US2716586A - Wet spinning of acrylonitrile polymers - Google Patents

Wet spinning of acrylonitrile polymers Download PDF

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US2716586A
US2716586A US245697A US24569751A US2716586A US 2716586 A US2716586 A US 2716586A US 245697 A US245697 A US 245697A US 24569751 A US24569751 A US 24569751A US 2716586 A US2716586 A US 2716586A
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water
ethylene carbonate
bath
weight
spinning solution
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John M Terpay
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Industrial Rayon Corp
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Industrial Rayon Corp
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Priority to NL79123D priority Critical patent/NL79123C/xx
Priority to NLAANVRAGE7303598,A priority patent/NL172230B/xx
Priority to BE513901D priority patent/BE513901A/xx
Priority to US245697A priority patent/US2716586A/en
Application filed by Industrial Rayon Corp filed Critical Industrial Rayon Corp
Priority to GB21409/52A priority patent/GB716081A/en
Priority to FR1065710D priority patent/FR1065710A/fr
Priority to DEI6305A priority patent/DE1030970B/de
Priority to CH311155D priority patent/CH311155A/fr
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—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
    • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
    • D01F13/04—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of synthetic polymers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • This invention relates to the production of fibers from acrylonitrile polymers and copolymers by the wet-spinning method. More particularly, this invention is concerned with a process employing aqueous baths for the coagulation of ethylene carbonate-type spinning solutions of such polymers.
  • a highly advantageous selection would involve one which could satisfy, among others, the following conditions: (a) a bath made with low cost coagulant components; (b) a bath which could be continuously regenerated with facility and high efficiency, particularly as to the recovery and recycling of the solvent component therein for reuse in making a spinning solution; and (c) a bath capable of successful and continuous spinning and of producing suitable fibers under normal-type operating conditions, e. g. temperature, yarn speed, equipment, etc.
  • Aqueous-type baths provide an answer to condition (a) because of their relatively lower material cost.
  • condition (b) calling for high efiiciency in the used-bath reclamation operation, the most desirable situation would appear to be an aqueous bath comprising a minimum number of coagulant components so as to minimize the number of separation steps and the extent of treatment necessary to recover and recycle the polymer solvent. Accordingly, an aqueous bath which can be handled and treated during the recovery operation as an essentially two-component bath system, i.
  • the polymer solvent could be recovered from a minimum quantity of used bath and recycled substantially directly after only one separation step, i. e., the evaporation of water from the used bath.
  • successful water-bath spinning is said to be achieved by maintaining very low bath temperatures, i. e., below 10 C. and preferably, about 0 C.
  • very low bath temperatures i. e., below 10 C. and preferably, about 0 C.
  • Methods employing exceedingly 10w bath temperatures are not considered desirable because of the inherent operational difficulties presented such as, for example, the additional refrigeration cost required and the exceedingly low spinning speeds in such low temperature operations.
  • aqueous-bath spinning conditions have been discovered under which successful spinning can be achieved with a water bath consisting essentially of only two components, i. e., water and solvent. Moreover, these spinning conditions permit normal-type operations particularly as to spinning temperatures, yarn speeds, and equipment.
  • this may be accomplished by forming a spinning solution of acrylonitrile polymers and copolymers containing in the polymer molecule at least about by weight of acrylonitrile, such spinning solution comprising the acrylonitrile polymer, ethylene carbonate as a solvent, and water in an amount between about 2.5% and 18.5% by weight.
  • This spinning solution is extruded through a spinneret into a coagulating liquid comprising water and between about 10% and 50% by weight of ethylene carbonate, and the total of the water and the ethylene carbonate in the coagulating liquid comprising at least about by weight thereof.
  • the cloud point of the spinning solution should be below about 65 C.
  • the polymeric spinning solutions of the present invention contain water, in an amount between about 2.5% and 18.5% by Weight, in combination with the ethylene carbonate and the acrylonitrile polymer.
  • Particular advantages are derived when the water in the spinning solution is maintained at between about 10% and 15%.
  • polymer solids at a concentration of between about 8% and 30% by weight and preferably, between about 12% and 18% solids, the balance of the spinning solution, with advantage, consisting essentially of ethylene carbonate and water.
  • small amounts, i. e., less than about 8% by weight, of polyhydric alcohol compounds, e. g., ethylene glycol, propylene glycol, dipropylene glycol, etc. may also be incorporated in the spinning solution of the present process. This procedure for incorporating such materials is the subject of the H. A. Bruson and T. W.
