US3112161A - Method for the manufacture of acrylic fibers - Google Patents

Method for the manufacture of acrylic fibers Download PDF

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Publication number
US3112161A
US3112161A US139413A US13941361A US3112161A US 3112161 A US3112161 A US 3112161A US 139413 A US139413 A US 139413A US 13941361 A US13941361 A US 13941361A US 3112161 A US3112161 A US 3112161A
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US
United States
Prior art keywords
fibers
relaxation
water
spinning
bath
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Expired - Lifetime
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US139413A
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English (en)
Inventor
Nagata Hirofumi
Takikawa Masahiko
Kurioka Shohel
Sukai Kiyoshi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Ltd
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Toho Rayon Co Ltd
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Publication date
Application filed by Toho Rayon Co Ltd filed Critical Toho Rayon Co Ltd
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Publication of US3112161A publication Critical patent/US3112161A/en
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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

Definitions

  • the present invention relates to a method for the manufacture of excellent acrylic fibers by consecutive treatments, such as water-rinsing under tension, stretching and reh .ng in hot water bath and so forth for filaments spun at room temperature into a low concentration coagulating bath from a spinning solution comprising acrylonitrile polymer or copolymers in an aqueous zinc chloride solution.
  • An object of the present invention is to avoid unfavorable effects of salts remaining in fibers on qualities of same.
  • the salt residue is regarded as a general defect in the spinning method which uses a spinning solution comprising aqueous zinc chloride solution of acrylonitrile.
  • Another object is to improve the strength and resilience of fibers obtained by the spinning method.
  • T he process of this invention is characterized in that:
  • a polymer solution of an average concentration of zinc chloride from 50 to 60% may be used satisfactorily as a spinning solution, which has been obtained by polymerizing acrylonitrile alone or acrylonitrile added with a comonomer in an aqueous zinc chloride solution of a relatively high concentration:
  • the spinning is effected in a relatively low concentration bath of coagulant having the same composition as that of the above-mentioned solvent at an ordinary temperature.
  • the spinning operation is carried out at an ordinary temperature
  • the spinning operation will be simpler and also the concentration may be easier to control.
  • the latter conditions i.e., a lower concentration range at around the ordinary temperature, is favorable as an industrial operation or convenient also for the subsequent desalting water rinsing operation.
  • the second ste that is, the water rinsing operation is carried out for spun fibers at an ordinary temperature or in hot water below C. under slight tension.
  • a stretching may be effected to approximately 1 to 4 times the original length under such a tension that does not break fibers.
  • the third step of operation that is, stretching and relaxation are carried out, in such a manner that water rinsed fibers are first stretched to more than 300% elongation in boiling water at above C. and thereafter are instantly relaxed in boiling water at the same temperature or thereabove.
  • tows showing generally a high water-retaining state after water rinsing are stretched at least 300% in a boiling water bath, or fibers rinsed in water and dried are stretched at least 300% under no tension in a boiling water bath, after thorough adjustment of moisture in a water bath at a temperature at least near that of the stretching bath.
  • the relaxation process should be effected on tows instantly from the stretching in such a way that they may be relaxed continuously at the same temperature or above as used in stretching without lowering the temperature of tows.
  • FIG. 1 is a graph of the relation between the knot strength and elongation:
  • FIG. 2 is a graph of the relations between the time and rate of relaxation and between the time of relaxation and the knot strength of final fibers obtained.
  • Fl. 3 is a graph of the relation between the knot strength of fibers and the time interval from the stretching to the relaxation process.
  • Both the stretching and relaxation operations must be performed in an excess of water content, or in liquid bath, and continuity between both operations must be sustained, that is, the operations should be carried out so that the time interval between them may not be so long that a lowering of the temperature of tows or variations of water content can take place.
  • the degrees of stretching and relaxation are determined appropriately, and from a practical point of view, as illustrated in FIG. 1, the stretching is required to be at least 300%.
  • the qualities of fibers obtained are not substantially affected by an interval of time for stretching, unless it is within the range of ordinary industrial spinning velocity.
  • the fibers obtained by the method according to this invention show strikingly improved qualities as illustrated in Table 1.
  • the salt remaining in fibers is as shown in Table 2, and can be lowered down to a range practically negligible in the last step of operation.
  • 92 parts acrylonitrile, 8 parts methyl methacrylate and 0.1 part ammonium persulfate were polymerized in 900 parts of 57% aqueous zinc chloride solution at 50 C.
  • the resulting solution was used as a spinning solution, which was spun out into a spinning bath of 20% aqueous zinc chloride solution at 20 C.
  • the spun fiber was directly rinsed in water at room temperature for several minutes. The salt remaining in the water rinsed fibers was 0.65% and the water content was 200%.
  • Example 2 The spinning solution of the same composition as that of solution used in Example 1 was spun into the same spinning bath.
  • the spun fibers were instantly rinsed in a multiple type water rinsing bath, the temperatures of same being consecutively raised. However, in order to avoid a loss of transparency due to abrupt heating, heating at above C. was avoided. Moreover, during such water rinsing, the fibers were put under a slight tension incapable of breaking the fibers. In the particular example, the spinning velocity was twice the ordinary industrial spinning velocity. Thereafter the rinsed fibers were dried. Then, the dried fibers were put into a boiling water bath at 95 C. and heated thoroughly, and then the water content was adjusted to a water retaining ratio of 200%.
  • the fibers were stretched to a 400% elongation in the boiling water bath, and immediately relaxed under no tension in the boiling water bath.
  • the relaxed fibers were dried at 120 C. over a drying drum without tension and fibers of the properties as shown in the following table were obtained:
  • a method for the manufacture of acrylic fibers comprising spinning into filaments a polymer solution containing at least acrylonitrile and a solvent containing 50-60% zinc chloride into a coagulating bath containing 10-20% zinc chloride at a temperature below 30 C., rinsing said filaments in an aqueous medium at room temperature, stretching the rinsed filaments more than 300% in water at a temperature above C., and then relaxing the stretched filaments in water at a temperature above 95 C. for a period of more than thirty seconds.

