US2833738A - Method of producing a spinning solution of an acrylonitrile polymer - Google Patents

Method of producing a spinning solution of an acrylonitrile polymer Download PDF

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Publication number
US2833738A
US2833738A US437285A US43728554A US2833738A US 2833738 A US2833738 A US 2833738A US 437285 A US437285 A US 437285A US 43728554 A US43728554 A US 43728554A US 2833738 A US2833738 A US 2833738A
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United States
Prior art keywords
spinning solution
weight
producing
glycolic acid
acid nitrile
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Expired - Lifetime
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US437285A
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Pirot Ernst
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VER GLANZTOFF FABRIKEN AG
VEREINIGTE GLANZTOFF-FABRIKEN AG
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VER GLANZTOFF FABRIKEN AG
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Classifications

    • 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
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/10—Homopolymers or copolymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate

Definitions

  • This invention relates. to a process for producing a spinning solution from polyacrylonitrile or copolymers thereof.
  • Example 1 200 g of polyacrylonitrile having a K-value of were stirred in 800 g of a solvent mixture consisting of 80 percent by Weight of glycolic acid nitrile and 20 percent by weight of methylene glycol diacetate, at a temperature of about 15 C., to form a suspension. While the suspension was stirred, it was deaerated in a vacuum. After about one hour the deaerated mixture was heated gradually to a temperature ranging between and C. and stirring was continued for another hour at this temperature.
  • the spinning solution thus obtained was found to be satisfactory in every way and was then spun continuously according to the dry-spinning method.
  • the threads or filaments were stretched in hot condition in two steps, to from 8 to 10 times their original length. These threads or filaments were found to present a particularly uniform cross-section and to display a favorable strength of about 40 breaking km. at an elongation of between 7 and 8 percent.
  • Example 2 200 g of a copolymer consisting of 90 percent by weight of acrylonitrile and 10 percent of acrylic acid amide were stirred in cold condition together with 800 g of a solvent mixture containing 75 percent by weight of glycolic acid nitrile and 25 percent by weight of methylene glycol dibutyrate, to form a suspension which was then Worked up, in accordance with Example 1. On being spun the solution thus obtained proved very satisfactory and the threads or filaments produced from it had a particularly favorable strength of about 45 breaking km. at an elongation of about 8 percent.
  • n may be a numeral between 0 and 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Description

United States Patent METHOD OF PRODUCING A SPINNING SOLUTION OF AN ACRYLONITRILE POLYMER No Drawing. Application June 16, 1954 Serial No. 437,285
Claims priority, application Germany June 25, 1953 3 Claims. (Cl. 260-3145) This invention relates. to a process for producing a spinning solution from polyacrylonitrile or copolymers thereof.
Polyacrylonitrile and copolymers thereof which are soluble in the usual organic solvents only with difliculty, or not at all, heretofore were dissolved in solvents such as dimethylformamide or glycolic acid nitrile, and the solu-. tions thus obtained were used in the production of threads or filaments. It was found, however, that the preparation of the spinning solutions by means of any of the known solvents was accompanied by serious drawbacks, more particularly a tendency of the solutions thus obtained to form jellies. Even when all possible precautions were taken this jelly-forming tendency persisted and could not be inhibited.
However, apart from the jelly-forming tendency, if glycolic acid nitrile was used as a solvent another very inconvenient drawback occurred and this was the tendency of glycolic acid nitrile to decompose at an elevated temperature.
It has been tried to get rid of the jellies formed in the solution by heating the solution to a more elevated temperature, but this requires heating to temperatures where the glycolic acid nitrile starts decomposing and this tendency to decompose creates other disturbances when the solution is used for spinning.
On the whole it proved impossible, according to the methods hitherto used, to obtain spinning solutions giving full satisfaction. Even the addition of other substances such as nitromethane to the glycolic acid nitrile did not counter-balance the drawbacks mentioned above.
I have now found that it is possible to produce fully satisfactory spinning solutions which do not display the tendency of forming jellies and from which high-grade threads or filaments can be obtained by spinning, if the polyacrylonitrile or copolymcrs thereof are dissolved in a well defined mixture of solvents. I have found that in order to obtain a fully satisfactory solvent, glycolic acid nitrile must be mixed with an adequate quantity of an aliphatic diester of the general formula solvent characterized hereabove is used in the production 2,833,738 Patented May 6, 1958 of spinning solutions from polyacrylonitrile or copolymers thereof, the often observed tendency of the spinning solution to form a jelly and thereby creating undesirable disturbances will be found to have disappeared.
I have ascertained also that if this solvent mixture is used, the spinning solution itself as well as threads or filaments obtained therefrom are colorless and remain colorless.
In practicing my invention I may for instance proceed as follows.
Example 1 200 g of polyacrylonitrile having a K-value of were stirred in 800 g of a solvent mixture consisting of 80 percent by Weight of glycolic acid nitrile and 20 percent by weight of methylene glycol diacetate, at a temperature of about 15 C., to form a suspension. While the suspension was stirred, it was deaerated in a vacuum. After about one hour the deaerated mixture was heated gradually to a temperature ranging between and C. and stirring was continued for another hour at this temperature.
The spinning solution thus obtained was found to be satisfactory in every way and was then spun continuously according to the dry-spinning method.
The threads or filaments were stretched in hot condition in two steps, to from 8 to 10 times their original length. These threads or filaments were found to present a particularly uniform cross-section and to display a favorable strength of about 40 breaking km. at an elongation of between 7 and 8 percent.
Example 2 200 g of a copolymer consisting of 90 percent by weight of acrylonitrile and 10 percent of acrylic acid amide were stirred in cold condition together with 800 g of a solvent mixture containing 75 percent by weight of glycolic acid nitrile and 25 percent by weight of methylene glycol dibutyrate, to form a suspension which was then Worked up, in accordance with Example 1. On being spun the solution thus obtained proved very satisfactory and the threads or filaments produced from it had a particularly favorable strength of about 45 breaking km. at an elongation of about 8 percent.
' Various changes may be made in the proportions and compositions of the materials and solvents reported in the foregoing specification without departing from the invention or sacrificing the advantages thereof.
I claim:
1. The method of producing a spinning solution of a polymer of the group consisting of polyacrylonitrile and a copolymer of 90% by weight of acrylonitrile and 10% by weight of acrylic acid amide which comprises dissolving the said polymer in a solvent mixture consisting of glycolic acid nitrile and a diester of the general formula CH .(CH .CO.O.CH .O.CO.(CH ),,.CH
wherein n may be a numeral between 0 and 2.
2. The method of claim 1 in which the solvent mixture contains from 5 to 30% by weight of the diester calculated on the weight of the glycolic acid nitrile.
3. The method of claim 1 in which the solvent mixture contains from 10 to 15% by weight of the diester calculated on the weight of the glycolic acid nitrile.
References Cited in the file of this patent UNITED STATES PATENTS 2,620,324 Coover Dec. 2, 1952

