US3701820A - Process for high speed wet spinning of acrylonitrile fibers - Google Patents

Process for high speed wet spinning of acrylonitrile fibers Download PDF

Info

Publication number
US3701820A
US3701820A US843437A US3701820DA US3701820A US 3701820 A US3701820 A US 3701820A US 843437 A US843437 A US 843437A US 3701820D A US3701820D A US 3701820DA US 3701820 A US3701820 A US 3701820A
Authority
US
United States
Prior art keywords
fibers
spinning
stretching
speed
fiber
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
US843437A
Other languages
English (en)
Inventor
Keijiro Kuratani
Keitaro Fukushima
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.)
Japan Exlan Co Ltd
Original Assignee
Japan Exlan Co Ltd
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 Japan Exlan Co Ltd filed Critical Japan Exlan Co Ltd
Application granted granted Critical
Publication of US3701820A publication Critical patent/US3701820A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • ABSTRACT OF THE DISCLOSURE A process for producing acrylic synthetic fibers which have a uniform cross-sectional shape and luster at a high speed comprising extruding a spinning solution prepared from acrylonitrile polymers into an inert gas medium, then leading them into an aqueous coagulating bath to form unoriented gel fibers, washing with water, stretching and drying obtained fibrous materials and then re-stretching said fibrous materials in the presence of steam.
  • the present invention relates to a process for producing acrylic synthetic fibers at a high speed comprising extruding a spinning solution prepared by dissolving acrylonitrile polymers in an inorganic solvent into air or an inert gas which is noncoagulative with respect to said spinning solution.
  • the extruded solution is then lead into an aqueous coagulating bath so as to be coagulated as unoriented gel fibers which are then washed with water.
  • the fibers are then stretched and dried and then re-stretched in steam.
  • the above discussed difiiculties can be overcome by integrally combining a re-stretching step in a steaming heat medium, a drying step for adjusting the water content in the fibers to be in a required range prior to said re-stretching step and further a primary stretching step for imparting a required orientation to the gel fibers prior to the drying step so that the fibers to be dried in said drying step will not be made brittle.
  • a main object of the present invention is to provide a practical process for spinning, at a high speed, acrylic synthetic fibers which have excellent high uniformity of fineness, strength, elongation and cross-sectional shape as compared with a conventional wet-spinning process.
  • Another object of the present invention is to provide a process for producing acrylic synthetic fibers having an excellent brightness or luster.
  • a further object of the present invention is to provide a process for producing at a high speed, acrylic synthetic fibers small in denier and of excellent uniformity with respect to fineness, strength and elongation.
  • FIG. 1 depicts a flowsheet of the process.
  • FIG. 2 depicts a different mode of the present process.
  • FIG. 1 DESCRIPTION OF PREFERRED EMBODIMENTS
  • a spinning solution which is extruded out of a spinnerette 1 passing through an inert gas or air is coagulated a coagulating bath 2 provided in below the spinnerette 1.
  • the coagulated unoriented gel fibers 9 are drawn out from the coagulating bath 2 with a godet roller 3, are washed with Water, then are stretched in a thermal stretching bath 4, are dried on a drying roller 5, then are re-stretched in a stretching apparatus 6 into which steam has been introduced and further are treated to relax them by dry heat with a relaxing roller 7.
  • the distance between the bottom surface of the spinnerette and the liquid surface of the coagulating bath should be made more than 0.2 cm., since otherwise the slightest vibration of the spinnerette device will cause the spinnerette to be dipped into the coagulating bath and it will be difiicult to carry on the spinning.
  • the coagulating liquid to be used in the present invention requires a temperature less than 30 C. Water or an aqueous solution of an inorganic solvent having a concentration of less than 20% is used as the coagulant liquid.
  • the coagulating bath temperature is higher than the above mentioned temperature, the spun fibers will be devitrified, further will become brittle and will lose toughness and ductility.
  • the viscosity of the spinning solution to be applied to the process of the present invention be in a range of 2x10 to 1X 10' centipoises of more preferably 4x10 to 2 l0 centipoises at 30 C.
  • the spinning solution viscosity at 30 C. is lower than KEIJIRO KURATANl ET AL Oct. 31, 1972 3,701,820
