US2814603A - Dimethylformamide-aliphatic diester spinning solutions of polyacrylonitriles - Google Patents

Dimethylformamide-aliphatic diester spinning solutions of polyacrylonitriles Download PDF

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Publication number
US2814603A
US2814603A US392045A US39204553A US2814603A US 2814603 A US2814603 A US 2814603A US 392045 A US392045 A US 392045A US 39204553 A US39204553 A US 39204553A US 2814603 A US2814603 A US 2814603A
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United States
Prior art keywords
dimethylformamide
percent
solvent
spinning solutions
polyacrylonitriles
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US392045A
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Pirot Ernst
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Glanzstoff AG
Vereinigte Glanzstoff Fabriken AG
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Glanzstoff 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
    • 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

Definitions

  • This invention relates to the production of filaments from polyacrylonitrile or from mixed polymerisates containing polyacrylonitrile, dissolved in a solvent consisting of, or containing, dimethylformamide.
  • the number of solvents suitable for practical use in the preparation of spinning solutions from polyacrylonitrile or mixed polymerisates containing this compound is particularly limited. It is equally known that dimethylformamide is on the Whole a satisfactory solvent, but requires being improved in several directions. Thus, for instance, the dispersion which is first formed when trying to dissolve the polyacrylonitrile in dimethylformamide, causes a tendency of the nitrile to form a jelly and renders the spinning solution inhomogenous to the extent that the spinning process is disturbed and the filament breaks.
  • the compound to be added to the dimethylformamide is methyleneglycol-diacetate, methyleneglycoldipropionate or methyleneglycol-dibutyrate.
  • I may, for instance, proceed as follows:
  • Example 1 22 parts by weight of polyacrylonitrile, having a K-value of 87, were added to 78 parts of a solvent mixture consisting of 85 percent by weight dimethylformamide and 15 percent methyleneglycol-diacetate.
  • the polymerisate was stirred according to well-known methods to form a dispersion which then dissolved in the solvent mixture under heating.
  • the solution thus obtained yielded an unobjectionable liquid of high filament-forming capacity.
  • the filaments spun from it had a particularly high stretching capacity and stretching velocities of 300-350 meters per minute could be employed.
  • the filaments possessed particularly favorable mechanical properties and showed a resistance to breaking of 42 kilometers.
  • Example 2 19 parts by weight of a co-polymer formed of 95 percent acrylonitrile and 5 percent vinylimidazol, having a K-value of about 92, was stirred to form a dispersion in percent of a solvent mixture consisting of percent by weight dimethylformarnide and 20 percent ethylideneglycol-diacetate. After heating to fusion temperature a light-colored solution was obtained, which could be spun without any disturbances. The filaments from the solution could be stretched at a velocity of 250-300 meters per minute. The resistance to breaking extended to 40 kilometers.
  • Example 3 21 parts by weight of a co-polymer formed from percent by weight acrylonitrile and 10 percent acrylic acid amide (K-value near 87) were dispersed in 79 parts of a solvent mixture formed of 82 percent dimethylformamide and 18 percent methyleneglycol-dipropionate.
  • Example 2 In following the methods reported with reference to Example 1 a solution of high filament-forming capacity was obtained. The resistance of the filaments extended to about 42 kilometers.
  • the process of preparing spinning solutions which comprises dissolving a member selected from the group consisting of polyacrylonitrile and a copolymer of acrylo nitrile with another polymerizable unsaturated compound in minor proportion in a solvent comprising dimethylformamide in admixture with from 5 to 20 percent by weight of an aliphatic diester of the formula and n has the value zero to two inclusive.
  • the process of preparing spinning solutions which 4 comprises dissolving a member selected from the group consisting of polyacrylonitn'le and a copolymer of acrylonitrile with another polymerizable unsaturated compound in minor proportion in a solvent comprising dimethylformarnide in admixture with from 7 to 10 percent by weight of an aliphatic diester of the formula CI'h-(CH2)11,.C0.0.R.O.CO. (CH2)nCH3 wherein R is a member of the group consisting of -OH;- and --0H- and n has the value zero to two inclusive.

