US3626049A - Process for producing cross-linked acrylic fibers or films - Google Patents

Process for producing cross-linked acrylic fibers or films Download PDF

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US3626049A
US3626049A US753515A US3626049DA US3626049A US 3626049 A US3626049 A US 3626049A US 753515 A US753515 A US 753515A US 3626049D A US3626049D A US 3626049DA US 3626049 A US3626049 A US 3626049A
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protein
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Akira Yamamoto
Kunio Nakaoji
Kunio Oohara
Zenjiro Momiyama
Heiichiro Murakami
Akira Tomita
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Toyobo 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
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • 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
    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles

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  • Woo Auorney-Wenderoth, Lind & Ponack ABSTRACT Cross-linked acrylic fibers or films which are of improved hot water-resistance and have a silky hand or feel, are obtained by (i) preparing an acidic solution of a copolymer obtained by copolymerizing in an acidic medium (a) a vinyl monomeric material consisting mainly of acrylonitrile and (b) a polymerizable unsaturated monomer having a halogenated s-triazinyl group or halogenated pyrimidinyl group in the presence of (c) a polymerizable unsaturated monomer having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or quinolyl group, and/or (d) protein, and then (ii) extruding a very stable acidic solution of the resulting polymer into the form of fibers or films, and then heat-treating.
  • This invention relates to improved acrylic fibers and films high in the hot water-resistance, and also to processes for producing the same.
  • An object of the present invention is to provide fibers and films of novel cross-linked acrylonitrile copolymers high in hot water-resistance and a process for producing the same.
  • a further object of the present invention is to provide improved protein-acrylonitrile graft copolymer fibers and films having a silky hand or feel and high in hot water-resistance.
  • a still further object of the present invention is to provide a very stable solution for forming cross-linked acrylic fibers or films.
  • FIG. 1 is a graph showing the relation between the elongation and the strength of fibers of this invention as compared with conventional fibers, and
  • FIG. 2 is a graph similar to FIG. 1 but showing the same relation in respect of other fibers of this invention as compared with the conventional fibers.
  • These objects of the present invention may be accomplished by preparing an acidic solution of a copolymer obtained by copolymerizing in an acidic medium (a) a vinyl monomeric material consisting mainly of acrylonitrile and (b) a polymerizable unsaturated monomer having a halogenated striazinyl group or halogenated pyrimidinyl group in the presence of (c) a polymerizable unsaturated monomer having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or quinolyl group, and/or (d) protein, and then extruding an acidic solution ofthe resulting polymer in the form of fibers or films and then heat-treating.
  • the vinyl monomeric material consisting mainly of acrylonitrile in the present invention includes acrylonitrile alone or a mixture of acrylonitrile and vinyl monomer(s) copolymerizable with acrylonitrile. Said vinyl monomers are, of course, other than those of the (b) and (c) monomers. In a monomeric mixture, acrylonitrile must be contained in an amount ofat least 70 percent by weight.
  • vinyl monomers are acrylic acid and methacrylic, their esters such as methyl acrylate, methyl methacrylate and ethylacrylate, their amide derivatives such as acrylamide and methacrylamide, methacrylonitrile, allyl chloride, allyl sulfonic acid and its salts, ethylene sulfonic acid and its salts, itaconic acid and its ester derivatives, fumaronitrile, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, methyl vinyl ketone, styrene, a-substituted styrenes such as a-methyl styrene, nucleus-substituted styrenes such as 0-, mor p-methyl styrene, styrene sulfonic acid and its salts, vinyl esters such as vinyl chloride and vinyl acetate, vinyl lactams such as vinyl caprolactnm and vinyl
  • halogenated s-triazinyl group or halogenated pyrimidinyl group in the polymerizable unsaturated monomer (hereinafter referred to as monomer A) having a halogenated s-triazinyl group or halogenated pyrimidinyl group is of the following structure:
  • Examples of preferable monomers A are of the following structural formulas:
  • R represents hydrogen or an alkyl group.
  • halogenated s-triazinyl group in the above-mentioned compounds substituted with a halogenated pyrimidinyl group may also be used.
  • both X and X in the monomer A are halogens. Particularly, among the halogens, chlorine is 5 preferable.
  • the most preferable examples of the monomer A are 2-allylamino-4,6-dichloro-s-triazine, 2-amino-4-allyloxy-6-chloros-triazine, 2-(p-vinylanilino)-4,6-dichloropyrimidine and 2-allylamino-4,6-dichloropyrimidine.
  • e content of the monomer A in the resulting acrylic copolymer is 0.03 to 10 percent by weight and, more preferably 0.3 to 5 percent by weight.
  • the content of the monomer A component is lower than the above mentioned range, the hot water-resistance of the obtained fibers and films cannot be improved to a desirable degree.
  • the elongation and softness properties in the dry state of the thus-obtained fibers and films are reduced.
  • monomer B having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or a quinolyl group are as follows:
  • the monomers B are not limited to the above exemplified particular compounds but may be any of polymerizable unsaturated monomers having in the molecule a group containing active hydrogen such as an amino group, imino group or hydroxyl group, a group (e.g. epoxy group) capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or a quinolyl group.
  • a group containing active hydrogen such as an amino group, imino group or hydroxyl group, a group (e.g. epoxy group) capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or a quinolyl group.
  • Particularly preferable among the monomers B are allylamine, allyl alcohol and vinyl pyridine.
  • the content of the monomer B in the resulting acrylic copolymer is 0.3 to percent by weight, more preferably 0.5 to 5 percent by weight.
  • the content of the monomer B component is lower than the above mentioned range, the hot water-resistance of the obtained fibers and films cannot be improved to any desired degree.
