ethers~ such as vinyl acetate, vinyl stearate, vinyl butyl - ether and vinyl halogenoacetates 9 suGh as vinyl bromoace-t-25 ate, vinyl dichloroacetate and vinyl trichloroace-ta-t.e~
styrene, maleimide, vinyl hali.des, such asJ for example, .inyl chlori.de, vinyli.den.e chloride and vinyl bromide, and unsaturated compounds whi.ch carry su]fonate groups, and the like.
., , ' ' ~3~
Po~ymers which have relative solution viscosi-ties - mcasured in 0.5 % s-trength dimethylIorlnamide solutions - in the range from 1.7 to 6.0 can be employed.
Good results are achieved under economical condi-tions using polymers within a viscosity range f'rom abou-t 1.~5 to 3.5, and polymers within -t~e viscosi-ty range frorn 2.5 to 3.5 give particularly good resul-ts.
The polymers employed should preferably contain a-t least 90 % o~ acrylonitrile ~mits. Particularly good tex'tile ~alues are achieved with polymers ~^Jhich are built up ~rom acrylonitrile units to -the exten-t of a-t least 99 %.
The solution condi-tions for the preparation of the spinning solutions should be chosen such that spin-ning so]u-tions which are as far as possible homogeneous and free from gel par-ticles are ob-tained. Light scattering measuremcnts using a laser as the ligh-t source are particularly suitable for checking -the quality of the spinning solution. Only high-cluality spinning solu-tions ~/hich exhibit very low ligh-t scat-tering values make possible the high stretchings required according to -the invention. The spinning solvtions can be run either con-tinuously or discontinuously~ Inorganic or organic additives, such as, f'or example, delus-tering agen-ts, stabilizers, ~lameproofing additives and the like, c~n be incorporated into the spinning solu-tionO
The splnning process according to the invention is dis-tinguished by a high effec-tive overall stre-tching o~ at leas-t l:9~ As alreac1y nlen-tioned above, in .
3 ~ 70(~
detel~li.ning -the effec-tive overall stretching, on~Ly the we-t s-tre-tchillg within -the washing process and the con tac-t stre-tchi.ng are -taken in-to considera-tion, and shrink--age of -the fi.laments is allowed for. The spin draw ratio or 5 spinneret attenuation is not included i.n the overall streching values; rather, -the fresh spun filamen-ts obtained after a dry or wet spinning process are evaluated as unstretched materialO ln -the process according -to the invention, the effective overall stretching should be a-t least 1:9.
10 ~ffective overall stretching ratios of 1:10 to 1:25 are preferred, and effective overall stre-tching ratios between about 1:12 and 1:22 a~e particularly preferred.
. The process according to the inventi.on ca~ be carried out on conven-tional filament- or fiber-spinning -15 units. New -tech~i~ues ~hich were not hi-therto cus-tom-ary are not required. In particular, it is no-t necessary to employ a special stretching chamber in which the fila- :
.. ments, for exarnple in tow form, are exposed to the action of s-team under pressure. The process is distinguished ~0 by high overall stre-tching values for -the freshly 5pun filaments, an effective minimum s-tretching of 900 ~
being required. This effective overall stre-tching is carried out in several stages. The filaments are first subjected to wet stre-tching in one or step~ise in several 25 hot baths, before or af-ter the resi.dual con-tent o~ solven-t has been washed ou-t~ The tel~perature of the stretching bath media, which generally comprise mix-tures of water and -the solv~n-t, should be kept as high as possible Temperatv.resslightly below -the.boiling poi.n-t o~ -the ba.-th t 1 7 ~
_ g ~
liquid are preferred. However, baths ~hich con-tain other stretchi.ng bath rnedia, ~or example gl.ycol or glycerol, i~ appropriate mixed with the polymer solvent, are also possi.ble, and in -the case of -these baths 5 stretching -temperatures above 100C can also be chosen A~-ter the s-tre-tching operation ancl after -the residual content of solvent has been washed out, it also being possible firs-t to wash out the solvent and then to stretch -the filaments, the filaments arefinished in a 10 finishing ba-th and are then as far as possible largely freed from .adhering water in the customary manner b~J the action of rota-ting nip roller pairs. The finish applied i.n thefinishing bath can influence the stretching proper ties of the ~ilaments. Of the known finishing mixtures, 15 that ~hich gi.ves a low filamen-t/~ilament friction shoul.d be chosen.
. The filaments are then dried under tenslon on hot drums. Slight shrinkage, which ~requen-tly proves to be advantageous for subsequent stretching; can be 20 permi-tted during drying; in adjusting -the shrinkage, however, it must be ensured that -the tow always runs over the dryi.ng drums under tension The temperatures o~
. the drv~s should be chosen such tha-t the tow leaves -the drier with a very low resid1la1 moisture o~, as far as 25 possib:Le, less than 1 ~0. Temperatures in the range ~rom 140 to 220C have proved -to be ad.van-tageous for -these dl~ums, bu-t th:i.x does notpreclude the use of higher or ].ower tempera-tures. I-t is also possi.ble to dry the f.i.laments on the drums at graduated tempera-tures~
" .
1 ~ 70 0 ~ :1 After drying, the -tow is stretched once more to at least 1.5 times it.s length with the application of dry heat. This stretching can also be effected in one or more stages. The t~w can be heated by the pro~
cesses cus-tomary in the ar-t, for example by being passed around hot drums, by contac-t over hot pla-tes, in a ho-t air -tunnel or by radia-tion, in par-ticular inf`rared radiation. Stepwise stretching in which the various heating processes can be applied can also be used.
Combina-tions which are always particularly advantageous are -thosein which -the filament is s-tretched by or be-t-ween hot drums in the ~irs-t s-tretching s-tage and one of the three o-ther processes described is applied in the second s-tage. The s-tre-tching -tempera-tures are influ~
enced by -the nature of -the polymers employed and to some extent by the preceding stretching and the drying con-ditions~ In general, a temperature range from about - 120 to 250C is sui-table, and the range from 140 to 200C is par-ti.cularly advantageousO
Af-ter the stre-tching, the fil.aments are cooled and are either wound by kno~m processes -to give continuous ma-terial or are cut to fibers wi-th the desired cut leng-th by kno~m processes. If required by the field of` use, the filamen-ts or fibers can also be subjected -to a special finish before or after -the cut-ting.
The following examples serve to illustrate -the i.nven-tion ~nless indicated o-therwise, the percen-tage data and parts relate to units by weigh-t.