  • the temperature of the spinning solution may be maintained with advantage between about 40 and 80 C. and preferably, between about 50 and 75 C. Maintaining these spinning solutions at temperatures above 80 C. for extended periods of time, e. g., by storing for periods of one-half hour or more, preparatory to extrusion, is not considered desirable in view of the accelerated rate of hydrolysis of the ethylene carbonate taking place at such higher temperatures.
  • the elevated temperatures are maintained for only a short period of time for a relatively small amount of material.
  • extrusion temperatures, or more specifically, spinneret ternperatures above about 80 C. may be employed, if desired, without excessive decomposition of ethylene carbonate.
  • the combined effect of these variable factors is best expressed by what is termed herein as the cloud point of a given water-containing spinning solution prepared within the general limits previously described.
  • the cloud point as defined herein is an expression in terms of temperature which characterizes the spinnability for a given spinning solution under the aqueous-bath conditions specified in the process. In general, it is the point of change from a cloudy or turbid solution to a clear, transparent solution.
  • the cloud point of the water-containing spinning solutions should be below about 65 C. With advantage, the cloud point of the spinning solutions should be between about and 65 C., and preferably between about and 55 C.
  • a spinning solution containing 10% water, 78% ethylene carbonate, and 12% of a polymer having a molecular weight of about 45,000, has a cloud point between about and C. Accordingly, this formulation calls for an extrusion temperature of at least about to C. and preferably, 50 to 60 C.
  • a similar spinning solution containing 15% water and 14% polymer has a cloud point between about and C., thus calling for an extrusion temperature of at least about C. and preferably, about C.
  • the coagulating liquid into which such spinning solutions are extruded comprises water and between about 10% and 50% by weight of ethylene carbonate measured at a distance within three inches from the spinneret, andadvantageously between about 10% and 40%.
  • the total of the water and the ethylene carbonate comprises at least about 95% by weight of the bath liquid.
  • coagulating baths consisting essentially of water and ethylene carbonate.
  • relatively small amounts of other compounds, preferably organic compounds may also be present in the bath provided, of course, that they do not amount to more than about 5% by weight of the coagulating bath, and further, that they do not other wise adversely affect the efficiency of the process.
  • the materials which can be tolerated in the water baths of the present process are those which are not harmful to the spinning operation and do not have to be separated from the reclaimed solvent by an additional recovery step at a later stage.
  • such additives may be characterized as those which are compatible with the solvent and do not materially reduce its solvent power when present in the solvent in concentrations up to about 8% by weight of the solvent, and in addition, which do not render it necessary to handle and treat the used bath as a three-component system rather than as a two-component system during the bath recovery and reclamation treatments.
  • glycol compounds e. g., ethylene glycol, dipropylene glycol, etc.
  • such compounds may be initially incorporated into the spinning solution in amounts up to about 8% for any desired purpose and then permitted to accumulate in the water bath at concentrations of not more than about 5% by weight of the bath.
  • concentrations of dipropylene glycol in the bath would be about 1.5%
  • concentration of dipropylene glycol therein would be about 2.8%.
  • Such baths are treated as if they were two-component systems, i. e., solvent and water.
  • the solvent recovery operation is performed in one major step, i. e., by evaporating the water from the used bath and recycling the solvent together with the glycol for re-use as polymer solvent.
  • the ethylene carbonate content of the bath particularly advantageous results are achieved when the concentration thereof in the bath is maintained between about 20% and 30% by weight of the coagulating bath.
  • the aqueous coagulating medium may be maintained with advantage at a temperature between about 45 and C; Ifdesired, or if found necessary, temperatures below or above this range may be employed provided, however, that difiiculties such as poor coagula tion, usually occurring at the lower temperatures, and excessive hydrolysis and decomposition of the ethylene carbonate, usually occurring at the higher temperatures, are successfully avoided.
  • a lower bath temperature such as, for example, about 5 or more below that of the extrusion temperature. Coagulants between 50" and 75 C. are particularly advantageous.
  • the resulting formed fibers after removal from thecoagulating liquid may then be subjected to one or more stretching operations, and thereafter if desired, may be heat treated in a relaxed condition.
  • the resulting product may be collected as a continuous filament yarn or it may be crimped and cut into staple fiber.
  • a spinning solution is extruded through a suitable spinneret 11 immersed in an aqueous coagulating bath liquid 12 contained in a trough 13.
  • the freshly formed thread 15 is withdrawn from the bath 12 and conducted to a roller 16.