  • the elongation in the dry state of the obtained fibers and films is reduced and the materials lose their softness.
  • proteins to be used in the present invention particularly preferable are natural proteins such as cow milk casein, yeast protein, gelatin, corn protein and soybean protein.
  • modified proteins such as cyanoethylated protein and carbamylethylated protein or synthetic proteins.
  • the content of the protein in the resulting acrylic copolymer is 5 to 50 percent, more preferably -40 percent by weight.
  • the content of the protein is lower than the above mentioned range, fibers high in the hot water-resistance and dyeability and having a silky hand and films high in the dyeability cannot be obtained.
  • the toughness of the obtained fibers and films is reduced.
  • an acidic medium of a pH of6 or less preferably a pH of4 or less.
  • Preferable media which can be used in the polymerization of the present invention are, for example, a concentrated aqueous solution of zinc chloride, aqueous solution of nitric acid, an aqueous solution of nitrate-containing nitric acid, an aqueous solution of perchloric acid, an aqueous solution of a thiocyanate adjusted to be acidic, dimethyl sulfoxide adjusted to be acidic, ethylene carbonate or an aqueous solution of ethylene carbonate adjusted to be acidic, an aqueous solution of formic acid, a concentrated aqueous solution of urea adjusted to be acidic, an aqueous system adjusted to be acidic, and a mixture of any two or more of the above-mentioned media.
  • Typical examples wherein the polymerization is conducted in a concentrated aqueous solution of zinc chloride and dimethyl sulfoxide shall be described as follows. It is preferable that the concentrated aqueous solution contains 40 percent by weight to the saturation of zinc chloride. If a second such substance as sodium chloride is to be added to the solution, the amount of such second substance is preferably in the range ofO to 20 percent by weight.
  • the total concentration of the vinyl monomeric material, monomer A protein and/or monomer B to be added and dissolved into said concentrated aqueous solution of zinc chloride is preferably 3 to 40 percent by weight.
  • the monomer B contains an amino group, imino group, pyridyl group, pyrazinyl group or quinolyl group, it is preferable that said monomer B is added in the form of a hydrochloride.
  • the polymerization catalyst may be used known radical polymerization initiators soluble in the concentrated aqueous solution of zinc chloride, such as azobisisobutylonitrile, ammonium persulfate, potassium persulfate or hydrogen peroxide.
  • the catalyst may also be a redox catalyst system in which is simultaneously used such reducing agents as sodium sulfite, acidic sodium sulfite, sodium thiosulfate or. a ferrous salt.
  • the polymerization may also be conducted under the irradiation of radioactive rays such as, for example, gamma rays of Co or a light irradiation.
  • the polymerization temperature is 0 to 60 C.
  • the polymerization time may be less than 40 hours.
  • dimethyl sulfoxide In case dimethyl sulfoxide is used as a medium, it should be adjusted to be acidic by adding an organic acid or inorganic acid before initiating the polymerization. Preferably, the amount of the acid to be added is less than l0 percent by weight of the dimethyl sulfoxide.
  • The: vinyl monomeric material and protein and/or monomer B and/or protein may be added and dissolved before the dimethyl sulfoxide is adjusted to be acidic but it is preferable, in preventing the gelling of the polymerization system, to add the monomer A after the dimethyl sulfoxide has been adjusted to be acidic.
  • soybean protein which is hardly soluble in dimethyl sulfoxide at the normal temperature :should be dissolved at an elevated temperature such as to C. It is preferable that the total concentration of the vinyl monomer material, monomer A and protein and/or monomer B be 3 to 40 percent by weight .of the dimethyl sulfoxide.
  • the polymerizing catalyst may be used radical polymerization initiators soluble in dimethyl sulfoxide, such as azobisisobutylonitrile or ammonium persulfate. Further, it may be a redox polymerization in which a proper reducing agent is simultaneously used.
  • the polymerization temperature is 0 to 100 C. and the polymerization time may be less than 50 hours.
  • the acrylic polymer solution obtained by the polymerization in a proper acidic medium can be used for forming fibers and films. It is also possible to pour the solution into a nonsolvent for said polymer so that the polymer is precipitated and separated, washed, dehydrated and then dissolved into a proper acidic solvent such as, for example, a concentrated aqueous solution of zinc chloride, dimethyl sulfoxide adjusted to be acidic, dimethyl formamide adjusted to be acidic or concentrated nitric acidl. In the latter case, it is preferable to use washing water which has been adjusted to be acidic and at a comparatively low temperature, preferably below 30 C. In such case, the washed and dehydrated polymer can be stably stored as it is in a wet state for a considerably long time.
  • a proper acidic solvent such as, for example, a concentrated aqueous solution of zinc chloride, dimethyl sulfoxide adjusted to be acidic, dimethyl formamide adjusted to be acidic or concentrated nitric acidl.
  • the acidic polymer solution is then extruded in the form of filament or film into an acidic or neutral coagulating bath or into a hot gaseous atmosphere such as hot air.
  • Fibers and films can be formed from the-polymer solution by any well-known method.
  • the spinning solution is first filtered and dleaerated and is then extruded through a spinnerette into an aqueous solution of 5 to 33 percent by weight ofzinc chloride so as to coagulate the extruded filaments.
  • the filaments are then water-washed to remove zinc chloride and other materials deposited on them,
  • an acidic dimethyl sulfoxide solution of the polymer As compared with conventional acrylic fibers and films, the is to be used as a spinning solution, there can be used a neutral fibers and films produced by the present invention are higher dimethyl sulfoxide-water mixed solution or n-butanol for the in the strength when dry and wet, and are remarkably supericoagulating bath. It is desirable to'add an acid to such coagu' or, particularly in such properties as the strength and elongalating bath so as to be acidic. tion in hot water.