) Q 1 ~
_ ..~
1~700 g of a suspenslon precipi-ta-tion po:lymer of 99.50b of acrylonitrile and 0.5% of methyl acryla-te wi-th a relative viscosi.-ty of 2.85 are dispersed in 8,300 g of dimethylforrnamide at ~30C and are dissolved at 90C for 90 minutes, with s-tirring, to give a homogeneous spinning solu-tion. After ~eing filtered, the solution is forced, at a feed rate of 16.2 ml/min~-te through a 100-hole jet with a ho:Le diameter of 0.06 mrn into a coagulating ba-th ~0 which cormprises 50 % of dimethylformamide and 50 % of wa-ter and has a -tempera-ture of 50C. When -the resulting filaments have reached an im~ersed length of 50 cm, -they are drawn off at a rate o~ 5.5 m/minute. The yarn is stretched by raisi-n~ the speed to 29.3 m/minu-te in 2 stretching baths comprising 60 % of dimethylforrnamicle and 40 % of water a-t a -tempera-ture of 99C, washed in wa-ter at a tempera-ture of 85C in further baths and, after passing -through a finishing ba-th, is dried on 2 hea-ted duos with surface temperatures of 140 and 185C respec-tively, a shrinkage to a speed reduced by 0,7 m/minutebeing allowed. The residence time on the first duo with a temperature of 140C is chosen such that the yarn is lus-trous when it lea~Jes -the duo, t'nat iS -to say -i-t no longer contains vacuoles. The yarn is .drawn off from -the second dUo at 33.3 rn/minute and is s-tretched by raising the speed to 95 m/rn:inu-te, ~ri-th the aid of an unheated duo, over 4 heated plates which touch the yarn alternately from below and above, at temperatures o~ 5, 1459 165 and 168 C, and is then wound on to bobbins O The ef:fc?c-tive overall stre tching ratio is calcula-ted as 1:17 . 3 in -this case . The filaments -thus ob-tainecl had the :l~o] lowing properties: deni.er: 275 dtex; tensile s-trength. 61 cl~/tex;
5 elongati.on at break: 6 %.; ini-tial modullls: 1, 836 cN/teY;
kno-t s treng-th of the i~dividual cap:illaries: 10 ~ 6 cN/ tex .
Exampl e 2 2 ~ 600 gr of a precipitation polymer o~ 93 . 7 %
of acrylonitrile~ 5.8 % OI methyl acryla-te and 0. 5 % of 10 sodium methallylsulfonate i,rith a relative viscosity OI
1.92 are dissolved in 7, 400 g of dimethylformamide -to give a homogeneous spinning solution. AI-ter -this solu-tion has been .îiltered, it is forced, at a feed rate of 19 ml/minu-te5 ~a jetwith 300 holes with a holè dia-15 me-ter of 0.06 mm into.a coagulating bath comprising 65 %
of dimethylformamide and 35 % of water a-t 50C When the resul-ting yarrl has reached an immersed length OI
50 cm5 i-t is dra~n off from -the coagula-ting bath a t 5 . 5 m/minute, stre-tc hed by raising the speed . 20 -tG 50.0 m/minute in 2 stretching ba-ths containing 6G ~0 o~ dime thy-Lformamide and 40 % of water a-t 99C, washed with wa-ter at ~35C and, after passing through a ~inishing bath, dried on 2 heated duos 5 no shrinkage being allo~re(l, The suri~ace tempera-tures OI duo 1 ~rere 25 120 C and those o:E duo 2 were 165C. The clried yarn was then passed over 4 pla-tes heated -to 145C
whi:Lc? béing s-tre-tched. a t a final ra-te. o: 79 . 0 m~f miml-tc-? with the aid o~ a .îur ther duo ~ : The individ.ual filaments OI the yarn thus produced ~ 13 -had the fol:lowing properties: denier: 2.1 d-tex; -tensile s-trength- 74 cN/~tex; elongatiorl a-t break: 9 ~'; initial modulus ~ 95 cN/-texO
Example_3 2,500 g of a precipitation polymPr of 99.5 %
of acrylonitrile,and 0.5 % of me-thyl acryla-te wi-th a relative viscosity of 1.92 were dissolved in 7,500 g of dimethylformamide, and, after being filtered, -the solu-tion was forcedJ at a ~eed rate of 16.4 ml/minute, -through 10 a 300 hole je-t with a hole diameter of 0.06 ~m into a coagulating bath ~hich comprised 70 % of dimethylformamide and 30 % of wa-ter and had a tempera-ture of 30C
A~ter tne resul-ti.ng yarn had reached an immer-sed length of 50 cm, it was drawn o~f ~t 5 0 m/
15 minute and stretched by raising the speed to 33 m/minu-te in a stretching bath containing 60 ~0 of dime-thylformamide and 40 % of l~a-ter at 9~C and then washed wi-th wa-ter and7 after passing through a finishing bath, dried on 2 duos, no shrinkage being allowed. The surface tempera-tures 20 of the duos were 120 and 140C. l`he yarn was then stretched by raising the speed to 68 m/minute, corres--ponding to an effective overall s-tretching ratio of 1:13 6, over 4 plates heatecl -to 135C. The individual filaments of the yarn had the following properties:
25 denier: 2.0 dtex; tensile s-trength: 58 cNjtex; elongation at break: 8 %, initial ~odulus: 1,500 cN/tex E~am~ 4 .~ _ 1,400 g of a precipita-tion polymer of 100 %.o~
acrylonitrile wlth a relative viscosity of 3.0 were , 7~
dissolved in 8,600 g of dimethylformamide -to gi.ve a spinning solu-tion and the so~Lu-ti.on was fil-tf.;red and forced, at afeed ra-te of 16 ml/mi.nu-te, through a lOO hole jet wi-th a ho]e diameter of o.o6 mm in-to a coagula-ting ba-Lh cornpr.ising 55 % of dime-thy]fo~namide and 45 % o~
wa-ter at 50 C. The resulting filament was drawn of~
from the coagulating bath at 5.5 m/mi.nu-te and stre-tched by raislng the speed to 29.~ m/minute in a s-tretching bath comprising 60 % of dime-thylformamide and 40 % of wa-ter at 99 C. The filament was -then washed in water at 85C and subsequen-tly passed -through a fir1i~hin~
bath9 and thereafter dried on 2 duos which had surface temperatures of 140 and 165C respectively. A shrink-age to a speed reduced by 2.5 m/minute was permitted on -the duos, but the yarn was drawn off from the second duo a-t 30 3 m/rninute and stretched by raising the speed to 72 m/minute over 4 hot plates wi-th surface tempera-tv.res 140, 140, 150 and 150 C. The individual filamen-ts of the yarn . -thus obtained had the following properties:
denier: 3.1 dtex; tensile strength: 65 cNltex; elongation at break: 8 ~0; ini.tial modulus: l,400 cN/tex D
~ ' .
