US2445042A - Method of treating oriented acrylonitrile structures - Google Patents

Method of treating oriented acrylonitrile structures Download PDF

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Publication number
US2445042A
US2445042A US496396A US49639643A US2445042A US 2445042 A US2445042 A US 2445042A US 496396 A US496396 A US 496396A US 49639643 A US49639643 A US 49639643A US 2445042 A US2445042 A US 2445042A
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United States
Prior art keywords
yarn
elongation
acrylonitrile
heating
temperature
Prior art date
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
Application number
US496396A
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English (en)
Inventor
Silverman Shirleigh
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US496396A priority Critical patent/US2445042A/en
Priority to GB14134/44A priority patent/GB585367A/en
Priority to FR924369D priority patent/FR924369A/fr
Priority to BE464523A priority patent/BE464523A/xx
Priority to CH283374D priority patent/CH283374A/fr
Priority to NL128726A priority patent/NL128726B/xx
Application granted granted Critical
Publication of US2445042A publication Critical patent/US2445042A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S425/00—Plastic article or earthenware shaping or treating: apparatus
    • Y10S425/017—Filament stretching apparatus

Definitions

  • This invention relates to shaped articles, such as yarns, films, tubings, fibers, etc., of an acrylonitrile polymer. More particularly, it relates to a method for improving the physical properties of such shaped articles which have been subjected to a drawing operation during or after their formation and which show a definite orientation on X-ray analysis.
  • the yarn is spun by a wet-spinning technique into a bath comprising, for example, a glycerol bath heated to a temperature of 140 C. or an aqueous 40% calcium chloride bath heated to a temperature of at least 100 0., the yarn being subjected during its passage through the bath to a tension of at least 0.5, and preferably 0.7 to 1.0 gram per denier.
  • the yarns obtained by either of these two methods are highly oriented and generally possess a tenacity of at least 3 grams per denier. However, they still possess an elongation that is relatively low, it being of the order of 8% to 12%. While they can be used for certain specialized purposes, wherein a low elongation is desirable,
  • the yarns are not generally suited for use in the textile art, which requires a yarn possessing an elongation of from 15% to 25%, and preferably of from 18% to 22%.
  • the objects of this invention are accomplished, in general, by heating an oriented acrylonitrile polymer yarn in a relaxed state to a temperature of at least 6., whereby the yarn is caused to shrink, and then maintaining the yarn at a temperature of at least 80 C. for a period of from 1 to 24 hours, the yarn during this time being maintained in a relaxed state or under very low tension, for example, a tension of approximately 0.05 gram per denier.
  • oriented acrylonitrile polymer yarn refers to an acrylonitrile polymer yarn that possesses a tenacity of at least 3 grams per denier and an elongation of from 8% to 12% and that showspn X-ray analysis a degree of orientation at least equal to that of an acrylonitrile polymer yarnspun by the dry-spinning technique without the application of stretching tension, as disclosed in Example I of copending application of George H. Latham, Serial No. 447,466, now abandoned, subsequently stretched to at least twice its original length while passing through a glycerol bath maintained at a temperature of C., as disclosed in said copending application of Daniel T. Meloon, Serial No. 496,397, filed July 28, 1943.
  • the initial step of this process involving the hot relaxing of the yarn, causes it to shrink 10% to 25% of its length, this shrinkage of the yarn not affecting its tenacity but causing a large increase in its elongation, substantially all of this shrinkage showing up as increased elongation.
  • This latter result is surprising and is in sharp contrast to the action of other stretched polymeric yarns, wherein only a portion of the total shrinkage of the yarn at elevated temperatures shows up in increased elongation.
  • this hot relaxing of the yarn causes an appreciable improvement in its other properties, including an approximate 50% increase in such properties as knot, loop and impact strength.
  • the final step of the process involving a prolonged heating of the shrunken yarn does not generally cause a further shrinkage of the yarn but rather causes an appreciable and surprising increase in its tenacity without any accompanying substantial loss in its elongation.
  • the yarn thus ebtained is in condition for subsequent use, for example, in the textile art.
  • the untreated yarn In contrast to the untreated yarn, it possesses a somewhat increased tenacity, a greatly improved elongation and a desirable increase in its other physical properties, including such properties as knot, loop and impact strength, etc. Moreover, the final yarn does not appear to'have been degraded by the successive heat treatments involved in the process of this invention.
  • Figure 1 shows a diagrammatic form of one embodiment 01' an apparatus suitable for use in the invention.
