US3088793A - Spinning of acrylonitrile polymers - Google Patents

Spinning of acrylonitrile polymers Download PDF

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US3088793A
US3088793A US315A US31560A US3088793A US 3088793 A US3088793 A US 3088793A US 315 A US315 A US 315A US 31560 A US31560 A US 31560A US 3088793 A US3088793 A US 3088793A
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Prior art keywords
filaments
bath
polymer
percent
spinning
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US315A
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John P Knudsen
Pompelio A Ucci
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Monsanto Chemicals Ltd
Monsanto Chemical Co
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Monsanto Chemicals Ltd
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Priority to NL259701D priority Critical patent/NL259701A/xx
Priority to BE582871D priority patent/BE582871A/xx
Priority to NL243961D priority patent/NL243961A/xx
Priority to GB28897/59A priority patent/GB888496A/en
Priority to FR805759A priority patent/FR1240159A/fr
Priority to CH7851359A priority patent/CH397949A/fr
Priority to DE19591410383 priority patent/DE1410383A1/de
Application filed by Monsanto Chemicals Ltd filed Critical Monsanto Chemicals Ltd
Priority to US315A priority patent/US3088793A/en
Priority to FR848797A priority patent/FR78986E/fr
Priority to ES263665A priority patent/ES263665A2/es
Priority to GB84/61A priority patent/GB977942A/en
Priority to CH1561A priority patent/CH469821A/fr
Priority to BE598817A priority patent/BE598817R/fr
Priority to DE1469044*CA priority patent/DE1469044B2/de
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    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/04—Supporting filaments or the like during their treatment
    • D01D10/0436—Supporting filaments or the like during their treatment while in continuous movement
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • 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 relates to the manufacture of improved shaped articles such as fibers, filaments, yarns and the like produced from acrylonitrile polymers. More particularly, this invention concerns said shaped articles characterized by having a normally lustrous appearance and possessing an optimum balance of longitudinal and later-a1 properties and a process for producing same.
  • filaments of such polymers are formed by dissolving the polymers in a suitable solvent and then removing the solvent from a flowing stream of the solution to form filaments therefrom.
  • filaments of acrylonitrile polymers are prepared either by the dry spinning process or by the wet spinning process, as is well known. The specific technique chosen results in a compromise among yarn properties, the economic aspects of the technique involved, and other considerations. I There are advantages and disadvantages associated with the employment of each process. For example, dry spinning has the advantage of considerably higher spinning speeds than those which can be attained with wet spinning.
  • filaments having voids which are merely crushed together are laterally weak.
  • the art has found that the lateral properties of the filaments can be improved substantially by subjecting the filaments to an annealing operation.
  • One such annealing procedure includes a series of elevated and reduced pressure treatments applied to the filaments. More specifically, annealing can be accomplished by placing the acrylonitrile polymer fila ments in a closed chamber, subjecting them to a high temperature and pressure in the presence of wet steam and then evacuating the chamber. This treating cycle is repeated as many times as needed. If will be appreciated that this annealing operation as just described is expensive and time consuming.
  • Omitting the annealing step in the aftertreatment of the wet spun acrylic filaments results in a filament having a tendency to splinter or fibrillate; and hence, the filaments have a low abrasion resistance. This tendency to fibrillate is minimized by annealing the filaments.
  • the improvement is thought to result from the interface surfaces of the collapsed voids being rendered less separable.
  • the polymer lattice has a pattern resembling that of a fine, extremely small meshwork, although the interstices are usually somewhat irregular in size and shape.
  • the micropores present in filaments produced by ordinary wet spinning techniques as they leave the coagulating bath are more or less spherical with the polymer lattice defining such interstitial spaces. The distances across these spaces are ordinarily about 250 A. to 3000 A. or greater.
  • the frequency of occurrence of the micropores in the filaments produced by ordinary wet spinning techniques employing aqueous coagulating baths can be estimated under an electron microscope and is usually around 35-90 10 per gram of polymer. The presence of these pores is believed to explain the anomalously low density of normal filaments as they leave the coagulating bath. At this point the apparent density of the filaments produced by ordinary wet spinning techniques employing aqueous coagulating baths is usually about 0.4 to 0.5 gram per cubic centimeter.
  • the voids that are visible under the optical phase microscope are quite different from the micropores or interstitial spaces not visible under an optical phase microscope but readily apparent under an electron microscope.
  • voids as used herein signifies enclosed spaces or surface pits of the filaments which are visible under an optical phase microscope and which do not contain acrylonitrile polymer, whether or not the enclosed spaces contain a fluid or are collapsed.
  • micropore as used herein signifies extremely diminutive enclosed spaces or surface pits of the filaments that .are not visible under an optical phase microscope but visible under an electron microscope and that do not contain acrylonitrile polymer, whether or not the enclosed spaces contain a fiuid or are collapsed.
  • these micropores When the freshly spun filaments are stretched, these micropores as would be expected assume the geometric configuration of ellipsoids. Subsequent collapsing of the porous structure of the filaments due to the presence of these micropores can be accomplished by drying the filaments under tension at an elevated temperature. Annealing the filaments renders the interstitial interface surfaces of the micropores less separable. Hence, annealing has been regarded as an important step in the attainment of acceptable lateral physical properties in the filaments.
  • the size and frequency of the interstitial spaces are correlated with each other so as to produce filaments offering an optimum combination of longitudinal and lateral properties. Therefore, a method is provided whereby the size and frequency of the normally occurring micropores are changed substantially to produce filaments having such properties. Moreover, a method has been found for the manufacture of filaments of acrylonitrile polymers in which certain desirable aspects of both the dry spinning process and the wet spinning process are combined in a most favorable manner provided the filaments are processed by the steps of the instant invention as de scribed hereinbelow. Although the method includes facets of both dry and wet spinning processes, it is most closely akin to the wet spinning process in that the coagulation of the filaments is accomplished in a liquid bath.
  • these objects are accomplished in accordance with the invention by continuously extruding a solution of an acrylonitrile polymer through a desired number of orifices in a spinneret disposed in air or other inert gaseous medium and continuously directing the thusformed streams of the solution for a short distance through the medium, wherein only a very small amount of the solvent, if any, is evaporated into the ambient medium as a gas.
