US3597501A - Acrylic synthetic fibers having novel structure - Google Patents

Acrylic synthetic fibers having novel structure Download PDF

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Publication number
US3597501A
US3597501A US723338A US3597501DA US3597501A US 3597501 A US3597501 A US 3597501A US 723338 A US723338 A US 723338A US 3597501D A US3597501D A US 3597501DA US 3597501 A US3597501 A US 3597501A
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United States
Prior art keywords
fibers
acrylonitrile
mole percent
solution
acrylic
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Expired - Lifetime
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US723338A
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English (en)
Inventor
Hiroshi Aotani
Masaharu Shimamura
Zenzi Izumi
Masamitsu Tanimura
Toyotaro Harada
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Toray Industries Inc
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Toyo Rayon Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/42—Nitriles
    • 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

  • Fibers of 0.30 to 0.70 have a durable wool-like waxy and soft feeling.
  • These fibers are produced by heterogeneously copolymerizing acrylonitrile with an acrylate having a longchain alkyl group with 1018 carbon atoms in a solvent which dissolves the acrylonitrile but does not dissolve the acrylate, and spinning the resulting solution; or spinning a blend of the said solution and a solution of an ordinary acrylonitrile copolymer.
  • the acrylate should be present in an amount of 210 mole percent in the acrylic fiber.
  • This invention concerns acrylic synthetic fibers having a Wool-like hand, and more particularly novel acrylic synthetic fibers having a waxy and soft feeling similar to Wool because of their unique structure not seen in the conventional acrylic fibers.
  • acrylic fibers because of their bulkiness, have been evaluated as fibers similar to wool, and have chiefly found applications in fields where wool is much used. In fact, however, the acrylic fibers are very coarse and stiff and have a feeling of creaky and coarse touch, thus lacking in a feeling of waxy and soft touch. With a view, therefore, to improving the surface touch of acrylic fibers, softening treatment by means of an oil preparation has generally been carried out. Cationic surface active agents have been much used particularly for imparting a woollike waxy feeling to the acrylic fibers, and tentative effects have been achieved by such treatment.
  • Another object of the invention is to provide acrylic fibers having a durable, closely wool-like feeling. Another object of the invention is to provide novel acrylic fibers which have a unique structure, and therefore, have a feeling of waxy and soft touch.
  • the acrylic fibers of the invention contain at least 85 mole percent of acrylonitrile and have an X-ray diffraction interference intensity ratio (to be referred to as LR. hereinafter) defined by of from 0.30 to 0.70 in their X-ray diffraction pattern.
  • LR X-ray diffraction interference intensity ratio
  • FIG. 1 shows photographs of X-ray diffraction patterns indicating the difference in structure between the acrylic fibers of the invention and ordinary acrylic fibers;
  • FIG. 2 shows phase contrast microscopic photographs indicating the difference in structure between the abovementioned two types of acrylic fibers
  • FIG. 3 shows X-ray diffraction. pattern photographs of acrylic fibers containing as a copolymer component an acrylic acid ester of a higher alcohol having a different number of carbon atoms.
  • the characteristic feature of the invention is that the acrylic fibers have an IR. of from 0.30 to 0.70.
  • Acrylic fibers having such characteristic structure have not been known heretofore. In the conventional ordinary acrylic fibers, interference is seen only in the vicinity of 20:17 in the direction of equator line, but no meridian interference at 20:21 appears.
  • the acrylic fibers of the invention have a feel very similar to wool, above all, a wool-like waxy and soft feel. Since this feel is based on the structure of the fibers themselves, it is durable and does not disappear even by such operation as dyeing, scouring and washing.