  • Figure 2 is a perspective view of one form oi. heating device which is suitable for use in the invention.
  • an oriented acrylonitrile polymer yarn I is unwound at a constant rate from a supply bobbin 2 by a metering device comprising a positively driven roller 3 and displacement guide I, and is led through a heating means 5 by a second metering device comprising a positively driven roller 6 and displacement guide I.
  • the speed of the positively driven roller 6 is so adjusted with respect to that of the positively driven roller 3 that the yarn I, passing through the heating means 5, is in a relaxed state and free to shrink.
  • the shrunken yarn leaving the second metering device is then collected in package form on a rotating bobbin 8, the yarn being preferably wound into the package under the lowest possible tension commensurate with good winding and unwinding performance.
  • the wound package is then placed in an oven where it is maintained at a temperature of at least 80 C. for a period of 1 or more hours.
  • the heating means 5 must, of course, be so constructed that it is capable of heating the yarn passing through it to the desired temperature without exerting any tension on it, the yarn being free to shrink at all times during its passage through the device.
  • the reference numeral 20 designates a solid block provided along one 'surface with a. slot 2
  • the block 20 is provided with a bore 22 in which there is positioned an electrical resistant 23 capable of maintaining the block at the desired temperature of at least 80 C.
  • the block 20 is preferably made of metal whereby the yarn I, passing through the slot 2 I, will be heated both by convection and radiation.
  • the slot II is preferably enlarged at that portion thereof through which the yarn passes.
  • An acrylonitrile polymer yarn was prepared by the extrusion oi. a 25% solution of an acrylonitrile polymer having a molecular weight of 66,000 in tetramethylene cyclic sultone through a, Ill-hole spinneret into a tubular cell through which heated air was circulated in an opposite direction.
  • the yarn issuing from the cell had a denier of 310 and possessed a tenacity of 0.8 gram per denier and an elongation 01' 8.0%.
  • X- ray analysis showed it to be crystalline in nature but substantlallyunorlented.
  • the yarn was then stretched between positively driven rollers and, while passing about a stationary pin, heated to a temperature of C. to 8 times its original length.
  • the stretched yarn possessed a tenacity 01 3.7 grams per denier and an elongation of 10.1%.
  • x-ray analysis showed it to be crystalline in nature and highly oriented in the direction of its fiber axis
  • the yarn was then passed in the continuous, relaxed manner of Figure 1 oi! the accompanying drawings through a slot formed in a metal block 10 inches long and maintained at a temperature of 130 C.
  • the yarn which shrank approximately 20% while passing through the slot, was then collected on a rotating bobbin under the lowest tension commensurate with good winding and unwinding performance.
  • the bobbin package thus formed was then heated in an oven' (dry air) for a period of 1 hour at a temperature of C.
  • the final yarn possessed a tenacity of 4.66 grams per denier and an elongation of 20%, with loop and knot tenacities 01' 3.3 and 2.3 grams per denier respectively.
  • the yam was substantially colorless and showed no signs of having been degraded by the heat treatment.
  • a crystalline oriented acrylonitrile polymer yarn was formed by extruding a 20% solution of acrylonitrile polymer possessing an average molecular weight of appnoximately 120,000 in dimethyl formamide into a glycerol bath maintained at a temperature of 125 C., the yarn being passed through the bath for a distance of 24 inches and subjected to a spinning tension of approximately 1 gram per denier.
  • the physical properties of this yarn, as spun, are given in the accompanying table.
  • tures employed'in these operations should generally be of the order of at least 80 C.; for example, desirable results are obtained with the use of a temperature of 100 C. to 150 C., and even higher temperatures, such as up to and including 300 (Lean be used if desired. 1
  • this step can be performed in a continuous manner (on the run by leading the yarn in a relaxed manner through a heating'means) or in a batch manner (by suspending a quantity of yarn in a relaxed manner,
  • the exact manner of heating the yarn in this operation is not critical to the invention, it only being necessary that the yarn be free to shrink during the heating operation; for example, the yarn may be heated by passing through a slot formed in a heated block, as in Example I, or it can be passed about a heated roller, or it can be passed through a heated inert fluid, such as air,
  • the second step of the process of this invention may also be conducted in either a continuous or batch manner.
  • a heating means such as an oven
  • the exact time required for the development of optimum physical properties in the yarn is, of course, dependent on the temperatures employed. Desirable results are obtained when using a heating period of 3 hours at 150 C. while somewhat longer periods should be used at a temperature of 80 C.
  • the heated medium employed for this operation comprises an atmosphere of air maintained at the desired temperature.
