US3035884A - Spinning polyacrylonitrile filaments and washing the filaments in contact with an absrbent surface - Google Patents

Spinning polyacrylonitrile filaments and washing the filaments in contact with an absrbent surface Download PDF

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Publication number
US3035884A
US3035884A US817876A US81787659A US3035884A US 3035884 A US3035884 A US 3035884A US 817876 A US817876 A US 817876A US 81787659 A US81787659 A US 81787659A US 3035884 A US3035884 A US 3035884A
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United States
Prior art keywords
filaments
nitric acid
coagulating bath
spinning
washing
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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
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US817876A
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English (en)
Inventor
Halbig Paul
Nordmann Camille
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lonza Electric and Chemical Works Ltd
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Lonza Electric and Chemical Works Ltd
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Publication date
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Classifications

    • 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
    • D01D10/04—Supporting filaments or the like during their treatment
    • D01D10/0436—Supporting filaments or the like during their treatment while in continuous movement
    • D01D10/0445—Supporting filaments or the like during their treatment while in continuous movement using rollers with mutually inclined axes
    • 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
    • D01D10/06—Washing or drying
    • 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
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • 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
    • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
    • D01F13/04—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of synthetic polymers
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • the invention relates to the production of filaments by the wet spinning process from polymers which consist entirely of polyacrylonitrile, or of copolymers which contain at least 85 percent by weight of acrylonitrile monomer units, the balance being polymers of compounds polymerizable with acrylonitrile.
  • polyacrylonitrile is used to include such polymers and copolymers.
  • the invention relates to improvements in the spinning of nitric acid solutions of polyacrylonitrile.
  • nitric acid solutions of polyacrylonitrile contain the polyacrylonitrile dissolved in nitric acid of more than 52% and are extruded into a spinning bath which consists of aqueous nitric acid containing less than 50% HNO It is a principal object of the invention to provide a method of recovering the nitric acid adhered to the filaments in a concentration which can directly be re-used as spinning bath.
  • wash water can be applied in only such small amounts as required to maintain a uniform concentration of the spinning bath, whereby almost the entire nitric acid entrained by the filaments can be returned to the spinning bath in a continuous and fast operation readily incorporated in the overall spinning process. In this way, substantially the entire amount of solvent is recovered in the highest possible concentration for its repeated use, and the filaments are quickly, completely and very gently deacidified.
  • the required amount of wash water is readily calculated from the concentrations of the spinning solution and co agulating bath, taking into account the amount of water entrained by the acid-free washed filaments.
  • the concentration of the polymer in the spinning solution is practically between 8 and 14 percent
  • the concentration of HNO in the solvent, which consists of H and HNO is between 52% and 65%, preferably 58 to 62%
  • the concentration of HNO in the coagulating bath is between 50% and 40%, preferably 43 to 46%.
  • the Washed filaments entrain an amount of water corresponding to about 500 to 700 percent of the weight of the filament.
  • a continuous uniform and eflicient distribution of the wash water on the filaments countercurrentwise is necessary.
  • This distribution is accomplished by passing the filaments in helical turns over a vertical pair of rollers, which consists of the wellknown combination of a wash roll proper with a threadadvancing auxiliary roll.
  • the rolls are equipped with an absorbent and readily wetted surface.
  • Such surface may be readily provided by means of a suitable fabric, felt or fibrous fleece.
  • Polyvinyl chloride is a suitable material for such surface layers.
  • the coagulated filaments pass upwardly around said roller pair in countercurrent to the water supplied to the top of the rollers.
  • Such a device is simple and does not afiect the filaments because it eliminates the otherwise used doctor blades and squeezing means for squeezing out the liquid.
  • the reference numeral 1 designates a vessel containing the acid which is pumped by pump 2 through line 10 into the vessel 3 containing the spinning bath, from which it returns through the overflow 11 into reservoir 1. Excess coagulating acid drains off through overflow 12. Said acid may be upgraded to the concentration required for the solvent nitric acid, for instance by fractional distillation.