  • the roller 16 may be a thread-advancing device, and thus, if desired, a further aqueous treating liquid may be applied to the thread on the roller 16 by means of a delivery tube 18.
  • the thread 15 discharged from the roller 16 is conducted to a succeeding roller 19 similar to roller 16 but operating at a greater peripheral speed, thereby imparting an air stretch to the thread between the rollers.
  • treating or washing liquid e. g., water, may be applied to the thread on the roller 19 by means of a delivery tube 20.
  • the thread 15 from the roller 19 is then conducted through a stretching chamber 22 containing a heated aqueous medium24 entering the chamber through tube 25 and leaving through tube 26.
  • the heated medium 24 may be an aqueous liquid, e. g., water, above about 80 C. or it may be steam.
  • the thread withdrawn from the chamber 22 is then conducted to a succeeding roller 28 also similar to roller 16 and operating at a greater peripheral speed than the roller 19, thereby stretching the thread between the roller 19 and the roller 28.
  • the thread 15 from the roller 28 is conducted through a heated aqueous medium 29 contained in a trough 30 and thereafter conducted to a roller 32, also similar to roller 16 and operating at a lower peripheral speed than the roller 23, thereby causing the thread 15 to relax between the roller 28 and the roller 32.
  • the heated medium 29 may be an aqueous liquid, e. g., water, above about 80 C., and preferably closer to 100 C. If de sired, an aqueous washing liquid, e. g., water with or without dispersed oleaginous materials, may be applied to the thread on the roller 32 by means of a delivery tube 33.
  • the thread 15 from the roller 32 may be conducted directly to a thread-collecting device 37 and wound thereby as a package on a bobbin 38, or if desired, the thread may be conducted first to an internally heated, thread-advancing device having a progressively dimin ishing periphery in the direction of thread advance and thereafter collected by the device 37.
  • Advancing device 35 may be employed both to dry and, if desired, to heat treat under relaxed tension at temperatures higher than 100 C.
  • Example I 14 parts of polyacrylonitrile having an average molecular weight of about 47,000 is dissolved in 51 parts of ethylene carbonate and the resulting solution is then filtered and deaerated. To this solution is added a mixture of 20 parts of ethylene carbonate and 15 parts of water. The resulting solution having a cloud point of about 55 C. is heated to 70 C. and extruded at a rate of about 200 grams per minute through a spinneret having 412 holes (0.003 inch diameter) into a coagulating bath containing 75 parts of water and 25 parts of ethylene carbonate. The bath temperature is maintained at about 60 C. while the freshly formed filaments are drawn through the bath for a distance of about 48 inches.
  • the thread is withdrawn from the bath at a rate of about 9.3 meters per minute and passed over two positivelydriven rolls positioned outside of the baths, the first roll being driven at a linear velocity of 9.3 meters per minute and the second roll at 44.5 meters per minute, thereby airstretching the yarn 4.8 times.
  • the yarn is then drawn through a stretching bath containing water and about 13% of accumulated ethylene carbonate at a temperature of about 100 C. for a distance of about 25 inches and thereby given an additional stretch of 1.64 times resulting in an over-all stretch of about 7.7 times.
  • the stretched thread is then passed under relaxed tension through a substantially all water bath at about 90 C. for a distance of about 25 inches.
  • the resulting relaxed thread is collected at a rate of about 66 meters per minute and thereafter dried.
  • the final product is a colorless, white thread having a tenacity of about 3.3 grams per denier and an elongation at break of about 18%.
  • Example II of about 20 C. is heated to 50 C. and. extruded at a rate of about 19 grams per minute through a spinneret having 40 holes (0.003 inch diameter) into a coagulating bath containing parts of water and 20 parts of ethylene carbonate.
  • the bath temperature is maintained at about 65 C. while the freshly formed filaments are drawn through the bath for a distance of about 40 inches.
  • the thread is withdrawn from the bath at a rate of about 41 meters per minute and passed over a positivelydriven thread-advancing device on which it is washed with a stream of water at 60 C. delivered at the rate of about 60 cubic centimeters per minute.
  • the washed thread leaving the thread-advancing device is passed through a tube in which it is brought into direct contact with a jet of steam and stretched about ten times.
  • the resulting stretched thread is then relaxed and dried at a rate of about 400 meters per minute on a tapered thread-advancing device internally heated to about 135-l45 C.
  • the final product is a colorless white thread having a tenacity of about 2.3 grams per denier and an elongation at break of about 10%.
