US3885013A - Method for producing acrylic synthetic fibers - Google Patents

Method for producing acrylic synthetic fibers Download PDF

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Publication number
US3885013A
US3885013A US342430A US34243073A US3885013A US 3885013 A US3885013 A US 3885013A US 342430 A US342430 A US 342430A US 34243073 A US34243073 A US 34243073A US 3885013 A US3885013 A US 3885013A
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coagulation bath
acrylic synthetic
spinning solution
filaments
linear velocity
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US342430A
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English (en)
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Mitsunori Sato
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Japan Exlan Co Ltd
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Japan Exlan Co Ltd
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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
    • 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

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  • ABSTRACT Flexing abrasion resistance and anti-fibrillation of acrylic synthetic fibers are improved by wet-spinning a solution of acrylonitrile polymer in an inorganic solvent through spinnerette orifices while maintaining the linear velocity ratio of the free-extrusion above 1 and the jet-stretch ratio above 1.5.
  • the present invention relates to a method of producing a new acrylic synthetic fiber. More particularly, the invention is concerned with a method of producing a new acrylic synthetic fiber improved in anti-fibrillation and anti-abrasion.
  • acrylic synthetic fibers have wool-like soft touch and good dyeability and are widely used in the field of textile materials as well as interior decoration materials.
  • One of the main objects of the present invention is to provide a new technical knowledge which will improve the anti-fibrillation as well as the anit-abrasion of acrylic synthetic fibers.
  • Another main object of the present invention is to provide a method of producing a new acrylic synthetic fiber whose color and luster characteristics of the dyed final products are at a level satisfactory enough for practical use.
  • a further object of the present invention is to establish a production means for acrylic synthetic fibers which is at a level of productivity advantageous to industrial scale practice, while improving the antiabrasion and anti-fibrillation of acrylic synthetic fibers, as mentioned above.
  • FIG. 1 is a schematic view of a horizontal type coagulation bath to measure the linear velocity ratio of the free-extrusion
  • FIG. 2 is a graph illustrating the relationship between the linear velocity ratio of the free-extrusion and coagulation bath composition.
  • the coagulation medium for the spinning solution (dope) extruded through spinnerette orifices is a liquid.
  • the spinning solution (dope) extruded through the spinnerette orifices travels nearly horizontal through the coagulation bath, while being removed from the solvent, the the resulting filaments are withdrawn from the coagulation bath.
  • the takeup tension of the coagulated filaments will gradually increase to finally break the filaments.
  • the takeup speed is decreased, the tension of the coagulated filaments gradually decrease to reach a relaxed condition substantially free from the influence of external force except the weight itself of the coagulated filaments.
  • Such variation of the takeup tension of the coagulated filaments is influenced by the desolvation behavior of the spinning solution (dope) extruded into the coagulation bath through the spinnerette orifices.
  • the desolvation behavior is more greatly influenced by the concentration of the fiberforming polymer in the spinning solution as well as by the composition of the coagulation bath.
  • the takeup speed upon breaking of the coagulated filaments is usually called maximum takeup speed, and the quotient obtained by dividing the maximum takeup speed by an extrusion linear velocity of the spinning solution.(dope) from the spinnerette orifices is defined as maximum jet-stretch ratio, which is used as a physical quantity to evaluate the spinnability.
  • spinnerettes having a large number of orifices are used.
  • the coagulated filaments will be broken uniformly at one time as a whole filament bundle by increased takeup tension. Accordingly, it is quite impractical to use the maximum jet-stretch ratio measured on a single coagulated filament as a physical quantity expressing the spinnability or filament-forming characteristics of the extruded fiber bundle. Such tendency of coagulation behavior is particularly noticed when the coagulation ability of the coagulation bath is small for the extruded spinning solution, that is, when the coagulation rate of the swollen gel filaments in the coagulation bath is slow.