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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)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
US139413A 1960-09-24 1961-09-20 Method for the manufacture of acrylic fibers Expired - Lifetime US3112161A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3974660 1960-09-24

Publications (1)

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US3112161A true US3112161A (en) 1963-11-26

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US139413A Expired - Lifetime US3112161A (en) 1960-09-24 1961-09-20 Method for the manufacture of acrylic fibers

Country Status (5)

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US (1) US3112161A (fr)
BE (1) BE608205A (fr)
DE (1) DE1289615B (fr)
FI (1) FI42854B (fr)
GB (1) GB1002767A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330898A (en) * 1963-08-07 1967-07-11 Dow Chemical Co Method for preparing highly shrinkable acrylonitrile polymer fibers

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB816841A (en) * 1955-10-07 1959-07-22 Dow Chemical Co Method for preparing acrylonitrile containing fibres

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1069819B (fr) * 1959-11-26
US2445042A (en) * 1943-07-28 1948-07-13 Du Pont Method of treating oriented acrylonitrile structures
NL72124C (fr) * 1947-02-13
US2681265A (en) * 1948-11-27 1954-06-15 American Viscose Corp Spinning artificial filaments
NL74683C (fr) * 1949-06-13
DE850213C (de) * 1949-11-01 1952-09-22 Kunstseidefabrik Bobingen Verfahren zur Herstellung von geformten Gebilden aus Polyvinyl- oder Polyacrylverbindungen
GB690553A (en) * 1950-01-05 1953-04-22 British Celanese Improvements in or relating to the production and use of solutions of acrylic polymers
US2558793A (en) * 1950-03-24 1951-07-03 Eastman Kodak Co Mixtures comprising polyacrylonitrile and polyvinyl formate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB816841A (en) * 1955-10-07 1959-07-22 Dow Chemical Co Method for preparing acrylonitrile containing fibres

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330898A (en) * 1963-08-07 1967-07-11 Dow Chemical Co Method for preparing highly shrinkable acrylonitrile polymer fibers

Also Published As

Publication number Publication date
BE608205A (fr) 1962-01-02
GB1002767A (en) 1965-08-25
FI42854B (fr) 1970-08-03
DE1289615B (de) 1969-02-20

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