US3636187A - Process for the manufacture of acrylonitrile synthetic fibers - Google Patents

Process for the manufacture of acrylonitrile synthetic fibers Download PDF

Info

Publication number
US3636187A
US3636187A US772955A US3636187DA US3636187A US 3636187 A US3636187 A US 3636187A US 772955 A US772955 A US 772955A US 3636187D A US3636187D A US 3636187DA US 3636187 A US3636187 A US 3636187A
Authority
US
United States
Prior art keywords
filaments
bath
nitric acid
spinning
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.)
Expired - Lifetime
Application number
US772955A
Other languages
English (en)
Inventor
Toshio Ohfuka
Kazunori Sagara
Hideo Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Application granted granted Critical
Publication of US3636187A publication Critical patent/US3636187A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • D01D5/06—Wet spinning methods
    • 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
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

  • This invention concerns a process for the manufacture of acrylonitrile synthetic fibers wherein an acrylonitrile polymer is dissolved in nitric acid for providing a spinning liquid which is extruded into a coagulation bath and coagulated filaments are then taken out from the coagulation bath and washed with fresh water and finally dried.
  • said spinning liquid is passed through a gaseous medium space provided above the free liquid surface of said bath under conditions such that evaporation of the solvent nitric acid contained in the extruded spinning liquid is suppressed and the degree of swelling of the produced filaments is maintained to less than 350 wt. percent and less than 300 wt. percent when measured upon the coagulation and water-washing operations for Obtaining improved characteristics of the produced fibers.
  • This invention relates to a process for the manufacture of acrylonitrile synthetic fibers.
  • acrylonitrile synthetic fibers have superior physical and chemical characteristics such as favorable feeling and bulkiness, lighter weight, superior warmth retaining performance, and sharp coloring capability.
  • the invention in its broadest aspect resides in such a process for the manufacture of acrylonitrile synthetic fibers, as comprising steps of: extruding a spinning liquid of an acrylonitrile polymer dissolved in nitric acid having a concentration of about 60-80 wt. percent from a spinneret positioned at about 1100 mm.
  • bulky yarns are manufactured preferably in such a way that two kinds of fibers having different coefiicients of thermal contraction are mixedly spun and the thus spun yarns are subjected to a heat treatment by contact with a heated medium such as boiling water, stream or the like, thereby causing the more contractive fiber elements to contract substantially relative to the less contractive elements, for the generation of a bulkiness of the yarns.
  • This bulky processing technique is broadly utilized in the texile industry and for this purpose, turbo staplers or perlok machines are used in the preparatory stage for cutting the continuously spun filaments into staple fibers.
  • a tow of acrylonitrile filaments is conveyed into a thermal drafting stage which comprises two hot plates and subjected to a draft under tension at -160 C. and then cut into fibers by application of impulsive shocks thereto by means of breaker bars.
  • a thermal drafting stage which comprises two hot plates and subjected to a draft under tension at -160 C. and then cut into fibers by application of impulsive shocks thereto by means of breaker bars.
  • the present invention improves the conventional comparative process wherein an acrylonitrile polymer dissolved in a nitric acid solution to provide a spinning liquid which is then extruded from a spinneret kept immersed in a coagulation bath comprising a dilute nitric acid solution into the latter, and the thus coagulated filaments are taken out from the bath, washed with water and subjected to several steps for drafting, drying and occasional oiling, heating, crimping and others, mainly in the following three points:
  • the spinning liquid is extruded from a spinneret which is positioned at 1l00 mm. above the free liquid surface of the coagulation bath thereinto, thereby the extruded spinning liquid runs through the free air space above the bath surface without substantially any loss of the solvent contained in the spinning liquid.
  • the degree of swelling of the coagulated filaments as taken out from the coagulation bath is maintained less than 350%.
  • the degree of the swelling as washed with water is maintained less than 300%.
