US3758659A - Mer method of manufacturing fibers and films from an acrylonitrile copoly - Google Patents

Mer method of manufacturing fibers and films from an acrylonitrile copoly Download PDF

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US3758659A
US3758659A US00212374A US3758659DA US3758659A US 3758659 A US3758659 A US 3758659A US 00212374 A US00212374 A US 00212374A US 3758659D A US3758659D A US 3758659DA US 3758659 A US3758659 A US 3758659A
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filaments
acrylonitrile
copolymer
films
spinning
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US00212374A
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H Takeda
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Toray Industries Inc
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Toray Industries Inc
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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
    • 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

  • Miller 57 ABSTRACT A methodv is provided for manufacturing shaped articles especially fibers and films from a solvent solution of copolymer comprised of at least 85 mol of acrylonitrile and at least one other compound of the formula wherein R is hydrogen, an alkyl group, an aryl group or alkylaryl group.
  • the solvent solution is shaped and thereafter coagulated in a bath comprised of at least 60 percent by weight of methanol.
  • the shaped articles for example, filaments, because of their superior properties, are especially useful as textile fibers.
  • acrylic fibers from a polyacrylonitrile or an acrylonitrile copolymer have been produced commercially in substantial amounts by wet spinning processes and dry spinning processes.
  • wet spinning processes coagulation is ordinarly accomplished by extruding the polymer solution into an aqueous bath which can contain solvents or dissolved salt.
  • an aqueous or water bath refers to a composition having water as one of its main components.
  • Another object of the present invention is to provide a method for a wet system for spinning fibers or forming fibers of acrylonitrile copolymers without requiring a dry collapsing step.
  • Another object of the present invention is to provide acrylic fibers and films which are substantially void free and transparent, having stabilized physical properties and a very high tenacity and modulus.
  • a further object of the present invention is to provide a method of producing acrylic fibers or film of acrylonitrile copolymers which can be made with a predetermined cross sectional configuration corresponding to lower tenacity, and lower abrasion resistance as compared with filaments which do not contain microvoids. Therefore, to overcome the inherentphysical weakness of these coagulated filaments, certain aftertreatment steps have heretofore been conducted during the processing of the filaments to fully collapse the microvoids.
  • the filaments for example, were dried at high temperatures.
  • the degree of collapsing of the filaments differs depending upon the copolymer composition of the acrylonitrile copolymers, the kind of the solvents, the composition of the coagulation bath and the coagulating conditions. l-iowevenunless the coagulated-filaments or films are collapsed by drying or homogenifactory properties. lnaddition, in methods of producing acrylic fibers or films by such conventional wet spinning processes the drawability differed according to the collapsing condition (drying conditions, etc.) of the coagulated filamentsor films. Moreover, by secondary processing, for example, dyeing and washing of products, dcvitrification (the loss of the transparency) is brought about again and the dimensional stability as well as the physical properties change.
  • a method for producing shaped articles such as acrylonitrile copolymers which are compact and excellent in crystallinity, tenacity and modulus.
  • an organic solvent solution of AN copolymer consisting of at least 85 mol of AN and at least one compound represented of the general formula zation steps the resulting fibers or films have unsatis- .
  • R is a radical selected from 'thegroiip consisting of hydrogen, alkyl, monoc'yclic aryl, and alkylaryl, wherein the alkyl group has up to 5 carbon atoms, is shaped and then coagulated in a coagulating bath containing not less thanabout 60 percent by weight of methanol.
  • the AN copolymers suitable for use in the present invention are known and are disclosed, for example, in U.S. Pat. No. 3,499,024.
  • U.S. Pat. No. 3,499,024 only relates .to the AN copolymers of the present invention, and at best, discloses that such AN copolymers show improved dyeability and absorption property.
  • the prior art does not, however, suggest a method of producing the acrylic fibers or films of the present invention which have improved physical properties.
  • R is a radical selected from the group consisting of hydrogen, an alkyl group having up to five carbon atoms, an aryl group such as phenyl group oran al kylaryl group.
  • Typical compounds which may be used in the present invention are, for example, 2- hydroxymethyl acrylonitrile, 2-hydroxyethyl acrylonitrile, 2-( l -hydroxypropyl) acrylonitrile, 2-(1- hydroxyethyl) acrylonitrile, 2-(l-hydroxybutyl) acrylonitrile, 2-( l-hydroxy-2-methylpropyl) acrylonitrile and 2-( l-hydrohexyl) acrylonitrile.