  • any inert atmosphere such as carbon dioxide or nitrogen gas, or even in an inert liquid, such as glycerine, glycol, etc.
  • the process of the invention preferably comprises the combined steps of successively subjecting an oriented acrylonitrile polymer yarn to a hot relaxing treatment and to a prolonged heat treatment because of the desirable effects of such treatment on both the tenacity. and elongation of the yarn.
  • a combined treatment is not essential for the production of an improved yarn, and desirable yarns for certain purposes can be obtained by the application of only the relaxing treatment or the heat treatment; for example, in the case of the yarn of Example I above, the omission of the final heating of the bobbin package yields a yarn possessing a tenacity of 3.5 grams per denier and an ,6 s elongation of 23%.
  • Example II the omission of the relaxing step results in the formation of a yarn that possesses a greatly improved tenacity but only a slightly improved elongation.
  • the two steps are performed separately in different' apparatus, the two steps may becombined and performed in a single apparatus.
  • the yarn is placed'into a heated chamber and maintained therein at the appro priate temperature until the yarn has completely shrunk and the shrunken yarn has been'given I the prolonged heat treatment.
  • The'acrylonitrile polymer constituting the shaped articles treated in accordance with this invention must, of course, be of a-sumciently high molecular weight to pos sess filmor filament-forming properties, and
  • the polymer preferably comprises a simple polymer of acrylonitrile, the invention is not restricted thereto. Interpolymers of acrylonitrile and other polymerizable substances, such as vinyl compounds, unsaturated carboxylic acid and their derivatives, oleflnic' compoun'cL'and other polymerizable substances, may also be used.
  • the interpolymer contain a major portion of acrylonitrile, and those interpolymers that are prepared from at least 80 parts of acrylonitrile and no more than 20 parts of another polymerizable substance are preferred.
  • the structure to be treated possess an orientation as determined by X-ray analysis; that is, at least equal to that of an unoriented acrylonitrile polymer yarn that has subsequently been drawn to at least twice its original length. If the structure does not possess an orientation of at least this value, the process of this invention will not generally improve its physical properties.
  • This invention makes possible the production or an acrylonitrile polymer yarn that is eminently suited for use in the textile art.
  • the practice of the invention not only greatly increases the elongation of such a yarn but also makes possible a substantial improvement in its tenacity. It also serves to greatly improve the knot and loop tenacities and elongations of the yarn.
  • the invention makes possible for the first me the production of an acrylonitrile polymer yarn possessing a tenacity of at least 4 grams per denier and an elongation of the'order of 20%. At the same time the yarn retains such other desirable properties, characteristic of acrylonitrile polymer yarn, as high resistance to chemical agents, such as common organic solvents, cleaning agents,etc.
  • the process of the invention does not cause the yarn to become colored to any appreciable extent.
  • This fact together with their greatly improved physical properties, makes the yarn of this invention highly suited for use in the textile art.
  • the yarns do not tend to shrink to any appreciable extent on subuquent exposure to elevated temperatures for example, shrinkage of the yarns under conditions Since it is obvious that many changes sntl modifications can be made in the above-described details without departing from the nature and spirit of the invention, it is to be understood that the invention is not to be limited thereto except as set forth in the appended claims.
  • a method oi improving the physical properties of an oriented shaped article formed -1'rom a polymer containing a ajor proportion or acrylonitrile which comprises heating the shaped article 'in a relaxed, iree-to-shrink condition. at a temperature of 80C. to 300 C. andmaintain ing the shrunken shaped article under a tension insuihcient to stretch said shrlmlr'en article at a temperature oi 80 C. to 300 C. for at least one hour. both of said heating stepsbeing carriedvout in the presence of an inert heating medium.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Artificial Filaments (AREA)
US496396A 1943-07-28 1943-07-28 Method of treating oriented acrylonitrile structures Expired - Lifetime US2445042A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US496396A US2445042A (en) 1943-07-28 1943-07-28 Method of treating oriented acrylonitrile structures
GB14134/44A GB585367A (en) 1943-07-28 1944-07-28 Production of an improved acrylonitrile polymer yarn
FR924369D FR924369A (fr) 1943-07-28 1946-03-22 Procédé de traitement de fils et autres articles en forme et produits en résultant
BE464523A BE464523A (sr) 1943-07-28 1946-04-12
CH283374D CH283374A (fr) 1943-07-28 1946-10-08 Procédé de fabrication d'un article en acrylonitrile orienté, appareil pour la mise en oeuvre de ce procédé, et article obtenu par ledit procédé.
NL128726A NL128726B (sr) 1943-07-28 1946-11-13