  • the drawing shows schematically in section a preferred spinning arrangement adapted for carrying out the process according to the invention.
  • numeral 1 denotes a feed pipe which is arranged to supply from a reservoir and a metering pump, both not being shown, a spinning liquid prepared by dissolving an acrylonitrile polymer in nitric acid of about 60-80% concentration, and at a certain predetermined rate to a spinneret 2 which is of conventional design and formed therein a large number, for instance, 10,000 spinning orifices.
  • the thus extruded spinning liquid is in the form of finely divided streams shown schematically at 3 and flows through the free air space from the outlet of said orifices to the free liquid surface of a coagulating bath 4 contained in a reservoir 5 and without any remarkable loss of the solvent contained in the spinning liquid, said bath comprising a dilute aqueous solution of nitric acid for instance, of 33%-concentration.
  • the thus extruded fine streams are introduced into the bath for coagulation and then taken out by means of rotating rollers 6 and 8 mounted as shown. More specifically, these rollers 6 and 8 are driven to constantly rotate, with the filaments threaded around the both as at 9.
  • the concentration of the bath and the duration period of passage of the thus coagulated filaments through the bath is so selected that the degree of swelling of the filaments amounts to less than 350%.
  • the swollen and taken-out filaments are led through a washing bath 7 consisting of water and contained in a reservoir 10 for the removal of nitric acid contained in the coagulated filaments.
  • the duration period of passage of the filaments through the bath 7 is so selected that the degree of swelling of the filaments amounts to 300% at the highest.
  • the filaments are then led as at 13 through guide rollers 11 and 12 driven by a drive means, not shown, and fed under tension through a drafting bath 14 comprising boiling water and contained in a reservoir 15 for subjecting filaments to a draft of 300% or more between rotating rollers 11 and 16 and then dried.
  • the filaments at 18 are threaded around guide rollers 16 and 17 which are driven by a certain drive means, not shown.
  • the thus drafted and dried filaments may be further processed by several additional steps for oiling, heat treating, crimping and the like.
  • the products may be composite conjugated filaments to be prepared by the conjugated spinning technique.
  • the final products may be modified to tows or staple fibers.
  • the spinning liquid used in the present process is a solution of acrylonitrile polymer in nitric acid having a concentration of 6080% by wt. According to our experiments, it has been found that with nitric acid having a concentration lying outside the above specified range, it is very difiicult to acquire the desirous effects, even when other spinning and treating conditions are adopted as suggested by the present invention.
  • the bath liquid will arrive at the spinneret outlet along the extruded spinning liquid streams on account of the inherent surface tension of the bath liquid so that in effect the conventional dip spinning process where the spinneret is completely immersed in the bath would be brought about, thus the desirous effect attainable with the present invention would not be realized.
  • the spun product when the spinneret is positioned at a more distant place than the above specified upper limit or mm., the spun product will represent a considerable difference in its coloring performance. In this case, the green filaments as extruded from the spinneret are liable to conjoin with each other in the course of passage through the free air space above the bath surface. In addition, it has been ascertained that the thus spun and coagulated final products represent normally a large amount of naps formed thereon. Therefore, under the above-mentioned spinning condition, it is unable to manufacture superior polyacrylonitrile synthetic fibers.
  • the swelling degree of the coagulated filaments at the outlet of the coagulating bath is adjusted to be less than 350%.
  • this specified uppermost range is exceeded, the desirous homogeneity in the coloring performance appearing at a later step may be considerably injured. Similarly, alarge amount of naps and turbo-flies may frequently be encountered.
  • the nitric acid component contained in the coagulated filaments must be removed as much as possible therefrom and for this purpose the filaments are washed with fresh water.