Claims (1)

1. THE METHOD OF PRODUCING A SPINNING SOLUTION OF A POLYMER OF THE GROUP CONSISTING OF POLYACRYLONITRILE AND A COPOLYMER OF 90% BY WEIGHT OF ACRYLONITRILE AND 10% BY WEIGHT OF ACRYLIC ACID AMIDE WHICH COMPRISES DISSOLVING THE SAID POLYMER IN A SOLVENT MIXTURE CONSISTING OF GLYCOLIC ACID NITRILE AND A DIESTER OF THE GENERAL FORMULA
US437285A 1953-06-25 1954-06-16 Method of producing a spinning solution of an acrylonitrile polymer Expired - Lifetime US2833738A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE326493X 1953-06-25
DEV6481A DE1004340B (en) 1953-06-25 1953-11-06 Process for the production of threads from polyacrylonitrile or its copolymers with improved textile properties

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US2833738A true US2833738A (en) 1958-05-06

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US466197A Expired - Lifetime US2851435A (en) 1953-06-25 1954-11-01 Method of improving the textile properties of polyacrylonitrile threads

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US (2) US2833738A (en)
BE (2) BE528519A (en)
CH (3) CH326493A (en)
DE (1) DE1004340B (en)
FR (3) FR1230409A (en)
GB (3) GB752703A (en)
NL (1) NL83932C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7199176B2 (en) 1995-05-22 2007-04-03 Cabot Corporation Elastomeric compounds incorporating silicon-treated carbon blacks

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379794A (en) * 1966-04-27 1968-04-23 Du Pont Blends of fiber forming acrylonitrile polymers and polymeric 2, 2-disubstituted propioleactone
DE2947824A1 (en) 1979-11-28 1981-07-23 Bayer Ag, 5090 Leverkusen CROSS-SECTION STABLE, HYGROSCOPIC CORE / SHEATH STRUCTURE, FIBERS AND THREADS AND METHOD FOR THE PRODUCTION THEREOF
DE3225267A1 (en) * 1982-07-06 1984-01-12 Bayer Ag, 5090 Leverkusen MANUFACTURE OF LOW-SOLVENT POLYACRYLNITRILE SPIDER THREADS
DE3225268A1 (en) * 1982-07-06 1984-01-12 Bayer Ag, 5090 Leverkusen CONTINUOUS DRY SPINNING PROCESS FOR HIGH-SHRINKABLE ACRYLNITRILE THREADS AND FIBERS

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2620324A (en) * 1950-12-01 1952-12-02 Eastman Kodak Co Polymerization of acrylonitrile in the presence of amide polymers

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2123599A (en) * 1930-01-28 1938-07-12 Ig Farbenindustrie Ag Production of polymerization products
BE465697A (en) * 1942-06-17
US2404725A (en) * 1944-11-18 1946-07-23 Du Pont Polymer solutions
US2571777A (en) * 1950-04-08 1951-10-16 Eastman Kodak Co Acrylonitrile polymer mixed with copolymer of vinyl acetate and isopropenyl acetate
US2571683A (en) * 1950-04-13 1951-10-16 Eastman Kodak Co Mixtures comprising polyacrylonitrile and a polyvinyl acetal
BE502706A (en) * 1950-04-26

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2620324A (en) * 1950-12-01 1952-12-02 Eastman Kodak Co Polymerization of acrylonitrile in the presence of amide polymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7199176B2 (en) 1995-05-22 2007-04-03 Cabot Corporation Elastomeric compounds incorporating silicon-treated carbon blacks

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CH326493A (en) 1957-12-31
FR1230409A (en) 1960-09-15
FR1100646A (en) 1955-09-22
GB754775A (en) 1956-08-15
NL83932C (en)
GB752507A (en) 1956-07-11
US2851435A (en) 1958-09-09
BE528519A (en)
CH329999A (en) 1958-05-15
DE1004340B (en) 1957-03-14
BE528051A (en)
GB752703A (en) 1956-07-11
CH326494A (en) 1957-12-31
FR66290E (en) 1956-06-28

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