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US496396A US2445042A (en) 1943-07-28 1943-07-28 Method of treating oriented acrylonitrile structures

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BE (1) BE464523A (sr)
CH (1) CH283374A (sr)
FR (1) FR924369A (sr)
GB (1) GB585367A (sr)
NL (1) NL128726B (sr)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2499142A (en) * 1948-07-14 1950-02-28 Fair Lawn Finishing Company Heat setting of textile fabrics
US2558733A (en) * 1949-06-08 1951-07-03 American Cyanamid Co Method of producing synthetic fibers from polymers and copolymers of acrylonitrile
US2584779A (en) * 1947-11-12 1952-02-05 Courtaulds Ltd Production of threads of thermoplastic cellulose derivatives
US2591670A (en) * 1948-03-23 1952-04-08 Eastman Kodak Co Production of filaments from acrylonitrile-2-methallyl alcohol polymer
US2677591A (en) * 1950-07-07 1954-05-04 Du Pont Removal of porosity in wet-spun acrylonitrile filaments by pressing against a hot surface
DE930891C (de) * 1951-05-01 1955-07-28 Phrix Werke Ag Verfahren zur Nachbehandlung von nach dem Trockenspinnverfahren hergestellten, fertig verstreckten Gebilden aus Polyacrylnitril oder Mischpolymerisaten des Acrylnitrils
DE943191C (de) * 1950-02-08 1956-05-17 Phrix Werke Ag Verfahren und Vorrichtung zum kontinuierlichen, stufenweisen Verstrecken endloser Faeden aus organischen Hochpolymeren
US2758003A (en) * 1949-07-27 1956-08-07 Bayer Ag Treatment of polyacrylonitrile fiber with ethylene diamine and product resulting therefrom
US2759910A (en) * 1951-11-06 1956-08-21 Distillers Co Yeast Ltd Polymerised compositions
DE952548C (de) * 1947-09-04 1956-11-15 American Cyanamid Co Verfahren zur Herstellung von geformten Gebilden aus thermoplastischen Polymerisationsprodukten
US2821458A (en) * 1954-04-08 1958-01-28 Du Pont Process for producing uniform polyacrylonitrile fibers by heat relaxing solvent containing undrawn fibers, removing solvent and drawing the fibers
DE971676C (de) * 1954-06-17 1959-03-12 Dow Chemical Co Verfahren und Vorrichtung zum Stabilisieren der Abmessungen von gereckten organischen thermoplastischen Folien
US2883260A (en) * 1953-09-21 1959-04-21 American Cyanamid Co Production of monofilament of a polymer or copolymer of acrylonitrile
DE1083492B (de) * 1955-10-07 1960-06-15 Dow Chemical Co Verfahren zur Verbesserung der Anfaerbbarkeit von acrylsaeurenitrilhaltigen Faeden oder Fasern
US2956330A (en) * 1957-05-23 1960-10-18 Du Pont Stabilized yarn
US2957204A (en) * 1953-05-12 1960-10-25 Conmar Prod Corp Method of manufacture of slide fasteners
US2974391A (en) * 1955-11-30 1961-03-14 Ici Ltd Process and apparatus for making crimped filaments
DE974749C (de) * 1951-10-09 1961-04-27 Phrix Werke Ag Verfahren zur Herstellung von Faeden od. dgl. aus Polymerisaten des Acrylnitrils
US2982760A (en) * 1953-09-29 1961-05-02 Polymer Soc Process for spinning vinyl resin solution
US3000691A (en) * 1955-10-05 1961-09-19 American Cyanamid Co Fluid treatment of rectangularly piled polyacrylonitrile tow
US3047909A (en) * 1955-12-29 1962-08-07 Du Pont Process for treating elastic fibers
US3116197A (en) * 1956-08-31 1963-12-31 Du Pont Nubbed filament and dyed fabric of same
US3429861A (en) * 1965-12-21 1969-02-25 Monsanto Co Processes for polymerization of acrylonitrile using organometallic coordination complexes as catalysts
US4206300A (en) * 1978-06-12 1980-06-03 Standand Oil Company Method for improving color and impact strength of nitrile polymers
US4524105A (en) * 1977-11-17 1985-06-18 American Cyanamid Company Melt-spun acrylonitrile polymer fiber of improved properties