  • Example 111 12 parts of a copolymer containing acrylonitrile and 5% of 2-vinylpyridine having an average molecular weight of about 45,000 is dissolved in 48 parts of ethylene carbonate and the resulting solution is filtered and deaerated. To this solution is added a mixture of 30 parts of ethylene carbonate and 10 parts of water to yield a spinning solution having a cloud point of about 23 C. The resulting solution is then heated to 70 C. and extruded at the rate of about 35 grams per minute through a spinneret having 412 holes (0.003 inch diameter) into a coagulating bath containing 80 parts of water and 20 parts of ethylene carbonate. The bath temperature is maintained at about 60 C.
  • the thread is then withdrawn from the bath at a rate of about 8.8 meters per minute by means of a driven roll positioned above the bath and then passed over a second similar roll, driven at a sufliciently higher peripheral speed to effect an air stretch between the rolls of about 2.95 times.
  • the thread is then drawn through a stretching bath consisting of water and about l3% of accumulated ethylene carbonate at a temperature of about C. for a distance of about 20 inches.
  • the thread in this bath is given an additional stretch of 2.73 times resulting in an overall stretch of about eight times.
  • the stretched thread is then passed under relaxed tension through a bath consisting of water at about 80 C. for a distance of about 20 inches.
  • the resulting thread is continuously collected at about 62 meters per minute and thereafter washed and dried.
  • the resulting white thread has a tenacity of about 2.8 grams per denier and an elongation at break of about 18%.
  • the dried yarn is then crimped and cut into staple lengths.
  • Example IV The procedure and conditions of this. example were the same as Example Ill except that the washed and dried thread is passed through an aqueous liquid containing 0.05% of an oleaginous yarn finishing agent to a tapered internally heated thread-advancing device which has a uniform decrease in periphery at a rate of about 9% for each 17.5 meters of yarn stored thereon. Steam at pounds per square inch gauge pressure is introduced and circulated in the device. The resulting thread is then collected at a rate of about 77 meters per minute and has a tenacity of about 3.1 grams per denier and an elongation at break of about 17% and a free shrinkage in boiling water of 12%.
  • Example V 14 parts of polyacrylonitrile having an average molecular weight of about 45,000 is dissolved in a mixture of 50 parts of ethylene carbonate and 6 parts of dipropylene glycol and the resulting solution is then filtered and deaerated. To this solution, there is added a mixture of 20 parts of ethylene carbonate and 10 parts of water. The resulting solution having a cloud point of about 46 C. is heated to 55 C. and extruded at a rate of about 66 grams per minute through a spinneret having 412 holes (0.003 inch diameter) into a coagulating bath consisting initially of about 70% water and 30% ethylene carbonate. The bath temperature is maintained at about 60 C. while the freshly formed filaments are drawn through the bath for a distance of about 55 inches.
  • the dipropylene glycol By maintaining the ethylene carbonate content in the bath at about 30%, the dipropylene glycol accumulates therein to a maximum of about 3 the balance being about 64% water.
  • the thread withdrawn from the coagulating bath is processed according to the procedure of Example I, to yield a final product similar to the product of Example I.
  • the portions of the coagulating bath liquid which are continuously removed from the bath to maintain the ethylene carbonate content at 30% are processed as follows:
  • the bath liquid is subjected to a flash distillation under sub-atmospheric pressure so as to remove the water present therein.
  • the residual mixture of ethylene carbonate and dipropylene glycol is then treated with decolorizing carbon, filtered and recycled directly for use as solvent in the preparation of additional quantities of spinning solution.
  • the spinning solution cloud point values which are referred to in the examples, and which were previously characterized as indices of good spinnability, are determined in the following manner.
  • a solution containing the desired proportions of polymer, ethylene carbonate and water is heated until a clear, transparent solution is obtained.
  • the resulting solution is then permitted to cool slowly, with stirring, until the first signs of cloudiness appear.
  • the temperature at which this change takes place is termed the cloud point.
  • the turbidity or cloudiness in the solution at the cloud point temperature is believed to be a precipitation of the polymer from the solution, whereas with solutions which are still clear and non-turbid at about 20 C., the turbidity or cloudiness which appears upon further cooling may be the precipitation of the polymer component or it may be a freezing or crystallization of the solvent component and more likely a combination of both.
  • the cloud point it is particularly important that the solution be cooled slowly. Accordingly, when making cloud point determinations, a
  • cooling medium should be employed which is about 5 C.
  • this invention may be practiced under a variety of spinning solution conditions which are, of course, within the general limits hereinbefore described.