  • the degree of swelling of the filaments is selected to less than 300%, as was mentioned hereinbefore. With a higher degree of swelling, it has been found upon a large number of our practical experiments that the homogeneously dyeing characteristics are substantially affected adversely and the amount of turbo-flies and naps will be considerably and disadvantageously increased, as with higher swelling degree at the end of the coagulation step.
  • the amount of turboflies encountered in the process according to this invention will amount generally to 0.20.3 g. per 1 kg. of the filaments, while the value amounts to 0.7l.6 g.
  • Acrylonitrile synthetic fibers as produced by the process according to this invention indicate those manufactured from acrylonitrile polymers by the wet or dry spinning method or the like.
  • the acrylonitrile polymer as used herein throughout the present invention includes not only the polymer per se, but also copolymers or a mixture of said polymer and copolymer.
  • copolymer as used throughout the present specification should be interpreted as including every copolymer (including block copolymers and graft polymers) of a copolymerizable monomer with acrylonitrile.
  • Representative monomers copolymerizable with acrylonitrile and employable in the present process are acrylic acid; alpha-chloroacrylic acid; alpha-bromoacrylic acid; methacrylic acid, acrylates such as methylmethacrylate, methoxymethacrylate, ethylmethacrylate, methylacrylate, ethylacrylate, alpha-chloroacrylic acid methyl or -ethyl ester; vinyl chloride, -fiuoride, or -bromide; vinylidene chloride; methacrylonitrile, acrylamide; methacrylamide; alpha-chloroacrylamide and their alkyl substitutes; methylor ethyl vinylketone; vinyl carboxylates such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl stearate; N-vinyl imids such as N-vinyl phthalimid, N-vinyl succinoimid; methyl malonic acid esters; it
  • the spinning liquid is prepared by dissolving the acrylonitrile polymer in nitric acid of about 6080%-concentration.
  • nitric acid it is preferable to remove therefrom occasionally included nitrous compounds as carefully as possible.
  • solvent nitric acid either having a lower concentration than 60% or a higher concentration than 80%, it is difficult to obtain the desirous results even when other operating conditions should be selected within the respective limits as specified for carrying out the present invention.
  • Salts, acid, and like, impurities may be included within a certain range in the solvent nitric acid without inviting an appreciably adverse effect if the solvent has a proper acid concentration as above specified.
  • the spinning liquid is forcibly extruded from the spinneret orifices and the temperature of the liquid should be kept between 20 C. and 50 C., preferably between C. and C.
  • the ambient atmosphere around the spinneret is generally and preferably selected to be air which constitutes an open atmospheric space. But, under certain circumstances, air may be replaced by an inert gas or gases such as nitrogen, carbon dioxide or the like which should preferably be confined in a limited space.
  • the atmosphere in the above sense must be preferably kept between -20 C. and 50 C., advantageously between 5 C. and 35 C. It is disadvantageous that the ambient atmosphere should contain a considerable amount of mist of nitric acid or water, because it will injure the evenly coloring characteristics of the manufactured filaments or the like.
  • the coagulation bath liquid is composed of nitric acid of l045 wt. percent concentration and the temperature of the bath should be kept between 20 C. and 5 C., preferably -10 C. and 0 C. Other acids, salts and like impurities may be included in the bath without any appreciable adverse effect, if the quantity of the contained impurities is within an allowable range.
  • the bath may be of the horizontal type. Under circumstances, however, the bath may be of the vertical type such as the funnel spinning type. In the latter case, the flow velocity of the bath liquid is so selected that no considerable tension is induced in the green filaments as extruded and accompanied by the down-flowing bath liquid. Under these operating conditions, the swelling degree of the spun and coagulated filaments as measured at the outlet of said bath should be selected to be 350% or less.
  • the temperature of the Water washing bath providing for the removal of the nitric acid content in the spun filaments after coagulation is set to 40 C. at the highest. It is naturally preferable to keep the treating filaments under the lowest tension as posible. It is the requisite operating condition to keep the swelling degree of the filaments to be less than 300% as measured at the outlet of the water washing bath by properly selecting the coagulating conditions and the water washing conditions.
