US3066008A - Process for producing fibers from copolymers of acrylonitrile and vinylidene chloride - Google Patents

Process for producing fibers from copolymers of acrylonitrile and vinylidene chloride Download PDF

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US3066008A
US3066008A US10880A US1088060A US3066008A US 3066008 A US3066008 A US 3066008A US 10880 A US10880 A US 10880A US 1088060 A US1088060 A US 1088060A US 3066008 A US3066008 A US 3066008A
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Prior art keywords
fibres
percent
stretching
acrylonitrile
fibers
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US10880A
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English (en)
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Carpenter Albert Stanley
Timms Richard Neville
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Akzo Nobel UK PLC
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Courtaulds PLC
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    • 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
    • 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
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent

Definitions

  • This invention relates to the manufacture of synthetic fibres and is particularly concerned with the manufacture of fibres from the copolymers of acrylonitrile and vinylidene chloride which are soluble in acetone.
  • the invention is applicable to acetone-soluble binary copolymers of acrylonitrile and vinylidene chloride and also acetonesoluble copolymers of the two compounds with small amounts, for example up to about percent by weight, of other monomers such as vinyl pyridine or itaconic acid which may be used to modify the dyeing properties of the copolymer.
  • acetonesoluble copolymers of acrylonitrile and vinylidene chloride see for example British patent specification No. 643,198 and the Carpenter application Serial No. 788,045, now Patent No. 3,004,008.
  • the acetone solutions of the copolymers may be wet or dry spun to form fibres as described for example in British patent specification No. 674,323 of British Celanese Limited.
  • This latter specification also describes the step of stretching the resultant fibres in a heat-softened condition, for example in a hot water bath or in saturated steam; the stretching step may be followed by an annealing treatment so as to reduce the tendency of the fibres to shrink when heated to moderately elevated temperatures such as 60 to 100. C.
  • the term cold stretching means that the fibres are stretched at a temperature not greater than C. In general, for economic reasons, the fibres are stretched at the ordinary temperatures.
  • the degree of stretching should be at least 75 percent and may conveniently be from 100 to 300 percent. Throughout this specification the degree of stretching is expressed as the percentage of the increased length on the original length of the fibre; for example for a fibre stretched to twice its original length the stretch is 100 percent.
  • the cold stretching of the freshly extruded fibres is preferably effected between godets, the fibres leaving the spinning cell or the coagulating bath, as the case may be, being passed round a first godet and then to a second godet the peripheral speed of which is arranged to give the fibres the required degree of stretching.
  • godets the fibres leaving the spinning cell or the coagulating bath, as the case may be, being passed round a first godet and then to a second godet the peripheral speed of which is arranged to give the fibres the required degree of stretching.
  • other known methods of stretching for example using reels or rollers, or a combination of a godet and reel, may be used.
  • the cold stretching is preferably elfected in air, particularly when dry spun fibres are being stretched, but stretching may be effected in water or other non-solvent estates Patented Nov. 27, 1962 at 15-40 C., and the liquid may contain a textile lubricant.
  • One efiect of the cold stretching operation is to make the fibres less rubbery in character.
  • a second eifect is to reduce appreciably or to eliminate entirely the risk of stuck filaments in the collected yarn.
  • the fibres produced by the cold stretching operation are not however suitable for general textile uses and they are therefore given a further stretch treatment at elevated temperature.
  • Such further stretching should be from 500 to 2,000 percent and preferably 700 to 1,500 percent.
  • Suitable elevated temperatures are temperatures not less than C.
  • Such hot stretching may be carried out in hot air, steam or hot water under pressure as described in the above mentioned British specification No. 674,323 and United States Patent No. 2,679,450, and the hot stretching process may be followed by an annealing treatment to reduce the shrinkage of the fibre on heating.
  • the hot stretching treatment is carried out at temperatures above C. using saturated steam at superatmospheric pressure, for example up to 50 lbs. per square inch, as the heating medium.
  • the fibres obtained as a result of stretching the cold-stretched fibres in saturated steam at superatmospheric pressure have high dimensional stabilities to wet and dry heat which are adequate for many textile purposes.
  • the fibres so stretched contract only a few percent in boiling water or in air at 136 C. and, moreover, a marked improvement in colour stability on exposure to dry heat is also obtained.
  • still further stabilization can be effected by an annealing treatment carried out by immersing the fibres in hot or boiling water, in open steam, in steam under pressure or in hot air while allowing the natural contraction of the fibre to take place freely.
  • the fibres after the stretching treatment in saturated steam at superatmospheric pressure, may be passed continuously, under conditions of free relaxation, through a bath of water at, or near, its boiling point (that is to say at about 90-100 C.), or through a tube containing saturated steam at atmospheric pressure.
  • the resulting fibres show virtually no contraction on subsequent immersion in boiling water.
  • the present invention is illustrated by the accompanying drawings.
  • the acetone solution of the acrylonitrilevinylidene chloride copolymer is extruded through a jet 1 within a spinning cell 2 to form filaments 3; hot air is continuously circulated within the cell 2 in known manner.
  • the filaments 3 leaving the cell 2 are lapped round a godet 4 and are passed directly to a second godet 5 moving at 'a peripheral speed designed to stretch the filaments at least 75 percent in air between the two godets. From the godet 5 the filaments 3 are collected, without twist, on a bobbin 6.
  • the cold stretched filaments are hot stretched.
  • the filaments 3 are withdrawn from the bobbin 6 and lapped round a godet 7 before being drawn through a steam chest 8 by a godet 9 which stretches the filament in contact with the steam at least 500 percent.
  • the hot stretched filaments are then passed by way of guides 10,.
  • Example 1 amide solution was dissolved in acetone to give a 22 percent by weight solution. This solution was dry spun on conventional dry spinning equipment and the resulting fibres leaving the spinning cell were cold stretched 100 percent between godets and were then collected, untwisted, on a bobbin. The final collection speed was 40 metres per minute and the denier was 266. Examination of the collected yarn showed no stuck filaments and the yarn could be removed from the bobbin without difficulty, even after prolonged storage.
  • the yarn was then withdrawn from the bobbin and passed continuously, with stretching, through saturated steam at 30 lbs. per square inch using an apparatus consisting of two adjoining chambers, containing respectively hot water under pressure and then steam under pressure, and was finally collected as a twisted yarn.
  • the yarn was passed into the water through a plate containing a fine orifice, and from the water into the steam through a second orifice and out of the steam through a third orifice.
  • the stretching tension was 2 grams.
  • the denier of the collected yarn was 26, its tenacity was 4.35 grams denier, its extensibility was 10.7 percent and its contraction on immersion in boiling water for seconds was 4.6 percent.
  • the cold-stretched yarn before the hot stretching process had a tenacity of 1.47 grams/denier, an extensibility of 53.8 percent and a contraction in boiling water of 37 percent.
  • the yarn was finally passed continuously through a bath of boiling water under conditions of free relaxation, the immersion time being 11 seconds. Its tenacity was then 3.40, grams/ denier, its extensibility 13.8 percent and its contraction in boiling water about 0.5 percent; it
  • Example 2 A copolymer of acrylonitrile and vinylidene chloride was produced by the method described in the Carpenter application Serial No. 788,045, now Patent No. 3,004,008, the copolymer containing 47 percent by weight of acrylonitrile and having an intrinsic viscosity, measured in dimethyl formamide, of 1.73. It was dissolved in acetone to produce a 22 percent by weight solution which was then dry spun through a 40 hole jet as described in Example l to produce fibres which Were stretched 100 percent at ordinary temperatures between a godet and a thread-advancing reel and then collected on bobbins without twist. The collected yarn was 900 denier/ 40 filament yarn.
  • the yarn was withdrawn from the bobbin by a godet having a peripheral speed of 4 metres/minute and stretched 1,150 percent in saturated steam at lbs. per
  • the yarn obtained had a tenacity of 4 grams/denier and an extensibility of 14 percent. It was dimensionally stable to dry and wet heat. It was woven into a fabric which was found to be flame-proof according to the British standards specification. Samples of the fabric were unaffected by contact for 5 seconds with a hot iron at temperatures up to 220 C.
  • thermoforming the hotstretched fibres are subjected to an annealing treatment in which they are heated while allowing the natural contraction of the fibres to take place freely.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
US10880A 1959-03-09 1960-02-25 Process for producing fibers from copolymers of acrylonitrile and vinylidene chloride Expired - Lifetime US3066008A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7998/59A GB898734A (en) 1959-03-09 1959-03-09 Improvements in the manufacture of filamentary material from copolymers of acrylonitrile and vinylidene chloride