  • the linear velocity ratio of the free-extrusion is not only useful as a practical measure for evaluating the spinnability but has a physicochemical significance as a measure for quantitatively expressing the volumetric diminution rate due to desolvation of the swollen gel filaments in the coagulation bath. Namely, in the case of a large desolvation rate, the volumetric diminution tendency of the extruded swollen gel filaments is large, so that the linear velocity ratio of the free-extrusion becomes reduced. On the contrary, when the desolvation rate is small, the volumetric diminution rate of the swollen gel filaments in the coagulation step becomes reduced to increase the linear velocity ratio of the free-extrusion.
  • the coagulated filaments are made to travel in a straight line between the spinnerette orifices and the drawing rollers under the takeup tension, as shown in FIG. 1.
  • the exit point C of the coagulated filaments from the coagulation bath surface into an inert medium such as air.
  • the takeup speed is gradually reduced so that the coagulated filaments are sus pended in a relaxed condition between the spinnerette orifices and the drawing rollers, to observe the movement of the point C.
  • the exit point C of the coagulated filaments from the coagulation bath surface moves gradually toward the drawing roller side.
  • the coagulated filaments are then held straight in a tensioned condition between the spinnerette orifices and the drawing rollers.
  • This takeup speed is taken as the linear velocity of the free-extrusion.
  • FIG. 2 shows an example of the relation between the linear velocity ratio of the free-extrusion and coagulation bath composition, anti-fibrillation observed with varying concentrations of the fiber-forming polymer in the spinning solution, in the case of using a horizontal coagulation bath in which the immersion length of the coagulated filaments is 300 mm. and the termperature is maintained at -3C.
  • the concentration of the inorganic solvent used in the coagulation bath is desirably adjusted to the range of 40 to percent of the concentration of the inorganic solvent used for dissolving the acrylonitrile polymer in preparing the spinning solution.
  • such concentration of the inorganic solvent used in preparing the spinning solution in the present invention is in the range of 40 to 70 percent.
  • the spinning solution extruded through the spinnerette orifices in the case that the composition of the coagulation bath is outside the foregoing preferred range, it is practically impossible for the spinning solution extruded through the spinnerette orifices to be maintained at a linear velocity ratio of the free-extrusion above 1 and also at a jet stretch ratio above 1.5, the maintaining of this ratio being effective for improving the antiabrasion and anti-fibrillation, together with the maintaining of the foregoing linear velocity ratio of the freeextrusion.
  • the gel filaments extruded into the coagulation bath become excessively sagged and consequently wind around the drawing rollers on being drawn from the coagulation bath, the spinnability thus being seriously lowered.
  • the process conditions in the subsequent heat stretch step, drying step and heat-relaxation step may be regulated, the uniformity of the cross section of the fiber or the high speed spinnability is impaired, and the luster characteristics of the final products, i.e. a secondary effect of the present invention, are greatly lowered.
  • the following two-stage coagulation process can be carried out without departing from the invention so far as the first bath can staisfy the foregoing preferred range of the linear velocity ratio of free-extrusion and jet-stretch ratio.
  • the following multistage coagulation process to form filaments may be of course used as an embodiment of the present invention. Namely, after the first-stage coagulation step satisfying the above mentioned linear velocity ratio of the freeextrusion and jet-stretch ratio, the coagulated filaments are further introduced into a second-stage coagulation bath having a solvent concentration of 20 to 30 percent based on the concentration of the inorganic solvent used for the preparation of the spinning solution.
  • acrylic synthetic fibers as referred to in the present invention is a generic term for the fibers composed of an acrylonitrile polymer containing at least 80 percent by weight of combined acrylonitrile.
  • allyltype alcohols e.g. allyl alcohol, methallyl alcohol, ethallyl alcohol, etc.; allyl, methallyl and other unsaturated monohydric alcohol esters of monobasic acids, e.g. allyl and methallyl acetates, laurates, cyanides, etc,; acrylic and alkacrylic acids (e.g. methacrylic, ethacrylic, etc.) and esters and amides of such acids (e.g. methyl, ethyl, propyl, butyl, etc. acrylates and methacrylates, acrylamide, methacrylamide, N-methyl, -ethyl, -propyl, butyl,
