US2773047A - Preparation of spinnable solutions of polyacrylonitrile and related polymerisates - Google Patents

Preparation of spinnable solutions of polyacrylonitrile and related polymerisates Download PDF

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Publication number
US2773047A
US2773047A US469495A US46949554A US2773047A US 2773047 A US2773047 A US 2773047A US 469495 A US469495 A US 469495A US 46949554 A US46949554 A US 46949554A US 2773047 A US2773047 A US 2773047A
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US
United States
Prior art keywords
solution
polyacrylonitrile
spinning
dispersion
dimethylformamide
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Expired - Lifetime
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US469495A
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English (en)
Inventor
Pirot Ernst
Hantelmann Eduart
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Glanzstoff AG
Vereinigte Glanzstoff Fabriken AG
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Glanzstoff AG
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Publication date
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • 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
    • D01D1/02—Preparation of spinning solutions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18—Homopolymers or copolymers of nitriles
    • C08J2333/20—Homopolymers or copolymers of acrylonitrile

Definitions

  • This invention relates to the preparation of a solution ofpolyacrylonitrile or the mixed polymerisates thereof forthe purpose of'spinning the same. In' particular it is directed to 'the preparation of a solution which, after usual filtratiomcanbe spun'without diflic'ulty into threads with good textile properties.
  • Such extremely finely pulverized high polymers are then dispersed in known solvents, as for example, dimethylformamide at low temperatures, then vigorously stirred and the temperature of the dispersion gradually elevated to about 120 until a spinning solution is formed. It has also been proposed to apply a vacuum during the formation of the dispersion at low temperatures for the purpose of simultaneously deaerating the spinning solution. According to still other proposals, the dispersion is prepared at temperatures below freezing, that is, at temperatures of about 5 to 20 C., and subsequently converting the same into spinnable solutions by rapid heating.
  • very finely pulverized polymerisates are injected, by means of an inert gas current, as for example, by means of a current of nitrogen into a reaction vessel through a nozzle while the solvent is simultaneously fed into the reaction vessel.
  • the dispersion which is formed is then heated to temperatures up to 100 C., and the resulting spinning solution is spun by conventional methods.
  • the vacuum" vessel are 'most'vigorously heated by-a suitableelectric heating device, whereas the heating continuou'sly diminishes toward' the upper and the lower parts of the vacuum vessel. This resultsin the heating gradient required for carrying out themiethod in accordance with thisinvention.
  • An additional step forcarrying out the instant method is that of introducing a freshly prepared" reactionvessel. -The dispersion within the reaction vesselis continuously stirredby suitable mechanical means.
  • the temperature of the dispersion in the vacuum vessel may be elevated to about to C.
  • very vigorous boiling of the solution in the vacuum vessel is initiated and thereby maintained.
  • This step of very vigorous" ebullition is of very great importance in carrying out the method of the invention.
  • the efiect of the strong ebullition to'produce; vigorous agitation of the entire solution whereby rapid and complete dissolution of the very finely pulverized and distributed particles is attained.
  • the surface of the-solution obviously, will be enriched with ;thesolvent, as for'example dimethylformamide, and in thefree-space of the vacuum vessel above the liquid, a layer of--vap'or of the solvent willbe formed.
  • a refiux condenser serves continuously to condense the excess of the vapor, causing the condensed solvent, as for example dimethylformamide, to flow back onto the surface of the solution. The effect of this step is to prevent the formation of films or skins on the surface of the solution which would interfere with the homogeneity of the spinning solution.
  • the agitator and pump are preferably provided with double glands and a suction jacket to prevent the ingress of air into the vacuum vessel during the preparation of the spinning solution.
  • the installation as illustrated comprises a vacuum vessel 1, an agitator 2 with several arms, a feed hopper 3 for simultaneously charging the vessel with polymerisate and solvent, a heating jacket 4 for producing the required temperature gradient, a condenser 5, a vacuum pump 6, a pump 7, that delivers the solution to the spinning site, and filter 8 through which the solution is passed on its way to spinning site 9.
  • the vacuum vessel is charged with a freshly prepared dispersion consisting of very finely pulverized polyacrylonitrile or its mixed polymerisates and a solvent, for instance, dimethylformamide.
  • the vessel is filled with the dispersion to an extent such that only a small space remains in which a vapor phase can be formed, the level of the dispersion being slightly higher than the upper level of the heating jacket.
  • the vacuum vessel is first heated to a temperature of 100 C. and after having reached this temperature, it is charged with the still cold dispersion through hopper 3. Simultaneously, the spin- Patented Dec.
  • the method in accordance with this invention can be carried out under the optimum conditions when, during the heating, a vacuum of preferably 100 to 200 mm. Hg and a temperature of preferably 90 to 110 C. are maintained.
  • Suitable solvents having a boiling point of 100 C. or above are typified by dimethylformamide, dimethylacetamide, glycolic acid nitrile, ethylenecarbonate and similar solvents, as well as mixtures of solvents, such as for instance, a mixture of dimethylformamide and methyleneglycoldiacetate.
  • Example A vacuum vessel, as illustrated, and having a capacity of 15 liters is filled with 10 liters of a dispersion consisting of polyacrylonitrile and dimethylformamide formed by mixing 22% of very finely pulverized polyacrylonitrile and 78% of dimethylformamide.
  • the vessel is heated and simultaneously evacuated. At a temperature of 95 C. and at a vacuum of 100 mm. Hg, the solvent begins vigorously to boil so that the free space in the vacuum vessel above the liquid level is filled with dimethylformamide vapors which are continuously condensed by the reflux condenser 5, disposed above the vacuum vessel, and the condensed dimethylformamide is returned.
  • the strongly boiling solution is vigorously stirred by the agitator 2.
  • thermometer and a constant vacuum control device are preferably provided to permit control of the dissolving step.
  • the rate of charging the vessel with the dispersion consisting of 22% of polyacrylonitrile and 78% of dimethylformamide is regulated in accordance with the rate that the solution is withdrawn for spinning.
  • pump 7 pumps about 10 liters of spinning solution to the spinning site 9 and a corresponding quantity of dispersion is fed into the vacuum vessel through hopper 3.
  • the dispersion and the spinning solution produced therefrom dwell in the vacuum vessel for a period of one hour only.
  • the dispersion is converted into a solution which is free of gelatinous inclusions, is homogeneous and is deaerated.
  • Such a solution makes it possible to produce threads having excellent textile properties.
  • Method of preparing a solution of polyacrylonitrile for spinning which comprises maintaining a solution of polyacrylonitrile in dimethylformamide in the boiling state under reflux at a pressure of 100 mm. Hg, continuously introducing a stream of a cold dispersion of polyacrylonitrile in dimethylformamide and simultaneously withdrawing andfiltering the same to obtain a filtrate for spinning.
  • Process of preparing a solution of polyacrylonitrile for spinning which comprises maintaining a solution of polyacrylonitrile in a solvent having a normal boiling point of at least 100 C. in the boiling state at an approximate temperature of from 90 C. to 110 C. and under an approximate subatmospheric pressure of from 100 mm. to 200 mm. Hg, continuously introducing into said boiling solution a cold dispersion of the polyacrylonitrile in the said solvent and simultaneously with-' drawing an equivalent stream of the boiling solution, and filtering the same to obtain a filtrate for spinning.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
US469495A 1953-11-21 1954-11-17 Preparation of spinnable solutions of polyacrylonitrile and related polymerisates Expired - Lifetime US2773047A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE331801X 1953-11-21