  • the streams then are passed into a liquid which is a precipitant for the polymer and an extractant for the solvent, such as an aqueous coagulating bath. In the liquid bath the streams of polymer are coagulated into filaments by the substantial removal therefrom of the solvent as a liquid.
  • the solvent employed is preferably N,N-dimethylacetamide, N,N-dimethylformamide or the like; and the coagulating bath preferably is composed essentially of the solvent and water.
  • the filaments produced possess most advantageous physical properties and differ in structure from other acrylonitrile polymer filaments heretofore known in the art.
  • the extrusion rate of the polymer and the speed of withdrawal of the filaments from the coagulating bath are correlated so that the filaments are subjected to a draw ratio usually of 0.820.
  • the filaments may be stretched at this point up to just short of the point at which filamentary breakage occurs.
  • the draw ratio is between 0.5 and 5.0 times. Often higher draw ratios are desired whereby to obtain higher spinning speeds.
  • Draw ratio is a convenient term for designating the attenuation or shrinkage that often occurs during various steps in the production of manmade filaments. Draw ratio is the number resulting from the division of the speed of withdrawal by the speed of feed of the filaments between two given points. In the production of wet-spun filaments draw ratio as applied to the attenuation or shrinkage in the coagulating bath is the number derived by dividing the measured length of filaments produced by the length that should have been produced as calculated from the extrusion rate of polymer through the spinneret.
  • the filaments are continuously removed therefrom and directed through a second bath.
  • This bath is preferably composed of hot water wherein additional solvent remaining in the coagulated filaments is removed therefrom and a considerable stretch is imparted thereto to orient the polymer molecules thereof.
  • the filaments are permitted to relax continuously under a low tension in a hot liquid or hot gaseous atmosphere and/or then continuously dried.
  • the necessity of the continuous relaxation depends upon the spinning conditions employed. It has been found that when N,N-dimethylacetamide or N,N*dimethylformamide is employed as the solvent for the acrylonitrile polymer and when an aqueous coagulating bath consisting primarily of Water and solvent and maintained within the critical temperature range of +10 C. and 40 C. is used, the relaxing step unexpectedly can be omitted and yet produce filaments of textile grade. Moreover, it is not neces sary to dry the filaments under tension since the filaments are substantially free of voids and when dried at room temperature whether relaxed or under tension display densities corresponding to normally produced filaments dried under tension to insure that the voids and micropores therein are collapsed.
  • FIGURE 1 is a side elevational view partly in section showing schematically an apparatus arrangement of the type which can be used in carrying out the process of the present invention
  • FIGURE 2 is a schematic view showing the produced filaments being dried by a different drying means
  • FIGURE 3 is a flow sheet illustrating the manipulative steps used in carrying out the process of the invention.
  • FIGURE 4 is a reproduction of a photomicrograph at a magnification of about times of acrylonitrile polymer filaments of textile grade which give the appearance of smooth, glassy rods;
  • FIGURE 5 is a reproduction of a photomicrograph of greater magnification of an acrylonitrile polymer filament that contains numerous voids along the length thereof;
  • FIGURE 6 is a reproduction of a photomicrograph of an acrylonitrile polymer filament substantially free of voids.
  • FIGURE 7 is a schematic view of a simple laboratory abrasion testing apparatus.
  • the present invention provides novel filaments which differ markedly from previous wet-spun acrylonitrile polymer filaments.
  • the novel filaments are obtained by dissolving an acrylonitrile polymer in N,N-dimethylacetamide, N,N-dimethylformamide or the like and by extruding the resulting solution through a short air gap and into a coagulating bath composed pri marily of water and the selected solvent.
  • the coagulating bath In order to produce the filaments novel herein the coagulating bath must be maintained below +10 C. The lowest temperature employed is limited to the point just above where the water-solvent mixture of the coagulating bath freezes.
  • acrylonitrile polymer polyacrylonitrile, copolymers, and terpolymers of acrylonitrile, and blends of polyacrylonitrile and copolymers of acrylonitrile with other polymerizable mono-olefinic materials, as well as blends of polyacrylonitrile and such copolymers with small amounts of other polymeric materials, such as polystyrene.
  • a polymer made from a monomeric mixture of which acrylonitrile is at least '70 percent by weight of the polymerizable content is useful in the practice of the present invention.
  • useful copolymers are those of 80 or more percent of acrylonitrile and one or more percent of other mono-olefinic monomers.
  • Block and graft copolymers of the same general type are Within the purview of the invention. Suitable other monomers include vinyl acetate,
  • vinyl esters of monocarboxylic acids vinylidene chloride, vinyl chloride and other vinyl halides, dimethyl fumarate and other dialkyl esters of fumaric acid, dimethyl maleate and other dialkyl esters of maleic acid, methyl acrylate and other alkyl esters of acrylic acid, styrene and other vinyl-substituted aromatic hydrocarbons, methyl methacrylate and other alkyl esters of methacrylic acid, vinyl-substituted heterocyclic nitrogen ring compounds, such as the vinyl imidazoles, etc., the alkylsubstituted vinylpyridines, vinyl chloroacetate, allyl chloroacetate, methallyl chloroacetate, allyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl phthalate, and the corresponding esters of other aliphatic and aromatic dicarboxylic acids, glycidyl acrylate, glycid
  • these non-dyeable fiber-forming copolymers may be blended with polymers or copolymers which are in themselves more dye-receptive by reason of their physical structure or by reason of the presence of functional groups chemically reactive with the dyestuif, whereby the dyestufi is permanently bonded to the polymer in a manner which lends resistance to removal thereof by the usual laundering and dry cleaning procedures.
  • Suitable blending polymers may be polyvinylpyridine, polymers of alkyl-substituted vinylpyridine, polymers of other vinyl-substituted N-heterocyclic compounds, the copolymers of the various vinyl-substituted N-heterocyclic compounds and other copolymerizable monomers, particularly acrylonitrile.
  • the polymers just described may be prepared by any conventional polymerization procedure, such as mass polymerization methods, solution polymerization methods, or aqueous emulsion methods.
  • the polymerization is normally catalyzed by known catalysts and is carried out in However, the preferred practice utilizes suspension polymerization wherein the polymer is prepared in finely divided form for immediate use in the filament-forming operations.
