US3701819A - Method for production of acrylic composite fiber - Google Patents

Method for production of acrylic composite fiber Download PDF

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Publication number
US3701819A
US3701819A US850036A US3701819DA US3701819A US 3701819 A US3701819 A US 3701819A US 850036 A US850036 A US 850036A US 3701819D A US3701819D A US 3701819DA US 3701819 A US3701819 A US 3701819A
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United States
Prior art keywords
solution
fiber
fibers
polymer
acrylonitrile
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Expired - Lifetime
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US850036A
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English (en)
Inventor
Masatoshi Yoshida
Yasuo Saji
Kazuhisa Saito
Shigeru Ikegami
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Teijin Ltd
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Toho Beslon Co Ltd
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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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]

Definitions

  • spiral crimps are usually prepared by spinning together two different types of polymer solutions to form a composite fiber. If the two components employed possess different contraction behaviors under heating or other special conditions, spiral crimps may then be obtained by suitable treatment after spinning.
  • the crimping properties of a composite fiber may thus depend upon the difference between the polymeric chemical constituents, the spinning procedure, treatment conditions and the like.
  • An acrylic fiber shows a characteristic thermal contraction behavior in aqueous 80% (v./v.) dimethyl formamide solution as shown in FIG. 1 and the structural characteristics of the fiber, such as orientation, cohesive structure and polymer composition reflect on the shape of the contraction curve.
  • the temperature at maximum contraction of a fiber (T is lowered as heat treatment of the polymer solution is increased, mainly because of chemical changes.
  • composite fibers with satisfactory spiral crimping properties may be produced by conjugate spinning together of a polymer solution and the heat treated polymer solution thereof, wherein the difference in T of the fibers produced from the two solutions is more than 5 C.
  • the thermal change of the polymer solution is carried out at a temperature of 60 150 0, preferably -130" C. in the presence of concentrated aqueous zinc chloride solution as the solvent wherein a basic compound is present in an amount of 0005-02 wt. percent, calculated as zinc oxide.
  • a basic compound is present in an amount of 0005-02 wt. percent, calculated as zinc oxide.
  • the higher the temperature and the larger the amount of basic compound present the faster the thermal change proceeds.
  • the amount of basic compound present is less than 0.005% as zinc oxide, it requires too long a time to obtain the desired heat-treated solution on an industrial scale.
  • the amount of basic compound present is more than 0.2%, the thermal change proceeds at an uncontrollably fast rate.
  • Such a large amount of basic compound also inhibits polymerization, particularly when a peroxide is used as the polymerization catalyst in solution polymerization.
  • the concentrated aqueous zinc chloride solution is taken up by 10 gr. as pure zinc chloride constituent to be added in about 10 ml. of water and then several drops of the indicator, methyl orange solution (0.1%) is added to the resulting solution.
  • the basic compound concentration can be calculated from the following equation from the color changing point of the indicator:
  • C represents the basic compound concentration (percent wt.)
  • S represents the weight in grams of the material being tested
  • D is the amount of 1 N hydrochloric acid used (ml.).
  • basic compounds which may be employed, there may be mentioned zinc oxide, zinc carbonate, sodium hydroxide, sodium carbonate, ammonium hydroxide etc. Zinc oxide and zinc carbonate are preferred for use with the zinc chloride solution of this invention.
  • the salt solution contains an excess amount of basic compound, it may be adjusted to a desired concentration by adding hydrochloric acid.
  • polymer concentration is 10 wt. percent
  • T of the resulting fiber changed as shown in the table.
  • the resulting composite fiber is not suitable for fabric uses because of excessive crimps, which result in a hard hand feeling.
  • FIGS. 2 and 3 illustrate the effects of treatment temperature and concentration of zinc oxide, respectively, on the difference in T obtained.
  • any desired difference in T can be adjusted by controlling the heating temperature, heating time or basic compound concentration in the solvent used.
  • AT A t exp (B/T) wherein t represents heating time, T heating temperature (K) and A and B are constants.
  • the inventors have found that the most suitable number of crimps in a composite fiber is not always fixed, but depends on the type of end use contemplated.
  • the polymer composition or conditions of aftertreatment must be changed.
  • the process of the invention provides that it may be easily carried out by changing of heating temperature or time.
  • Another feature of the composite fiber produced by the method of this invention is the excellent laminating property of the two components to each other.
  • two difierent types of polymers are spun side by side to form a composite fiber