  • INVENIORS KEIJIRO KURATANI KEITARO FUKUSHIMA ATTORNEYS aqueous solution of a thiocyanate having a concentration of 47 to 65% by weight so as to be at a rate of 15 to 35 parts per 100 parts of the spinning solution.
  • an inorganic solvent to be used in the present invention there can be enumerated a concentrated aqueous solution of such thiocyanate as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate or calcium thiocyanate, of a mixture of such thiocyanates, of such inorganic salt as zinc chloride or lithium chloride or of sulfuric acid or nitric acid.
  • the total stretching multiplication is defined as the product of the primary stretching ratio and the restretching ratio.
  • the present invention by integrally combining in a series suchrespective processes as in the above, it is possible to continuously spin acrylic synthetic fibers having a collapsed fiber structure, uniform cross-sectional shape and remarkable luster at such high spinning speed of 1500 m./min., for example, as has never been obtained in any conventional wet-spinning process. Together with excellent spinnability of the fibers which have finer deniers thereby, the advantages brought to the industry by the present invention are very valuable.
  • the viscosity of the spinning solution at 30 C. in this case was 523x centipoises.
  • Said spinning solution was warmed to 65 C., was extruded into air at the rate of 118 g./min. with a clearance of 1.0 cm.
  • the fibers were spun under the same spinning conditions as were mentioned above by using the same spinning solution and spinnerette as were used in producing the above mentioned fiber A, were coagulated, were drawn at a peripheral speed of 150 m./ min. of a godet roller, then were washed with water and were stretched to be 10 times as long in steam at 127 C.
  • the spinning speed in this case was 1500 m./min. They were then dried for 1 minute in contact with the peripheral surface of a roller which was heated to 115 C. and further were treated to relax for 15 minutes in steam at 120 C. to obtain acrylic synthetic fibers which had monofilament fineness of 3 deniers.
  • This fiber is hereinafter called fiber B.
  • the same polymer as was used in producing the fiber A was dissolved in an aqueous solution of 44% sodium thiocyanate to prepare a spinning solution having a concentration of 11.3% of the copolymer.
  • the viscosity of this spinning solution at 30 C. was 45 x10 centipoises.
  • Said spinning solution was warmed to 70 C. and was extruded directly into an aqueous solution of 12% sodium thiocyanate at a temperature of -3 C. while maintaining an amount of delivery of 15.9 g./min. by using a spinnerette having 50 spinning orifices of a diameter of 0.09 mm. and coagulated to form the fibers.
  • the fibers were drawn at a peripheral speed of 13.5 m./ min.
  • fiber C acrylic synthetic fibers of a monofilament fineness of 3 deniers. This fiber is hereinafter called fiber C.
  • the fibers were spun under the same spinning conditions as in spinning the fiber C by using the same spinning solution and spinnerette as were used in producing the fiber C, were coagulated, were washed with water, were stretched to be 4 times as long in boiling water, then were dried for 45 seconds in contact with the peripheral surface of a roller heated to 115 C. and were re-stretched to be 2.5 times as long in steam at 143 C.
  • the spinning speed in this case was m./min.
  • they were heatrelaxed in the same conditions as in producing the fiber A to obtain acrylic synthetic fibers of a monofilament fineness of 3 deniers. This fiber is called as fiber D.
  • Nonuniform e.g. guitarshaped.
  • Cross-sectional shape 1 All circular.
  • the luster was measured by the following method:
  • the fibers A and B obtained by the spinning process wherein a spinning solution having as a main component an acrylonitrile polymer dissolved in an aqueous solution of an inorganic salt is once extruded into air or an inert gas which is a noncoagulative gas for said spinning solution and is then coagulated in an aqueous coagulating bath have the same filament properties as of the fibers C and D produced by a wet-spinning process wherein a spinning solution of an acrylonitrile polymer is extruded directly into an aqueous coagulating liquid and have a luster far superior to that of the above mentioned fibers C and D obtained by the ordinary wet-spinning process.
  • Example 2 v The same spinning solution as was used in the production of the fiber A in Example 1 was used. Said spinning solution was warmed to 70 C., was extruded into air while maintaining the rate of 17-6 g./min. A clearance of 0.8 cm. was maintained between the bottom surface of the spinneretteand the liquid surface of the coagulating bath. A spinnerette having 80 spinning orifices of a diameter of 0.1 mm. and orifice distance 2.6 mm. yielded as long in steam at 143 C. The spinning speed in the re-stretching was 500 m./min.