  • the respective swelling degrees of the spun filaments as measured at the outlets of the coagulating bath and the washing bath vary considerably depending upon the composition of the polymer, the conditions of the spinning liquid, the coagulating conditions and the like, ranging generally from about to about 600%.
  • the swelling degree of the filaments under treatment will decrease when the polymer contains a hydrophilic copolymer and increases with an increase of the temperature of the coagulating bath. It will decrease with an increase of polymer concentration, viscosity of spinning liquid, concentration of solvent nitric acid and that of the coagulating acid bath. Under consideration of these tendencies, the swelling degrees in the above sense of the filaments under spinning are conditioned to the aforementioned specific ranges.
  • the water-washed filaments are subjected finally to a considerable draft of 300% or more while being heated by contact with boiling water, steam or hot air.
  • the filaments should be dried preferably under tension to a certain degree. If the filaments not yet dried should be heat treated under slackened conditions, for instance, by contact with boiling water, the generation of naps could be increased considerably, and in addition, the dyeing characteristics would be adversely affected in the direction of increase of dyed specks when dyed at a later stage.
  • the aforementioned advantageous phenomenon is found to be peculiar to the process according to this invention, in contrast to the conventional wet spinning process. Therefore it was found that for carrying out the 7 process in accordance with the present invention the filaments should be dried preferably under tension.
  • the swelling degree as used throughout the present specification is measured as follows:
  • EXAMPLE 1 A certain quantity of acrylonitrile polymer consisting of acrylonitrile 90% and methyl acrylate 10% was dissolved in a quantity of 70%-nitric acid so as to provide a spinning solution of the polymer having a concentration of 18%.
  • a coagulating bath was prepared by introducing a certain quantity of 30%-nitric acid in a bath vessel such as shown at 5 on the drawing and kept at C.
  • a spinneret was held at a distance of 3 mm. from the free liquid surface of said bath and the spinning solution at C., was extruded from the orifices of said spinneret and caused to travel vertically through the free air space above the bath surface into the acid bath.
  • the temperature of the ambient atmosphere was 3 C.
  • the thus coagulated filaments were taken out from the coagulating bath and washed under nearly no tension with fresh water kept at 15 C.
  • the swelling degrees of the filaments as measured upon said coagulation and water washing operations were respectively as 241% and 230%.
  • the water washed filaments were then drafted in boiling water to 700% of their length, and further oiled, dried and crimped as in the usual way.
  • EXAMPLE 2 An acrylonitrile polymer comprising acrylonitrile 95%, acrylamide 4.5% and sodium methallyl sulfonate 0.5% was dissolved in 75%-nitric acid to provide a spinning solution having a polymer concentration of 14%. This spinning solution was processed in the following two different ways:
  • the spinning solution, 3 C. was extruded through 100 orifices, each of 0.20 mm. bore, of a spinneret kept at a 5 mm.-distance above a coagulation bath consisting of 33%-nitric acid solution, 3 C., into the latter.
  • the temperature of the ambient air atmosphere was 3 C.
  • the thus coagulated filaments were taken out from the bath at a speed of 40 m./min., washed with fresh water at 15 C., drafted to 1,000% of their length in a steam atmosphere at 100 C., dried under continuous tension and finally wound up on a conventional winder.
  • the filaments thus produced represented 2 denier per filament.
  • the solution was extruded from 100 orifices, each of 0.09 mm. bore, into a coagulation bath containing 33%- nitric acid, 3 C.
  • the thus coagulated filaments were taken out from the coagulation bath at a speed of 7 m./ min., washed with fresh water at 15 C., drafted to 1,000% of their length in a steam atmosphere at 100 C., dried under continuous tension, and finally wound up on a conventional winder.
  • the denier per filament amounted to 2.
  • the degrees of swelling were measured to 316% and 294%, respectively, when measured after the coagulation and water washing operations.