  • the fibers produced by the In the case of forming a film, the acidic polymer solution is present invention, or their woven and knitted fabrics, and the extruded in the form of a film into an acidic or neutral coaguto films produced by the present invention are very high in the lating bath or into a hot atmosphere through a slit instead of dimensional stability in a wet hot processing step such as dyethe spinnerette and the film is washed with water and thering.
  • a wet hot processing step such as dyethe spinnerette
  • the film is washed with water and thering.
  • the protein-acrylonitrile graft-co-polymer mally stretched.
  • fibers produced by the present invention have a silky luster The filaments or films extruded into the acidic or neutral and a soft elegant peculiar hand.
  • the viscosity of the resulting polymer solution stance thereon is removed or while the said acidic substance IS was 250 poises at 0
  • the acidic substance is first was 488 Percent (Na removed, and immediately thereafter or after travelling in an The Same procedures were repeated except that AAT was of the normal temperature for a Very Short period of time added in an amount of 3.0 percent on the total amount of the the filaments or films are stretched.
  • the formed coagulated filaments were washed with and immediately thereafter or after travelling in an air of the water and stretched l 5 times the length in steam at to normal or for a Short period Oftime to obtain fibers of a silky luster.
  • the properties, dry and wet, of i l stretching m a heme? Steam hot water or hot bath 45 the fibers are shown in table 1. Their load-elongation curves in taming salt(s) such as sodium sulfate.
  • EXAMPLE 4 Twenty two and a half parts of dried cow milk protein were added and dissolved into 277.5 parts of anhydrous dimethyl sulfoxide. A small amount of acetic acid was added to the solution to adjust the pH to about 3.5. Then 49.5 parts of AN, 0.5 parts of AAT (corresponding to 1.0 percent on the total weight of the monomers) and 0.75 part of ammonium per- As evident from table 2, as compared with the control fibers (No. 5), the fibers (No. 4) of the present invention were higher in the strength both in dry and wet state and were remarkably superior particularly in the strength and elongation and in the dimensional stability in hot water.
  • EXAMPLE 3 Fifty parts of soybean protein were dissolved in 1,940 parts of an aqueous solution containing 55 percent zinc chloride and 5 percent sodium chloride. 0 this solution were added 115 parts of AN, 6.25 parts of acrylamide (referred to as AAM hereinafter) and 3.75 parts of 2-amino-4-allyloxy-6- chloro-s-triazine (hereinafter referred to as AAOT). While the solution was kept at 8 C.
  • the fibers (Nos. 8 and 9) of the invention were higher in the strength and initial modulus of elasticity both in dry and wet, and were remarkably superior particularly in strength and elongation in hot water at 90 C.
  • the fibers (No. 6) of the invention were higher in the strength both in dry and wet, and were remarkably superior particularly in strength and elongation in hot water at 90 C.
  • VAP 2-(P-vinylanilino)--dichloro-pyrimidine
  • polymerization conversion rate in this example was 93.4 per- TABLE 7 (Nu AN MA AAT AA Total For comparison, the same procedure was repeated except that VAP was not added to obtain a control polymer solution 1 3 100 (No. 12 5 g g 1% Each of these polymer solutions was formed into filaments n 100 under the same conditions as in example 4 to obtain fibers having a silky luster. The properties of the fibers thus obtained are shown in table 5. l 0
  • EXAMPLE 6 Twenty two and a half parts of dried soybean protein were dispersed and heated at 120 C. to dissolve in 277.5 parts of anhydrous dimethyl sulfoxide. Then formic acid was added to the solution to adjust the pH to 3.0. To this solution were added 47 parts of acrylonitrile, 1.5 parts of vinyl acetate and l .5 parts of 2-amino-4-allyloxy-6-chloro-s-triazine (hereinafter referred to as AAOT). To this solution was further added 0.75 part of ammonium persulfate. The polymerization was conducted at C. under a reduced pressure for 18 hours. The polymerization conversion rate in this example was 96.8 percent (No. 13).
  • AA allylamine
  • the monomer compositions were as in table 7.
  • polymerization was conducted at a total monomer concentration of 8 percent by weight in an aqueous solution of 60 percent zinc chloride at C.
  • the polymerizing catalyst and other polymerizing conditions were the same as in example 7 (but the polymerizing temperature in No. 24 was C.).
  • the monomer compositions, polymerization conversion rates and the viscosities (poises at C.) of the polymer solutions were as shown in table I l.
  • the fibers (No. 22) of the present invention were superior particularly in the strength and elongation in hot water at 90 C.
  • Elonga- Elonga- Elonga- Stren th tion Strength tion Strength tion (g. d.) (percent) (g./d.) (percent) (g./d.) (percent) No.:
  • Elonga- Elonga- Elonga- Elonga- Strength tion Strength tion Strength tion (g./d.) (percent) (g./d.) (percent) (g./d..) (percent)
  • the fibers (No. 25) of the present invention were superior particularly in strength and elongation in hot water at 90 C.
  • EXAMPLE 1 1 By using AN, MA, 2-allylaminc-4,6-dichloro-pyrimidine (referred to as AAP) and AA as monomers in various proportions the polymerization was conducted at C. for No 27 and at C. for No. 28 in an aqueous solution of 60 percent zinc chloride and otherwise under the same conditions as in example 7. The monomer compositions and the viscosities (poises at C.) of the obtained polymer solutions were as shown in table 15.
  • the fibers (No. 29) of the present invention were superior particularly in the strength and elongation in hot water at 90 C.