  • the thus obtained fibers were preheated for 1 second in contact with the peripheral surface of a heated roller and then were treated to relax for 2 seconds in contact with a relaxing roll heated to fibrous material which was then dipped into an aqueous 5 250 C. so as to shrink by to obtain acrylic synsolution of 12% sodium thiocyanate at 5 C. to form thetic fibers of a monofilament fineness of 3 deniers. fibers. Said fibers then were drawn in the condition of The obtained fiber was of a luster of 71, knot strength peripheral speed of 150 m./min. of a godet roller, and of 1.7 g./d. and Youngs modulus of 1.60 g./d. in hot were washed with water and further were stretched to be 10 water and the cross-sections of the respective fibers were 4 times their length in boiling water. Then said fibers all circular and showed a remarkable uniformity.
  • Example 4 were primarily dried for 30 seconds in contact with the Example 4 peripheral surface of a roller heated to 115 C.
  • the possi- F E bility of the continuous spinning was investigated by vary- Primary drying temperature Q) 85 n5 mg as 1n the following table the amount of delivery, the Water content after primary drying (percent) 20.3 5.1 peripheral'speed of the godet roller, the stretching condifigig g -m -ag ggg g zga ags: z tiOI IS in the re-stretching step and the stretching multipli- Monofilament deniers .45 2. 53 cation in the process of producing these fibers.
  • Example 5 The same spinning solution as in Example l-A was Example 3 warmed to 70 C. and was extruded so as to be coagulated as fibers into an aqueous solution of 12% sodium The same spinning solution as was used in Example thiocyanate at a temperature of 5 C. while maintaining 1-A was warmed to 6 5 C.
  • the obtained fibrous materials then were dipped coagulating bath step, in order to make the direction of into an aqueous solution of 12% sodium thiocyanate at the fiow of the coagulating liquid coincide normally with 5 C. to form fibers.
  • Said fibers were drawn at a periphthe direction of the advance of the filamentary materials, eral speed of 50 m./min. of a godet roller, Were washed such flowing bath type spinning apparatus as is exempliwith water and then were stretched to be 1.2 or 2.0 times fied in FIG. 2 was also used.
  • Example 6 The same spinning solution as in Example l-A was extruded into air by varying the amount of delivery as hown in Table with a clearance of 1.0 cm. between the bottom surface of the spinnerette and the liquid surface of the coagulating bath by using a spinnerette having 8 spinning orifices of a diameter of 0.1 mm. and dipped into an aqueous solution of 12% sodium thiocyanate at a temperature of 3 C.
  • such flowing bath type spinning apparatus as is shown in FIG. 2 was used so that the direction of the flow of the coagulating liquid might be normally the same as the direction of the advance of the filamentary materials.
  • the depth of the coagulating bath in the funnel body was 14 cm., the diameter of the narrowest part of the tube part 13 was 0.6 cm. and its length was made 30 cm.
  • the coagulating liquid was fed through the coagulating liquid feeding pipe 14 while always keeping the constant liquid height.
  • the average flowing speed of the coagulating liquid was 102 cm./min.
  • the peripheral speeds of the godet roller corresponding to the respective amounts of delivery and the optimum peripheral speeds of the godet roller at which the continuous spinning is possible are shown in Table 5.
  • the maximum peripheral speeds of the godet roller corresponding to the amount of delivery of the spinning solution and the maximum pheripheral speeds of the godet roller at which the continuous spinning is possible if the flowing bath type spinning apparatus shown in the Example 5 is not used are also mentioned in Table 5.
  • a high speed process for producing acrylic fibers wherein the acrylic polymer used is polyacrylonitrile or a copolymer containing at least by weight of acrylonitrile the remainder being other unsaturated vinyl monomers copolymerizable with acrylonitrile, said polymer having a molecular weight corresponding to an intrinsic viscosity [1 of 0.4 to 4.0 in dimethyl formamide at a temperature of 30 0., characterized by the following steps performed in continuous sequence:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
US843437A 1968-07-22 1969-07-22 Process for high speed wet spinning of acrylonitrile fibers Expired - Lifetime US3701820A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5201168 1968-07-22