  • variables already mentioned in this connection are polymer solids content, water content, molecular weight of the polymer and a choice of homopolymer or copolymer.
  • thread deniers as the final yarn product, i. e., thread deniers as low as 75 to 100 up to heavy denier tows for staple.
  • the process is found particularly useful in making the heavy denier type, i. e. over 500 denier and up to 3,000 or more.
  • these denier can be produced at low speeds or more advantageously, at higher speeds ranging from 30 meters per minute or higher.
  • the extrusionrto-withdrawal ratio is advantageously maintained greater than about 1.3' to 1.
  • the withdrawal speeds are increased to about 45 to 55 meters per minute, the extrusion-to-withdrawal ratio is decreased.
  • an extrusion-to-withdrawal ratio greater than about 1 to 1.
  • the formed fibers after withdrawal from the coagulating bath may then be subjected to a stretching operation, the amount of stretch varying from about 3 to 10 times or more as desired.
  • a stretching operation may be accomplished in the presence of hot aqueous media such as, for example, in a stretching bath consisting essentially of water at about 100 C. or at higher temperatures, e. g., in steam or in higher boiling-point aqueous baths containing organic or inorganc compounds.
  • the stretching operation may be accomplished in two steps, the first, an air stretch immediately after leaving the coagulating bath, and the second, in a hot aqueous stretching bath, e.
  • the thread which is withdrawn from the coagulating bath may with advantage be preliminarily washed or rinsed with water to remove solvent therefrom and thereafter, stretched at temperatures of 100 C. or over, e. g., in steam. In general, more stretch can be obtained at the higher stretch temperatures.
  • the resulting stretched thread thereafter may be collected directly in package form and subsequently relaxed or, if desired, the relaxing operation may be performed immediately after the stretching operation in a continuous manner.
  • the stretched thread may be relaxed in hot aqueous media, e. g., water, steam, etc. at'temperatures above about 80 C. and preferably 100 C. or above.
  • the relaxing operation may be combined with greater advantage with a treatment on an internally heated roll at the higher temperatures, e. g., on a tapered, thread-advancing reel or pair of threadadvancing drums into which heated fluid such as steam under pressure is circulated.
  • the proportion of acrylonitrile in the polymer molecule should be at least about 80% by weight and more advantageously, at least about by weight.
  • a minor proportion of one or more vinyl compounds can be copolymerized with the acrylonitrile, for example: vinyl esters (vinyl acetate, vinyl formate, vinyl benzoate), vinyl ethers, and vinyl ketones; acrylic acid and its esters and amides; methacrylic acid and its esters, amides, and nitrile; maleic, itaconic, fumaric, crotonic acids and their esters, amides and nitriles; allyl alcohol and its esters and ethers; styrene and nuclear substituted styrenes, e.
  • chloroand dichloro-styrene halogenated monoethylenic compounds such as vinyl chloride, vinyl fluoride, vinylidene chloride, 1,2-dichloro-propene-1, 1,2- dichloro-propene-2, allyl chloride, methallyl chloride, 2-chloro-allyl alcohol, and l-allyloxy-3-chloro-2-propanol; N-vinyl compounds such as N-vinyl pyrrolidone, N-vinyl succinimide, N-vinyl carbazole, N-tertiary butyl acryl-" amide, N-tertiary octyl acrylamide; 2- or 4-vinylpyridine; and the like.
  • halogenated monoethylenic compounds such as vinyl chloride, vinyl fluoride, vinylidene chloride, 1,2-dichloro-propene-1, 1,2- dichloro-propene-2, allyl chloride, methallyl chlor
  • the acrylonitrile polymers may be prepared by any suitable polymerization method such as, for example, polymerization with oxygen-yielding catalysts, e. g., benzoyl peroxide, hydrogen peroxide, tertiary butyl hydroperoxide, potassium or ammonium persulfate, etc.
  • oxygen-yielding catalysts e. g., benzoyl peroxide, hydrogen peroxide, tertiary butyl hydroperoxide, potassium or ammonium persulfate, etc.
  • Redox polymerization systems employing oxygen-yielding catalysts such as the above in combination with reducing agents such as sodium bisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, etc., may be used with advantage.
  • the resulting polymer is washed with water to remove any remaining impurities, and preferably, distilled or demineralized water is employed so as to achieve a minimum of impurities in the final poly
  • the molecular weights of the polymeric materials are preferably within the range of 10,000 and 250,000, or even higher, although copolymers having molecular weights between 30,000 and 100,000 may be used with particular advantage in the production of fibers.