In a conti.nuous procedure, 80 g per minute of a precipi.tation polymer of 9~ 7 % of acry]oni-trile, 5.8 %
of methyl acrylate and 0.5 % of sodium methallylsulfona-te were dissolved in dime-thy:Lformamide to g.ive a 26 % by weight spi.nning soLution, and the solu-tion was fil-tered and .~orced through a jet wi-th 5,000 holes with a hole diame-ter of 0.06 r~n into a coagula-ting ba-th, which com~
D !~0 prised 60 ~' of dirnethylformamlde and 40 % of wa-ter a-t 45 c. A~-ter a ba-th zone of 13 cm, -the -tow was dra~m off at 6.5 m/mimlte, . drawn by raislng -the speed -to 39.0 m/minute in 2 s~re~tching baths containing 45 % of dimethyl:Eormamide and 55 % of wa-ter a-t 99C and -then washed wi-th wa-ter a-t 90C, and simul-taneously shrunk back to a speed reduced to 35.2 m/minu-te, and subsequently dried on drum driers In the drum drier, ~the -tow was dried at 165C in a first stage, no shrinkage being permit-te(d, and after-treated at 180C in a second s-tage, the tow being drawn by raîsing the speed to 63.9 m/minute between the first and second s-tage. The tow then passed into a third stage of -the drum drier, whlch was opera-ted at 175C, the ~ow being .15 dra~m again,- by raising the speed -to 69.2 m./minute, be-tween the second and third stage, Finally9 the tow pas3ed over 8 hot pla-tes which were arranged alter-na.tely above and below and had a surface tempera-ture of 180 C, -the tow being drawn between the plates by rais-20 ing the speed to 77.2 m/minu-te, correspondin~ to an ef~ec-ti.ve overall drawing of 1:11.9. After the tow had been cu-t into staple fibers, the ~ollowing -tex-l;ile proper-ties were measured: denier: 2.2 dtex; tensile strength: 73 cN/tex; elon~ation at break: 10 %; initial modulus : 1,373 cN/te~.
Exa~ple 6 .~
Example 1 was repeated, bu-t 5 %, rela-ti~e -to the polymer, o~ -titaniurn dioxide was added to the spi~ling solution as a delus-tering agent. The individual filaments of the yarn had the following properties:
denier: 3.6 dtex; tensile strength: 61 cN/tex; elongation at break: 7 %; initial modulus: 1,389 cN/tex.
Example 7 In a continuous procedure, a polymer such as has already been described in Example 2 was dissolved in dimethylformamide to give a 30.5% strength spinning solution, and, after it had been filtered, the solution was forced, at a feed rate of 72 ml/minute, through a 50-hole jet with a hole diameter of 0.15 mm into a dry-spinning tunnel. Hot air at 360°C was blown in the filament direction at a tunnel temperature of 200°C.
The take-off rate of the filaments was 220ml/minute.
In each case 11 of the strands thus obtained were collected to form a tow and the tow was stretched to 606 times its length in 2 stretching baths, which comprise 6 % of dimethylformamide and 94 % of water at 99°C, washed with water at 80 to 85°C, a shrinkage of 11 % being allowed, and, after passing through a finish-ing bath, dried on 2 duos with surface temperatures of 140 and 160°C, a shrinkage of 5 % being allowed. The filaments were drawn off from the second drier duo at a stretching ratio of 1:1.07 and stretched at 1:1.64 over four hot plates at 140°C. The following textile properties were measured on individual filaments of the resulting tow: denier: 2.0 dtex; tensile strength: 65 cN/tex; elongation at break: 9 %; initial modulus:
1,491 cN/tex.
Examp].e 8 _~ .
In a continuous procedure, a polymer~ as already descri.bed in Example 3 9 was dissolved to give a 26 % .
strength spinning solu-tion and -this solu-tion ~.as subjec-ted to dry spinni..ng, at a feed rate of 85.2 ml/minute,under -the condi-tions described in EY.ample 7.
In each case 11 of the strand~ thus ob-tained were collected to form a -tow and the tow was stretched to five times its length in 2 stre-tching ba-~.hs, which comprise~ 6 % of dime-thylformamide and 94 % of wa-ter at 99C 9 washed wi-th water a-t 80 to 85C 9 a shri.nkage of 7 % being allowed, and9 after passing -through a finish~
ing ba-th, dried on. 2 duos at 140 and 160C~ a shri.nlsage of 5 ~0 being allowed, The tow was drawn off from the second drying duo with a stretching ratio of 1:1.02 and s-tretched at 1:2.65 over -four hot plates a-t 140C. The individual filamen-ts had the following proper-ti.es:
. denier: 1.7 dtex7 tensile streng-th: 81 cN/tex; elongation at break: 9 %; initial modulus: 1,482 cN/tex.
.Ex.ample 9 ln a continuous procedure, a pol~ner, as described in Example 1, was dissolved to ~ive an 18 % s-trength spinning solution and this solution was spun, at a feed rate of 58,8 cm3/minuteS through a jet wi-th 18 holes with a hoJ.e diameter of 00250 mm in-to a dry-spinning tunnel which had a tunnel wall tempera-ture of 240C. Air heated to 3~0C was blown in the f.ilamen-t direc-tion.
The fllaments were drawn off at 200 m/minute ln each case 20 of these s~r~nds were collected 1 1 7~) Q ,g 1 , - 18 ~
and the resu]ting -tow was stretched from 10 m/minute by raising the speed -to 60 m/minu-te in 2 stre-tching baths which con-tain 6 % of dime-thylformamide and 94 ,'0 of water at 99G, washed in water at 85C, finished and -then dried on 3 duos at a -temperat.ure of 140, 170 and 200C, a shrinkage to a speed reduced by 7 m/minu-te bein~ allowed.
The tow was then stre-tched by raising -the speed -to 120.2 m/minute over four plates heated -to 165C. The é~fec-tive overall stretching ratio was thus 1:1.2Ø The resu].tir~g indi.vidual fllaments had the following proper-ti.es: denier: 2.~ dtex; tensile strength: 7~ cN/tex7 elongation at break: 8 % 9 initial modulus: 1,600 cN/-tex;
. knot strength: 13.6 cN/tex.