  • EXAMPLE l3 By using various monomers as shown in table 19. the polymerization was conducted in a nonuniform system at a total monomer concentration of 8.7 percent by weight in deoxygenated water adjusted to a pH of 1.5 with sulfuric acid.
  • Elonga- Elonga- Elonga- Elonga- Strength tion Strength tlon Strength tlon (g./ (percent) (g./d.) (percent) (g./d.) (percent)
  • the fibers (No. 27) of the present invention were superior particularly in the strength and elongation in hot water at 90 C.
  • the resulting polymer solution was deaerated while being kept at C. and was extruded through a spinnerette into an aqueous solution of 35 percent nitric acid at 10 C.
  • the formed coagulated filaments were washed with water, stretched 7 times their length in boiling water and were dried.
  • Elonga- Elonga- Elonga- Elonga- Stren th tion Strength tion Strength tion (g. d.) (percent) (g. /d.) (percent) (g./d.) (percent) As evident from table 20, even in case the polymerization percent (No. 36).
  • EXAMPLEM With the same monomers as in example 13, the polymerization was conducted at a total monomer concentration of about 20 percent by weight in dimethyl sulfoxide at a temperature of C. adjusted to a pH of 1.2 with sulfuric acid.
  • the fibers (No. 36) of the present invention were remarkably superior particularly in the strength and elongation in hot water at 90 C.
  • Elonge- Elongu- Elonga- Stren tll tion Stren th tion Strength tion (g. (1.) (percent) (g. d.) (percent) (g./d.) (percent) 36 2. 62 8 2. 52 25. (i l. 28 42. U 37 2. 23 27. 6 2. 09 29. 1 0. 87 73. 2
  • Elonga Elonga- Elonga- Strength tion Strength tion Strength tion (g./d.) (percent) (g./d.) (percent) (g./d.) (percent)
  • the fibers of the present invention were superior particularly in the strength and elongation in hot water at 90 C.
  • Each of the polymers obtained in. example 13 was added and dissolved with stirring into dimethyl acetamide adjusted to a pH of 1.2 with sulfuric acid, so as to produce a polymer concentration of 20 percent.
  • the polymer solution was filtered, deaerated and then extruded through a spinnerette into an aqueous solution of 55 percent dimethyl acetamide at 20 C.
  • the formed filaments were washed with water, then stretched 6 times their length in boiling water at 95 to I C. and were dried.
  • the properties of the obtained fibers are shown in table 24.
  • the hydrous polymer was processed in the same manner as in example 17 to obtain fibers having a silky luster (No. 42).
  • the same procedure was repeated except As evident from table 24, as compared with the control fibers (No. 39), the fibers (No. 38) of the present invention were remarkably superior particularly in the strength and elongation in hot water at 90 C.
  • EXAMPLE l7 Four parts of soybean protein were dissolved in 180 parts of formic acid. Then 15.5 parts of AN, 0.5 part of AAT and 0.6 part of aa-azoisobutylonitrile were added thereto and the mixture was polymerized at 60 C. under a reduced pressure for 6 hours (No. 40). Then, the resulting reaction mixture was put into 500 parts of water and was dehydrated with a centrifugal separator to obtain 23.4 parts of a hydrous polymer of a moisture content of 30 percent. This hydrous polymer was added and dissolved with stirring into an aqueous solution of 60 percent zinc chloride to obtain a solution of a polymer concentration of 8 percent.
  • the polymer solution was filtered and deaerated and was then extruded through a spinnerette into an aqueous solution of 28 percent zinc chloride at 0 C.
  • the formed filaments were washed with water, then stretched l times their length in steam at l C. and were dried to obtain fibers having a silky luster.
  • the fibers (No. 42) of the present invention were remarkably superior particularly in their strength and elongation in hot water at 90 C.
  • EXAMPLE l9 Five parts of corn protein were added to 80 parts of dimethyl formamide adjusted to a pH of 2.0 with phosphoric acid and were dissolved therein with stirring at the room temperature. Then, to this solution were added 14.85 parts of AN and 0.l5 part of ATT and, as catalysts, 0.006 part of cupric nitrate and 0.225 part of potassium persulfate. The mixture was polymerized with stirring in a nitrogen gas current for 5 hours (No. 44). The polymerization conversion rate was 94.3 percent.
  • Each of the three polymer solutions was extruded through a spinnerette into a hot air spinning tube at 200 to 250 C. and the formed filaments were taken at a velocity of 1 l0 m./min. The filaments were then stretched 5 times their length in hot 25. water at 100 C. and were dried to obtain fibers having a silky TABLE 25 Dry Wet In hot water at 90 C.
  • Elonga- Elonga- Elonga- Elonga- Strength tlon Strength tion Strength tion (g.s/d.s) (percent) (g.s/d.s) (percent) (g.s/d.s) (percent) No.:
  • Elonga- Elonga- Elonga- Elonga- Strength tion Strength tlon Strength tion (g.s/d.'s) (percent) (g.s/d.s) (percent) (g.s/d.s) (percent)
  • the fibers (No. 40) of the present invention were remarkably superior particularly in their strength and elongation in hot water at 90 C.
  • EXAMPLE 18 Four parts of cow milk casein were dissolved in 190 parts of an aqueous solution of percent urea adjusted to a pH of 6.01 with hydrochloric acid. To this solution were added 15.5 parts of AN, 0.5 part of ATT and 1 part of a,a-azoisobutylonitrile. The mixture was polymerized at C. for 6 hours (No. 42). Then the polymer precipitate was centrifugally separated, washed with water adjusted to a pH of 6 and was luster. The properties of the fibers thus obtained are shown in table 27.