Publications (1)

Publication Number Publication Date
US2773047A true US2773047A (en) 1956-12-04

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US469495A Expired - Lifetime US2773047A (en) 1953-11-21 1954-11-17 Preparation of spinnable solutions of polyacrylonitrile and related polymerisates

Country Status (6)

Country Link
US (1) US2773047A (en。)
BE (1) BE531668A (en。)
CH (1) CH331801A (en。)
FR (1) FR1108508A (en。)
GB (1) GB759342A (en。)
NL (1) NL191102A (en。)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2962466A (en) * 1957-02-07 1960-11-29 Du Pont Process of introducing modifier into a polymer melt
US3010932A (en) * 1958-06-18 1961-11-28 Du Pont Process for continuously dissolving acrylonitrile polymer and spinning the resulting solution
US4427613A (en) 1979-01-18 1984-01-24 Bayer Aktiengesellschaft Continuous process for the production of filaments or fibers from difficultly soluble synthetic polymers
US20250256449A1 (en) * 2022-09-23 2025-08-14 Electric Power Research Institute. China Southern Power Grid Antioxidant addition device and method for 500 kv cross-linked polyethylene insulating material

Citations (1)

* 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

Patent Citations (1)

* 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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2962466A (en) * 1957-02-07 1960-11-29 Du Pont Process of introducing modifier into a polymer melt
US3010932A (en) * 1958-06-18 1961-11-28 Du Pont Process for continuously dissolving acrylonitrile polymer and spinning the resulting solution
US4427613A (en) 1979-01-18 1984-01-24 Bayer Aktiengesellschaft Continuous process for the production of filaments or fibers from difficultly soluble synthetic polymers
US20250256449A1 (en) * 2022-09-23 2025-08-14 Electric Power Research Institute. China Southern Power Grid Antioxidant addition device and method for 500 kv cross-linked polyethylene insulating material

Also Published As

Publication number Publication date
CH331801A (de) 1958-08-15
BE531668A (en。)
GB759342A (en) 1956-10-17
FR1108508A (fr) 1956-01-13
NL191102A (en。)

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