Exam~æ_e 10 Three of the dry-~spun filaments spv.n according to Example ~ were plied and -the tow was s-tretched from 7.5 b~- rais-ing the speed to 30.7 m/minute in 2 stretching baths which contain 60 % of dimethylformamide and 40 % of water a-t 99C, and then washed with wa-ter at -. . 20 85C, a shri~age to a speed redu.ced by 1 m/minu-te bei.ng allowed, ~inished dried on 2 duos wi-th a surface -tem-perature o~ 140 and 185C respec-tively, a shrinkage -to a speed reduced by 2 m/minute being al-l.owed, drawn off from the second duo, which was heated -to 185C, at 30.5 m/ .
mi.nu-te and stretched by raising -thc speed -to 120.7 m/
minute over four plates hea-tecl -to 160, 160, 166 and 166C.
The plied yarn thus obta].ned had the fol:Lowing properties: deni.er: 93 dtex; -tensile strength: 68 cN/tex;
elongation at break: 6 /0; initial rnodulus: 1,989 cN/tex.
~ 3 7 (~
- lg E~ ~e 11 . ~_ .
1~500 g of a pol~ner of 99.5 % o~ acrylonitrile and 0.5 % of methyl acryla-te wi-th a rela-tive viscosi-ty o~ 3,3 were dissolved in 8,500 g of dimethylformamide.
5 This solution was filtered, and forced, at a feed rate of 18 ml/minute, through a jet wi-th 100 holes with a hole diame-ter o~ 0.06 mm in-to a coagula-ting bath which com--prised 55 % of dimethylformamide and 45 % of water at 50C, After the filamen-t had reached an ir~nersed 10 leng-th of 45 cm, it was drawn o~ a-t a ra-te of 5.0 ~1/
minu-te, stretched by raising the speed to 29.3 m/mi.nute in two s-tretching baths which contained 60 % o~ dimethyl-- formamide and 40 % of water at 99C, washed at 85C, finished , dried on 2 duos at 140 and 165C, a shrinkage 15 to a speed reducedby 2.9 m~inute being allowed, drawn off ~rom the second duo at 30.3 m/rninu-te and s-tretched by raising the speed to 100 m/minute on four hot plates at 140, 150, 167 and 177C. The effective overall stretch-ing ratio in this case was thus 1:20.00 The yarn 20 spun in this way had the following proper-ties: denier:
270 dte~; tensile s-trength: 67 cN/tex; elongation a-t break: 7 % 7 initial :modulus: 1,981 cN/tex~
, . .
detel~li.ning -the effec-tive overall stretching, on~Ly the we-t s-tre-tchillg within -the washing process and the con tac-t stre-tchi.ng are -taken in-to considera-tion, and shrink--age of -the fi.laments is allowed for. The spin draw ratio or 5 spinneret attenuation is not included i.n the overall streching values; rather, -the fresh spun filamen-ts obtained after a dry or wet spinning process are evaluated as unstretched materialO ln -the process according -to the invention, the effective overall stretching should be a-t least 1:9.
10 ~ffective overall stretching ratios of 1:10 to 1:25 are preferred, and effective overall stre-tching ratios between about 1:12 and 1:22 a~e particularly preferred.
. The process according to the inventi.on ca~ be carried out on conven-tional filament- or fiber-spinning -15 units. New -tech~i~ues ~hich were not hi-therto cus-tom-ary are not required. In particular, it is no-t necessary to employ a special stretching chamber in which the fila- :
.. ments, for exarnple in tow form, are exposed to the action of s-team under pressure. The process is distinguished ~0 by high overall stre-tching values for -the freshly 5pun filaments, an effective minimum s-tretching of 900 ~
being required. This effective overall stre-tching is carried out in several stages. The filaments are first subjected to wet stre-tching in one or step~ise in several 25 hot baths, before or af-ter the resi.dual con-tent o~ solven-t has been washed ou-t~ The tel~perature of the stretching bath media, which generally comprise mix-tures of water and -the solv~n-t, should be kept as high as possible Temperatv.resslightly below -the.boiling poi.n-t o~ -the ba.-th t 1 7 ~
_ g ~
liquid are preferred. However, baths ~hich con-tain other stretchi.ng bath rnedia, ~or example gl.ycol or glycerol, i~ appropriate mixed with the polymer solvent, are also possi.ble, and in -the case of -these baths 5 stretching -temperatures above 100C can also be chosen A~-ter the s-tre-tching operation ancl after -the residual content of solvent has been washed out, it also being possible firs-t to wash out the solvent and then to stretch -the filaments, the filaments arefinished in a 10 finishing ba-th and are then as far as possible largely freed from .adhering water in the customary manner b~J the action of rota-ting nip roller pairs. The finish applied i.n thefinishing bath can influence the stretching proper ties of the ~ilaments. Of the known finishing mixtures, 15 that ~hich gi.ves a low filamen-t/~ilament friction shoul.d be chosen.
. The filaments are then dried under tenslon on hot drums. Slight shrinkage, which ~requen-tly proves to be advantageous for subsequent stretching; can be 20 permi-tted during drying; in adjusting -the shrinkage, however, it must be ensured that -the tow always runs over the dryi.ng drums under tension The temperatures o~
. the drv~s should be chosen such tha-t the tow leaves -the drier with a very low resid1la1 moisture o~, as far as 25 possib:Le, less than 1 ~0. Temperatures in the range ~rom 140 to 220C have proved -to be ad.van-tageous for -these dl~ums, bu-t th:i.x does notpreclude the use of higher or ].ower tempera-tures. I-t is also possi.ble to dry the f.i.laments on the drums at graduated tempera-tures~
" .
1 ~ 70 0 ~ :1 After drying, the -tow is stretched once more to at least 1.5 times it.s length with the application of dry heat. This stretching can also be effected in one or more stages. The t~w can be heated by the pro~
cesses cus-tomary in the ar-t, for example by being passed around hot drums, by contac-t over hot pla-tes, in a ho-t air -tunnel or by radia-tion, in par-ticular inf`rared radiation. Stepwise stretching in which the various heating processes can be applied can also be used.
Combina-tions which are always particularly advantageous are -thosein which -the filament is s-tretched by or be-t-ween hot drums in the ~irs-t s-tretching s-tage and one of the three o-ther processes described is applied in the second s-tage. The s-tre-tching -tempera-tures are influ~
enced by -the nature of -the polymers employed and to some extent by the preceding stretching and the drying con-ditions~ In general, a temperature range from about - 120 to 250C is sui-table, and the range from 140 to 200C is par-ti.cularly advantageousO
Af-ter the stre-tching, the fil.aments are cooled and are either wound by kno~m processes -to give continuous ma-terial or are cut to fibers wi-th the desired cut leng-th by kno~m processes. If required by the field of` use, the filamen-ts or fibers can also be subjected -to a special finish before or after -the cut-ting.