Description

No Drawing. Application November 13,1953
' Serial No- 39 ,045
Claims priority, application Germany December 18, 1952 2 Claims. (Cl. 260--31.6)
This invention relates to the production of filaments from polyacrylonitrile or from mixed polymerisates containing polyacrylonitrile, dissolved in a solvent consisting of, or containing, dimethylformamide.
It is an object of this invention to provide a solvent for the polymerised compounds which is free from the tendency of allowing the matter dissolved therein to swell or form jellies and to thereby disturb the spinning operation.
It is a further object of this invention to provide a solvent for the materials mentioned above which does not lead to discoloration of the filaments.
It is a particularly important object of this invention to improve solutions in dimethylformamide, which is a particularly good solvent for the said materials, by doing away with any tendency of jelly-formation and discoloration.
As is well known to those skilled in the art, the number of solvents suitable for practical use in the preparation of spinning solutions from polyacrylonitrile or mixed polymerisates containing this compound is particularly limited. It is equally known that dimethylformamide is on the Whole a satisfactory solvent, but requires being improved in several directions. Thus, for instance, the dispersion which is first formed when trying to dissolve the polyacrylonitrile in dimethylformamide, causes a tendency of the nitrile to form a jelly and renders the spinning solution inhomogenous to the extent that the spinning process is disturbed and the filament breaks.
Apart from this, solutions of the polyacrylonitrile in dimethylformamide have hitherto suffered from slight discolorations of the spinning solution and of the filaments produced from them.
I have now found that altogether satisfactory spinning solutions containing dimethylformamide as predominant solvent can be obtained by adding to this solvent a certain quantity of an aliphatic diester constituted according to the formula wherein R stands for --CH:- or for OH H8 and n is an integer ranging from zero to two.
For instance, if R is replaced by the methylene group (CH2), the compound to be added to the dimethylformamide is methyleneglycol-diacetate, methyleneglycoldipropionate or methyleneglycol-dibutyrate.
If R is replaced by the ethylidene group I CH3 there are obtained the corresponding ethylidene compounds, viz. ethylideneglycol-diacetate, ethylideneglycoldipropionate or ethylideneglycol-dibutyrate.
The mixtures of dimethylformamide with one of the nited States Patent 2,814,603 Pa ent-e5 Ne 2.6 1.95.
ubsta tors id. o ns anc a mixtu o im th formamide with 'inethyleneglycol-diacetate, form with polyacrylonitrile, or? its mixtureswith other polymerisates teih 's i jia tor' spinning solu i n I have found that the best solvent is obtained if 5-20 percent by weight, and preferably 7 -10 percent of the diester calculated onthe' weight of the dimethylformamide, are added .to it.
When using solvent mixtures of the kind aforesaid in the preparation of spinning solutions from polyacrylonitrile or mixtures of the nitrile with other polymerisates, the tendency of the polymers for the formation of jellies is altogether doneaway with and the disturbances arising when operating with dimethylformamide alone are avoided altogether.
I have further found that the spinning solution is improved also in that neither the solutions nor the filament obtained with their aid do show any discoloration worth speaking of.
I have noticed also that the use of mixtures of the kind forming the object of this invention increases the stretching capacity of the filaments obtained from the solutions.
In operating this invention, I may, for instance, proceed as follows:
Example 1 22 parts by weight of polyacrylonitrile, having a K-value of 87, were added to 78 parts of a solvent mixture consisting of 85 percent by weight dimethylformamide and 15 percent methyleneglycol-diacetate.
The polymerisate was stirred according to well-known methods to form a dispersion which then dissolved in the solvent mixture under heating. The solution thus obtained yielded an unobjectionable liquid of high filament-forming capacity. The filaments spun from it had a particularly high stretching capacity and stretching velocities of 300-350 meters per minute could be employed.
The filaments possessed particularly favorable mechanical properties and showed a resistance to breaking of 42 kilometers.
In comparison therewith, when using the same starting products, however, without the addition of methyleneglycol-diacetate the dispersion formed in the solvent showed an undesirable tendency of jelly-formation and the filaments obtained from the solution could be stretched only at the normal velocity of 200 meters per minute. Their resistance to breaking amounted to 38 kilometers.
Example 2 19 parts by weight of a co-polymer formed of 95 percent acrylonitrile and 5 percent vinylimidazol, having a K-value of about 92, was stirred to form a dispersion in percent of a solvent mixture consisting of percent by weight dimethylformarnide and 20 percent ethylideneglycol-diacetate. After heating to fusion temperature a light-colored solution was obtained, which could be spun without any disturbances. The filaments from the solution could be stretched at a velocity of 250-300 meters per minute. The resistance to breaking extended to 40 kilometers.
Example 3 21 parts by weight of a co-polymer formed from percent by weight acrylonitrile and 10 percent acrylic acid amide (K-value near 87) were dispersed in 79 parts of a solvent mixture formed of 82 percent dimethylformamide and 18 percent methyleneglycol-dipropionate.
In following the methods reported with reference to Example 1 a solution of high filament-forming capacity was obtained. The resistance of the filaments extended to about 42 kilometers.
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 process of preparing spinning solutions which comprises dissolving a member selected from the group consisting of polyacrylonitrile and a copolymer of acrylo nitrile with another polymerizable unsaturated compound in minor proportion in a solvent comprising dimethylformamide in admixture with from 5 to 20 percent by weight of an aliphatic diester of the formula and n has the value zero to two inclusive.
2. The process of preparing spinning solutions which 4 comprises dissolving a member selected from the group consisting of polyacrylonitn'le and a copolymer of acrylonitrile with another polymerizable unsaturated compound in minor proportion in a solvent comprising dimethylformarnide in admixture with from 7 to 10 percent by weight of an aliphatic diester of the formula CI'h-(CH2)11,.C0.0.R.O.CO. (CH2)nCH3 wherein R is a member of the group consisting of -OH;- and --0H- and n has the value zero to two inclusive.
References Cited in the file of this patent UNITED STATES PATENTS 2,589,055 Coover et a1 Mar. 11, 1952