  • the thus coagulated filaments were taken out from the bath at a speed of 8 m./min., washed with fresh water at 18 C., drafted to 1,000% of their length in a steam atmosphere at 100 C., dried under constant tension, and finally wound up by a conventional winder.
  • the obtained results were as follows:
  • EXAMPLE 4 An acrylonitrile polymer comprising acrylonitrile 95%, methyl methacrylate 4.5% and sodium salt of styrene sulfonic acid 0.5% was dissolved in 65 %-nitric acid containing about 1% of sodium sulfate for the preparation of a spinning solution containing 15% of the polymer. Then, this spinning solution was extruded under pressure through 80 orifices each being of 0.10 mm. bore, of a conventional spinneret in the following three different ways:
  • a coagulating bath liquid consisting of a 39%-nitric acid solution was constantly recirculated at 2 C. through a bath reservoir, and the above prepared spinning liquid, 5 C., was extruded under pressure into the bath liquid after passage through an air space, 5 C., having a travel distance about 3 mm. for the extruded solution.
  • the thus coagulated filaments were taken out under slight tension from the bath at a speed of 7 m./min., washed with fresh water at C., drafted to 1,000% of their length in steam at 100 C., dried under constant tension and finally wound up on a conventional winder.
  • the swelling degrees of the thus prepared filaments were measured to 21 and 227%. resnectivelv. at the termination of the coagulating and water-washing operations.
  • EXAMPLE 5 An acrylonitrile polymer comprising acrylonitrile 90%, methacrylamide 5% and methyl methacrylate 5% was employed as the starting material for the preparation of the spinning liquid, and synthetic fibers were prepared therefrom in the following four different ways as shown at I, II, III and IV. The resulted filaments were tested as to the quantity of generated turbo-flies, the evenness of the coloring characteristics and the amount of generated naps, as in the several foregoing experiments. The two last mentioned data were determined as in the foregoing Example 2. Turbo-flies were measured under the following turbo-stapling conditions:
  • EXAMPLE 6 An acrylonitrile polymer comprising acrylonitrile methyl acrylate 8% and allylsulfonic acid 2% was dissolved in 65%-nitric acid so as to provide a spinning solu tion having a polymer concentration of 14%, while a 35 %-nitric acid solution, kept at 2 C., was recirculated through a horizontal type coagulation bath tank. Then, the spinning solution, 0 C., was extruded through orifices, each being of 0.20 mm. bore, through variously different air passages of 5, 25, 50, 100 and mm., into said acid bath. The ambient temperature around the spinneret was measured to 15 C.
  • a process for the manufacture of acrylonitrile synthetic fibers comprising preparing a spinning solution by dissolving a polymer selected from the group consisting of a homopolymer of acrylonitrile and copolymers of acrylonitrile and monomers copolymerizable therewith in nitric acid having a concentration of from 60 to 80 weight percent, and wherein the temperature of said spinning solution varies from 20 C. to 50 C., extruding all of said spinning solution through a spinneret which is disposed from 1 to 100 mm.
  • said coagulating bath comprises an aqueous solution of nitric acid having a concentration of from to 40 weight percent wherein the temperature of said gaseous medium varies from 20 to 50 0, wherein the temperature of said coagulating bath varies between 20 and 5 C., whereby the evaporation of nitric acid solvent of said spinning solution is substan tially depressed, guiding the resulting filaments through said coagulating bath wherein the swelling of said filaments exiting from said coagulating bath is less than 350 weight percent, washing the resulting filaments have a swelling of less than 300 weight percent, stretching the filaments to at least 300% and drying the filaments.
  • gaseous medium is atmospheric air, carbon dioxide or nitrogen.
  • said polymer is a homopolymer of acrylonitrile or a copolymer of acrylonitrile with a monomer selected from the group consisting of methylacrylate, acrylamide, sodium methallyl sulfonate, vinyl acetate, methyl methacrylate, sodium salt of styrene sulfonic acid, methacrylamide, and allyl sulfonic acid.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
US772955A 1967-11-09 1968-11-04 Process for the manufacture of acrylonitrile synthetic fibers Expired - Lifetime US3636187A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7169267 1967-11-09
ZA703425A ZA703425B (en) 1967-11-09 1970-05-20 Process for the manufacture of acrylonitrile synthetic fibprocess for the manufacture of acrylo-nitrile synthetic fiers bers

