US3121765A - Process for the manufacture of acrylic synthetic fiber - Google Patents

Process for the manufacture of acrylic synthetic fiber Download PDF

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Publication number
US3121765A
US3121765A US138581A US13858161A US3121765A US 3121765 A US3121765 A US 3121765A US 138581 A US138581 A US 138581A US 13858161 A US13858161 A US 13858161A US 3121765 A US3121765 A US 3121765A
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US
United States
Prior art keywords
tow
chloride
aqueous solution
solution
percent
Prior art date
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Expired - Lifetime
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US138581A
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English (en)
Inventor
Kanda Ichiro
Nakajima Michiaki
Amiya Makoto
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 US3121765A publication Critical patent/US3121765A/en
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Classifications

    • 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 a process for the manufacture of a synthetic acrylic fiber by spinning a spinning solution comprising zinc chloride solution and polymer containing acrylonitrile as a principal constituent, and then treating .the coagulated tow with an aqueous solution of a compound so as to produce a zinc complex ion with the object of avoiding the degradation of fiber quali ty due to remaining salts.
  • the present invention has been reached by our new knowledge on the effect of compounds, forming complex ion with zinc ion, such as ammonium, amine or chlorine, and the process is industrially useful and practicable.
  • Desalting agents are sodium chloride, potassium chloride, ammonium chloride, urea, thiourea and others, that is, election donor compounds which coordinate to cation forming complex ion.
  • These compounds which have chloride, ammonium ion, or amino group can form complex ions with the zinc ion as in the following.
  • Halides, such as NaCl, KCl, NH Cl form complex ions, some of which are [ZnCld and [ZnCl 0H and in the case of NH Cl occur, moreover, amine complexes, such as and so on.
  • urea and thiourea occur [ZH(NHQCONHQ)4]++ and [ZI1(NH2CSNH2)4]++ respectively. All of these complex ions have tetrahedral 4-coordinated structure.
  • the salt removal treatment based on the above discovery may be applied to a dried fiber, but from the point of easiness in removing the salt and of simplification in industrial fiber process, it is effected during or after the washing process of coagulated tow with water which has been coagulated from a spinning solution as is a common practice, and then the coagulated tow is treated with an aqueous solution of above mentioned compounds.
  • zinc compounds which remained in the tow as hydroxide or hydrated oxide of zinc, can diffuse and dissolve out into the solution as water soluble complex ions.
  • the tow which is formed by extruding a polymer solu- 3,121,765 Patented Feb. 18, 1964 tion into a coagulating bath comprised of a more dilute aqueous salt solution of the same or similar salt system as employed in the solvent of the polymer solution, may be stretched at moderate temperature in water, or stretched under moderate temperature and humidity after water washing. Thereafter, it may go through required aftertreatments, such as oiling, heat stretching and relaxing processes that are in common practice.
  • the salt removing treatment is accomplished, according to this invention, by using 1 to 20 percent aqueous solution of desalting agent, preferably 5 to 15 percent, at 70 C. to boiling temperature, preferably over C.
  • Tow B is composed of 52.6% polymer, 45.1% water and 2.3% zinc chloride, and, when squeezed and dried in air, it contains 0.39% residual zinc.
  • T he tow B treated with various salt removal treatments (I, II, III, IV and V) and dried in air to 1 percent moisture content was analyzed and found to include residual zinc chloride as follows:
  • Example 1 A solution was prepared consisting of 9% by weight of copolymer containing mole percent of acrylonitrile and 5 mole percent of methyl acrylate having a Standinger molecular weight of 82,000, 50.9% by weight of zinc chloride and 41% of water. This solution, having a viscosity of 360 poises at 30 C., was extruded through a -hole spinneret having openings respectively 0.08 mm. in diameter, into an aqueous solution of 15% by weight of zinc chloride at 15 C. The so-coagulated tow of filament was stretched 1.6 times its original length during washing with water (the sample here called A), and then stretched in boiling water three times its cold stretched length (sample B).
  • This tow B of stretched fibers was washed with water and, when dried in air to 1% moisture content, had 0.39% of zinc chloride.
  • This tow was boiled in an aqueous solution of 5% by weight of ammonium chloride for 2 minutes, then washed with water and, when dried, had 0.024% of zinc chloride.
  • Example 2 The tow A in Example 1 was stretched in boiling water containing 7% of sodium chloride two times its original length and then in boiling water 5 times its original length, and when dried, had only 0.034% of zinc chloride in it.
  • Example 3 The other portion of tow A was treated with aqueous solution of 10% of urea, washed with water and, when dried, had 0.039% of zinc chloride.
  • the other portion of tow B was treated similarly as A and had had only 0.029% of zinc chloride.
  • a method for manufacturing acrylic synthetic fibers comprising spinning into a coagulated tow a solution of a polymer containing acrylonitrile and a solvent of aqueous zinc chloride, contacting the coagulated toW with an aqueous solution containing 1 to 20 percent of a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea, and maintaining the aqueous solution in a temperature range of from 70 to 100 C.
  • a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea
  • a method for manufacturing acrylic synthetic fibers comprising spinning into a coagulated tow a solution of a polymer containing acrylonitrile and a solvent of aqueous zinc chloride, contacting the coagulated tow With an aqueous solution containing 1 to percent of a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea, and maintaining the aqueous solution in a temperature range of from to C.
  • a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea

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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)
US138581A 1960-09-24 1961-09-18 Process for the manufacture of acrylic synthetic fiber Expired - Lifetime US3121765A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3974560 1960-09-24

Publications (1)

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US3121765A true US3121765A (en) 1964-02-18

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US138581A Expired - Lifetime US3121765A (en) 1960-09-24 1961-09-18 Process for the manufacture of acrylic synthetic fiber

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US (1) US3121765A (cs)
BE (1) BE608206A (cs)
DE (1) DE1267783B (cs)
FI (1) FI40194B (cs)
GB (1) GB954860A (cs)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622658A (en) * 1969-09-11 1971-11-23 Japan Exlan Co Ltd Method of treating acrylonitrile synthetic fiber
US4925604A (en) * 1984-10-16 1990-05-15 Nikkiso Co., Ltd. Process for preparing a carbon fiber of high strength
CN112645653A (zh) * 2020-12-17 2021-04-13 江苏长路交通工程有限公司 一种纤维增韧抗裂型水泥稳定碎石、制备方法和施工方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB636476A (en) * 1949-02-02 1950-05-03 Edgar Bertie Johnson Improvements in or relating to the production of textile materials having a basis ofpolyacrylonitrile
US2558781A (en) * 1947-09-04 1951-07-03 American Cyanamid Co Method of treating water-swollen polymers
US2558730A (en) * 1947-09-04 1951-07-03 American Cyanamid Co Method of preparing shaped products from polymers and copolymers of acrylonitrile
US2648592A (en) * 1951-05-28 1953-08-11 Dow Chemical Co Removing salts from polyacrylonitrile
CA564327A (en) * 1958-10-07 B. Bates Emile Wet heat treatment of material of poor electrical conductivity

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA564327A (en) * 1958-10-07 B. Bates Emile Wet heat treatment of material of poor electrical conductivity
US2558781A (en) * 1947-09-04 1951-07-03 American Cyanamid Co Method of treating water-swollen polymers
US2558730A (en) * 1947-09-04 1951-07-03 American Cyanamid Co Method of preparing shaped products from polymers and copolymers of acrylonitrile
GB636476A (en) * 1949-02-02 1950-05-03 Edgar Bertie Johnson Improvements in or relating to the production of textile materials having a basis ofpolyacrylonitrile
US2648592A (en) * 1951-05-28 1953-08-11 Dow Chemical Co Removing salts from polyacrylonitrile

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622658A (en) * 1969-09-11 1971-11-23 Japan Exlan Co Ltd Method of treating acrylonitrile synthetic fiber
US4925604A (en) * 1984-10-16 1990-05-15 Nikkiso Co., Ltd. Process for preparing a carbon fiber of high strength
CN112645653A (zh) * 2020-12-17 2021-04-13 江苏长路交通工程有限公司 一种纤维增韧抗裂型水泥稳定碎石、制备方法和施工方法

Also Published As

Publication number Publication date
DE1267783B (de) 1968-05-09
GB954860A (en) 1964-04-08
FI40194B (cs) 1968-07-31
BE608206A (fr) 1962-01-02

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