Claims (1)

1. THE PROCESS OF PREPARING SPINNING SOLUTIONS WHICH COMPRISES DISSOLVING A MEMBER SELECTED FROM THE GROUP CONSISTING OF POLYACRYLONITRILE AND A COPOLYMER OF ACRYLONITRILE WITH ANOTHER POLYMERIZABLE UNSATURATED COMPOUND IN MINOR PROPORTION IN A SOLVENT COMPRISING DIMETHYLFORMAMIDE IN ADMIXTURE WITH FROM 5 TO 20 PERCENT BY WEIGHT OF AN ALIPHATIC DIESTER OF THE FORMULA
US392045A 1952-12-18 1953-11-13 Dimethylformamide-aliphatic diester spinning solutions of polyacrylonitriles Expired - Lifetime US2814603A (en)

Applications Claiming Priority (1)

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DEV5267A DE926567C (en) 1952-12-18 1952-12-18 Process for the production of spinning solutions from polyacrylic acid nitrile or its copolymers

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BE (1) BE525129A (en)
CH (1) CH316128A (en)
DE (1) DE926567C (en)
FR (1) FR1080225A (en)
GB (1) GB731789A (en)
NL (1) NL83914C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3437628A (en) * 1966-09-06 1969-04-08 Standard Oil Co Impact resistant nitrile polymer articles
US9816310B2 (en) 2014-01-13 2017-11-14 Donatello Doors Inc. Thermal break system and method for doors and windows

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1060781B (en) * 1954-10-13 1959-07-02 Eickhoff Maschinenfabrik Geb Planetary compensating gear for belt drives with two drive drums wrapped around one another by the belt
US2889192A (en) * 1956-12-19 1959-06-02 American Cyanamid Co Method of treating cellulose-containing textile materials, materials so treated and diester composition therefor

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2589055A (en) * 1950-04-29 1952-03-11 Eastman Kodak Co Mixtures comprising polyacrylonitrile and polyalkyl alpha-acylaminoacrylates and articles obtained therefrom

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2589055A (en) * 1950-04-29 1952-03-11 Eastman Kodak Co Mixtures comprising polyacrylonitrile and polyalkyl alpha-acylaminoacrylates and articles obtained therefrom

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3437628A (en) * 1966-09-06 1969-04-08 Standard Oil Co Impact resistant nitrile polymer articles
US9816310B2 (en) 2014-01-13 2017-11-14 Donatello Doors Inc. Thermal break system and method for doors and windows
US9885210B2 (en) 2014-01-13 2018-02-06 Donatello Doors Inc. Thermal break system and method for doors and windows

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GB731789A (en) 1955-06-15
DE926567C (en) 1955-04-21
BE525129A (en)
NL83914C (en)
FR1080225A (en) 1954-12-07
CH316128A (en) 1956-09-30

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