US3681275A - Acrylonitrile composition improved in yellowness and brightness and production of fibers therefrom - Google Patents

Acrylonitrile composition improved in yellowness and brightness and production of fibers therefrom Download PDF

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Publication number
US3681275A
US3681275A US3317A US3681275DA US3681275A US 3681275 A US3681275 A US 3681275A US 3317 A US3317 A US 3317A US 3681275D A US3681275D A US 3681275DA US 3681275 A US3681275 A US 3681275A
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United States
Prior art keywords
acrylonitrile
brightness
fiber
yellowness
polymer
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Expired - Lifetime
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US3317A
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English (en)
Inventor
Kenji Takeya
Hideto Sekiguchi
Kunio Tanahashi
Junji Tsuge
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Japan Exlan Co Ltd
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Japan Exlan 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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

  • This invention relates to an acrylic fiber improved'in the yellowness and brightness, and more particularly to an acrylic fiber containing a monoester of glycerin with a higher fatty acid or a derivative of its monoester, and improved in the yellowness and "brightness.
  • This invention also. relates to a composition for producing such improved acrylic fibers.
  • An improvement in the yellowness and brightness of an acrylic fiber means an improvement in the whiteness and brightness of said fiber. It is important to improve these properties in elevating the commodity 'value of acrylonitrile fibers.
  • the improvement in the whiteness and brightness of an acrylonitrile fiber is an essential condition for imparting to the fiber the inherent color of a dye used in dyeing said fiber. Further, the higher the,
  • a main object of the present invention is to provide an acrylonitrile fiber having an improved tone characteristic.
  • Another object of the present invention is to provide an acrylonitrile fiber highly improved in the yellowness and brightness, and excellent in the dyeing characteristic.
  • a still further object of this invention is to provide. a homogeneous solution which isv capable of beingspun into acrylic fibers having improved yellowness and brightness.
  • a homogeneous spinning solution which comprises an acrylonitrile polymer, an inert solvent for said polymer, and from 0.2% to 20% by weight (based on the weight of said polymer) of a monoglyceride or its derivative having the general formula (I):
  • R is an alkyl or alkenyl group containing to 22 carbon atoms
  • each of m and n is an integeri'sat- 3,681,275 Patented Aug. 1, 1972 .isfying the formula 0m+nl0.
  • the spinning solution may be extruded through orifices of a spinneret to form fibers in a conventional manner.
  • Such acrylonitrile fiber containing the compound representedby the General Formula I of the present invention is far higher in the yellowness and brightness than conventional acrylonitrile fiber. Therefore, even if the fiber of the present invention and the conventional fiber are compared with each other with the naked eye, the fiber of the present invention will be found to be remarkably brighter. Further, whereas the conventional acrylic fiber is somewhat yellowish, the acrylic fiber of the present invention has a snow-whiteness. Therefore, in the .dyeing of the fiber obtained according to the present inin a light color, there will be obtained a dyed product having a very bright tone.
  • the compound represented by the General Formula I has a plasticizing effect in the acrylic fiber. It is therefore possible to practically dye such fibers containing said compound at such low temperature as below 100 C. or particularly at about to C. Thus, owing to the plasticizing effect of the compound having the General Formula I, the permeation of the dye into the acrylonitrile fiber will be made easy and, therefore, even at a low temperature, the dye can be absorbed in the fiber to a sufficient extent. Such low temperature dyeing is advantageous to keep a desired hand peculiar to acrylonitrile fibers. On the other hand, in the conventional boiling dyeing, there has been a disadvantage that utmost care must be taken by using a special technique in order to retain said hand. Thus the acrylonitrile fiber of the present invention is fareasier to dye than conventional acrylonitrile fiber.
  • a monoester of glycerin with lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid or behenic acid and its ethylene oxide additives a monoester of glycerin with myristoleic acid, palmitoleic acid, petroselinic acid, vaccenic acid, oleic acid, linoleic acid, linolenc acid, elaidic acid, eleostearic acid, parinaric acid, gadoleic acid or arachidonic acid and its ethylene oxide additives.
  • a fiber highly improved in the yellowness andbrightness can be produced.
  • the spinning can be conducted in a manner known per se.
  • the compound represented by the above General Formula I of the present invention can be added before, simultaneously with or after the addition of the solvent in preparing the spinning solution.
  • the acrylonitrile polymer can be produced by suc conventional process (e.g. U.S. Pats. Nos. 2,751,374,
  • 2,648,646 through 2,648,649 is used, the efiect of the present invention will be increased.
  • the metal halides and thiocyanates are zinc chloride, calcium chloride, lithium bromide, cadmium bromide, cadmium iodide, sodium thiocyanate, calcium thiocyanate, potassium thiocyanate, zinc thiocyanate, ammonium thiocyanate, etc.