Publications (1)

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US3066008A true US3066008A (en) 1962-11-27

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US (1) US3066008A (enrdf_load_stackoverflow)
BE (1) BE588371A (enrdf_load_stackoverflow)
ES (1) ES256346A1 (enrdf_load_stackoverflow)
GB (1) GB898734A (enrdf_load_stackoverflow)
NL (1) NL249219A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3278663A (en) * 1963-02-04 1966-10-11 Union Carbide Corp Method for producing biaxially oriented extruded polymeric film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2658916A1 (de) * 1976-12-24 1978-07-06 Bayer Ag Polyacrylnitril-filamentgarne

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2420565A (en) * 1943-02-20 1947-05-13 Carbide & Carbon Chem Corp Synthetic textile articles
US2681265A (en) * 1948-11-27 1954-06-15 American Viscose Corp Spinning artificial filaments
US2697023A (en) * 1950-04-29 1954-12-14 Eastman Kodak Co Spinning acrylonitrile
US2716586A (en) * 1951-09-08 1955-08-30 Ind Rayon Corp Wet spinning of acrylonitrile polymers
US2775507A (en) * 1952-01-10 1956-12-25 British Celanese Manufacture of filamentary material from copolymers of acrylonitrile and vinylidene chloride

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2420565A (en) * 1943-02-20 1947-05-13 Carbide & Carbon Chem Corp Synthetic textile articles
US2681265A (en) * 1948-11-27 1954-06-15 American Viscose Corp Spinning artificial filaments
US2697023A (en) * 1950-04-29 1954-12-14 Eastman Kodak Co Spinning acrylonitrile
US2716586A (en) * 1951-09-08 1955-08-30 Ind Rayon Corp Wet spinning of acrylonitrile polymers
US2775507A (en) * 1952-01-10 1956-12-25 British Celanese Manufacture of filamentary material from copolymers of acrylonitrile and vinylidene chloride

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3278663A (en) * 1963-02-04 1966-10-11 Union Carbide Corp Method for producing biaxially oriented extruded polymeric film

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Publication number Publication date
ES256346A1 (es) 1960-06-16
GB898734A (en) 1962-06-14
BE588371A (enrdf_load_stackoverflow) 1900-01-01
NL249219A (enrdf_load_stackoverflow) 1900-01-01

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