Publications (1)

Publication Number Publication Date
US3701820A true US3701820A (en) 1972-10-31

Family

ID=12902857

Family Applications (1)

Application Number Title Priority Date Filing Date
US843437A Expired - Lifetime US3701820A (en) 1968-07-22 1969-07-22 Process for high speed wet spinning of acrylonitrile fibers

Country Status (7)

Country Link
US (1) US3701820A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE736380A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BR (1) BR6910034D0 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE1937266A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES368964A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1276533A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL6910709A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930105A (en) * 1972-09-12 1975-12-30 Rhone Poulenc Sa Hollow fibres
US3993719A (en) * 1974-02-15 1976-11-23 Japan Exlan Company Limited Process for producing carbon fibers
US4659529A (en) * 1983-04-20 1987-04-21 Japan Exlan Company, Ltd. Method for the production of high strength polyacrylonitrile fiber

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930105A (en) * 1972-09-12 1975-12-30 Rhone Poulenc Sa Hollow fibres
US3993719A (en) * 1974-02-15 1976-11-23 Japan Exlan Company Limited Process for producing carbon fibers
US4659529A (en) * 1983-04-20 1987-04-21 Japan Exlan Company, Ltd. Method for the production of high strength polyacrylonitrile fiber

Also Published As

Publication number Publication date
BE736380A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1970-01-22
BR6910034D0 (pt) 1973-01-16
NL6910709A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1970-01-26
DE1937266A1 (de) 1970-01-22
GB1276533A (en) 1972-06-01
ES368964A1 (es) 1971-05-16

Similar Documents

Publication Publication Date Title
US2445042A (en) Method of treating oriented acrylonitrile structures
US2210774A (en) Fibers from ethylene polymers
US2988802A (en) Apparatus for spinning polyvinyl alcohol fibers and product
US2558735A (en) Method of forming dyed shaped articles from acrylonitrile polymerization products
US2957747A (en) Process for producing crimpable polyamide filaments
US3408277A (en) Process and apparatus for producing high-bulk synthetic yarns
US3412191A (en) Method for producing artificial fibers
SE443164B (sv) Forfarande for framstellning av polyetenfibrer med hog draghallfasthet och elasticitetsmodul
US3600491A (en) Production of hollow acrylic fibers
US2948581A (en) Method of producing a synthetic fiber
US2577763A (en) Wet spinning process
US2953428A (en) Production of polychlorotrifluoroethylene textiles
US3088793A (en) Spinning of acrylonitrile polymers
US2426719A (en) Wet spinning of acrylonitrile polymers
US3066006A (en) Method of processing a tow
US3655857A (en) Process for preparing acrylonitrile polymer solution
US2790700A (en) Controlled coagulation of salt-spun polyacrylonitrile
US3523150A (en) Manufacture of industrial acrylic fibers
US2764468A (en) Method of preparing resilient acrylonitrile polymer fibers
US2697023A (en) Spinning acrylonitrile
US4497868A (en) Very fine denier synthetic fibers
US2530962A (en) Formation of shaped articles from acrylonitrile polymers
USRE25831E (en) Method for dyeing acrylonitrile polymer fibers
US3080210A (en) Spinning of acrylonitrile polymers
US2907096A (en) Shaped polyacrylonitrile structures