The following examples serve to illustrate -the i.nven-tion ~nless indicated o-therwise, the percen-tage data and parts relate to units by weigh-t.
) Q 1 ~
_ ..~
1~700 g of a suspenslon precipi-ta-tion po:lymer of 99.50b of acrylonitrile and 0.5% of methyl acryla-te wi-th a relative viscosi.-ty of 2.85 are dispersed in 8,300 g of dimethylforrnamide at ~30C and are dissolved at 90C for 90 minutes, with s-tirring, to give a homogeneous spinning solu-tion. After ~eing filtered, the solution is forced, at a feed rate of 16.2 ml/min~-te through a 100-hole jet with a ho:Le diameter of 0.06 mrn into a coagulating ba-th ~0 which cormprises 50 % of dimethylformamide and 50 % of wa-ter and has a -tempera-ture of 50C. When -the resulting filaments have reached an im~ersed length of 50 cm, -they are drawn off at a rate o~ 5.5 m/minute. The yarn is stretched by raisi-n~ the speed to 29.3 m/minu-te in 2 stretching baths comprising 60 % of dimethylforrnamicle and 40 % of water a-t a -tempera-ture of 99C, washed in wa-ter at a tempera-ture of 85C in further baths and, after passing -through a finishing ba-th, is dried on 2 hea-ted duos with surface temperatures of 140 and 185C respec-tively, a shrinkage to a speed reduced by 0,7 m/minutebeing allowed. The residence time on the first duo with a temperature of 140C is chosen such that the yarn is lus-trous when it lea~Jes -the duo, t'nat iS -to say -i-t no longer contains vacuoles. The yarn is .drawn off from -the second dUo at 33.3 rn/minute and is s-tretched by raising the speed to 95 m/rn:inu-te, ~ri-th the aid of an unheated duo, over 4 heated plates which touch the yarn alternately from below and above, at temperatures o~ 5, 1459 165 and 168 C, and is then wound on to bobbins O The ef:fc?c-tive overall stre tching ratio is calcula-ted as 1:17 . 3 in -this case . The filaments -thus ob-tainecl had the :l~o] lowing properties: deni.er: 275 dtex; tensile s-trength. 61 cl~/tex;
5 elongati.on at break: 6 %.; ini-tial modullls: 1, 836 cN/teY;
kno-t s treng-th of the i~dividual cap:illaries: 10 ~ 6 cN/ tex .
Exampl e 2 2 ~ 600 gr of a precipitation polymer o~ 93 . 7 %
of acrylonitrile~ 5.8 % OI methyl acryla-te and 0. 5 % of 10 sodium methallylsulfonate i,rith a relative viscosity OI
1.92 are dissolved in 7, 400 g of dimethylformamide -to give a homogeneous spinning solution. AI-ter -this solu-tion has been .îiltered, it is forced, at a feed rate of 19 ml/minu-te5 ~a jetwith 300 holes with a holè dia-15 me-ter of 0.06 mm into.a coagulating bath comprising 65 %
of dimethylformamide and 35 % of water a-t 50C When the resul-ting yarrl has reached an immersed length OI
50 cm5 i-t is dra~n off from -the coagula-ting bath a t 5 . 5 m/minute, stre-tc hed by raising the speed . 20 -tG 50.0 m/minute in 2 stretching ba-ths containing 6G ~0 o~ dime thy-Lformamide and 40 % of water a-t 99C, washed with wa-ter at ~35C and, after passing through a ~inishing bath, dried on 2 heated duos 5 no shrinkage being allo~re(l, The suri~ace tempera-tures OI duo 1 ~rere 25 120 C and those o:E duo 2 were 165C. The clried yarn was then passed over 4 pla-tes heated -to 145C
whi:Lc? béing s-tre-tched. a t a final ra-te. o: 79 . 0 m~f miml-tc-? with the aid o~ a .îur ther duo ~ : The individ.ual filaments OI the yarn thus produced ~ 13 -had the fol:lowing properties: denier: 2.1 d-tex; -tensile s-trength- 74 cN/~tex; elongatiorl a-t break: 9 ~'; initial modulus ~ 95 cN/-texO
Example_3 2,500 g of a precipitation polymPr of 99.5 %
of acrylonitrile,and 0.5 % of me-thyl acryla-te wi-th a relative viscosity of 1.92 were dissolved in 7,500 g of dimethylformamide, and, after being filtered, -the solu-tion was forcedJ at a ~eed rate of 16.4 ml/minute, -through 10 a 300 hole je-t with a hole diameter of 0.06 ~m into a coagulating bath ~hich comprised 70 % of dimethylformamide and 30 % of wa-ter and had a tempera-ture of 30C
A~ter tne resul-ti.ng yarn had reached an immer-sed length of 50 cm, it was drawn o~f ~t 5 0 m/
15 minute and stretched by raising the speed to 33 m/minu-te in a stretching bath containing 60 ~0 of dime-thylformamide and 40 % of l~a-ter at 9~C and then washed wi-th wa-ter and7 after passing through a finishing bath, dried on 2 duos, no shrinkage being allowed. The surface tempera-tures 20 of the duos were 120 and 140C. l`he yarn was then stretched by raising the speed to 68 m/minute, corres--ponding to an effective overall s-tretching ratio of 1:13 6, over 4 plates heatecl -to 135C. The individual filaments of the yarn had the following properties:
25 denier: 2.0 dtex; tensile s-trength: 58 cNjtex; elongation at break: 8 %, initial ~odulus: 1,500 cN/tex E~am~ 4 .~ _ 1,400 g of a precipita-tion polymer of 100 %.o~
acrylonitrile wlth a relative viscosity of 3.0 were , 7~
dissolved in 8,600 g of dimethylformamide -to gi.ve a spinning solu-tion and the so~Lu-ti.on was fil-tf.;red and forced, at afeed ra-te of 16 ml/mi.nu-te, through a lOO hole jet wi-th a ho]e diameter of o.o6 mm in-to a coagula-ting ba-Lh cornpr.ising 55 % of dime-thy]fo~namide and 45 % o~
wa-ter at 50 C. The resulting filament was drawn of~
from the coagulating bath at 5.5 m/mi.nu-te and stre-tched by raislng the speed to 29.~ m/minute in a s-tretching bath comprising 60 % of dime-thylformamide and 40 % of wa-ter at 99 C. The filament was -then washed in water at 85C and subsequen-tly passed -through a fir1i~hin~
bath9 and thereafter dried on 2 duos which had surface temperatures of 140 and 165C respectively. A shrink-age to a speed reduced by 2.5 m/minute was permitted on -the duos, but the yarn was drawn off from the second duo a-t 30 3 m/rninute and stretched by raising the speed to 72 m/minute over 4 hot plates wi-th surface tempera-tv.res 140, 140, 150 and 150 C. The individual filamen-ts of the yarn . -thus obtained had the following properties:
denier: 3.1 dtex; tensile strength: 65 cNltex; elongation at break: 8 ~0; ini.tial modulus: l,400 cN/tex D
~ ' .