  • the AN copolymer can contain as a third component a compound which copolymerizes with AN, such as, for example, acrylic acid, methacrylic acid, and esters thereof, styrene, an a halogenated vinyl compound such as vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, acrylamide, methacrylamide, an arylsulfonic acid, styrene sulfonic acid and salts thereof.
  • a compound which copolymerizes with AN such as, for example, acrylic acid, methacrylic acid, and esters thereof, styrene, an a halogenated vinyl compound such as vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, acrylamide, methacrylamide, an arylsulfonic acid, styrene sulfonic acid and salts thereof.
  • the ratio of the compound represented by Formula I in the AN copolymer must be at least about 0.01 mol preferably at least about 0.1 mol with the content of the acrylonitrile being at least 85 mol
  • the amount of the compound shown by the Formula 1 is less than 0.0] mol the compact filaments of the present invention are not obtained and the ability to spin into a coagulating bath is not sufficiently developed.
  • the AN content is less than 85 mol the desired properties of an acrylic fiber are not obtained.
  • a solvent for the copolymer of the AN series it is preferable to use an organic solvent such as dimethyl sulfoxide, dimethylacetamide, dimcthyl formmnide or a mixed solvent consisting mainly of these organic solvents.
  • concentration of the AN copolymer in the solvent should be within the range normally used with, for example, 10-35 percent by weightbeing preferable.
  • the solution of AN copolymer is spun from a spinneret into a coagulating bath containing mainly methanol.
  • the composition of the coagulating bath is not particularly critical, provided it contains at least about 60 percent by weight and preferably at least about 65 percent by weight of methanol. When the content of methanol is less than 60 percent by weight, transparent and compact filaments are not obtained unless collapsing or homogenization aftertreatments are employed. If the coagulating bath contains at least 60 percent by weight of methanol, even if said bath contains solvent extracted from the spinning solution or water produced by absorption of moisture, the objects of the present.
  • the temperature and other conditions of the coagulating bath are not particularly critical. However, normally a temperature within the range of 0-35C is commercially advantageous because the evaporation rate of methanol is low in this temperature range.
  • the spinning conditions which are employed are those conventionally employed in order to obtain filaments.
  • the filaments are devitrified and it is not possible to obtain good drawn yarn.
  • the drawing has to be conducted under specified limited conditions.
  • the coagulated filaments are substantially voidless, the filaments may be drawn at once.
  • drawing means which employed hot water, hot air, a hot plate, a hot pin, steam or combination thereof can be advantageously employed.
  • the filaments are initially drawn in hot water or steam and thereafter drawn by a hot plate. Drawing to a high magnification is possible.
  • An additional advantage is that the methanol in the coagulating'bath is removed by the hot water or steam before the filaments are drawn by the hot plate, which is commercially advantageous.
  • the first stage drawing is in hot water or steam, it is advisable to use a low magnification of drawing of an extent such that the methanol in the filaments is removed, namely, to draw the filaments at least about 1.5 times at a temperature of at least C and preferably at least about 50C.
  • As conditions for second stage drawing by a hot plate it is advisable to draw the filaments at least 5 times their length at a temperature of at least about 0C and preferably l00200C.
  • the FIGURE is a photomicrograph (200 times) showing the crosssectional area of coagulated filaments obtained by one example of the present invention.
  • the cross sectional configuration of the filaments of the present invention are substantially truly circular and said filaments are very compact and void free.
  • PAN Polyacrylonitrile
  • Table 3 the measured results of values of the tenacity and elongation of the undrawn filaments are shown.
  • the number of the sample in Table 3 corresponds to that in Table 2.
  • the five copolymer solutions described above were then coagulated in a methanol bath to prepare films having a thickness of 0.08 mm.
  • the obtained films were subjected to the same treatments shown in Table l and values of the X-ray small angle scattering intensity were measured. The results are shown in Table 4. It can be seen that the films of the present invention are superior in compactness and homogeneity and excellent in transparency.
  • the mixture was polymerized at 50C for hours to obtain a polymer solution of P(AN-HEN-SAS) whose lNl measured at a concentration of 19 percent by weight at C in DMF (dimethyl formamide) was l,52.
  • This solution was spun from a spinneret having 100 circular holes each having a diameter of 0.08 mm into coagulating baths of the various compositions shown in Table 5. The spinning was carried out at a take-up speed of 2.5 m/min" to obtain 12 denier undrawn filaments.
  • the obtained undrawn filaments were washed with water (25C) and dried in relaxed states at room temperature.