  • the required amount of water is added through the liter counter '13 on the washing device 7, which consists of two polyvinyl chloride rolls and a collecting dish 14 for the drained wash liquid. Both rolls are coated with a polyvinyl chloride fabric 15 of about 0.4 mm. thickness.
  • the washing liquid flows from the dish 14 through conduit 11, where it is mixed with the acid from the coagulating bath, into the reservoir 1.
  • the washing device 8 is similar to device 7 and serves to rinse out from the filaments the last traces of nitric acid with suflicient water metered by the counter 17.
  • the liquid flowing from the dish 16 is collected in the vessel 9. It contains only traces of HNO' and can, therefore, be discarded. However, it is important to test the nitric acid content of said washing liquid as a control of the satisfactory operation of the washing device 7.
  • a spinning solution is prepared, which consists of 120 parts by weight of polyacrylonitnile and 880 parts by Weight of 59% nitric acid. 600 g./ hour of said solution, which contain 72 g. of polymer, 312 g. of HNO and 2116 g. of water, are extruded through the spinneret 4, which has 100 holes of 0.4 mm. diameter, into the coagulating bath 3, in which aqueous nitric acid containing 44i0.5% HNO circulates at a temperature of -2 to +6 C. About 10 cm. behind the spinneret, the coagulated filaments are received by the drawing rolls 5 and subsequently by the second drawing roller pair 6 and the Washing devices 7 and 8.
  • the rate of travel of the filaments in the devices is adjusted to 3.5 m./min. on 5, 13.0 m./min. on 6, and 13.5 m./min. on 7 and 8.
  • the filaments leaving 8 are then processed in the conventional stretching, cutting, shrinking, and other devices.
  • the metering device 13 By means of the metering device 13, about 600 g./hour are uniformly fed to the top of the wash roll.
  • the acid concentration of the coagulating bath is continuously checked'by determination of the specific gravity. If the concentration rises above 44.2% HNO the water amount is slightly increased, for instance to about 620 g.; if the concentration falls below 43.8%, the water amount is slightly reduced, for instance to 580 g. In this way the concentration of the coagulating bath is readily kept within 44:0.5. About 700 g./hour of 44% nitric acid lflow off through the overflow 12 and are passed to distillation. 1
  • the filament On the washing device 8, the filament is washed in the same way as on 7 but with 1200 g. of water per hour.
  • the nitric acid content of the wash liquid leaving the device 8 is only 0.9 to 2.0 g. per hour, corresponding to 0.29 to 0.64 percent of the nitric acid amount contained in the solution of the polymer.
  • the filament When leaving the device 8, the filament is entirely free of nitric acid.
  • the solvent is,
  • the etfect of the absorbent surface of the wash 'rolls is illustrated by the following comparative tests, carried out as set forth hereinabove.
  • test A the pair of rolls consisted of two polyvinyl chloride rolls, the surface of which had been made water repellant by a single rubbing with silicone oil.
  • test B the same rolls had been made water wcttable by a single treatment with sodium dodecylsulfonate.
  • test C the rolls had been covered with a polyvinyl chloride fabric of about 0.4 mm. thickness.
  • the following table gives the number of grams of 100% nitric acid found after conversion of 600 g. of spinning solution each to 72 g. of filament within 1 hour in the wash liquid of the Wash device 9.
  • Test A 86.00 g. HNo Test B6.20 g. HNOS Test c 1.15 g. HNOS
  • Test C The outstanding effect of Test C is due to the absorbent cover, which apparently causes a more uniform distribution of the wash water on the filament.
  • a method of producing polyacrylonitrile filaments comprising spinning a solution of a polymer selected from the group consisting of polyacrylonitrile and copolymers containing at least 85 percent by weight of acrylonitrile monomer units, the balance being polymers of compounds copolymerizable with acrylonitrile, in aqueous nitric acid containing 52 to 65 percent by weight of HNO into a coagulating bath formed by an aqueous nitric acid solution containing about to percent by weight of HNO washing the newly formed filaments in contact with an absorbent surface continuously and countercurrently with an amount of water just sufiicient to dilute the nitric acid washed out of said filaments to substantially .the concentration of said coagulating bath, and recycling said washed out acid into said coagulating bath, thereby recovering substantially the entire amount of the nitric acid introduced as solvent of said polymer in the form of about 40 to 50% nitric acid directly available for said coagulating bath.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)
US817876A 1958-06-06 1959-06-03 Spinning polyacrylonitrile filaments and washing the filaments in contact with an absrbent surface Expired - Lifetime US3035884A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH6033858A CH373860A (de) 1958-06-06 1958-06-06 Verfahren zur Herstellung von Fäden