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1145298B (de) * 1954-01-16 1963-03-14 Deering Milliken Res Corp Verfahren zum Herstellen gekraeuselter Faeden oder Fadenbuendel aus synthetischen, thermoplastischen, linearen Kondensationspolymeren
NL238052A (sr) * 1958-04-14
GB937685A (en) * 1960-08-11 1963-09-25 Tohu Rayon Kabushiki Kaisha Method for producing filamentary tows from polymers and co-polymers of acrylonitrile
GB1002767A (en) * 1960-09-24 1965-08-25 Toho Rayon Kk Method for the manufacture of polyacrylonitrile

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1867297A (en) * 1927-12-22 1932-07-12 American Bemberg Corp Artificial cellulose yarns produced by the stretch spinning process
GB387956A (en) * 1931-09-12 1933-02-16 Ig Farbenindustrie Ag Improvements in or relating to the manufacture of new dyestuffs of the triarylmethane series
US2161766A (en) * 1937-09-15 1939-06-06 Carbide & Carbon Chem Corp Synthetic fiber
US2170439A (en) * 1936-04-02 1939-08-22 Standard Oil Dev Co Elastic fiber
US2176153A (en) * 1937-12-07 1939-10-17 Goodrich Co B F Method of stress-relieving plastics
US2199411A (en) * 1938-11-01 1940-05-07 Du Pont Artificial structure and method for producing same
US2239780A (en) * 1937-05-19 1941-04-29 Gen Aniline & Film Corp Process for improving the properties of thermoplastic, film-forming, organic substances
US2273071A (en) * 1939-10-27 1942-02-17 Carbide & Carbon Chem Corp Hosiery and method for producing the same
US2309370A (en) * 1940-12-12 1943-01-26 Dow Chemical Co Heat treatment of vinylidene chloride polymers
US2317409A (en) * 1940-01-05 1943-04-27 Goodrich Co B F Method for stress-relieving plastics
US2325060A (en) * 1942-02-25 1943-07-27 Du Pont Nonshrinking yarn
US2346208A (en) * 1941-04-08 1944-04-11 Du Pont Treatment of high tenacity yarn of synthetic origin

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1867297A (en) * 1927-12-22 1932-07-12 American Bemberg Corp Artificial cellulose yarns produced by the stretch spinning process
GB387956A (en) * 1931-09-12 1933-02-16 Ig Farbenindustrie Ag Improvements in or relating to the manufacture of new dyestuffs of the triarylmethane series
US2170439A (en) * 1936-04-02 1939-08-22 Standard Oil Dev Co Elastic fiber
US2239780A (en) * 1937-05-19 1941-04-29 Gen Aniline & Film Corp Process for improving the properties of thermoplastic, film-forming, organic substances
US2161766A (en) * 1937-09-15 1939-06-06 Carbide & Carbon Chem Corp Synthetic fiber
US2176153A (en) * 1937-12-07 1939-10-17 Goodrich Co B F Method of stress-relieving plastics
US2199411A (en) * 1938-11-01 1940-05-07 Du Pont Artificial structure and method for producing same
US2273071A (en) * 1939-10-27 1942-02-17 Carbide & Carbon Chem Corp Hosiery and method for producing the same
US2317409A (en) * 1940-01-05 1943-04-27 Goodrich Co B F Method for stress-relieving plastics
US2309370A (en) * 1940-12-12 1943-01-26 Dow Chemical Co Heat treatment of vinylidene chloride polymers
US2346208A (en) * 1941-04-08 1944-04-11 Du Pont Treatment of high tenacity yarn of synthetic origin
US2325060A (en) * 1942-02-25 1943-07-27 Du Pont Nonshrinking yarn