  • the acrylonitrile polymer consisting mainlyof acrylonitrile is a homopolymer of acrylonitrile or a copolymer of at least 70%, preferably at least 80% by weight of acrylonitrile and up to 30%, preferably up to by weight of at least one monoethylenically unsaturated monomers copolymerizable with acrylonitrile.
  • Such monoethylenically unsaturated monomers include acrylic acid; methacrylic acid; such acrylic esters as ethyl acrylate, methyl acrylate, butyl acrylate, octyl acrylate, methoxyethyl acrylate, phenyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and dimethyl aminoethyl acrylate; such methacrylic esters as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methoxyethyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and hydroxyethyl methacrylate, hydroxypropyl methacrylate and dirnethyl aminoethyl methacrylate; acrylic amides and methacrylic amides or their alkyl substituents;
  • the polymers have an average molecular weight of 40,000 to 150,000, although a molecular weight may range from 15,000 to 250,000.
  • FIG. 1 and FIG. 2. are graphs respectively showing the brightness and yellowness of acrylonitrile fiber in relation to the glyceryl monostearate content in the fiber.
  • all percentages and parts are by weight unless otherwise specified.
  • EXAMPLE 1 Eleven parts of an acrylonitrile polymer consisting of 91.0% acrylonitrile, 8.6% methylacrylate and 0.4% sodium methallyl sulfonate, produced by an aqueous suspension polymerization process with a sodium chloratesodium sulfite redox catalyst system, were dissolved in 89 parts of a 44.3% aqueous solution of sodium thiocyanate to prepare a homogeneous polymer solution. Then, each of monoester compounds of glycerin with higher fatty acids mentioned in Table 1 was added and mixed. The thus obtained spinning solution was extruded into a 12% aqueous solution of sodium thiocyanate at 3 C.
  • GMS represents glyceryl'monostearate
  • GMS (POE-2) or GMS (POE-6) represents an additive of 2' or 6 mols of ethylene oxide to glyceryl monostearate
  • GMO represents glyceryl mono-oleate
  • GML represents glyceryl monolaurate.
  • Example 2 In the same manner as in Example 1, a homogeneous? solution of an acrylonitrile polymer with an aqueous solution of sodium thiocyanate was prepared. Into said poly- I, mer solution was added and mixed glyc'erylmonostearate at each of such rates as shown in Table 2. The thus obtained spinning solution was wet-spun according to Example 1 and was then after-treated to obtain an acrylonitrile fiber of 3 deniers. The yellowness and brightness of each of the thus obtained acrylonitrile fibers were lowness and brightness were remarkably improved.
  • the compound represented by the General Formula I according to the present invention'and the acrylonitrile polymer are so highin the compatibility that the holdabilit'y of said compound in the fiber is high. (The drop of said compound is little in the spinning, water-washing and after-treating steps.)
  • a homogeneous spinning solution comprising an acrylonitrile polymer selected from the group consisting of homopolymers of acrylonitrile and copolymers containing at least 70% of acrylonitrile and up to 30% by weight of at least one monoethylenically unsaturated monomer copolymerized therewith, an inert solvent for said polymer, and from 0.2% to 20% based on the weight of said polymer of a mono-glyceride or its derivative having the general formula wherein R is an alkyl or alkenyl group containing 10 to 22 carbon atoms and each of m and n is an integer satisfying a range of Om-l-n l0.
  • composition of claim 1 wherein said solution contains from about 5% to about 35% by weight of said polymer.
  • composition of claim 1 wherein said solution contains from 1% to by weight of said mono-glyceride or its derivative.
  • composition of claim 1 wherein said mono glyceride is glyceryl monostearate.
  • composition of claim 1 in which said polymer contains at least 80% acrylonitrile by weight in polymerized form.
  • composition of claim 1 wherein said solvent is inorganic solvent for the acrylonitrile polymer.
  • composition of claim 6 wherein said inorganic solvent is a concentrated aqueous solution of sodium thiocyanate.
  • a process for preparing filaments improved in the yellowness and brightness which comprises extending a 6 homogeneous solution comprising from about 5% to about 35% by weight of a polymer containing at least acrylonitrile in polymerized form, an inert solvent for said polymer, and from 0.2% to 20% based on the weight of said polymer of a mono-glyceride or its derivative having the general formula wherein R is an alkyl or alkenyl group containing 10 to 22 carbon atoms and each of m and n is an integer satisfying a range of 0m+nl0, through spinning orifices to form filaments, washing said filaments in an aqueous bath whereby said solvent is substantially removed from said filaments, and thereafter drying said filaments.
  • a filament comprising an acrylonitrile polymer selected from the group consisting of homopolymers of acrylonitrile and copolymers containing at least 70% acrylonitrile and up to 30% of at least one monoethylenically unsaturated monomer copolymerized therewith having included therein from 1% to 15% by weight of a monoglyceride or its derivative having the general formula wherein R is an alkyl or alkenyl group containing 10 to 22 carbon atoms and each of m and n is an integer satisfying a range of 0m+n10.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
US3317A 1969-01-27 1970-01-16 Acrylonitrile composition improved in yellowness and brightness and production of fibers therefrom Expired - Lifetime US3681275A (en)