  • Alkyl esters of alpha, beta-unsaturated polycarboxylic acids may also be copolymerized with acrylonitrile to form copolymers, e.g. dimethyl, -ethyl, -propyl, -butyl, etc. esters of maleic, fumaric, citraconic, etc. acids.
  • inorganic solvents which may be used in the present invention may be mentioned; rhodanides e.g. sodium rhodanides, potassium rhodanide, ammonium rhodanide and calcium rhodanide and mixtures of these rhodanides; concentrated aqueous solutions of inorganic salts, e.g. zinc chloride, lithium chloride, etc.; and concentrated aqueous solutions of inorganic acids, e.g. sulfuric acid, nitric acid, etc.
  • inorganic salts e.g. zinc chloride, lithium chloride, etc.
  • inorganic acids e.g. sulfuric acid, nitric acid, etc.
  • the co agulation bath may be the same aqueous inorganic solvent solution as used for the preparation of the spinning solution, although in a concentration of 40 to percent with respect to the concentration of the inorganic solvent in the spinning solution.
  • the coagulated filaments withdrawn out of the coagulation bath thereafter pass through water-washing, stretching, drying and heat-relaxing treatment, or further followed by a secondary stretching under dry heat, etc. to be formed into an acrylic synthetic fiber im proved in anti-fibrillation and anit-abrasion, to which improvement the present invention is directed.
  • the acrylic synthetic fibers improved in surface smoothness by the use of the peculiar coagulation bath of the present invention become more condensed in structure, and furthermore become remarkably improved not only in anti-fibrillation and anti-abrasion but also in optical characteristics, e.g. luster, etc.
  • the knot strength and elongation characteristics of the final product may be remarkably improved by supplying the acrylic synthetic fiber of the present invention after the heatrelaxing treatment to a Turbo Stapler or the like and subjecting it to a secondary stretching of l.05 to 1.60 times in a dry heat atmosphere at I00 to 200C.
  • the method of the present invention can remarkably improve the anit-fibrillation and anti-abrasion of the fibers and, in its industrial practice, greatly contribute to the industry.
  • EXAMPLE 1 An acrylonitrile copolymer consisting of 91 parts of acrylonitrile, 9 parts of methyl acrylate, and 0.5 part of sodium methallylsulfonate was dissolved in an aqueous solution of sodium rhodanide to prepare a spinning solution representing the polymer concentration as well as the solvent concentration shown in Table l. The spinning solution was then extruded through circular spinnerette orifices into a low temperature coagulation bath of various concentrations of sodium rhodanide, while varying the linear velocity ratio of the freeextrusion and jet-stretch ratio, to form coagulated filaments.
  • the fiber was washed with water and stretched in the usual way, and dried in a humidityconditioned atmosphere of dry bulb temperature of l22C. and wet bulb temperature of 62C. to eliminate the fiber structure, followed by the ordinary heatrelaxing treatment in saturated steam.
  • the heat sample represented as Experiment No 1 caused frequent filament breaking even at the jetstretch stage in the coagulation bath because its linear velocity ratio of the free-extrusion was less than 1, so that it became impossible to continue spinning.
  • flexing abrasion resistance and degree of fibrillation are used, whose methods of determination are defined and explained in the followings.
  • EXAMPLE 2 The same spinning solution as in Example 1 was extruded through rectangular spinnerette orifices into a coagulation bath. Thereafter, the resulting filaments were passed through the same process steps as in Example l to produce and acrylic synthetic fiber.
  • the coagulation bath conditions and the flexing abrasion resistance as well as the degree of fibrillation of the finally obtained sample fiber are shown in Table 2.
  • COMPARATIVE EXAMPLE I The acrylonitrile copolymer as described in Example 1 was dissolved in an aqueous solution of sodium rhodanide, and an acrylic synthetic fiber was spun in the usual way.
  • the linear velocity ratio of the free-extrusion and jet-stretch ratio are mentioned in Table 3. From this comparative example, it can be understood that the flexing abrasion resistance and degree of fibrillation of the acrylic synthetic fiber thus obtained are much lower than those of the acrylic synthetic fiber produced according to the method of the present invention.
  • Knot strength Experiment Knot elongation number EXAMPLE 4 The sample fibers shown as Experiment No. 5, No. 6, No. 7 and No. 9 in Example 2 and Comparative Example l were subjected to a secondary stretching in the same dry heat atmosphere as in Example 3. The knot strength and elongation of the final fiber are shown in Table 5.