  • the preferred suspension polymerization involves batch procedures, wherein monomers are charged with an aqueous medium containing the necessary catalyst and dispersing agents.
  • a more desirable method involves the semicontinuous procedure in which the polymerization reactor containing the aqueous medium is charged with the desired monomers gradually throughout the course of the reaction. Entirely continuous methods involving the gradual addition of monomers and the continuous withdrawal of polymer can also be employed.
  • the polymerization is catalyzed by means of a watersoluble peroxy compound, for example, the potassium, ammonium and other water-soluble salts of peroxy acids, sodium peroxide, hydrogen peroxide, sodium perborate, the sodium salts of other peroxy acids, and other watersoluble compounds containing the peroxy group:
  • a watersoluble peroxy compound for example, the potassium, ammonium and other water-soluble salts of peroxy acids, sodium peroxide, hydrogen peroxide, sodium perborate, the sodium salts of other peroxy acids, and other watersoluble compounds containing the peroxy group:
  • a wide variation in the quantity of peroxy compound is possible. For example, from 0.1 to 3.0 percent by weight of the polymerizable monomer may be used.
  • the socalled redox catalyst system also may be used.
  • Redox agents are generally compounds in a lower valent state which are readily oxidized to the higher valent state under the conditions of reaction. Through the use of this reduction-oxidation system, it is possible to obtain polymerization to a substantial extent at lower temperatures than otherwise ⁇ Would be required.
  • Suitable redox agents are sulfur dioxide, the alkali metal and ammonium bisulfites, and sodium formaldehyde sulfoxylate.
  • the catalyst may be charged at the outset of the reaction, or it may be added continuously or in increments throughout the reaction for the purpose of maintaining a more uniform concentration of catalyst in the reaction mass.
  • the latter method is preferred because it tends to make the resultant polymer more uniform in regard to its chemical and physical properties.
  • Suitable reagents for this purpose are the water-soluble salts of fatty acids, such as sodium oleate and potassium stearate, mixtures of water-soluble fatty acid salts, such as common soaps prepared by the saponification of animal and vegetable oils, the amino soaps, such as salts of triethanolamine and dodecylmethylamine, salts of rosin acids and mixtures thereof, the water-soluble salts of half esters of sulfonic' acids and long chain aliphatic alcohols, sulfonated hydrocarbons, such as.
  • alkyl aryl 'sul fonates and any other of a wide variety of wetting agents, which are in general organic compounds containing both hydropho-b'c and hydrophilic radicals.
  • the quantity of emulsifying agent will depend upon the particular agent selected, the ratio of monomer to :be used and the conditions of polymerization. In general, however, from 0.1 to 1.0 weight percent based on the Weight of the monomers can be employed.
  • the emulsion polymerizations are preferably conducted in glass or glass-lined vessels provided with means for agitating the contents therein.
  • rotary stirring devices are the most effective means of insuring the intimate contact of the reagents, but other methods may be successfully employed, for example, by rocking or rotating the reactors.
  • the polymerization equipment generally used is conventional in the art and the adaptation of a particular type of apparatus to the reaction contemplated is within the province of one skilled in the art.
  • the optimum methods of polymerization for preparing fibepforming acrylonitrile polymers involve the use of polymerization regulators to prevent the formation of polymer units of excessive molecular weight.
  • Suitable regulators are the alkyl and aryl mercaptans, carbon tetrachloride, chloroform, dithioglycidol and alcohols.
  • the regulators may be used in amounts varying from 0.001
  • the polymers from which the filaments are produced in accordance with the present invention have specific viscosities within the range of 0.10 to 0.40.
  • the specific viscosity value, as employed herein, is represented by the formula:
  • the die filter 11 wherein undissolved particles and foreign materials in the solution are removed.
  • gear pumps are used to propel the solution through the filter 11 and to meter same to the spinneret assembly 12.
  • This assembly is suitably mounted and positioned such that the face 13 of the spinneret is horizontally disposed preferably along a plane substantially parallel to the upper surface of the coagulating liquid 14- contained in an opentop spinning trough or bath 15.
  • the solution may be extruded through a single orifice or a plurality of orifices in the spinneret to form a filament or a bundle of filaments 16 as desired.
  • the extruded streams of polymer are directed substantially vertically downward and under filament guide 17 disposed in said trough
  • a second filament guide 18 is suitably positioned in said trough so that the filaments directed thereunder will pass through the liquid 14 for a predetermined distance sufiicient to cause the solution to coagulate as desired.
  • Fresh liquid 14 is supplied to trough 15 through pipe 2% (which may be water or Water containing a desirable quantity of solvent) and is withdrawn therefrom through pipe 21.
  • the coagulated filaments are withdrawn by employment of a positively driven roller 22 or other thread advancing means, the peripheral speed of which preferably is synchronized with the extrusion speed so that the filaments during their travel between the spinneret and the rollers may be attenuated, and if desired attenuated up to the point just short of where filamentary breakage occurs. As indicated above, most of the attenuation will take place between the face of the spinneret and the upper surface of the coagulating bath.
  • the filaments After passing around roller 22 and an idler roll 23, the filaments are directed into a second spinning trough 24 containing a liquid 25. Fresh liquid is supplied to trough 24 through pipe 26 and is withdrawn therefrom through pipe 27.
  • a washing liquid such as hot water is supplied from a spray or shower head 33, the liquid being collected in a container or 'tray 34. It will be recognized that the washing operation can be accomplished in more than one stage of the process and by employment of other known washing means.
  • the filaments After leaving rollers 28 and 30, the filaments are directed through a liquid in 8 a third trough 35 by being passed under guides 36 and 37.
  • the liquid 38 in this trough is normally water at an elevated temperature.
  • the filaments are withdrawn therefrom by means of a driven roller 40* and associated idle roller 41 operated at a peripheral speed less than that of the peripheral speed of rollers 28 and 30 so that the filaments are permitted to relax substantially com pletely and thereby to shrink during their travel in trough 35.
  • Fresh water is supplied to trough 65 through an inlet pipe 42 and is withdrawn through an outlet pipe 43.