  • the spinning solutions employed in the process of the present invention may be prepared by various methods.
  • one may prepare a room-temperature slurry of the polymer, ethylene carbonate and water and thereafter heat the slurry to effect dissolution of the polymer.
  • the spinning solution may be prepared by first preparing a polymer solution without the water comprising ethylene carbonate and between about and of the polymer solids, deaerating this solution and then making the final spinning solution by adding the desired quantity of water in the form of a waterethylene carbonate mixture.
  • the ethylene carbonate may be recovered from those portions of the coagulating bath liquid which are continuously removed from the bath to iaintain the desired water-ethylene carbonate ratio.
  • the recovery operation involves evaporating the water from the bath portion and then recycling the residuum comprising substantially ethylene carbonate for use as solvent in the preparation of additional quantities of spinning solution.
  • the ethylene carbonate may be treated with decolorizing carbon and filtered prior to its re-use in the preparation of additional spinning solution.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 2.5% and 18.5% by weight and a polymer of acrylonitrile containing in the polymer molecule at least about 80% by Weight of acrylonitrile; extruding the resulting spinning solution into a coagulating liquid comprising water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 10% and 50% by weight, and the total of the water and the ethylene carbonate in said coagulating liquid comprising at least about 95 by weight thereof.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 2.5 and 18.5% by weight and between about 8% and by weight of a polymer of acrylo nitrile containing in the polymer molecule at least about 80% by Weight of acrylonitrile, said spinning solution having a cloud point below about 65 C.; extruding the resulting spinning solution into a coagulating liquid comprising water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 10% and by weight, and the total of the water and the ethylene carbonate in said coagulating liquid comprising at least about 95% by Weight thereof.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 2.5% and 18.5% by weight and a polymer of acrylonitrile containing in the polymer molecule at least about 80% by weight of acrylonitrile, said spinning solution having a cloud point below about 65 C.; extruding the resulting spinning solution into a coagulating liquid comprising water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 10% and 40% by weight, and the total of the water and the ethylene carbonate in said coagulating liquid comprising at least about 95% by weight thereof.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 2.5% and 18.5% by weight and a polymer of acrylonitrile containing in the polymer molecule at least about by weight of acrylonitrile, said spinning solution having a cloud point below about 65 C.; extruding the resulting spinning solution into a coagulating liquid consisting essentially of water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 10% and 40% by weight.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 2.5% and 18.5% by weight and between about 8% and 30% by weight of a polymer of acrylonitrile containing in the polymer molecule at least about 80% by weight of acrylonitrile, said spinning solution having a cloud point below about 65 C.; extruding the resulting spinning solution into a coagulating liquid com prising water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 20% and 30% by weight, and the total of the water and the ethylene carbonate in said coagulating liquid comprising at least about by weight thereof.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 2.5 and 18.5% by weight and between about 8% and 30% by weight of a polymer of acrylonitrile containing in the polymer molecule at least about 80% by weight of acrylonitrile, said spinning solution having a cloud point below about 65 C.; extruding the resulting spinning solution into a coagulating liquid consisting essentially of water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 20% and 30% by weight.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 2.5% and 18.5% by Weight and between about 8% and 30% by weight of a polymer of acrylonitrile containing in the polymer molecule at least about 80% by weight of acrylonitrile, said spinning solution having a cloud point below about 65 C.; maintaining said spinning solution between about 40 and 80 C.; extruding the resulting spinning solution into a coagulating liquid comprising water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 10% and 40% by weight, and the total of the water and the ethylene carbonate in said coagulating liquid comprising at least about 95% by weight thereof.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount be tween about 2.5% and 18.5% by weight and between about 8% and 30% by weight of a polymer of acrylonitrile containing in the polymer molecule at least about 80% by Weight of acrylonitrile, said spinning solution having a cloud point below about 65 C.; maintaining said spinning solution between about 40 and 80 C.; extruding the resulting spinning solution into a coagulating liquid comprising water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 10% and 40% by weight, and the total of the water and the ethylene carbonate in said coagulating liquid comprising at least about 95% by weight thereof; maintaining said coagulating liquid between about 45 and 80 C.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 10% and 15% by weight and between about 12% and 18% by weight of a polymer of acrylonitrile containing in the polymer molecule at least about 90% by Weight of acrylonitrile, said spinning solution having a cloud point below about 65 C.; maintaining said spinning solution between about 50 and 75 C.; extruding the resulting spinning solution into a coagulating liquid consisting essentially of water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 20% and by weight; maintaining said coagulating liquid between about 50 and 75 C.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, water in an amount between about 2.5% and 18.5% by Weight and between about 8% and 30% by weight of a polymer of acrylonitrile containing in the polymer molecule at least about 80% by weight of acrylonitrile, said spinning solution having a cloud point between about 15 and 65 C.; maintaining said spinning solution between about and 80 C.; extruding the resulting spinning solution into a coagulating liquid comprising water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 10% and 40% by weight, and the total of the water and the ethylene carbonate in said coagulating liquid comprising at least about 95% by weight thereof; maintaining said coagulating liquid between about and 80 C.; stretching the resulting fiber in the presence of an aqueous medium at a temperature above about 80 C.