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE952548C (de) * 1947-09-04 1956-11-15 American Cyanamid Co Verfahren zur Herstellung von geformten Gebilden aus thermoplastischen Polymerisationsprodukten
US2584779A (en) * 1947-11-12 1952-02-05 Courtaulds Ltd Production of threads of thermoplastic cellulose derivatives
US2591670A (en) * 1948-03-23 1952-04-08 Eastman Kodak Co Production of filaments from acrylonitrile-2-methallyl alcohol polymer
US2499142A (en) * 1948-07-14 1950-02-28 Fair Lawn Finishing Company Heat setting of textile fabrics
US2558733A (en) * 1949-06-08 1951-07-03 American Cyanamid Co Method of producing synthetic fibers from polymers and copolymers of acrylonitrile
US2758003A (en) * 1949-07-27 1956-08-07 Bayer Ag Treatment of polyacrylonitrile fiber with ethylene diamine and product resulting therefrom
DE943191C (de) * 1950-02-08 1956-05-17 Phrix Werke Ag Verfahren und Vorrichtung zum kontinuierlichen, stufenweisen Verstrecken endloser Faeden aus organischen Hochpolymeren
US2677591A (en) * 1950-07-07 1954-05-04 Du Pont Removal of porosity in wet-spun acrylonitrile filaments by pressing against a hot surface
DE930891C (de) * 1951-05-01 1955-07-28 Phrix Werke Ag Verfahren zur Nachbehandlung von nach dem Trockenspinnverfahren hergestellten, fertig verstreckten Gebilden aus Polyacrylnitril oder Mischpolymerisaten des Acrylnitrils
DE976043C (de) * 1951-10-09 1963-01-31 Phrix Werke Ag Verfahren zur Herstellung von Faeden od. dgl. aus Polymerisaten des Acrylnitrils
DE974749C (de) * 1951-10-09 1961-04-27 Phrix Werke Ag Verfahren zur Herstellung von Faeden od. dgl. aus Polymerisaten des Acrylnitrils
US2759910A (en) * 1951-11-06 1956-08-21 Distillers Co Yeast Ltd Polymerised compositions
US2957204A (en) * 1953-05-12 1960-10-25 Conmar Prod Corp Method of manufacture of slide fasteners
US2883260A (en) * 1953-09-21 1959-04-21 American Cyanamid Co Production of monofilament of a polymer or copolymer of acrylonitrile
US2982760A (en) * 1953-09-29 1961-05-02 Polymer Soc Process for spinning vinyl resin solution
US2821458A (en) * 1954-04-08 1958-01-28 Du Pont Process for producing uniform polyacrylonitrile fibers by heat relaxing solvent containing undrawn fibers, removing solvent and drawing the fibers
DE971676C (de) * 1954-06-17 1959-03-12 Dow Chemical Co Verfahren und Vorrichtung zum Stabilisieren der Abmessungen von gereckten organischen thermoplastischen Folien
US3000691A (en) * 1955-10-05 1961-09-19 American Cyanamid Co Fluid treatment of rectangularly piled polyacrylonitrile tow
DE1083492B (de) * 1955-10-07 1960-06-15 Dow Chemical Co Verfahren zur Verbesserung der Anfaerbbarkeit von acrylsaeurenitrilhaltigen Faeden oder Fasern
US2974391A (en) * 1955-11-30 1961-03-14 Ici Ltd Process and apparatus for making crimped filaments
US3047909A (en) * 1955-12-29 1962-08-07 Du Pont Process for treating elastic fibers
US3116197A (en) * 1956-08-31 1963-12-31 Du Pont Nubbed filament and dyed fabric of same
US2956330A (en) * 1957-05-23 1960-10-18 Du Pont Stabilized yarn
US3429861A (en) * 1965-12-21 1969-02-25 Monsanto Co Processes for polymerization of acrylonitrile using organometallic coordination complexes as catalysts
US4524105A (en) * 1977-11-17 1985-06-18 American Cyanamid Company Melt-spun acrylonitrile polymer fiber of improved properties
US4206300A (en) * 1978-06-12 1980-06-03 Standand Oil Company Method for improving color and impact strength of nitrile polymers

Also Published As

Publication number Publication date
CH283374A (fr) 1952-06-15
BE464523A (sr) 1946-05-31
GB585367A (en) 1947-02-05
NL128726B (sr) 1951-12-15
FR924369A (fr) 1947-08-04

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