  • the filaments may be directed around a tapered roller or rollers and progressively led from the end having the larger circumference to the end having the smaller circumference, the rollers being immersed in a liquid or having a liquid applied thereto.
  • the filaments are passed through a finish bath liquid 44 contained in a vessel 45 and com posed of a lubricant or like beneficial treating agent.
  • the filaments after being withdrawn from liquid 44 are dried.
  • the filaments are continuously directed around a pair of driven drying drums 46 and 47 heated internally with steam or the like. Thereafter, the filaments are subjected to additional operations such as crimping, cutting, and then are collected in the form of stable filter, continuous filament yarn, or tow.
  • the filaments after being stretched and washed are layed by means of a traversing piddler 48 or like guide means onto a moving endless belt 50 (in a zig-zag pattern).
  • This belt passes through a drying cabinet 51 in which hot air or other suitable drying gas at an elevated temperature is directed onto the filaments therein.
  • the filaments are continuously dried in a tension-free condition.
  • An advantage of this embodiment is that the filaments are permitted to relax and are dried; thus the relaxing and the drying of the filaments are accomplished in one step. It should be understood that it is entirely possible to dry the filaments while not being tensioned by the employment of other drying means.
  • the filaments may be dried suitably by being conveyed by and suspended in a stream of air.
  • FIGURE 3 is a flow sheet illustrating another and preferred arrangement of the manipulative steps used herein.
  • the acrylonitrile polymer is dissolved in N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF) or the like to form a spinning solution.
  • DMA N,N-dimethylacetamide
  • DMF N,N-dimethylformamide
  • This solution is extruded from a spinneret through a short air gap into a cold aqueous coagulating bath to form a bundle of filaments.
  • the temperature of bath is critical in this embodiment and is maintained in the range of +10 C. to 40 C.
  • the bath may be composed of l00 20 percent water with a corresponding 0-8() percent of the solvent.
  • the filaments possess an initially dense structure and such structure is believed to be closely related to the improved ultimate physical properties.
  • the filaments may be stretched between the spinneret and the means used to withdraw them from the coagulating bath to a substantial extent, if desired. From the coagulating bath the dense filaments so produced are passed through a hot aqueous bath Where they are given an orientation stretch. The filaments can be washed free or substantially free of solvent either before or after they have been stretched in the second bath. Continuously relaxing of the stretched filaments is an optional step in that satisfactory filaments can be produced by omitting the relaxation step in accordance with this aspect of the invention. HoW- ever, relaxing of the filaments is recommended. Maximum relaxation of 15 to 18% usually can be obtained by passing the filaments through boiling water where the filaments have been stretched in the second bath 3-6 times.
  • Filaments which have been continuously relaxed show about 10% higher elongation than unrelaxed filaments similarly produced. This increase in elongation is not accompanied by a significant reduction in tenacity.
  • the filaments require a surprisingly low finish pick-up for adequate lubricity and static control. Drying is easily accomplished, the ease probably being due to the initially dense structure.
  • FIGURE is a drawing prepared from a photomicrograph showing a View of part of a filament containing voids or cavities. Enclosed voids in the filament also can be seen by observing a cross section of the filament. Due to the presence of the voids, the light rays impinging thereon are scattered, imparting a dull or subdued luster to the filament.
  • FIGURE 6 is a drawing prepared from a photomicrograph showing a corresponding view of part of a filament substantially free of voids or cavities. Due to the substantial absence of voids, the filament has a lustrous appearance.
  • the novel filaments of the present invention are substantially free of voids and hence have a normally lustrous appearance. However, when desired, delustrants, pigments, and the like can be incorporated in the filaments to produce dull filaments.
  • the marked differences of the novel filaments herein and those heretofore known become more apparent when a comparison of the reticulate filamentary structures is made at magnifications obtainable by the use of an electron microscope.
  • the spinning solution can be prepared by heating and stirring a mixture of a finely divided acrylonitrile polymer of the type described above with a suitable solvent until the polymer is dissolved.
  • a suitable solvent e.g., N,N-dimethylformamide, butyrolactone, dimethyl sulfoxide, N,N-dimethylacetamide and the like are particularly suitable solvents.
  • ethylene carbonate and the like iconcentrated solutions of certain water-soluble inorganic salts, such as zinc chloride, calcium chloride, lithium bromide, cadmium bromide, sodium thiocyanate, etc.
  • the percentage of polymer based on the weight of the solution will depend upon the particular polymer and solvent employed, as well as upon the temperature at which the polymer is spun. It is desirable to employ a solution containing a high percentage of polymer for obvious reasons.
  • An advantage of the present invention is the fact that spinning solutions having much higher temperatures can be employed than ordinarily used in wet spinning. Hence, a greater percentage of polymer in the solution can be used with success.
  • the spinning solution may be maintained prior to and at extrusion at temperatures from about to 180 C. Room temperature is highly satisfactory from an operational standpoint. Ordinarily a solution containing at least 10 percent acrylonitrile polymer is desirable.
  • the spinneret used in accordance with the instant invention can be of the type ordinarly used in dry spinning oper-' ation.
  • An important variable in any spinning process is the orifice diameter of the spinneret. From practical aspects it is often desirable to employ the largest diameter consistent with good spinning. By increasing the orifice size the filtration of the spinning solution becomes less important and the number of spinneret changes due to clogging thereof is reduced. In the present invention one may employ orifices having relatively large diameters due to the fact that the filaments may be given a considerable attenuation immediately after extrusion of the spinning solution. This in practical terms means a reduction in operating cost.
  • filament deniers below 1.0 can be spun readily without difficulty whereas 1.2 to 2.0 denier per filament is generally the least that can be spun in the ordinary wet spinning process.
  • Another advantage of the present process is that a wide range of filament deniers can be spun from a single spinneret, For example, filament deniers from 0.8 to 22 and higher having satisfactory textile properties may be spun from a single spinneret having an orifice diameter of 0.005 inch. This means that filaments having various deniers may be spun conveniently without shut down being required to change from production of one diameter to another.
  • the distance that the spinneret is disposed above the coagulating bath may be varied. Ordinarily, the spinneret is positioned so that its face is between A; and 1 /2 inches above the bath. However, one can increase this distance by taking precaution that adjacent polymer streams do not come in contact with and cohere to each other. For example, a cell through which the streams coaxially pass may be provided to minimize any disturbance thereof.