Publications (1)

Publication Number Publication Date
US3035884A true US3035884A (en) 1962-05-22

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US817876A Expired - Lifetime US3035884A (en) 1958-06-06 1959-06-03 Spinning polyacrylonitrile filaments and washing the filaments in contact with an absrbent surface

Country Status (7)

Country Link
US (1) US3035884A (en, 2012)
BE (1) BE579106A (en, 2012)
CH (1) CH373860A (en, 2012)
DE (1) DE1284031B (en, 2012)
FR (1) FR1226284A (en, 2012)
GB (1) GB921483A (en, 2012)
NL (2) NL129518C (en, 2012)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11970788B2 (en) * 2013-10-29 2024-04-30 Braskem America, Inc. System and method of dosing a polymer mixture with a first solvent, device, system and method of extracting solvent from at least one polymeric yarn, system and method of mechanical pre-recovery of at least one liquid in at least one polymeric yarn, and continuous system and method for producing at least one polymeric yarn

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1225811B (de) * 1959-03-19 1966-09-29 Asahi Chemical Ind Verfahren zum Wiedergewinnen der Loesungsmittel
CN103912856B (zh) * 2013-01-04 2017-09-19 东莞巨扬电器有限公司 可转动的结构及应用可转动的结构的感应组件与照明装置

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2436028A (en) * 1944-12-19 1948-02-17 American Viscose Corp Microporous roll for drying continuous filaments
US2562199A (en) * 1948-12-23 1951-07-31 Ind Rayon Corp Liquid treatment of thread on a thread-advancing, thread-storage device
US2593555A (en) * 1948-01-23 1952-04-22 American Viscose Corp Apparatus for the treatment of filamentary materials, particularly with liquids
US2723900A (en) * 1952-12-03 1955-11-15 Ind Rayon Corp Spinning of acrylonitrile polymers
US2730889A (en) * 1950-10-14 1956-01-17 Ind Rayon Corp Reel for the fluid treatment of thread
US2871090A (en) * 1953-06-29 1959-01-27 Ind Rayon Corp Method for the manufacture and treatment of polyamide fibers
US2878097A (en) * 1956-08-27 1959-03-17 Halbig Paul Spinning of polyacrylonitrile filaments

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2436028A (en) * 1944-12-19 1948-02-17 American Viscose Corp Microporous roll for drying continuous filaments
US2593555A (en) * 1948-01-23 1952-04-22 American Viscose Corp Apparatus for the treatment of filamentary materials, particularly with liquids
US2562199A (en) * 1948-12-23 1951-07-31 Ind Rayon Corp Liquid treatment of thread on a thread-advancing, thread-storage device
US2730889A (en) * 1950-10-14 1956-01-17 Ind Rayon Corp Reel for the fluid treatment of thread
US2723900A (en) * 1952-12-03 1955-11-15 Ind Rayon Corp Spinning of acrylonitrile polymers
US2871090A (en) * 1953-06-29 1959-01-27 Ind Rayon Corp Method for the manufacture and treatment of polyamide fibers
US2878097A (en) * 1956-08-27 1959-03-17 Halbig Paul Spinning of polyacrylonitrile filaments

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11970788B2 (en) * 2013-10-29 2024-04-30 Braskem America, Inc. System and method of dosing a polymer mixture with a first solvent, device, system and method of extracting solvent from at least one polymeric yarn, system and method of mechanical pre-recovery of at least one liquid in at least one polymeric yarn, and continuous system and method for producing at least one polymeric yarn

Also Published As

Publication number Publication date
CH373860A (de) 1963-12-15
GB921483A (en) 1963-03-20
BE579106A (fr) 1959-09-16
DE1284031B (de) 1968-11-28
FR1226284A (fr) 1960-07-11
NL129518C (en, 2012) 1900-01-01
NL239537A (en, 2012) 1900-01-01

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