  • the coagulated film rated monomer containing a group selected from the was transferred to a water-washing bath, and was then class consisting of amin imin an hydroxyl gr p stretched 5 times their length in one direction in hot water to glycidyl groups, pyridyl, pyrazinyl groups and quinolyl obtain a stretched transparent film (No. 47).
  • films were prepared from the polymer 5 extruding an acidic solution of the polymer in the forms wherein the amount of AAT was 3.0 percent based on the of filaments into an acid or neutral coagulating bath or total amount of the monomers (No.
  • the films of the present invention (Nos. 47 and 48) 'protein selected from the group consisting of cow milk casein, were remarkably superior particularly in the strength, elongayeast protein, gelatin, corn protein, soybean protein, tlon and shrinkage in hot water at 90 C. 25 cyanoethylated protein or carbamylethylated protein.
  • dichloropyrimidine OO-acryloyloxyethylene amino-4,6- 1.
  • a process for producing acrylic fibers characterized by dichloropyrimidine, 2-vinyloxyethylene amino-4,6- polymerizing, in an acidic medium, (a) a vinyl monomeric 50 dichloropyrimidine or 2-(p-vinylphenoxy)-4,6- material consisting mainly of acrylonitrile and (b) a dichloropyrimidine. polymerizable unsaturated monomer having a group selected 5.
  • the protein is f h class consisting f h l d i i groups f selected from the class consisting of natural proteins, modified the general formula: proteins and synthetic proteins.
  • a process according to claim 1 wherein the polymeriza- Xl ble unsaturated monomer having a group containing active N l hydrogen, a group capable of forming active hydrogen, a N pyridyl group, pyrazinyl group or quinolyl group is ailylamine,
  • glycidyl acrylate ethylene glycol monovinyl ether. diethylene i glycol monovinyl ether, 2,3-dihydroxypropyl methacrylate, l-
  • f X, n X is a halogen, hydrogen. alkyl methacryloyl-D-galactose, Z-N-methacryloyl glucosamine, 1- group, amino group, hydroxyl group, mercapto group, or acrylamide-l-dioxy-glucitol, l-o-p-vinylphenyl glucose, pcarboxyl group, and wherein at least one of X and X hydroxystyrene, vinyl pyridine, 2-methyl-5-vinyl pyridine, must be a halogen, in the presence of a material selected vinyl pyrazine, or 2-vinyl-quinoline.
  • pyrazinyl group or a quinolyl group is 0.3 to l percent by weight on the polymer.
  • a process according to claim 1 wherein the acidic medium is an aqueous solution of more than 40 percent by weight zinc chloride.
  • said acidic medium is dimethyl sulfoxide, dimethyl formamide, ethylene carbonate, an aqueous solution of ethylene carbonate, deoxygenated water, a concentrated aqueous solution of urea, or formic acid, all being adjusted to a pH not higher than 6.
  • a process according to claim 1 wherein the stretching is conducted in heated steam, hot water or a hot bath containing sodium sulfate, after an acidic substance in the fibers or films has been removed by washing.

Abstract

Cross-linked acrylic fibers or films which are of improved hot water-resistance and have a silky hand or feel, are obtained by (i) preparing an acidic solution of a copolymer obtained by copolymerizing in an acidic medium (a) a vinyl monomeric material consisting mainly of acrylonitrile and (b) a polymerizable unsaturated monomer having a halogenated s-triazinyl group or halogenated pyrimidinyl group in the presence of (c) a polymerizable unsaturated monomer having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or quinolyl group, and/or (d) protein, and then (ii) extruding a very stable acidic solution of the resulting polymer into the form of fibers or films, and then heat-treating. The obtained fibers, for example, are useful in making woven or knitted fabrics of correspondingly superior properties.

Description

United States Patent Akira Yamamoto;
Kunio Nakaoji; Kunio Oohara; Zenjiro Momiyama; Heiichiro Murakami; Akira Tomita, all of Otsu, Japan Aug. 19, 1968 Dec. 7, 1971 [72] Inventors [21] Appl. No. [22] Filed [45] Patented [73] Assignee Toyo Boseki Kabushiki Kaisha [32] Priorities Sept. 2, 1967 [33] Japan [31] 42/56502;
Sept. 2, 1967,,Iapan, No. 42/82509 [54] PROCESS FOR PRODUCING CROSS-LINKED ACRYLIC FIBERS 0R FILMS 14 Claims, 2 Drawing Figs.
[52] U.S. Cl 264/236, 260/8, 260/17.4, 260/8072, 260/883, 264/182, 264/183, 264/184, 264/202, 264/205, 264/206,
264/210 [51] Int. Cl B28bll/00, DOlf 7/00 [50] Field of Search 260/8, 17.4, 80.72, 88.3, 88.5 R;264/182, 183, 236, 202, 205, 206, 210
[56] References Cited UNITED STATES PATENTS 2,510,503 6/1950 Kropa 260/8072 2,540,826 2/1951 Larcher 260/8072 STRENGTH (g/d) 2,687,400 8/1954 D'Alelio 260/8072 2,712,537 7/1955 D'A1elio..... 260/8072 2,734,888 2/1956 D'Alelio 260/8072 3,050,496 8/1962 D'Alelio 260/8072 3,053,812 9/1962 DAlelio .1 260/8072 3,104,154 9/1963 Morimoto et al.. 264/202 3,153,015 10/1964 DAlelio 260/8072 3,154,523 10/1964 DAlelio 260/8072 3,445,438 5/1969 Honig et a1. 260/8072 FOREIGN PATENTS 41/6213 4/1966 Japan 264/182 Primary E.raminer.lay H. Woo Auorney-Wenderoth, Lind & Ponack ABSTRACT: Cross-linked acrylic fibers or films which are of improved hot water-resistance and have a silky hand or feel, are obtained by (i) preparing an acidic solution of a copolymer obtained by copolymerizing in an acidic medium (a) a vinyl monomeric material consisting mainly of acrylonitrile and (b) a polymerizable unsaturated monomer having a halogenated s-triazinyl group or halogenated pyrimidinyl group in the presence of (c) a polymerizable unsaturated monomer having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or quinolyl group, and/or (d) protein, and then (ii) extruding a very stable acidic solution of the resulting polymer into the form of fibers or films, and then heat-treating. The obtained fibers, for example, are useful in making woven or knitted fabrics of correspondingly superior properties.