  • the LR. When the LR. is less than 0.30, acrylic fibers do not exhibit a sufficient waxy and soft feeling. If, on the other hand, the LR. is larger than 0.70, the acrylic fibers have an excessive waxy and soft feeling, and become gluey with a decrease in tenacity. Thus, such acrylic fibers cannot be offered for practical use.
  • One method of manufacturing the acrylic fibers of the present invention having such unique structure is a copolymerization method which comprises heterogeneously polymerizing acrylonitrile with a monoethylenic ester containing a higher alkyl group (hereinafter to be referred to as a higher alkyl acrylate) expressed by the general formula wherein R is a hydrogen atom or a methyl group; R is an alkyl group having 10 to 18 carbon atoms, in the presence of a polymerization catalyst in a solvent which completely dissolves acrylonitrile but does not dissolve the higher alkyl acrylate to thereby form a copolymer comprising at least mole percent of acrylonitrile and 210 mole percent of a higher alkyl acrylate, and spinning a solution of the resulting copolymer.
  • a copolymerization method which comprises heterogeneously polymerizing acrylonitrile with a monoethylenic ester containing a higher alkyl group (hereinafter to
  • the meridian interference at 20:2l is due to an acrylate of the above-mentioned Formula 1 having a long-chain alkyl group with l0l8 carbon atoms. Acrylates having an alkyl group with less than 10 carbon atoms do not give a meridian interference at 20:21".
  • a copolymer solution (B) was prepared by heterogeneously polymerizing 70 mole percent of acrylonitrile, and 30.0 mole percent of an ester of vinyl alcohol and stearic acid under the same conditions as in Example 1. When this solution was spun, the obtained fibers completely glued with each other, and did not show any fibrous form.
  • the copolymer solution (B) was mixed with a solution (A) of a polymer obtained by reacting 93.5 mole percent of acrylonitrile, 6.0 mole percent of methyl acrylate and 0.5 mole percent of sodium allylsulfonate under the same conditions as employed in the preparation of solution (A) in Example 4, so that the ester of vinyl alcohol and stearic acid might be 3 mole percent based on the total amount of the polymer.
  • the resulting mixture was spun into a 60% aqueous solution of dimethyl sulfoxide so that the final monofilament denier of the fibers might be 3, drawn to 6 times the original length, washed with water, and dried. There were obtained fibers having a tenacity of 3.4 gfd. and an elongation of 28%.
  • the fibers had an X-ray interference intensity ratio of 0.44, and a ,u.s.,ud. value of 0.067.
  • the resulting fibers had an X-ray interference intensity ratio of 0, and a ,uS.-,ud. value of 0.110, showing a very remarkably creaky and coarse feeling.
  • Fibers are wound around a cylinder having an outer diameter of 8 mm. so that they may be in parallel to the axis of the cylinder.
  • a fiber taken from the same sample, and a prescribed load T is mounted on both ends of the fiber.
  • This fiber is then hung over the cylinder at right angle to the axis of the cylinder. While the cylinder is being rotated, the load at one end of the hung fiber is caused to increase, and the load T at a time when the fiber begins to slide over the cylinder is measured.
  • the frictional coelficient ,u. is calculated from the formula
  • the ,u. at the time when the rotating speed is is designated as #5.
  • the [L at the time when the rotating speed is a peripheral speed of 90 cm./min. is designated as ad.
  • the fiber gives a creaky and coarse feeling, and if it is medium, the fiber gives a feeling of smoothness. On the other hand, when it is small, the fiber gives a feeling of Waxy and soft touch (Guide to Surfactants, page 167, by Isoda and Fujimoto, published by Sanyo Kasei).
  • Table 1 shows the values of ,uS.,u.d. measured with respect to some kinds of fibers.
  • the X-ray measurement indicated no meridian interference at 20 21.
  • Example 1 Example 1 was repeated except that the ratio of acrylonitrile/stearyl acrylate/ sodium allylsulfonate was changed to 93.6/6.0/0.4 mole percent.