In a conti.nuous procedure, 80 g per minute of a precipi.tation polymer of 9~ 7 % of acry]oni-trile, 5.8 %
of methyl acrylate and 0.5 % of sodium methallylsulfona-te were dissolved in dime-thy:Lformamide to g.ive a 26 % by weight spi.nning soLution, and the solu-tion was fil-tered and .~orced through a jet wi-th 5,000 holes with a hole diame-ter of 0.06 r~n into a coagula-ting ba-th, which com~
D !~0 prised 60 ~' of dirnethylformamlde and 40 % of wa-ter a-t 45 c. A~-ter a ba-th zone of 13 cm, -the -tow was dra~m off at 6.5 m/mimlte, . drawn by raislng -the speed -to 39.0 m/minute in 2 s~re~tching baths containing 45 % of dimethyl:Eormamide and 55 % of wa-ter a-t 99C and -then washed wi-th wa-ter a-t 90C, and simul-taneously shrunk back to a speed reduced to 35.2 m/minu-te, and subsequently dried on drum driers In the drum drier, ~the -tow was dried at 165C in a first stage, no shrinkage being permit-te(d, and after-treated at 180C in a second s-tage, the tow being drawn by raîsing the speed to 63.9 m/minute between the first and second s-tage. The tow then passed into a third stage of -the drum drier, whlch was opera-ted at 175C, the ~ow being .15 dra~m again,- by raising the speed -to 69.2 m./minute, be-tween the second and third stage, Finally9 the tow pas3ed over 8 hot pla-tes which were arranged alter-na.tely above and below and had a surface tempera-ture of 180 C, -the tow being drawn between the plates by rais-20 ing the speed to 77.2 m/minu-te, correspondin~ to an ef~ec-ti.ve overall drawing of 1:11.9. After the tow had been cu-t into staple fibers, the ~ollowing -tex-l;ile proper-ties were measured: denier: 2.2 dtex; tensile strength: 73 cN/tex; elon~ation at break: 10 %; initial modulus : 1,373 cN/te~.
Exa~ple 6 .~
Example 1 was repeated, bu-t 5 %, rela-ti~e -to the polymer, o~ -titaniurn dioxide was added to the spi~ling solution as a delus-tering agent. The individual filaments of the yarn had the following properties:
denier: 3.6 dtex; tensile strength: 61 cN/tex; elongation at break: 7 %; initial modulus: 1,389 cN/tex.
Example 7 In a continuous procedure, a polymer such as has already been described in Example 2 was dissolved in dimethylformamide to give a 30.5% strength spinning solution, and, after it had been filtered, the solution was forced, at a feed rate of 72 ml/minute, through a 50-hole jet with a hole diameter of 0.15 mm into a dry-spinning tunnel. Hot air at 360°C was blown in the filament direction at a tunnel temperature of 200°C.
The take-off rate of the filaments was 220ml/minute.
In each case 11 of the strands thus obtained were collected to form a tow and the tow was stretched to 606 times its length in 2 stretching baths, which comprise 6 % of dimethylformamide and 94 % of water at 99°C, washed with water at 80 to 85°C, a shrinkage of 11 % being allowed, and, after passing through a finish-ing bath, dried on 2 duos with surface temperatures of 140 and 160°C, a shrinkage of 5 % being allowed. The filaments were drawn off from the second drier duo at a stretching ratio of 1:1.07 and stretched at 1:1.64 over four hot plates at 140°C. The following textile properties were measured on individual filaments of the resulting tow: denier: 2.0 dtex; tensile strength: 65 cN/tex; elongation at break: 9 %; initial modulus:
1,491 cN/tex.
Examp].e 8 _~ .
In a continuous procedure, a polymer~ as already descri.bed in Example 3 9 was dissolved to give a 26 % .
strength spinning solu-tion and -this solu-tion ~.as subjec-ted to dry spinni..ng, at a feed rate of 85.2 ml/minute,under -the condi-tions described in EY.ample 7.
In each case 11 of the strand~ thus ob-tained were collected to form a -tow and the tow was stretched to five times its length in 2 stre-tching ba-~.hs, which comprise~ 6 % of dime-thylformamide and 94 % of wa-ter at 99C 9 washed wi-th water a-t 80 to 85C 9 a shri.nkage of 7 % being allowed, and9 after passing -through a finish~
ing ba-th, dried on. 2 duos at 140 and 160C~ a shri.nlsage of 5 ~0 being allowed, The tow was drawn off from the second drying duo with a stretching ratio of 1:1.02 and s-tretched at 1:2.65 over -four hot plates a-t 140C. The individual filamen-ts had the following proper-ti.es:
. denier: 1.7 dtex7 tensile streng-th: 81 cN/tex; elongation at break: 9 %; initial modulus: 1,482 cN/tex.
.Ex.ample 9 ln a continuous procedure, a pol~ner, as described in Example 1, was dissolved to ~ive an 18 % s-trength spinning solution and this solution was spun, at a feed rate of 58,8 cm3/minuteS through a jet wi-th 18 holes with a hoJ.e diameter of 00250 mm in-to a dry-spinning tunnel which had a tunnel wall tempera-ture of 240C. Air heated to 3~0C was blown in the f.ilamen-t direc-tion.
The fllaments were drawn off at 200 m/minute ln each case 20 of these s~r~nds were collected 1 1 7~) Q ,g 1 , - 18 ~
and the resu]ting -tow was stretched from 10 m/minute by raising the speed -to 60 m/minu-te in 2 stre-tching baths which con-tain 6 % of dime-thylformamide and 94 ,'0 of water at 99G, washed in water at 85C, finished and -then dried on 3 duos at a -temperat.ure of 140, 170 and 200C, a shrinkage to a speed reduced by 7 m/minu-te bein~ allowed.
The tow was then stre-tched by raising -the speed -to 120.2 m/minute over four plates heated -to 165C. The é~fec-tive overall stretching ratio was thus 1:1.2Ø The resu].tir~g indi.vidual fllaments had the following proper-ti.es: denier: 2.~ dtex; tensile strength: 7~ cN/tex7 elongation at break: 8 % 9 initial modulus: 1,600 cN/-tex;
. knot strength: 13.6 cN/tex.