  • there is a tendency to delaminate perhaps because of poor compatibility of the two components. This tendency is more noticeable when the chemical compositions of the components must differ considerably in order to improve the crimping properties of the fiber.
  • delamination results in loss of crimping properties and deterioration of fabric qualities.
  • the laminating property of the composite fiber produced by the present invention is good, perhaps because the two components originate from the same polymer solution.
  • Dyed end products made from conventional acrylic composite fibers often have a nettled appearance owing to different take-up of dye in the two components, but such unfavorable appearance is not observed in the composite fibers of this invention.
  • the solvent used in the present invention is a concentrated salt solution containing zinc chloride as the main constituent.
  • Other constituents such as sodium chloride, magnesium chloride, ammonium chloride, etc. can be added if desired.
  • the total salt concentration is preferably in the range of 50-65 wt. percent.
  • the original polymer solution can be prepared by dissolving the polymer produced by a conventional suspension polymerization or, more preferably, by solution polymerization in the solvent.
  • peroxides such as ammonium persulfate, sodium persulfate and hydrogen peroxide as well as redox systems such as sodium persulfate-sodiurn bisulfite and sodium chlorate-sodium methabisulfite may be used as polymerization catalysts.
  • a continuous process, employing solution polymerization with heat treatment of the resulting polymer solution is preferred for industrial operation, rather than a batchwise process.
  • Applicants have further found that a homogeneous polymer solution can be prepared without the production of foam or gel-like substances and can be directly used as a spinning solution by performing the solu-- tion polymerization continuously, completely filling up the polymerization apparatus with the reaction mixture and applying a pressure of 1-5 kg./cm. gauge to the reaction system by means of reciprocating pumps or other suitable devices.
  • Polymers employed in the present invention are composed mainly of acrylonitrile and include copolymers of acrylonitrile with copolymerizable monomers.
  • monomers may be mentioned methyl acrylate, methyl methacrylate, vinyl acetate, acrylamide, methacrylamide as well as allylsulfonic acid, methallylsulfonic acid and derivatives thereof, in fact, any monomer copolymerizable with acrylonitrile.
  • a continuous heat treatment of the solution is carried out by applying a pressure of 1-10 kg./cm. gauge to the polymer solution in a heating vessel or vessels by means of reciprocating pumps or other suitable devices so as to prevent formation of any air foams or gel-like substances.
  • FIG. 4 One typical example of such processes is illustrated in FIG. 4, wherein 1 represents a polymerization reactor to which solvent (S), acrylonitrile (M comonomers (M and catalyst (C) are continuously supplied by reciprocating pumps or such devices.
  • the reactor is equipped with cooling and heating jackets for temperature control, a stirrer and a pressure gauge.
  • the resulting polymer solution is divided into two streams, A and B.
  • One side (A) is fed to spinning step 3 through a pool tank 2.
  • Another side (B) is fed into heating vessel 5 through a preheating zone 4.
  • Heating vessel 5 is equipped with a heating jacket, a stirrer and a pressure gauge.
  • Heat-treated polymer solution flows continuously to cooling zone 6, pool tank 7 and finally to spinning step 3 so as to be spun together with A.
  • the solvent used is recovered from the spinning process as in 8 and reused after concentration and purification.
  • the two types of polymer solutions thus obtained can be extruded at a temperature of preferably 10-30" C. into 'a coagulating bath composed of 10-40% of-the same saline constituents as those in the solvent by the use of a conjugate-type spinnere't.
  • the spun gel-tow thus obtained is washed with water, then heat-stretched under wet or dry conditions and relaxed in a suitable medium such as hot air, super-heated steam, saturated steam, etc.
  • a suitable medium such as hot air, super-heated steam, saturated steam, etc.
  • spinning processes applied in the present invention are not limited to those above mentioned.
  • EXAMPLE 1 A copolymer solution of 92% acrylonitrile, 7.0% methyl acrylate and 1.0% sodium methallyl sulfonate in aqueous 57% zinc chloride solution containing 0.08% of zinc oxide was obtained by solution polymerization at 55 C. using ammonium persulfate as the polymerization initiator. Half of the solution was heated at 120 C. for 40 min. Viscosities of the original solution and the heattrea-ted solution were 145 and 130.5 poise at 45 C. and the T of the fibers thereof were 92 C. and 85 C., respectively. These two polymer solutions were extruded together at 20 C.
  • the composite fibers thus obtained produced 23.4 spiral crimps per 2.5 cm. of length when the fiber was immersed in boiling water for 10 minutes and dried.
  • the yarns made from these composite fibers have good bulkiness and excellent wool-like hand due to development of spiral crimps.
  • the laminating property of the fibers obtained was excellent.
  • the temperature-contraction curves illustrated in FIG. 1 correspond to that of fibers of this example.
  • EXAMPLE 2 A co-polymer solution of 90% acrylonitrile, 8.5% of methyl acrylate and 1.5% sodium allyl sulfonate, in which the co-polymer concentration was 9.1%, was prepared by the continuous solution polymerization at 45 C. in an aqueous 58% zinc chloride-sodium chloride mixed salt solution (46% zinc chloride, 12% sodium chloride) containing 0.01% of zinc carbonate calculated as zinc oxide, using hydrogen peroxide as an initiator.