  • the gas between the spinneret and the coagulating bath and through which the streams of polymer travel is air, although any other gaseous medium that does not adversely affect the filaments may be used.
  • the temperature of the gas may be regulated; however, the temperature normally present during spinning is satisfactory. For best results the spinning variables should be correlated so that less than one percent of the solvent based on the weight of the solution is evaporated into the gaseous medium from the extruded stream.
  • the coagulating filaments as a result are passed through the coagulating bath under a minimum tension; that is, the tension exerted on the coagulat ing filament would be only that tension required to overcome the viscosity forces within the filaments and drag forces in the coagulating bath.
  • isotropic filaments exhibiting only an extremely thin outer skin formation and a reduced susceptibility to skin rupture or fissure to cause undesirable variations in the resulting filaments exist in this zone.
  • the coagulating baths suitable for use in the invention normally contain a non-solvent such as water, or a mixture of a solvent and a nonsolvent for the acrylonitrile polymer.
  • the solvent used in the coagulating bath is preferably the same as the one used in preparing the polymer solution; however, such need not be the case.
  • the bath contain 20 percent to 80 percent solvent.
  • the temperature range for the coagulating bath is preferred to be from 40 to +80 C.
  • one aspect of the invention involves maintaining the bath at a temperature below C. with the polymer being dissolved in N,N-dimethylacetamide, N,N-dimethylformamide or the like. It is preferred that the bath contain 60-70 percent solvent at the lower bath temperatures.
  • the filaments may be given a travel in the coagulating bath, for example, from 2 to 24 inches or more by employment of the two suitably spaced guides and withdrawal rolls as illustrated in FIGURE 1. Between the spinneret and the withdrawal rolls, the filaments, as indicated above, are subjected to a stretching operation to attain a desired substantial attenuation thereof.
  • a second bath is employed following the coagulating bath wherein the filaments are given an additional stretch in order to increase the strength, as well as otherwise to improve the physical properties of the filaments. This improvement results from orientation of the polymer molecules along the filament axis.
  • the second bath may consist simply of water, or it may have the same composition as the coagulating bath but at a greater dilution with water.
  • the temperature of the secondary bath is preferably between 50 and 100 C., the highest feasible temperature being preferred. Draw ratios of up to 10 or higher may be employed, the amount of stretch applied depends on the properties desired for the yarn. Preferred draw ratios are between 1.5 and 8.0.
  • the filaments are washed substantially free of solvent if desired. This may be accomplished by spraying water on the filaments traveling around positively driven rolls. The water extracts the solvent from the filaments as they pass gradually from one end of the rollers to the other end. Other washing means, of course, can be used. Moreover, the
  • washing can be carried out prior to applying the orientation stretch to the filaments as indicated above.
  • the next step is important to the proper practice of the present invention except when low temperature coagulating baths are used and consists of subjecting the filaments to sufiicient temperature at a low tension or zero tension to permit substantially complete relaxation of the filaments.
  • This may be accomplished preferably by continuously passing the filaments through a water bath maintained at a temperature near or at the boiling point of water by means of a thread-advancing device operated at a peripheral speed less than the linear velocity at which the filaments are fed to the water bath.
  • the filaments may shrink at least 15 percent and up to 40 percent of their original length or more.
  • the resulting filaments which are relaxed in hot or boiling water have higher elongation values as compared to filaments produced in a comparable manner but without being permitted to relax.
  • the higher elongation values are attained without a sacrifice of tenacity.
  • an inverse relationship exists between the elongation of the resulting filaments and the temperature at which the filaments are given the orientation stretch. That is to say, for a given orientar tion stretch, filaments having higher elongation are obtained generally where lower stretch temperatures are employed.
  • the step of relaxing is not entirely necessary when one follows the low temperature coagulating bath aspect of the invention.
  • the filaments are permitted to freely shrink, they are dried in a convenient manner. This may be done either under tension or under no tension. Preferably, the filaments are dried while in a completely relaxed condition so that the filaments are dried and relaxed in one operation.
  • the filaments produced by the present invention after leaving the relaxation bath have a substantially reduced porosity and have a smooth, mirror-like surface.
  • the disadvantages associated with drying under tension such as yellowing of the filaments when subjected to high local temperatures on the drying drums and like apparatus used in a tension drying operation, may be avoided and yet produce filaments that have a luster greater than normal wet-spun filaments dried under tension.
  • a spinning solution was prepared by dissolving in N,N- dimethylacetamide' a blend of (A) a coplymer of 97 percent acrylonitrile and 3 percent vinyl acetate and (B) a copolymer of 50 percent acrylonitrile and 50 percent 2-methly-5-viny1pyridine, said blend containing 6 percent vinylpyridine based on the total weight of the blend and having a specific viscosity of 0.12 to give a 26 percent solids solution. The solution was extruded at 25 C.
  • the filaments were withdrawn therefrom at a rate of '186 feet per minute so that a stretch of approximately 6.1 times was imparted to the filaments. Stretch in times, as seen, is the number 13 resulting from the division of the speed of withdrawal by the speed of feed between two points. Then, the filaments were passed around a pair of spaced rollers 30 to 40 times with a total length of the filaments around the rollers at one time being about 120 feet. Water at 50-80 C. was sprayed on the filaments during their travel around said rollers to wash the filaments. Following this washing operation, the filaments were directed into a relaxing bath containing water at 100 C.
  • the filaments so produced were lustrous with an excellent resistance to abrasion and had a tenacity of 2.5 grams per denier, an elongation of 26.0 percent, and a denier of 3.1.
  • EXAMPLE II A spinning solution was prepared in N,N-dimethylacetamide containing 22 percent polymer and 0.1 percent sulfuric acid based on the weight of the solution.
  • the polymer employed was the polymer blend used above in Example I and had a specific viscosity of 0.16.
  • the spinning solution was extruded at 25 C. through a spinneret containing 100 holes, each having a diameter of 0.009 inch, into air for a distance of one inch and into a coagulating bath containing 40 percent N,N-dimethylacetamide and 60 percent water by volume at a temperature of 25 C.