Publications (1)

Publication Number Publication Date
US3636187A true US3636187A (en) 1972-01-18

Family

ID=26412805

Family Applications (1)

Application Number Title Priority Date Filing Date
US772955A Expired - Lifetime US3636187A (en) 1967-11-09 1968-11-04 Process for the manufacture of acrylonitrile synthetic fibers

Country Status (5)

Country Link
US (1) US3636187A (de)
CH (1) CH509420A (de)
DE (1) DE1807781A1 (de)
FR (1) FR1593141A (de)
ZA (1) ZA703425B (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3871950A (en) * 1972-04-28 1975-03-18 Asahi Chemical Ind Hollow fibers of acrylonitrile polymers for ultrafilter and method for producing the same
US4181694A (en) * 1972-04-28 1980-01-01 Asahi Kasei Kogyo Kabushiki Kaisha Method for producing hollow fibers of acrylonitrile polymers for ultrafilter
US4695415A (en) * 1985-01-24 1987-09-22 Mitsubishi Rayon Co., Ltd. Method for producing acrylic fiber precursors

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3034635C2 (de) * 1980-09-13 1982-08-05 Hoechst Ag, 6000 Frankfurt Fäden und Fasern aus Carboxylgruppenhaltigen Acrylpolymeren, ihre Verwendung und Verfahren zu ihrer Herstellung

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3871950A (en) * 1972-04-28 1975-03-18 Asahi Chemical Ind Hollow fibers of acrylonitrile polymers for ultrafilter and method for producing the same
US4181694A (en) * 1972-04-28 1980-01-01 Asahi Kasei Kogyo Kabushiki Kaisha Method for producing hollow fibers of acrylonitrile polymers for ultrafilter
US4695415A (en) * 1985-01-24 1987-09-22 Mitsubishi Rayon Co., Ltd. Method for producing acrylic fiber precursors

Also Published As

Publication number Publication date
ZA703425B (en) 1971-05-27
DE1807781A1 (de) 1969-06-19
FR1593141A (de) 1970-05-25
CH509420A (de) 1971-06-30

Similar Documents

Publication Publication Date Title
US2558735A (en) Method of forming dyed shaped articles from acrylonitrile polymerization products
US2723900A (en) Spinning of acrylonitrile polymers
US2577763A (en) Wet spinning process
US3341645A (en) Method of producing viscose rayon staple and a spinning apparatus for use in the method
US2948581A (en) Method of producing a synthetic fiber
US2426719A (en) Wet spinning of acrylonitrile polymers
US3415922A (en) Mist spinning
US2697023A (en) Spinning acrylonitrile
US3088793A (en) Spinning of acrylonitrile polymers
US2284028A (en) Dry spinning process
US3855382A (en) Process for producing flame-retardant acrylic fibers
US3636187A (en) Process for the manufacture of acrylonitrile synthetic fibers
US3080210A (en) Spinning of acrylonitrile polymers
US3180845A (en) Method of preparing void free fibers from acrylonitrile polymers
US2743994A (en) Method of producing shaped articles from polymeric materials
US2920934A (en) Process of producing non-fibrillating acrylonitrile polymer filaments with wet steamtreatment and products produced thereby
US2734041A (en) Compositions of matter comprising
US2984912A (en) Art of producing filamentary polyacrylonitrile
US3384694A (en) Method of producing aligned acrylonitrile polymer filament yarns
US3885013A (en) Method for producing acrylic synthetic fibers
US3410940A (en) Mist spinning process
US4869856A (en) Method for producing carbon fibers from acrylonitrile fiber strands
US3451140A (en) Production of acrylic synthetic fibers
US3147322A (en) Method for preparing acrylonitrile synthetic fiber
US3052512A (en) Art of producing polyacrylonitrile filamentary materials