  • the method of forming an acrylonitrile polymer fiber comprising the steps, forming a spinning solution comprising ethylene carbonate, Water in an amount between about 2.5% and 18.5% by Weight and between about 8 and 30% by weight of a polymer of acrylonitrile containing in the polymer molecule at least about 80% by weight of acrylonitrile, said spinning solution having a cloud point between about 20 and C.; maintaining said spinning solution between about 40 and C.; extruding the resulting spinning solution into acoagulating liquid comprising water and ethylene carbonate; maintaining the ethylene carbonate concentration in said coagulating liquid between about 10% and 40% by weight, and the total of the water and the ethylene carbonate in said coagulating liquid comprising at least about by weight thereof; maintaining said coagulating liquid-between about 45 and 80 C.; stretching the resulting fiber in the presence of an aqueous medium at a'temperature above about 80 C.; heating the resulting stretched fiber under relaxed tension at a temperature above about 80 C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US245697A 1951-09-08 1951-09-08 Wet spinning of acrylonitrile polymers Expired - Lifetime US2716586A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
NL79123D NL79123C (fr) 1951-09-08
NLAANVRAGE7303598,A NL172230B (nl) 1951-09-08 Inrichting voor het trekken van glasvezels.
BE513901D BE513901A (fr) 1951-09-08
US245697A US2716586A (en) 1951-09-08 1951-09-08 Wet spinning of acrylonitrile polymers
GB21409/52A GB716081A (en) 1951-09-08 1952-08-26 Improvements in wet spinning of acrylonitrile polymers
FR1065710D FR1065710A (fr) 1951-09-08 1952-08-29 Perfectionnements à la préparation des polymères d'acrylonitrile
DEI6305A DE1030970B (de) 1951-09-08 1952-09-03 Verfahren zur Herstellung von Faeden und Fasern aus Polyacrylsaeurenitril
CH311155D CH311155A (fr) 1951-09-08 1952-09-06 Procédé de préparation de fibres en polymère d'acrylonitrile.

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CH (1) CH311155A (fr)
DE (1) DE1030970B (fr)
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GB (1) GB716081A (fr)
NL (2) NL79123C (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2869975A (en) * 1955-03-28 1959-01-20 Du Pont Process for shrinking and setting polyacrylonitrile textile filaments with specific chemical shrinking agents
US2869974A (en) * 1955-03-02 1959-01-20 Du Pont Process for shrinking polyacrylonitrile textiles with specific chemical shrinking agents
US2948581A (en) * 1955-12-20 1960-08-09 American Cyanamid Co Method of producing a synthetic fiber
US3066008A (en) * 1959-03-09 1962-11-27 Courtaulds Ltd Process for producing fibers from copolymers of acrylonitrile and vinylidene chloride
US3068188A (en) * 1957-03-27 1962-12-11 Du Pont Composition comprising a synthetic linear polymer, organic solvent, and an inorganic salt
US3069221A (en) * 1959-06-30 1962-12-18 Hermes Julius Dyeing of acrylonitrile polymeric structures
US3069218A (en) * 1959-06-30 1962-12-18 Hermes Julius Dyed acrylonitrile containing textile having controlled shrinkage and processes for forming same
US3069222A (en) * 1959-06-30 1962-12-18 Hermes Julius Acrylonitrile containing textile having controlled shrinkage and processes for forming same
US3073669A (en) * 1958-09-06 1963-01-15 Asahi Chemical Ind Method for producing shaped articles from polymers and copolymers of acrylonitrile
US3091507A (en) * 1956-08-27 1963-05-28 Dow Chemical Co Method of preventing ring dyeing in aquagel acrylonitrile polymer fibers by steamingthe fibers
US3268490A (en) * 1962-03-07 1966-08-23 Sunden Olof Method of preparing polyacrylonitrile fibers
US3404204A (en) * 1964-03-07 1968-10-01 American Cyanamid Co Method of producing high-shrinkage acrylic fibers