  • the bundle of the thus-formed filaments was removed from the coagulating bath at a rate of 38.4 feet per minute," the rate being correlated to stretch the filaments 6.6 times between the spinneret and the means used for withdrawing the filaments from the coagulating bath.
  • the filaments were passed into a stretch bath maintained at a temperature of 100 C. and containing water.
  • the filaments were withdrawn from the second bath at a rate of 186 feet per minute so that an additional stretch of approximately 4.9 times was imparted to the filaments by employing a thread advancing reel assembly.
  • Water was sprayed on the filaments during their storage on the assembly to wash same.
  • the filaments were relaxed thereby causing them to shrink 5 percent in air at room temperature.
  • a yarn lubricant was applied in a continuous fashion to the filaments, and then the filaments were dried in a tension-free condition by laying the filaments on an endless belt con veyor moving through a drying cabinet.
  • the dried filaments were crimped, cut into staple lengths, and baled.
  • the fibers so-produced were lustrous with an excellent resistance to abrasion and had a tenacity of 2.7 grams per denier and an elongation of 16.4 percent.
  • Example IV The spinning solution of Example II was extruded through various spinnerets having orifices of various diameters as indicated in Table 3. Diverse temperatures and concentrations of the coagulating bath were employed, also as indicated in the table. The filaments so formed were passed through the air above the bath for 4; inch and thence through the bath. The filaments were withdrawn from the bath at a speed such that the filaments were stretched just short of the point at which breaking thereof occurred. The maximum stretches that could be imparted to the filaments are given below.
  • a spinning solution was prepared in N,N-dimethylacetamide containing 18 percent polymer of the type employed above in Example I but having a specific viscosity of 0.25.
  • the spinning solution was extruded at C. through a spinneret containing holes, each having a diameter of 0.005 inch, into air for a distance of /2 inch and then into a coagulating bath containing 10 percent N,N-dimethylacetamide and 90 percent water by volume at a temperature of 27 C.
  • the thus-formed filaments were stretched 1.3 times and then passed through a second bath containing water at 100 C. During their travel through the second bath the filaments were stretched 5.0 times.
  • the filaments were washed and then dried while in a tension-free condition.
  • the spinneret was immersed in the coagulating bath and the same spinning solution was spun into filaments under like conditions. It was fiound that a second bath temperature of 95 C. or above was required to attain stretches of up to 4 to 5 times. Furthermore, stretches greater than 5 times were impossible; below this temperature the maximum stretch obtainable was even less than 4.
  • the filaments can be given an orientation stretch in the second bath over a relatively wide temperature range without sacrifice of yarn properties. From practical considerations this wide latitude of temperature assumes considerable significance, since there is no necessity of rigid temperature control and since more energy is required to maintain the bath at the high temperature required in regular wet spinning.
  • EXAMPLE VII The efiect of various orientation stretches in the second bath and continuous relaxation on the physical properties of the formed filaments in regard to tenacity and elongation was studied while employing a coagulating bath having a relatively low temperature.
  • a spinning solution was prepared in N,N-dimethylacetamide containing 18 percent polymer based on the weight of the solution.
  • the polymer employed was the polymer blend used in Example I above and had a specific viscosity of 0.25.
  • Samples of the spinning solution were extruded through a spinneret containing holes, each having a diameter of 0.0035 inch into air for a distance of inch.
  • the extruded streams of polymer were directed into a coagulating bath containing 70 percent N,N-dimethylacetamide and 30 percent water by volume. The coagulating bath was maintained at 5 C.:l.
  • the extruded streams were directed through this bath for 24 inchesythe bundle of filaments thusfonned was then removed therefrom at a rate of 22 to 4-4 feet per minute, the rate of withdrawal being established in relation to the rate of extrusion so that the filaments were subjected to a draw ratio of 0.8 between the spinneret and the means used to Withdraw the filaments from the coagulating bath.
  • the filaments were passed through a water bath at 60 C. so as to remove residual solvent from the filaments.
  • the filaments were next directed through a water bath at about 100 C. and stretched therein a predetermined extent. Various stretches were given the samples at this stage. Some of the samples were directed into a relaxing bath containing water at about 100 C. and other samples were not. The filaments were collected on cones and dried in air. The tenacity and elongation were measured on the filaments. These results are given in Table 6 below.
  • EXAMPLE VIII Additional spinnings were carried out following the procedure outlined above in Example VII.
  • the acrylonitrile polymer in this instance was a binary copolymer of 94 weight percent acrylonitrile and 6 weight percent vinyl acetate.
  • the effect of various orientation stretches in the second bath and continuous relaxation on the physical properties of the formed filaments in regard to tenacity and elongation while employing coagulating baths having various relatively low temperatures as set forth in Table 7 below was demonstrated.
  • the final filaments had a denier of about 3.1 when permitted to relax and a denier of about 2.7 when not so permitted.
  • a gradual reduction in bath temperature results in a corresponding increase in tenacity.
  • a higher tenacity is obtained when greater stretches are imparted to the filaments in the second bath.
  • the yarn not permitted to relax has physical properties comparable to the yarn permitted to relax.
  • the step of relaxing may be omitted with low temperature coagulating bath spinning without a substantial sacrifice of properties.
  • Spinning solutions were prepared in N,N-dimethylacetamide containing 18 percent polymer based on the weight of the solution.
  • polymer employed was the polymer blend used in Example I; in the second instance, the polymer was a copolymer of 94 weight percent acrylonitrile and 6 weight percent vinyl acetate. These samples in the data which follow in Table 8 are identified as A and B, respectively.
  • Samples of the spinning solution were extruded into filaments by the spinning technique described in Example VII.
  • the coagulating bath was composed of 70 percent N,N-dirnethylacetamide and percent water and was maintained at the temperature indicated in Table 8. The filaments were collected without permitting same to relax.
  • Table 8 Ooagulating Stretch in Tenacity, Elongation, Cycles to Sample bathtemp. second bath gins/den. percent break 100 C. times gm. load
  • the study indicates a general improvement in abrasion resistance as coagulating bath temperature is decreased.