  • a solution of the obtained copolymer was wet-spun in a 55% aqueous solution of dimethyl sulfoxide, drawn to 6 times the original length, washed with water, and dried to thereby form fibers having adenier of 10.
  • the obtained filaments had a tenacity of 2.4 g./d. and an elongation of 50%. It was confirmed by a phase contrast microscopic observation that the stearyl acrylate was polymerized in block form.
  • the fibers when measured by the X-ray method described in the specification, had an I.R. of 0.47, and a [.LS.,U.d. value of 0.060, and possessed a wool-like feel.
  • the resulting fibers had an X-ray interference intensity ratio of 0.21 and a ,uS.,u.d. value of 0.098, showing inability to give a waxy and soft feeling.
  • the acrylonitrile/ stearyl acrylate/sodium allylsulfonate was changed to 87.6/12.0/0.4 mole percent, the resulting fibers had an X-ray interference intensity ratio of 0.78 and a ns.;td. value of 0.016, showing a remarkably waxy and soft feeling.
  • EXAMPLE 1 Acrylonitrile (92.6 mole percent), 7.0 mole percent of stearyl acrylate and 0.4 mole percent of sodium allylsulfonate were polymerized while stirring in a polymerization vessel in dimethyl sulfoxide in the presence of a20- bisisobutyronitrile in an amount of 0.01 mole/liter for 30 hours at a temperature of C. The total monomer concentration in the reaction mixture was 3.5 mole/ liter. The yield of the obtained polymer was about 96%. The copolymer solution was wet-spun into a aqueous solution of dimethyl sulfoxide, drawn to 6 times the original length, washed with water, and dried to thereby form fibers having a denier of 6.
  • the obtained fibers had a tenacity of 2.7 g./d., and an elongation of 44%. It was confirmed by a phase contrast microscopic observation that the stearyl acrylate was polymerized in the form of block.
  • the fibers when measured by an X-ray as mentioned before, had an interference intensity ratio of 0.58, and a ,uS.p.Cl. value of 0.038. They exhibited a wool-like waxy and soft feel.
  • Example 1 was repeated except that dimethyl formamide was used in place of the dimethyl sulfoxide. A homogeneous solution-polymerization took place, and the resulting fibers had a ,us.-,ud. value of 0.115, showing no The X-ray diffraction photographs of the obtained filaments are shown in FIG. 3 in which A, B, C and D correspond respectively to C C C and C EXAMPLE 4
  • a copolymer solution (B) was prepared by reacting 79.6 mole percent of 'acrylonitrile, 20.0 mole percent of stearyl acrylate and 0.4 mole percent of sodium allylsulfonate under the same conditions as employed in Example 1.
  • a solution (A) of this. polymer was prepared as follows: 95.6 mole percent of acrylonitrile, 4.0 mole percent of methyl acrylate and 0.4 mole percent of sodium allylsulfonate were polymerized in dimethyl sulfoxide for 40 hours at 40 C. in the presence of 0.01 mole/ liter of azobisisobutyronitrile as a polymerization catalyst. The yield of the obtained polymer was 98%.
  • the solution (A) and solution (B) were mixed so that the stearyl acrylate might be 6 mole percent based on the total amount of the polymers, and the mixture was extruded into a 55% aqueous solution of dimethyl sulfoxide so that the final monofilament denier might be 6.
  • the extruded fibers were drawn to 6 times the original length, washed with water, and dried.
  • the obtained fibers had a tenacity of 3.2 g./d. and an elongation of 35%, and possessed a waxy and soft feeling and luster.
  • the fiber also had an X-ray interference intensity ratio of 0.60 and a ,uS.-,ud. value of 0.024.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
US723338A 1967-04-24 1968-04-22 Acrylic synthetic fibers having novel structure Expired - Lifetime US3597501A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5496510A (en) * 1994-08-23 1996-03-05 Capone; Gary J. Acrylonitrile filament process

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US6617471B2 (en) 2001-06-20 2003-09-09 Eastman Chemical Company Method for carbonylation of lower aliphatic alcohols using tin promoted iridium catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5496510A (en) * 1994-08-23 1996-03-05 Capone; Gary J. Acrylonitrile filament process

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GB1230174A (enrdf_load_stackoverflow) 1971-04-28

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