US3505445A (en) * 1967-11-17 1970-04-07 Monsanto Co Solvent removal process for wet spun fibers
US3523150A (en) * 1966-12-12 1970-08-04 Monsanto Co Manufacture of industrial acrylic fibers
WO2010106143A1 (fr) 2009-03-20 2010-09-23 Dsm Ip Assets B.V. Filet pour l'aquaculture

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1057285B (de) * 1955-08-18 1959-05-14 Dr Paul Halbig Verfahren zur Herstellung von Faeden oder Fasern aus Polymerisaten
DE1184896B (de) * 1960-09-07 1965-01-07 Hans J Zimmer Verfahrenstechni Verfahren zur Herstellung spinnbarer, nicht gelierender, etwa 15- bis 22 gewichtsprozentiger Loesungen von Polyacrylnitril oder dessen Mischpolymerisaten

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2558733A (en) * 1949-06-08 1951-07-03 American Cyanamid Co Method of producing synthetic fibers from polymers and copolymers of acrylonitrile
US2570257A (en) * 1950-06-17 1951-10-09 Ind Rayon Corp Spinning of acrylonitrile polymers
US2570200A (en) * 1949-06-13 1951-10-09 Ind Rayon Corp Wet extrusion of acrylonitrile polymers
US2577763A (en) * 1949-11-05 1951-12-11 American Viscose Corp Wet spinning process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2558733A (en) * 1949-06-08 1951-07-03 American Cyanamid Co Method of producing synthetic fibers from polymers and copolymers of acrylonitrile
US2570200A (en) * 1949-06-13 1951-10-09 Ind Rayon Corp Wet extrusion of acrylonitrile polymers
US2577763A (en) * 1949-11-05 1951-12-11 American Viscose Corp Wet spinning process
US2570257A (en) * 1950-06-17 1951-10-09 Ind Rayon Corp Spinning of acrylonitrile polymers

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2869974A (en) * 1955-03-02 1959-01-20 Du Pont Process for shrinking polyacrylonitrile textiles with specific chemical shrinking agents
US2869975A (en) * 1955-03-28 1959-01-20 Du Pont Process for shrinking and setting polyacrylonitrile textile filaments with specific chemical shrinking agents
US2948581A (en) * 1955-12-20 1960-08-09 American Cyanamid Co Method of producing a synthetic fiber
US3091507A (en) * 1956-08-27 1963-05-28 Dow Chemical Co Method of preventing ring dyeing in aquagel acrylonitrile polymer fibers by steamingthe fibers
US3068188A (en) * 1957-03-27 1962-12-11 Du Pont Composition comprising a synthetic linear polymer, organic solvent, and an inorganic salt
US3073669A (en) * 1958-09-06 1963-01-15 Asahi Chemical Ind Method for producing shaped articles from polymers and copolymers of acrylonitrile
US3066008A (en) * 1959-03-09 1962-11-27 Courtaulds Ltd Process for producing fibers from copolymers of acrylonitrile and vinylidene chloride
US3069222A (en) * 1959-06-30 1962-12-18 Hermes Julius Acrylonitrile containing textile having controlled shrinkage and processes for forming same
US3069218A (en) * 1959-06-30 1962-12-18 Hermes Julius Dyed acrylonitrile containing textile having controlled shrinkage and processes for forming same
US3069221A (en) * 1959-06-30 1962-12-18 Hermes Julius Dyeing of acrylonitrile polymeric structures
US3268490A (en) * 1962-03-07 1966-08-23 Sunden Olof Method of preparing polyacrylonitrile fibers
US3404204A (en) * 1964-03-07 1968-10-01 American Cyanamid Co Method of producing high-shrinkage acrylic fibers
US3523150A (en) * 1966-12-12 1970-08-04 Monsanto Co Manufacture of industrial acrylic fibers
US3505445A (en) * 1967-11-17 1970-04-07 Monsanto Co Solvent removal process for wet spun fibers
WO2010106143A1 (fr) 2009-03-20 2010-09-23 Dsm Ip Assets B.V. Filet pour l'aquaculture

Also Published As

Publication number Publication date
BE513901A (fr) 1900-01-01
CH311155A (fr) 1955-11-30
FR1065710A (fr) 1954-05-28
DE1030970B (de) 1958-05-29
NL79123C (fr) 1900-01-01
NL172230B (nl)
GB716081A (en) 1954-09-29

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