US2779746A - Method of spinning solutions of polyacrylonitrile or mixed polymers thereof - Google Patents

Method of spinning solutions of polyacrylonitrile or mixed polymers thereof Download PDF

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Publication number
US2779746A
US2779746A US320370A US32037052A US2779746A US 2779746 A US2779746 A US 2779746A US 320370 A US320370 A US 320370A US 32037052 A US32037052 A US 32037052A US 2779746 A US2779746 A US 2779746A
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United States
Prior art keywords
vinyl
polyacrylonitrile
acid amide
spinning
diamide
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US320370A
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English (en)
Inventor
Heisenberg Erwin
Pirot Ernst
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Glanzstoff AG
Vereinigte Glanzstoff Fabriken AG
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Glanzstoff AG
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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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • 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 spinning methods, and more particularly to processes of spinning solutions of polyacrylonitrile or mixed polymers thereof.
  • a homogeneous solution of acrylonitrile is obtained by converting a finely ground polyacrylonitrile having a particle size below 10011., by agitation in dimethyl formamide or some other suitable solvent, into a dispersion. Another significant step involves evacuation while the dispersion is being formed. To this end, the finely ground polyacrylonitrile is passed, under thorough agitation and in a uniform manner, into an evacuated vessel filled with dimethyl formamide or some other suitable solvent and, the vacuum is maintained .during the formation of the dispersion.
  • the preparation of a finely divided dispersion which, is freed from air signifies a particularly important advantage over the spinning processes of the prior art.
  • the invention contemplates further keeping, during formation of the dispersion, the temperature as low as possible while, at the same time, providing a high vacuum. Temperatures between and 30 C. are contemplated by the invention, the preferred temperature range extends from 0 to about 15 C.
  • the vacuum is so selected that the solvent used is heated almost to its boiling point. For example, if dimethyl formamide is used as the solvent, the temperature may be 10 C. and the vacuum 50 Torr.
  • the starting mixture is stirred further for to hours in vacuo and under cooling in order to insure a thorough equalization of the finished dispersion.
  • the dispersion freed from air thus obtained is passed through a dissolving apparatus equipped with an agitator, in such a manner that the solution is gradually heated from about 60 to about 150 C., and preferably from about 80 to about 100 C. After filtering in the usual manner, the solution is spun immediately.
  • the particle size of the polymers may vary from about 10 to 100 and may preferably be in the neighborhood of 3011..
  • Monomers contemplated for copolymerization with acrylonitrila may be acrylic acid amide, maleic acid amide, fumaric acid amide or their diamides; mcthacrylic acd methyl ester, styrene, vinyl chloride, viny-lidene chloride, vinyl acetate, vinyl carbazole, vinyl imidazole, vinyl pyridine etc.
  • the mixed polymers should contain at least percent of acrylonitrile so that the compound copolymerized therewith is present in an amount not exceeding 15 percent of the total.
  • a variety of solvents can be used as follows: N-formyl pyridine, dimethyl sulfoxide, methane sulfonic acid methyl ester, glycolic acid nitrile, glutaric acid dinitrile, adipic acid dinitrile, valerolactone, n-methyl pyrrolidone, glycol carbonate.
  • the storage tank 1 is shown to contain the finely powdered polyacrylonitrile having a particle size below p.
  • a vibrator 2 and a scattering device 3 provide for a continuous and uniform supply of the polymer to the kneader 5 which contains the solvent such as dimethyl formamide, for example.
  • the kneader can be evacuated.
  • the kneading device 6 effects an intensive working through and kneading of the dispersion formed in the kneader, whereupon the dispersion can be discharged into the storage vessel 7.
  • the dispersion is heated up e. g. to about 100 C.
  • the solution maintained at this temperature passes on, through a heated pressure pump 9, to the filtering device 10 which too can be heated and which is equipped with filtering candles. From the dosing pump 11 the solution which freed from air, is homogeneous and is heated to the required spinning temperature, is
  • the invention may be further illustrated by the following examples.
  • Example I In a vessel holding 20 liters, 2.4 kg. of finely ground polyacrylonitrile (K-value 89, particle size up to 100p) are added slowly, under thorough agitation, to 7.6 kg. of dimethyl formamide already contained in the vessel, at a temperature of 10 C. and a pressure of 20 Torr.
  • the feed of the polyacrylonitrile most advantageously takes place by means of a built-in bucket wheel in a chronologically precisely dosed form, so that after every 5 seconds about 6 g. of polyacrylonitrile are added.
  • the starting mixture On termination of the supply of polyacrylonitrile, the starting mixture is further stirred for another 8 hours at the same temperature in vacuo.
  • the fine dispersion thus formed is now forced by means of nitrogen under a pressure of 5 to 10 at, into a cooled storage tank, to be passed on from here into a dissolving cylinder equipped with a built-in agitator.
  • the dissolving cylinder is steam-heated to 100 C. It permits thorough dissolution of the dispersion; the finished solution is passed, at a temperature of about 100 C., through a filter press and from here to the dosing pump, whereupon the solution is spun, immediately, by the dry spinning method.
  • Example 11 22 kg. of polyacrylonitrile (K-value 89, particle size up to 100,u) are added from a storage container by means of a scattering device, to 78 kg. of dimethyl formamide, at a temperature of 15 C. and a pressure of 20-25 Torr. The solvent is placed in a kneader. By intensive kneading accompanied by evacuation which removes the air from the dispersion being formed, the dispersion is distributed after the lapse of 2-3 hours, by means of nitrogen under pressure, to two cooled storage containers.
  • K-value 89 particle size up to 100,u
  • the two storage vessels operate intermittently, i. e. while one passes the dispersion on to the dissolving vessel by means of nitrogen under pressure (e. g. 8 at.), the other is being evacuated.
  • the dispersion is heated e. g. to 100 C. to yield the homogeneous po'lyacrylonitrile solution free from air.
  • This solution is maintained at the elevated temperature until it passes, finally, through a heated pressure pump to the likewise heated filter device and from there to the dosing pump which conveys the solution to the spinning nozzle.
  • the threads obtained from this solution because of the protective character of the treatment, are extremely light and particularly uniform. They attain excellent mechanical strength. Thus for polyacrylonitrile, after the threads have been stretched to about ten times their original length, the strength amounts to about 4.4- g./den. (40-45 Rkm.).
  • Example III A copolymer consisting of 90 percent of acrylonitrile and 10 percent of acrylic acid amide, with a K-value of about 84, was treated as described in Example I, using glycolic acid nitrile as the solvent.
  • the method of spinning solutions of polymers selected from the group consisting of polyacrylonitrile and copolymers thereof containing at least percent by weight of combined acrylonitrile which comprises gradually dispersing the nitrile comminuted to a particle size ranging between about 10 and 1. at a temperature ranging between about 0 and 30 C. at the rate of about one gram per second in a cold solvent kept under vacuum, stirring the mixture 3 to 10 hours under continuous cooling, freeing the solution from air by gradually heating it to a temperature ranging from 60 to C. and then spinning after the continuous method.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Artificial Filaments (AREA)
US320370A 1951-11-17 1952-11-14 Method of spinning solutions of polyacrylonitrile or mixed polymers thereof Expired - Lifetime US2779746A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE312942X 1951-11-17