Exam~æ_e 10 Three of the dry-~spun filaments spv.n according to Example ~ were plied and -the tow was s-tretched from 7.5 b~- rais-ing the speed to 30.7 m/minute in 2 stretching baths which contain 60 % of dimethylformamide and 40 % of water a-t 99C, and then washed with wa-ter at -. . 20 85C, a shri~age to a speed redu.ced by 1 m/minu-te bei.ng allowed, ~inished dried on 2 duos wi-th a surface -tem-perature o~ 140 and 185C respec-tively, a shrinkage -to a speed reduced by 2 m/minute being al-l.owed, drawn off from the second duo, which was heated -to 185C, at 30.5 m/ .
mi.nu-te and stretched by raising -thc speed -to 120.7 m/
minute over four plates hea-tecl -to 160, 160, 166 and 166C.
The plied yarn thus obta].ned had the fol:Lowing properties: deni.er: 93 dtex; -tensile strength: 68 cN/tex;
elongation at break: 6 /0; initial rnodulus: 1,989 cN/tex.
~ 3 7 (~
- lg E~ ~e 11 . ~_ .
1~500 g of a pol~ner of 99.5 % o~ acrylonitrile and 0.5 % of methyl acryla-te wi-th a rela-tive viscosi-ty o~ 3,3 were dissolved in 8,500 g of dimethylformamide.
5 This solution was filtered, and forced, at a feed rate of 18 ml/minute, through a jet wi-th 100 holes with a hole diame-ter o~ 0.06 mm in-to a coagula-ting bath which com--prised 55 % of dimethylformamide and 45 % of water at 50C, After the filamen-t had reached an ir~nersed 10 leng-th of 45 cm, it was drawn o~ a-t a ra-te of 5.0 ~1/
minu-te, stretched by raising the speed to 29.3 m/mi.nute in two s-tretching baths which contained 60 % o~ dimethyl-- formamide and 40 % of water at 99C, washed at 85C, finished , dried on 2 duos at 140 and 165C, a shrinkage 15 to a speed reducedby 2.9 m~inute being allowed, drawn off ~rom the second duo at 30.3 m/rninu-te and s-tretched by raising the speed to 100 m/minute on four hot plates at 140, 150, 167 and 177C. The effective overall stretch-ing ratio in this case was thus 1:20.00 The yarn 20 spun in this way had the following proper-ties: denier:
270 dte~; tensile s-trength: 67 cN/tex; elongation a-t break: 7 % 7 initial :modulus: 1,981 cN/tex~
, . .
Claims (8)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A filament or a fiber of an acrylonitrile polymer, the filament-forming substance of which consists of 70 to 100%
by weight of acrylonitrile and 30 to 0 % by weight of other units which can be copolymerized with acrylonitrile, with the exception of units derived from branched hydroxyacrylonitriles, the filaments and fibers having an initial modulus greater than 1,300 cN/tex, based on 100 % elongation.
by weight of acrylonitrile and 30 to 0 % by weight of other units which can be copolymerized with acrylonitrile, with the exception of units derived from branched hydroxyacrylonitriles, the filaments and fibers having an initial modulus greater than 1,300 cN/tex, based on 100 % elongation.
2. A filament or fiber as claimed in claim 1 in which the filament-forming substance consists of at least 90 % by weight of acrylonitrile units.
3. The filament or fiber as claimed in claim 1 in which the filament-forming substance consists of at least 99 % by weight of acrylonitrile units.
4. A filament or fiber as claimed in claim 1, claim 2 or claim 3 which has an initial modulus of about 1,400 to about 2,200 cN/tex.
5. A filament or fiber as claimed in claim 1, claim 2 or claim 3 which has a tensile strength of at least 50 cN/tex at elongations at break of at most 15 %.
6. In a process for the production of filaments or fibers of an acrylonitrile polymer, the filament-forming substance of which consists of 70 to 100 % by weight of acrylonitrile and 30 to 0 % by weight of other units which can be copolymerized with acrylonitrile, with the exception of units derived from branched hydroxyacrylonitrile, by a spinning process, wet stretching of the spun filaments, drying and subsequent hot stretching, the improve-ment comprising dissolving an acrylonitrile polymer of the given composition in a solvent, metering the resulting spinning solution through spinnerettes into a hot gas according to a dry spinning process or into a mixture of the solvent and water according to a wet spinning process, subjecting the filaments so obtained to a wet stretching, followed by wash treatments and finishing, then drying the filaments under tension on hot drums, so that the residual moisture of the filaments is less than about 1 %, and then subjecting them to contact stretching of at least 1:1.5, the effective overall stretching being at least 1:9.
7. A process as claimed in claim 6, wherein the effective overall stretching is 1:10 to 1:25.
8. A process as claimed in claim 6, wherein the filaments are subjected to wet stretching in a bath comprising mixtures of water and the solvent at temperatures slightly below the boiling point of the bath liquid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3027844.5 | 1980-07-23 | ||
| DE19803027844 DE3027844A1 (en) | 1980-07-23 | 1980-07-23 | HIGH MODULAR POLYACRYLNITRILE FIBERS AND FIBERS AND METHOD FOR THEIR PRODUCTION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1170011A true CA1170011A (en) | 1984-07-03 |
Family
ID=6107884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000382253A Expired CA1170011A (en) | 1980-07-23 | 1981-07-22 | High-modulus polyacrylonitrile filaments and fibers and a process for their production |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0044534B1 (en) |
| JP (1) | JPS5751810A (en) |
| AT (1) | ATE7236T1 (en) |
| BR (1) | BR8104734A (en) |
| CA (1) | CA1170011A (en) |
| DD (1) | DD201702A5 (en) |
| DE (2) | DE3027844A1 (en) |
| DK (1) | DK326281A (en) |
| IL (1) | IL63377A (en) |
| NO (1) | NO152946C (en) |