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Application Number Priority Date Filing Date Title
JP619469 1969-01-27

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US3681275A true US3681275A (en) 1972-08-01

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US (1) US3681275A (xx)
BE (1) BE744916A (xx)
DE (1) DE2003383C3 (xx)
ES (1) ES375685A1 (xx)
FR (1) FR2029457A1 (xx)
GB (1) GB1256445A (xx)
NL (1) NL7000778A (xx)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867499A (en) * 1971-02-16 1975-02-18 Monsanto Co Process for wet-spinning fibers derived from acrylic polymers
US3931074A (en) * 1974-03-14 1976-01-06 Monsanto Company Modifiers for high nitrile polymers

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2611193A1 (de) * 1976-03-17 1977-09-29 Bayer Ag Verfahren zur herstellung von hydrophilen fasern und faeden aus synthetischen polymeren
US6939215B2 (en) 2003-01-17 2005-09-06 Kraft Foods Holdings, Inc. Method for reducing viscosity of mechanically separated meats and ground meats

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867499A (en) * 1971-02-16 1975-02-18 Monsanto Co Process for wet-spinning fibers derived from acrylic polymers
US3931074A (en) * 1974-03-14 1976-01-06 Monsanto Company Modifiers for high nitrile polymers

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Publication number Publication date
ES375685A1 (es) 1972-08-16
DE2003383A1 (de) 1970-07-30
NL7000778A (xx) 1970-07-29
BE744916A (fr) 1970-07-27
GB1256445A (en) 1971-12-08
FR2029457A1 (xx) 1970-10-23
DE2003383C3 (de) 1975-11-27

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