  • the abrasion resistance was measured by using the simple laboratory device disclosed in FIGURE 7. As seen, the device comprises a synchronous motor 80 adapted to drive wheel 81. Near the periphery of wheel 81 is a rotatably mounted peg 82. One end of the yarn 83 which is to be tested for abrasion resistance is attached to the peg as shown. The yarn is threaded around pulley 84 and around one side of a stationary horizontally disposed pin 85.
  • the yarn is passed around pulley 8 with a weight 87 being tied to the other end of the yarn.
  • the pin is a round long rigid metal wire having a smooth surface and a diameter of about 0.006 inch.
  • the motor is operated at 60 revolutions perminute and the revolutions are counted until the yarn breaks.
  • the denier of the yarn in each case was the same.
  • the weight, as indicated above, in the test was 100.grams.
  • a spinning solution was prepared by dissolving a copolymer of 94 weight percent acrylonitrile and 6 weight percent vinyl acetate in N,N-dimethylacetaniide in an amount that the solution contained 25 percent polymer.
  • the solution was extruded into a short air gap and spun into acrylic filaments as described in Example VII.
  • the coagulating bath had a composition of 70 percent N,N-dimethylaceta-mide and 30 percent water and was maintained at a temperature of 10 C.
  • the orientation stretch was 5 .5 times and the filament yarn before drying and collecting was not permitted to relax.
  • the resulting yarn was uptwisted to a twist of 3-5 turns per inch and knitted into a narrow tape 14 ends wide on a tricot knitting machine.
  • the resulting tape was then tested on the Stoll abrader until failure occurred. To break the knitted tape by the use of the Stoll abrader, 506 cycles were required when wet, and 365 cycles were required to break the tape when dry.
  • the polymer solution was extruded through a short air gap and into a coagulating bath composed of 30 percent N,N-dimethylacetamide and 70 percent water and maintained at a temperature of 5 C.
  • the orientation stretch was 5.5 times and the filament yarn before drying and collecting was not permitted to relax.
  • the yarn was knitted into tricot tape as described above and tested on the Stoll abrader. To break the wet tape required 635 cycles on the Stoll abrader whereas dry tape broke at 414 cycles.
  • the present invention makes possible the production of acrylonitrile polymer filaments that have an optimum balance of longitudinal and lateral properties and that are eminently suitable for use in the textile art.
  • the filaments have increased elongation realized without sacrifice of tenacity, the higher elongation enabling the filament to be tougher and to be able to absorb more energy without breakage.
  • the speed at which the filaments may be produced is notably high.
  • filaments that are substantially free from voids and have a high lustrous appearance can be produced. It is not necessary according to the present invention to dry the filaments under tension in order to produce a satisfactory dense fiber structure. Also, the present process lends itself readily to employment on a commercial scale without substantial modification of conventional spinning equipment. Numerous other advantages of the present invention will be apparent to those skilled in the art.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
US315A 1958-12-29 1960-01-04 Spinning of acrylonitrile polymers Expired - Lifetime US3088793A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
NL259701D NL259701A (xx) 1958-12-29
BE582871D BE582871A (xx) 1958-12-29
NL243961D NL243961A (xx) 1958-12-29
GB28897/59A GB888496A (en) 1958-12-29 1959-08-24 Spinning of acrylonitrile polymers
FR805759A FR1240159A (fr) 1958-12-29 1959-09-22 Filage de polymères d'acrylonitrile
CH7851359A CH397949A (fr) 1958-12-29 1959-09-22 Procédé de filage de polymères d'acrylonitrile
DE19591410383 DE1410383A1 (de) 1958-12-29 1959-12-29 Verfahren zur Herstellung von geformten Gegenstaenden aus Acrylnitrilpolymerisaten
US315A US3088793A (en) 1958-12-29 1960-01-04 Spinning of acrylonitrile polymers
FR848797A FR78986E (fr) 1958-12-29 1960-01-04 Filage de polymères d'acrylonitrile
ES263665A ES263665A2 (es) 1960-01-04 1960-12-30 Procedimiento perfeccionado para la obtención de hilados de polímeros de acrilonitrilo
GB84/61A GB977942A (en) 1958-12-29 1961-01-02 Spinning of acrylonitrile polymers
CH1561A CH469821A (fr) 1958-12-29 1961-01-03 Procédé de fabrication de filaments en polymères ou copolymères d'acrylonitrile
BE598817A BE598817R (fr) 1960-01-04 1961-01-04 Filage de polymères d'acrylonitrile
DE1469044*CA DE1469044B2 (de) 1958-12-29 1961-01-04 Verfahren zur Herstellung von Fäden aus einem Acrylnitrilpolymerisat

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3402236A (en) * 1964-01-29 1968-09-17 Chemstrand Ltd Manufacture and treatment of synthetic fibres and fabrics containing the same
US3404204A (en) * 1964-03-07 1968-10-01 American Cyanamid Co Method of producing high-shrinkage acrylic fibers
US3412191A (en) * 1964-12-18 1968-11-19 Mitsubishi Rayon Co Method for producing artificial fibers
US3507948A (en) * 1967-09-29 1970-04-21 Exxon Research Engineering Co Solution spinning of polypropylene
JPS5378326A (en) * 1976-12-17 1978-07-11 Japan Exlan Co Ltd Production of carbon
EP0144793B1 (en) 1983-12-05 1988-10-12 AlliedSignal Inc. High tenacity and modulus polyacrylonitrile fiber and method
US4818458A (en) * 1985-11-26 1989-04-04 Japan Exlan Company Limited Method of producing acrylic fibers
US4902452A (en) * 1986-07-28 1990-02-20 Mitsubishi Rayon Co., Ltd. Process for producing an acrylic fiber having high fiber characteristics
WO1996006209A1 (en) * 1994-08-23 1996-02-29 Monsanto Company Acrylonitrile filament process
US20040223708A1 (en) * 2003-03-24 2004-11-11 Cho Han Sol Enhancement of optical and mechanical properties in a polymeric optical element by annealing under a compressed gas
WO2016080103A1 (ja) * 2014-11-21 2016-05-26 株式会社カネカ アクリル系繊維の製造方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2558384C3 (de) * 1975-12-23 1984-11-08 Bayer Ag, 5090 Leverkusen Glanzstabile Modacrylfasern und -fäden und Verfahren zu ihrer Herstellung
DE2736065A1 (de) * 1977-08-10 1979-02-22 Bayer Ag Verfahren zur herstellung von hydrophilen faeden und fasern nach dem trocken-duesen-nasspinnverfahren
GB8522586D0 (en) * 1985-09-12 1985-10-16 Fursdon G M Electrical plug

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US888260A (en) * 1907-01-23 1908-05-19 Victor Planchon Apparatus for the manufacture of collodion filaments.