40 so so ELONGATIONI PATENTEU [15c Hen 3626x149 STRENGTH (g/d) 0 2'0 4'0 o so ELONGATION' STRENGTH /d) AKlRA YAMAMMO.
KllNlo NAKAOJ'I,
KUNIO OOHARA.
ZENJ'IRO MoMtYAIMA. HEIICHIQD MUIHKAM! mu AKIRA TOMITA Inventor;
Bywmmm Attorney! This invention relates to improved acrylic fibers and films high in the hot water-resistance, and also to processes for producing the same.
Generally fibers of acrylonitrile polymers have the disadvantage that they are much lower in strength and dimensional stability under heat, particularly in hot water, than any other synthetic fibers. The researches so far made to modify acrylic fibers have been directed mostly to the improvement of the dyeability and prevention of fibrillation by copolymerizing acrylonitrile with other monomer(s). Therefore, such modification has resulted in the reduction of the molecular chain orientation of the acrylic fibers and also in the deterioration in the hot water-resistance of the fibers.
There has recently been an attempt to improve the hot water-resistance of acrylic fibers by introducing a cross-linkage between the molecules of acrylic fibers. For example, in US. Pat. No. 3,399,007, there is disclosed a process wherein a cross-Iinkable monomer such as divinylbenzene is copolymerized with acrylonitrile. However, most of such cross- Iinkable comonomers have the disadvantage that the cross-linking reaction proceeds so quickly during the polymerizing step and up to the fiber formation step, that the polymer solution for forming shaped articles increases in viscosity r gels and the shaping operation becomes difficult.
An object of the present invention is to provide fibers and films of novel cross-linked acrylonitrile copolymers high in hot water-resistance and a process for producing the same.
A further object of the present invention is to provide improved protein-acrylonitrile graft copolymer fibers and films having a silky hand or feel and high in hot water-resistance.
A still further object of the present invention is to provide a very stable solution for forming cross-linked acrylic fibers or films.
Other objects of the present invention will become clear from the following descriptions which will be made partly by referring to the accompanying drawings wherein:
FIG. 1 is a graph showing the relation between the elongation and the strength of fibers of this invention as compared with conventional fibers, and
FIG. 2 is a graph similar to FIG. 1 but showing the same relation in respect of other fibers of this invention as compared with the conventional fibers.
These objects of the present invention may be accomplished by preparing an acidic solution of a copolymer obtained by copolymerizing in an acidic medium (a) a vinyl monomeric material consisting mainly of acrylonitrile and (b) a polymerizable unsaturated monomer having a halogenated striazinyl group or halogenated pyrimidinyl group in the presence of (c) a polymerizable unsaturated monomer having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or quinolyl group, and/or (d) protein, and then extruding an acidic solution ofthe resulting polymer in the form of fibers or films and then heat-treating.
The vinyl monomeric material consisting mainly of acrylonitrile in the present invention includes acrylonitrile alone or a mixture of acrylonitrile and vinyl monomer(s) copolymerizable with acrylonitrile. Said vinyl monomers are, of course, other than those of the (b) and (c) monomers. In a monomeric mixture, acrylonitrile must be contained in an amount ofat least 70 percent by weight.
Examples of vinyl monomers are acrylic acid and methacrylic, their esters such as methyl acrylate, methyl methacrylate and ethylacrylate, their amide derivatives such as acrylamide and methacrylamide, methacrylonitrile, allyl chloride, allyl sulfonic acid and its salts, ethylene sulfonic acid and its salts, itaconic acid and its ester derivatives, fumaronitrile, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, methyl vinyl ketone, styrene, a-substituted styrenes such as a-methyl styrene, nucleus-substituted styrenes such as 0-, mor p-methyl styrene, styrene sulfonic acid and its salts, vinyl esters such as vinyl chloride and vinyl acetate, vinyl lactams such as vinyl caprolactnm and vinyl pyrrolidone and vinyl imidazole.
The halogenated s-triazinyl group or halogenated pyrimidinyl group in the polymerizable unsaturated monomer (hereinafter referred to as monomer A) having a halogenated s-triazinyl group or halogenated pyrimidinyl group is of the following structure:
halogenated s-triazinyl group N c N halogenated pyrimidinyl group X! N l wherein each of X and X is a halogen, hydrogen, alkyl group, amino group, hydroxyl group, mercapto group, carboxyl group or a group derived from any of them and at least one of X and X must be a halogen.
Examples of preferable monomers A are of the following structural formulas:
2-allylamlno-4,6-dlchloro-s-trlnzlne,
Z-aeryloyloxyethylene amino4,6-dlchloro-s-triazine,
and, 2-(p-vinylphenoxy)-4,6-dichloro-s-triazine.
In the above formulas, R represents hydrogen or an alkyl group.
Further, those compounds in which the halogenated s-triazinyl group in the above-mentioned compounds substituted with a halogenated pyrimidinyl group may also be used. Further. it is preferable that both X and X in the monomer A are halogens. Particularly, among the halogens, chlorine is 5 preferable.