| ZA (1) | ZA815005B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4719150A (en) * | 1984-02-25 | 1988-01-12 | Hoechst Aktiengesellschaft | Monofils and bristles of homopolymers or copolymers of acrylonitrile, and a process for their manufacture |
| US4952453A (en) * | 1985-08-05 | 1990-08-28 | Japan Exlan Company Limited | Acrylic fibers with high physical properties |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH647271A5 (en) * | 1981-03-20 | 1985-01-15 | Hoechst Ag | FIXED THREADS AND FIBERS MADE OF ACRYLNITRILE HOMO OR COPOLYMERS, AND METHOD FOR THE PRODUCTION THEREOF. |
| FR2568273B1 (en) * | 1983-04-20 | 1986-12-19 | Japan Exlan Co Ltd | POLYACRYLONITRILE FIBER WITH HIGH MECHANICAL STRENGTH AND PROCESS FOR PRODUCING THE SAME |
| JPH0711086B2 (en) * | 1983-07-15 | 1995-02-08 | 東レ株式会社 | High-strength, high-modulus acrylic fiber manufacturing method |
| GB2149754A (en) * | 1983-11-14 | 1985-06-19 | Umberto Monacelli | Magazine for fasteners in coiled form |
| EP0144793B1 (en) * | 1983-12-05 | 1988-10-12 | AlliedSignal Inc. | High tenacity and modulus polyacrylonitrile fiber and method |
| NL8304263A (en) * | 1983-12-10 | 1985-07-01 | Stamicarbon | PROCESS FOR PREPARING HIGH TENSILE AND MODULUS POLYACRYLONITRIL FILAMENTS. |
| JPS60194110A (en) * | 1984-03-12 | 1985-10-02 | Asahi Chem Ind Co Ltd | Heat-resistant acrylic fiber and its manufacture |
| US4585154A (en) * | 1984-03-26 | 1986-04-29 | Bostitch Division Of Textron Inc. | Fastener driving tool with adjustable three-part magazine canister assembly |
| JPS616160A (en) * | 1984-06-19 | 1986-01-11 | 東レ株式会社 | Fiber reinforced hydraulic substance |
| JPS6197415A (en) * | 1984-10-12 | 1986-05-15 | Japan Exlan Co Ltd | Polyacrylonitrile fiber having high strength and modulus |
| JPS6197422A (en) * | 1984-10-16 | 1986-05-15 | Nikkiso Co Ltd | High-strength carbon fiber and its production |
| DE3567886D1 (en) | 1984-11-06 | 1989-03-02 | Mitsubishi Rayon Co | Process for producing acrylonitrile polymer |
| JPS61152811A (en) * | 1984-12-26 | 1986-07-11 | Toray Ind Inc | High tenacity acrylic fiber yarn and production thereof |
| JPS61167013A (en) * | 1985-01-10 | 1986-07-28 | Mitsubishi Rayon Co Ltd | Acrylonitrile fiber |
| JPS6233817A (en) * | 1985-08-05 | 1987-02-13 | Japan Exlan Co Ltd | Production of acrylic fiber having high tenacity and modulus |
| JPS62149908A (en) * | 1985-12-19 | 1987-07-03 | Toray Ind Inc | Acrylic fibrilated fiber of high performance |
| IT1227677B (en) * | 1988-12-02 | 1991-04-23 | Enichem Fibre S P A P | ACRYLIC PRECURSOR FOR CARBON FIBERS AND PROCEDURE TO OBTAIN IT |
| EP0554775A2 (en) * | 1992-02-01 | 1993-08-11 | Hoechst Aktiengesellschaft | Post-stretched yarns, twisted yarns or fabrics from staple fibres, process for their production and composites made therefrom |
| EP0645479A1 (en) * | 1993-09-24 | 1995-03-29 | Hoechst Aktiengesellschaft | High strength and high modulus polyacrylonitrile fibers, process for their production and their use |
| DE19651440A1 (en) * | 1996-12-11 | 1998-06-18 | Hoechst Ag | High tenacity high modulus polyacrylonitrile fibers, process for their manufacture and their use |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3846833A (en) * | 1970-04-14 | 1974-11-05 | Celanese Corp | Acrylic filaments which are particularly suited for thermal conversion to carbon filaments |
| CA980078A (en) * | 1970-11-16 | 1975-12-23 | E. I. Du Pont De Nemours And Company | Acrylic tow |
| JPS4842444B1 (en) * | 1970-12-26 | 1973-12-12 | ||
| JPS5119815A (en) * | 1974-08-08 | 1976-02-17 | Asahi Chemical Ind | AKURIRONITORIRUKEIGOSEISENINO SEIZOHO |
| JPS5248204A (en) * | 1975-10-14 | 1977-04-16 | Yoshirou Shigemori | Method of constructing wall body |
| GB2018188A (en) * | 1978-04-06 | 1979-10-17 | American Cyanamid Co | Wet spinning process for acrylonitrile polymer fiber |
| DD135509A1 (en) * | 1978-04-21 | 1979-05-09 | Volker Groebe | METHOD FOR PRODUCING HIGH-FIXED ENDLESS FAEDES FROM ACRYLIC NITRIL POLYMERISES |
-
1980
- 1980-07-23 DE DE19803027844 patent/DE3027844A1/en not_active Ceased
-
1981
- 1981-07-16 AT AT81105600T patent/ATE7236T1/en not_active IP Right Cessation
- 1981-07-16 DE DE8181105600T patent/DE3163294D1/en not_active Expired
- 1981-07-16 EP EP81105600A patent/EP0044534B1/en not_active Expired
- 1981-07-21 DD DD81231964A patent/DD201702A5/en unknown
- 1981-07-21 IL IL63377A patent/IL63377A/en unknown
- 1981-07-22 DK DK326281A patent/DK326281A/en not_active Application Discontinuation
- 1981-07-22 BR BR8104734A patent/BR8104734A/en unknown
- 1981-07-22 ZA ZA815005A patent/ZA815005B/en unknown
- 1981-07-22 NO NO812514A patent/NO152946C/en unknown
- 1981-07-22 CA CA000382253A patent/CA1170011A/en not_active Expired
- 1981-07-22 JP JP56113779A patent/JPS5751810A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4719150A (en) * | 1984-02-25 | 1988-01-12 | Hoechst Aktiengesellschaft | Monofils and bristles of homopolymers or copolymers of acrylonitrile, and a process for their manufacture |
| US4952453A (en) * | 1985-08-05 | 1990-08-28 | Japan Exlan Company Limited | Acrylic fibers with high physical properties |
Also Published As
| Publication number | Publication date |
|---|---|
| NO812514L (en) | 1982-01-25 |
| ZA815005B (en) | 1982-08-25 |
| IL63377A0 (en) | 1981-10-30 |
| EP0044534B1 (en) | 1984-04-25 |
| IL63377A (en) | 1984-06-29 |
| DK326281A (en) | 1982-01-24 |
| JPS5751810A (en) | 1982-03-26 |
| DE3027844A1 (en) | 1982-02-18 |
| BR8104734A (en) | 1982-04-13 |
| DD201702A5 (en) | 1983-08-03 |
| NO152946B (en) | 1985-09-09 |
| EP0044534A3 (en) | 1982-02-03 |
| DE3163294D1 (en) | 1984-05-30 |
| ATE7236T1 (en) | 1984-05-15 |
| NO152946C (en) | 1985-12-18 |
| EP0044534A2 (en) | 1982-01-27 |
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