  • the composite fiber obtained by the conjugation spinning of said original polymer solution and a solution of co-polymer comprising 90% of acrylonitrile, 8.5% of acrylamide and 1.5% of sodium all'yl sulfonate produced 23.5 spiral crimps per 2.5 cm. However, 42% of the fiber was delaminated by same tension and relaxing treatment as above.
  • EXAMPLE 3 90 parts of acrylonitrile, 8.5 parts of methyl acrylate, 1.5 parts of methallyl sulfonic acid sodium salt and 0.8 part of ammonium persulfate as a catalyst were dissolved in 900 parts of aqueous 58% zinc chloride solution containing 0.05% of zinc oxide. The mixture thus obtained was continuously fed into a polymerization apparatus kept at 45 C. under an internal pressure of 3 kg./cm. without permitting any empty space. A uniform and foamless polymer solution was obtained continuously after a mean residence time of 5 hours. The conversion was 97% and the viscosity of the solution was 145 poise at 45 C.
  • Half of the polymer solution thus obtained was fed continuously into a heating apparatus having a stirrer 'kept at 110 C. under internal pressure of 5 kg./cm. without permitting any empty space so as to prevent foams and gel-like substances from forming.
  • a heattreated foamless and uniform solution having a viscosity of 130 poise was continuously obtained after a mean residence time of 2 hours. T of the fibers made from these solutions were C. and 76 C., respectively.
  • the composite fiber thus obtained produced 21.5 spiral crimps per 2.5 cm. of length after treatment with hot water at 100 C. for 10 min.
  • the fiber obtained had good laminating properties between the two components.
  • the product When yarn made from the fiber was treated with steam at 103 C., the product had good bulkiness and excellent woollike hand due to the development of spiral crimps and the dyed end product had no nettled appearance, which was often observed in conventional acrylic composite fibers.
  • EXAMPLE 4 To 1000 parts of an aqueous salt solution containing 55% zinc chloride, 4% sodium chloride and 0.02% zinc oxide were added 89 parts of acrylonitrile, -10 parts of vinyl acetate, 1 part of sodium allylsulfonate and then 0.15 part of hydrogen peroxide as catalyst. The mixture thus obtained was continuously fed into polymerization apparatus kept at 50 C. under internal pressure of 4 kg./cm. gauge without permitting any empty space. A foamless, uniform and transparent polymer solution was obtained continuously after a mean residence time of 4 hours. Conversion was 96%, and the viscosity of the solution was 126- poise at 45 C.
  • Half of the polymer solution thus obtained was fed continuously into a heating apparatus kept at C. under an internal pressure of 6 kg./cm. gauge without permitting any empty space, so as to prevent the formation of any foam or gel-like substances.
  • a heat-treated foamless and uniform polymer solution was obtained continuously after a mean residence time of 1 hour.
  • the composite fiber thus obtained (3 denier) produced 17 spiral crimps per 2.5 cm. of length after treatment with boiling Water for 10 minutes.
  • the fiber was mixed into a conventional acrylic high-bulk yarn,.excellent woollike hand feel and good appearance were obtained in the end products.
  • the composite fiber has good laminating properties of the two components and the dyed end-products had no nettled appearance which was often observed in the con- 'ventional acrylic composite fiber.
  • EXAMPLE 5 To 1000 parts of an aqueous 59% mixed salt solution (zinc chloride 55%, sodium chloride 4%) containing 0.06% of zinc oxide, 89.5 parts of acrylonitrile, 9.5 parts of methyl acrylate and 1 part of sodium methallyl sulfonate were added. The mixture thus obtained was continuously fed into a polymerization apparatus without permitting any empty space. 0.3% of sodium persulfate and 0.7% of sodium bi'sulfide were continuously added while maintaining an internal pressure of 4 kg./cm. gauge in the apparatus. After the continuous redox polymerization at 50 C. and a mean residence time of 3 hours, a foamless and uniform polymer solution having a viscosity of 152 poise was obtained at a conversion rate of 98%.
  • an aqueous 59% mixed salt solution zinc chloride 55%, sodium chloride 4%) containing 0.06% of zinc oxide, 89.5 parts of acrylonitrile, 9.5 parts of methyl acrylate and 1 part of sodium methallyl
  • the fiber thus obtained was highly white and produced 37 spiral crimps per 2.5 cm. of length by treatment with hot water at 100 C. for 10 min.
  • the fiber, after relaxing, was again stretched 1.2 times its length.
  • the esulting fibers produced 44 spiral crimps per 2.5 cm. by treatment with hot water.
  • the basic compound is selected from the group consisting of zinc oxide, zinc carbonate, sodium hydroxide and sodium carbonate.
  • said concentrated aqueous zinc chloride solvent solution further contains at least one member selected from the group consisting of sodium chloride, magnesium chloride and ammonium chloride.
  • said monomer copolymerizable with said acrylonitrile is at least one monomer selected from the group consisting of methyl acrylate, methyl methacrylate, vinyl acetate, acrylamide,
  • methacrylamide allyl sulfonic acid, methallyl sulfonic acid and derivatives thereof.
  • said coagulating bath comprises an aqueous solution containing from about 10 to about 40% by weight of at least one member selected from the group consisting of zinc chloride, sodium chloride, magnesium chloride, and ammonium chloride.