The most preferable examples of the monomer A are 2-allylamino-4,6-dichloro-s-triazine, 2-amino-4-allyloxy-6-chloros-triazine, 2-(p-vinylanilino)-4,6-dichloropyrimidine and 2-allylamino-4,6-dichloropyrimidine.
It is preferable that e content of the monomer A in the resulting acrylic copolymer is 0.03 to 10 percent by weight and, more preferably 0.3 to 5 percent by weight. In case the content of the monomer A component is lower than the above mentioned range, the hot water-resistance of the obtained fibers and films cannot be improved to a desirable degree. On the contrary, in case it is higher than the above mentioned range, the elongation and softness properties in the dry state of the thus-obtained fibers and films are reduced.
Preferable examples of the polymerizable unsaturated monomer (hereinafter referred to as monomer B) having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or a quinolyl group are as follows:
Methallylmnlne: CHz=C (CH3) 0 HzNHz,
Allylmethylamlne: CHFCHCPDNH CH3,
Allylethylamine: CHz=CH CHzNHC HgCHa,
1- (N-ethylamlno) -3-butene: CH1=CHCH1C HzNH CH2CH3,
B-Aminoethyl methacrylate: CH =C CH 0 O O C H1O HzNHz,
B-(N-methylamino) ethyl acrylate: CHz=CHC OOCHzCHzNHCHg,
B (N methylamino) ethyl methacrylate:
CH==C (CH CO0 CH2CH2NHCH3, fi- (N-ethylamlno) ethyl methacrylate:
CHz=C (CH C O 0 CHzOHgNHCHzCIh,
Allyl alcohol: CH=CHCH2OH,
Methallyl alcohol: CHFC CH3) C HzOH,
3-butene-2-ol: CHFCHCH(OH) CH3, 4-pentene-2-ol: OH2=GHCH2CH OH) CH;,
fi-Hydroxyethylacrylate: C Hr -C H C O 0 0 H26 1120 H,
B-Hydroxyethyl methacrylate: C H 2:0 H C O O C HzCH-7 0 Hz Glycldyl acrylate: 0111:0110 0 0 CHzCH-CH2, 2, 3-dlhydroxypropy1 methacrylate:
CH=C (CH C O 0 CHzCH(OH) CHzOH, Ethylene glycol monovlnyl ether: CH2=CH O CH2CH2OH, Dlethylene glycol monovlnyl ether:
011,011 HO |-o H0 |-o H l \oH H H H H OH 2-N-methacryloyl glucosamine:
O OH 1'1 OH OH l-o-p-vinylphcnyl glucose:
OH; OH
0- CH=CH,
2-methyl-5-vinyl-pyridine:
2-vinyl quinoline:
and
Vinyl pyrazine:
Of course, the monomers B are not limited to the above exemplified particular compounds but may be any of polymerizable unsaturated monomers having in the molecule a group containing active hydrogen such as an amino group, imino group or hydroxyl group, a group (e.g. epoxy group) capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or a quinolyl group.
Particularly preferable among the monomers B are allylamine, allyl alcohol and vinyl pyridine.
It is preferable that the content of the monomer B in the resulting acrylic copolymer is 0.3 to percent by weight, more preferably 0.5 to 5 percent by weight. In case the content of the monomer B component is lower than the above mentioned range, the hot water-resistance of the obtained fibers and films cannot be improved to any desired degree. On the contrary, in case it is higher than the above mentioned range, the elongation in the dry state of the obtained fibers and films is reduced and the materials lose their softness.
In regard to the protein to be used in the present invention, particularly preferable are natural proteins such as cow milk casein, yeast protein, gelatin, corn protein and soybean protein. In addition, there can be used modified proteins such as cyanoethylated protein and carbamylethylated protein or synthetic proteins.
It is preferable that the content of the protein in the resulting acrylic copolymer is 5 to 50 percent, more preferably -40 percent by weight. In case the content of the protein is lower than the above mentioned range, fibers high in the hot water-resistance and dyeability and having a silky hand and films high in the dyeability cannot be obtained. On the contrary, in case it is higher than the above-mentioned range, the toughness of the obtained fibers and films is reduced.
In carrying out the polymerization it is preferable to use an acidic medium ofa pH of6 or less, preferably a pH of4 or less.
In case the polymerization is conducted in an acidic medium, substantially no cross-linking reaction proceeds during the polymerization reaction and therefore a polymer solution stable in viscosity is obtained. On the other hand, in case the polymerization is conducted in a neutral or alkaline medium, a cross-linking reaction quickly proceeds simultaneously with the polymerization reaction and the viscosity of the polymerization system increases so that the system gels and becomes unuseful as a solution for forming fibers and films in some cases. It is therefore recommended to conduct the polymerization in an acidic medium. Thus, in the present invention, it is most preferable to use such medium showing itself an acidity as, for example, a concentrated aqueous solution of zinc chloride. However, any medium which is inherently neutral or basic can be also used by adjusting the pH to be in the acidic range by adding an acid.
Preferable media which can be used in the polymerization of the present invention are, for example, a concentrated aqueous solution of zinc chloride, aqueous solution of nitric acid, an aqueous solution of nitrate-containing nitric acid, an aqueous solution of perchloric acid, an aqueous solution of a thiocyanate adjusted to be acidic, dimethyl sulfoxide adjusted to be acidic, ethylene carbonate or an aqueous solution of ethylene carbonate adjusted to be acidic, an aqueous solution of formic acid, a concentrated aqueous solution of urea adjusted to be acidic, an aqueous system adjusted to be acidic, and a mixture of any two or more of the above-mentioned media.