  • the measured results of values of the SASI and degree of circular cross section of the undrawn filamerits after being dried at room temperature are shown in Table 6.
  • the numbers in Table 6 correspond to those in Table 5.
  • the undrawn filaments were drawn 2 times first in hot water (98C) and then in steam at C immediately after the filaments coagulated.
  • the resulting drawn filaments were dried in air in a relaxed state and values of the SASI and degree of circular cross section of these filaments were measured. The results are shown in Table 7.
  • the properties of the obtained drawn filaments are shown in Table 8. It is apparent that by the method of the present invention, the maximum draw ratio became remarkably high and the obtained filaments had excel lent compactness and homogeneity despite the fact that the prior art collapsing treatment was not carried out. Further, it should be noted, that the drawn filaments produced according to the present invention exhibited excellent yarn characteristics including a tenacity of more than 7 g/d and a Youngs modulus of more than 190 g/d. These are considered to be due to the fact that a compact and homogeneous coagulated filament is obtained.
  • Washed with boiling water immediately after coagulation and dried in air Washed with boiling water immediately after coagulation and dried in air.
  • EXAMPLE 4 Using N,N-azobisisobutylonitrile (AlBN) as the cat- Spinning solutions were prepared using AN copolyalyst and dimethyl sulfoxide (DMSO) as a solvent, polymers shown in Table 10 were prepared by solution polymerization. The concentration of each of the spinning solutions was made 20 percent by weight and the spinning solutions were spun from a platinum gold spinneret having 200 circular holes each having a diameter of 0.08 mm into a methanol bath to obtain 15 d undrawn filaments. The spinning speed was 3 m/min.
  • AlBN N,N-azobisisobutylonitrile
  • DMSO dimethyl sulfoxide
  • the resulting undrawn filaments were subjected to scattering intensity (SASl) of each of the samples subjected to these four treatments was measured as well as the degree of circular cross section and boiling water I shrinkage of each of the samples subjected to treatment No. l in Table 9.
  • the measured results were shown in mer having an inherent viscosity of 1.58 copolymerizing 0.6 mol of 2-hydroxyethyl acrylonitrile (HEN) and using as a solvent DMSO, dimethyl formamide' (DMF), dimethyl acetamide (DMAC), ethylene carbonate (EC). propylene carbonate (PC) and nitromethane (NM). These solutions were stable and each had a concentration of 17 percent by weight.
  • the polymer concentration in the solution was percent by weight.
  • polymer solutions having a polymer concentration of 15,10 and 5 percent by weight were prepared, and by concentration of said solution, polymer solutions having polymer concentrations of 30, 35 and 40 percent by weight were prepared.
  • the inherent viscosity of said copolymer was 1.52.
  • filaments were spun from a spinneret having 100 circular holes each having a diameter of 0.06 mm into a methanol bath as a coagulating bath at a take-up speed of 3.5 m/min.
  • the denier of the resulting undrawn filaments was 10 d.
  • solution polymerization was carried out.
  • the composition of the obtained copolymer contained AN 99.0 mol HEN 0.6 mol and SAS 0.4 mol and the'inherent viscosity of the obtained polymer was 1.57.
  • the polymer concentration in the polymer solution was 21.3 percent by weight.
  • the polymer solution used as a spinning solution was spun from a spinneret having 200 circular holes each having a diameter of 0.06 mm into a methanol bath maintained at various temperatures.
  • the denier of the obtained undrawn filaments was 15 d.
  • the method for manufacturing shaped articles comprising (a) extruding an organic solvent solution of an acrylonitrile copolymer obtained by the copolymerization of a monomer mixture comprised of l. at least about 85 mol of acrylonitrile and 2. at least about 0.01 mol of a compound of the formula wherein R is a radical selected from the group consisting of hydrogen, alkyl, and alkylaryl, said alkyl group having up to five carbon atoms, and (b) coagulating the 14 extruded acrylonitrile solution in a coagulation bath comprised of at least about percent by weight of methanol.
  • organic solvent is comprised of at least one member selected from the group consisting of dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide and mixture thereof with water.

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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)
  • Artificial Filaments (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
US00212374A 1970-12-26 1971-12-27 Mer method of manufacturing fibers and films from an acrylonitrile copoly Expired - Lifetime US3758659A (en)

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JP (1) JPS4842444B1 (ref)
DE (1) DE2164479C3 (ref)
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DE3027844A1 (de) * 1980-07-23 1982-02-18 Hoechst Ag, 6000 Frankfurt Hochmodul-polyacrylnitrilfaeden und -fasern sowie verfahren zu ihrer herstellung

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GB1332030A (en) 1973-10-03
SE383765B (sv) 1976-03-29
JPS4842444B1 (ref) 1973-12-12
DE2164479A1 (de) 1972-07-13
DE2164479C3 (de) 1975-02-06

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