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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)
US342430A 1972-03-21 1973-03-19 Method for producing acrylic synthetic fibers Expired - Lifetime US3885013A (en)

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JP47028296A JPS52145B2 (enrdf_load_stackoverflow) 1972-03-21 1972-03-21

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JP (1) JPS52145B2 (enrdf_load_stackoverflow)
AU (1) AU5305773A (enrdf_load_stackoverflow)
GB (1) GB1372824A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975486A (en) * 1972-09-14 1976-08-17 Japan Exlan Company Limited Process for producing anti-pilling acrylic fiber
US3976737A (en) * 1972-09-14 1976-08-24 Japan Exlan Company Limited Process for producing high shrinking acrylic fiber
US4347203A (en) * 1979-05-30 1982-08-31 Mitsubishi Rayon Company, Ltd. Process for producing acrylic fiber
US4448740A (en) * 1982-01-26 1984-05-15 Japan Exlan Company Limited Process for producing acrylic fibers with excellent surface smoothness
US20040155377A1 (en) * 1999-06-25 2004-08-12 Mitsubishi Rayon Co., Ltd. Acrylic fiber and a manufacturing process therefor
US20060061005A1 (en) * 2004-09-22 2006-03-23 Henry Peng Method of producing layered polymeric articles

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2094099A (en) * 1932-05-11 1937-09-28 Dreyfus Henry Treatment of artificial filaments, fibers, and the like
US2975024A (en) * 1958-02-18 1961-03-14 Courtaulds Ltd Production of artificial threads
US3073669A (en) * 1958-09-06 1963-01-15 Asahi Chemical Ind Method for producing shaped articles from polymers and copolymers of acrylonitrile
US3412191A (en) * 1964-12-18 1968-11-19 Mitsubishi Rayon Co Method for producing artificial fibers
US3673053A (en) * 1969-02-03 1972-06-27 Japan Exlan Co Ltd Acrylic fibers with improved brightness and process for producing the same
US3676540A (en) * 1971-03-15 1972-07-11 American Cyanamid Co Wet-spinning shaped fibers
US3689621A (en) * 1969-03-02 1972-09-05 Toho Beslon Co Continuous wet spinning method of producing useful filamentary materials of an acrylonitrile copolymer
US3706828A (en) * 1969-08-19 1972-12-19 Dow Badische Co Wet spinning non-circular polyacrylonitrile fibers by utilizing circular orifices and sequential coagulation
US3760053A (en) * 1971-12-06 1973-09-18 American Cyanamid Co Wet-spinning process for {37 dog-bone{38 {0 shaped acrylonitrile polymer fibers

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2094099A (en) * 1932-05-11 1937-09-28 Dreyfus Henry Treatment of artificial filaments, fibers, and the like
US2975024A (en) * 1958-02-18 1961-03-14 Courtaulds Ltd Production of artificial threads
US3073669A (en) * 1958-09-06 1963-01-15 Asahi Chemical Ind Method for producing shaped articles from polymers and copolymers of acrylonitrile
US3412191A (en) * 1964-12-18 1968-11-19 Mitsubishi Rayon Co Method for producing artificial fibers
US3673053A (en) * 1969-02-03 1972-06-27 Japan Exlan Co Ltd Acrylic fibers with improved brightness and process for producing the same
US3689621A (en) * 1969-03-02 1972-09-05 Toho Beslon Co Continuous wet spinning method of producing useful filamentary materials of an acrylonitrile copolymer
US3706828A (en) * 1969-08-19 1972-12-19 Dow Badische Co Wet spinning non-circular polyacrylonitrile fibers by utilizing circular orifices and sequential coagulation
US3676540A (en) * 1971-03-15 1972-07-11 American Cyanamid Co Wet-spinning shaped fibers
US3760053A (en) * 1971-12-06 1973-09-18 American Cyanamid Co Wet-spinning process for {37 dog-bone{38 {0 shaped acrylonitrile polymer fibers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975486A (en) * 1972-09-14 1976-08-17 Japan Exlan Company Limited Process for producing anti-pilling acrylic fiber
US3976737A (en) * 1972-09-14 1976-08-24 Japan Exlan Company Limited Process for producing high shrinking acrylic fiber
US4347203A (en) * 1979-05-30 1982-08-31 Mitsubishi Rayon Company, Ltd. Process for producing acrylic fiber
US4448740A (en) * 1982-01-26 1984-05-15 Japan Exlan Company Limited Process for producing acrylic fibers with excellent surface smoothness
US20040155377A1 (en) * 1999-06-25 2004-08-12 Mitsubishi Rayon Co., Ltd. Acrylic fiber and a manufacturing process therefor
US20060061005A1 (en) * 2004-09-22 2006-03-23 Henry Peng Method of producing layered polymeric articles

Also Published As

Publication number Publication date
JPS52145B2 (enrdf_load_stackoverflow) 1977-01-05
JPS4893728A (enrdf_load_stackoverflow) 1973-12-04
GB1372824A (en) 1974-11-06
AU5305773A (en) 1974-09-12

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