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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)
  • Multicomponent Fibers (AREA)
US850036A 1968-08-16 1969-08-14 Method for production of acrylic composite fiber Expired - Lifetime US3701819A (en)

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JP5843568 1968-08-16

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DE (1) DE1941390C3 (en(2012))
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038452A (en) * 1975-05-07 1977-07-26 Asahi Kasei Kogyo Kabushiki Kaisha Bulky non-woven fabric
US4124673A (en) * 1975-03-26 1978-11-07 Bayer Aktiengesellschaft Process for the production of bifilar acrylic fibres
US4182601A (en) * 1977-08-20 1980-01-08 The General Engineering Co. (Radcliffe) Limited Extrusion apparatus
US4336022A (en) * 1979-08-01 1982-06-22 E. I. Du Pont De Nemours And Company Acrylic precursor fibers suitable for preparing carbon or graphite fibers
US4873142A (en) * 1986-04-03 1989-10-10 Monsanto Company Acrylic fibers having superior abrasion/fatigue resistance

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4124673A (en) * 1975-03-26 1978-11-07 Bayer Aktiengesellschaft Process for the production of bifilar acrylic fibres
US4038452A (en) * 1975-05-07 1977-07-26 Asahi Kasei Kogyo Kabushiki Kaisha Bulky non-woven fabric
US4182601A (en) * 1977-08-20 1980-01-08 The General Engineering Co. (Radcliffe) Limited Extrusion apparatus
US4336022A (en) * 1979-08-01 1982-06-22 E. I. Du Pont De Nemours And Company Acrylic precursor fibers suitable for preparing carbon or graphite fibers
US4873142A (en) * 1986-04-03 1989-10-10 Monsanto Company Acrylic fibers having superior abrasion/fatigue resistance

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DE1941390B2 (de) 1977-10-27
FI51716C (fi) 1977-03-10
GB1265874A (en(2012)) 1972-03-08
DE1941390A1 (de) 1970-02-26
DE1941390C3 (de) 1978-06-15
FI51716B (en(2012)) 1976-11-30

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