Publications (1)

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US2779746A true US2779746A (en) 1957-01-29

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US (1) US2779746A (en(2012))
BE (1) BE515569A (en(2012))
CH (1) CH312942A (en(2012))
FR (1) FR1066570A (en(2012))
GB (1) GB719760A (en(2012))
NL (1) NL173798B (en(2012))

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3006715A (en) * 1957-10-18 1961-10-31 Du Pont Process of spinning acrylonitrile polymer filaments from solution of dimethyl sulfoxide and a non-solvent
US3094502A (en) * 1959-12-02 1963-06-18 Du Pont Process for preparing filaments from acrylonitrile polymer-containing compositions
US3165488A (en) * 1959-12-15 1965-01-12 Kurashiki Rayon Co Spinning solutions of a mixture of polyvinyl alcohol and a vinyl acetate-vinylidene cyanide copolymer in dimethyl sulfoxide and fibers therefrom
EP0013889A1 (de) * 1979-01-18 1980-08-06 Bayer Ag Kontinuierliches Verfahren zur Herstellung von Fäden oder Fasern aus schwerlöslichen synthetischen Polymeren
CN103382580A (zh) * 2013-07-18 2013-11-06 浙江华欣新材料股份有限公司 在线注入连续切换装置及其切换方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2404713A (en) * 1943-06-23 1946-07-23 Du Pont Method for preparing polymeric solutions
US2573949A (en) * 1946-12-21 1951-11-06 Du Pont Dissolving of polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2404713A (en) * 1943-06-23 1946-07-23 Du Pont Method for preparing polymeric solutions
US2573949A (en) * 1946-12-21 1951-11-06 Du Pont Dissolving of polymers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3006715A (en) * 1957-10-18 1961-10-31 Du Pont Process of spinning acrylonitrile polymer filaments from solution of dimethyl sulfoxide and a non-solvent
US3094502A (en) * 1959-12-02 1963-06-18 Du Pont Process for preparing filaments from acrylonitrile polymer-containing compositions
US3165488A (en) * 1959-12-15 1965-01-12 Kurashiki Rayon Co Spinning solutions of a mixture of polyvinyl alcohol and a vinyl acetate-vinylidene cyanide copolymer in dimethyl sulfoxide and fibers therefrom
EP0013889A1 (de) * 1979-01-18 1980-08-06 Bayer Ag Kontinuierliches Verfahren zur Herstellung von Fäden oder Fasern aus schwerlöslichen synthetischen Polymeren
CN103382580A (zh) * 2013-07-18 2013-11-06 浙江华欣新材料股份有限公司 在线注入连续切换装置及其切换方法
CN103382580B (zh) * 2013-07-18 2016-01-27 浙江华欣新材料股份有限公司 在线注入连续切换装置及其切换方法

Also Published As

Publication number Publication date
NL173798B (nl)
FR1066570A (fr) 1954-06-08
CH312942A (de) 1956-03-15
GB719760A (en) 1954-12-08
BE515569A (en(2012))

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