US2045348A (en) * 1932-09-09 1936-06-23 Dreyfus Henry Manufacture of films, foils, and the like containing cellulose derivatives
US2068538A (en) * 1930-09-09 1937-01-19 Celanese Corp Manufacture of filaments or the like of cellulose derivatives
US2081171A (en) * 1928-11-09 1937-05-25 Dreyfus Henry Manufacture of artificial materials
US2367493A (en) * 1940-12-19 1945-01-16 Eastman Kodak Co Cellulose derivative extrusion process
US2425782A (en) * 1944-03-04 1947-08-19 Celanese Corp Preparation of filaments
US2558731A (en) * 1947-09-04 1951-07-03 American Cyanamid Co Method of producing synthetic fibers from polymers and copolymers of acrylonitrile
US2697023A (en) * 1950-04-29 1954-12-14 Eastman Kodak Co Spinning acrylonitrile
DE1024201B (de) * 1956-12-08 1958-02-13 Glanzstoff Ag Verfahren zur Herstellung von feinen Faeden aus hochmolekularen aliphatischen, nach einem Niederdruckverfahren erzeugten Polyolefinen
US2957748A (en) * 1957-08-28 1960-10-25 Basf Ag Production of fibers and threads having high dyestuff affinity from polyacrylonitrile
US2988418A (en) * 1954-10-13 1961-06-13 British Celanese Manufacture of artificial filaments, films and like shaped articles of cellulose triacetate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US888260A (en) * 1907-01-23 1908-05-19 Victor Planchon Apparatus for the manufacture of collodion filaments.
US2081171A (en) * 1928-11-09 1937-05-25 Dreyfus Henry Manufacture of artificial materials
US2068538A (en) * 1930-09-09 1937-01-19 Celanese Corp Manufacture of filaments or the like of cellulose derivatives
US2045348A (en) * 1932-09-09 1936-06-23 Dreyfus Henry Manufacture of films, foils, and the like containing cellulose derivatives
US2367493A (en) * 1940-12-19 1945-01-16 Eastman Kodak Co Cellulose derivative extrusion process
US2425782A (en) * 1944-03-04 1947-08-19 Celanese Corp Preparation of filaments
US2558731A (en) * 1947-09-04 1951-07-03 American Cyanamid Co Method of producing synthetic fibers from polymers and copolymers of acrylonitrile
US2697023A (en) * 1950-04-29 1954-12-14 Eastman Kodak Co Spinning acrylonitrile
US2988418A (en) * 1954-10-13 1961-06-13 British Celanese Manufacture of artificial filaments, films and like shaped articles of cellulose triacetate
DE1024201B (de) * 1956-12-08 1958-02-13 Glanzstoff Ag Verfahren zur Herstellung von feinen Faeden aus hochmolekularen aliphatischen, nach einem Niederdruckverfahren erzeugten Polyolefinen
US2957748A (en) * 1957-08-28 1960-10-25 Basf Ag Production of fibers and threads having high dyestuff affinity from polyacrylonitrile

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3402236A (en) * 1964-01-29 1968-09-17 Chemstrand Ltd Manufacture and treatment of synthetic fibres and fabrics containing the same
US3404204A (en) * 1964-03-07 1968-10-01 American Cyanamid Co Method of producing high-shrinkage acrylic fibers
US3412191A (en) * 1964-12-18 1968-11-19 Mitsubishi Rayon Co Method for producing artificial fibers
US3507948A (en) * 1967-09-29 1970-04-21 Exxon Research Engineering Co Solution spinning of polypropylene
JPS5378326A (en) * 1976-12-17 1978-07-11 Japan Exlan Co Ltd Production of carbon
JPS5650009B2 (xx) * 1976-12-17 1981-11-26
EP0144793B1 (en) 1983-12-05 1988-10-12 AlliedSignal Inc. High tenacity and modulus polyacrylonitrile fiber and method
US4818458A (en) * 1985-11-26 1989-04-04 Japan Exlan Company Limited Method of producing acrylic fibers
US4902452A (en) * 1986-07-28 1990-02-20 Mitsubishi Rayon Co., Ltd. Process for producing an acrylic fiber having high fiber characteristics
WO1996006209A1 (en) * 1994-08-23 1996-02-29 Monsanto Company Acrylonitrile filament process
US20040223708A1 (en) * 2003-03-24 2004-11-11 Cho Han Sol Enhancement of optical and mechanical properties in a polymeric optical element by annealing under a compressed gas
US7336875B2 (en) * 2003-03-24 2008-02-26 Samsung Electronics Co., Ltd. Enhancement of optical and mechanical properties in a polymeric optical element by annealing under a compressed gas
WO2016080103A1 (ja) * 2014-11-21 2016-05-26 株式会社カネカ アクリル系繊維の製造方法
JPWO2016080103A1 (ja) * 2014-11-21 2017-08-31 株式会社カネカ アクリル系繊維の製造方法
US20170253998A1 (en) * 2014-11-21 2017-09-07 Kaneka Corporation Acrylic-fiber manufacturing method
EP3222760A4 (en) * 2014-11-21 2018-06-20 Kaneka Corporation Acrylic-fiber manufacturing method
US10676843B2 (en) * 2014-11-21 2020-06-09 Kaneka Corporation Acrylic-fiber manufacturing method

Also Published As

Publication number Publication date
BE582871A (xx)
GB888496A (en) 1962-01-31
GB977942A (en) 1964-12-16
NL243961A (xx)
CH469821A (fr) 1969-03-15
DE1469044A1 (de) 1968-12-19
CH397949A (fr) 1965-08-31
NL259701A (xx)
DE1469044B2 (de) 1975-07-31
FR1240159A (fr) 1960-09-02
DE1410383A1 (de) 1969-01-16

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