Except above, such other polymerization conditions as the monomer concentration, catalyst, temperature and time may be those known, per se, in the art of polymerization or copolymerization, depending upon the particular medium. In this connection, reference may be made, for example, to U.S. Pat. No. 3,104,154.
Typical examples wherein the polymerization is conducted in a concentrated aqueous solution of zinc chloride and dimethyl sulfoxide shall be described as follows. It is preferable that the concentrated aqueous solution contains 40 percent by weight to the saturation of zinc chloride. If a second such substance as sodium chloride is to be added to the solution, the amount of such second substance is preferably in the range ofO to 20 percent by weight.
The total concentration of the vinyl monomeric material, monomer A protein and/or monomer B to be added and dissolved into said concentrated aqueous solution of zinc chloride is preferably 3 to 40 percent by weight.
In case the monomer B contains an amino group, imino group, pyridyl group, pyrazinyl group or quinolyl group, it is preferable that said monomer B is added in the form of a hydrochloride.
For the polymerization catalyst may be used known radical polymerization initiators soluble in the concentrated aqueous solution of zinc chloride, such as azobisisobutylonitrile, ammonium persulfate, potassium persulfate or hydrogen peroxide. The catalyst may also be a redox catalyst system in which is simultaneously used such reducing agents as sodium sulfite, acidic sodium sulfite, sodium thiosulfate or. a ferrous salt. Further, the polymerization may also be conducted under the irradiation of radioactive rays such as, for example, gamma rays of Co or a light irradiation.
The polymerization temperature is 0 to 60 C. The polymerization time may be less than 40 hours.
In case dimethyl sulfoxide is used as a medium, it should be adjusted to be acidic by adding an organic acid or inorganic acid before initiating the polymerization. Preferably, the amount of the acid to be added is less than l0 percent by weight of the dimethyl sulfoxide. The: vinyl monomeric material and protein and/or monomer B and/or protein may be added and dissolved before the dimethyl sulfoxide is adjusted to be acidic but it is preferable, in preventing the gelling of the polymerization system, to add the monomer A after the dimethyl sulfoxide has been adjusted to be acidic. It is necessary that soybean protein which is hardly soluble in dimethyl sulfoxide at the normal temperature :should be dissolved at an elevated temperature such as to C. It is preferable that the total concentration of the vinyl monomer material, monomer A and protein and/or monomer B be 3 to 40 percent by weight .of the dimethyl sulfoxide. For the polymerizing catalyst may be used radical polymerization initiators soluble in dimethyl sulfoxide, such as azobisisobutylonitrile or ammonium persulfate. Further, it may be a redox polymerization in which a proper reducing agent is simultaneously used. Further, it is also possible to conduct the polymerization with such radioactive rays as, for example, gamma rays of Co or a light-irradiation. The polymerization temperature is 0 to 100 C. and the polymerization time may be less than 50 hours.
The acrylic polymer solution obtained by the polymerization in a proper acidic medium, as mentioned above, can be used for forming fibers and films. It is also possible to pour the solution into a nonsolvent for said polymer so that the polymer is precipitated and separated, washed, dehydrated and then dissolved into a proper acidic solvent such as, for example, a concentrated aqueous solution of zinc chloride, dimethyl sulfoxide adjusted to be acidic, dimethyl formamide adjusted to be acidic or concentrated nitric acidl. In the latter case, it is preferable to use washing water which has been adjusted to be acidic and at a comparatively low temperature, preferably below 30 C. In such case, the washed and dehydrated polymer can be stably stored as it is in a wet state for a considerably long time.
The acidic polymer solution is then extruded in the form of filament or film into an acidic or neutral coagulating bath or into a hot gaseous atmosphere such as hot air.
Fibers and films can be formed from the-polymer solution by any well-known method. For example, in the case of forming fibers by a wet-spinning method from a concentrated aqueous solution of zinc chloride of the acrylic polymer, the spinning solution is first filtered and dleaerated and is then extruded through a spinnerette into an aqueous solution of 5 to 33 percent by weight ofzinc chloride so as to coagulate the extruded filaments. The filaments are then water-washed to remove zinc chloride and other materials deposited on them,
are then stretched in a wet heated medium such as steam, hot Once such intermolecular cross-linkage has been formed in water or a hot bath containing such salt as, for example, sodir the fibers and films, they do not dissolve again into the original um sulfate and are dried and wound up. solvent.
In case an acidic dimethyl sulfoxide solution of the polymer As compared with conventional acrylic fibers and films, the is to be used as a spinning solution, there can be used a neutral fibers and films produced by the present invention are higher dimethyl sulfoxide-water mixed solution or n-butanol for the in the strength when dry and wet, and are remarkably supericoagulating bath. It is desirable to'add an acid to such coagu' or, particularly in such properties as the strength and elongalating bath so as to be acidic. tion in hot water. Therefore, the fibers produced by the In the case of forming a film, the acidic polymer solution is present invention, or their woven and knitted fabrics, and the extruded in the form of a film into an acidic or neutral coaguto films produced by the present invention are very high in the lating bath or into a hot atmosphere through a slit instead of dimensional stability in a wet hot processing step such as dyethe spinnerette and the film is washed with water and thering. Particularly the protein-acrylonitrile graft-co-polymer mally stretched. fibers produced by the present invention have a silky luster The filaments or films extruded into the acidic or neutral and a soft elegant peculiar hand.
coagulating bath or into a hot atmosphere contain an acidic The present invention will be explained in more detail by substance having come from the original acidic polymer soluthe following examples wherein all parts and percentages are tion and/or the acidic coagulating bath. After the formation of by igh nl s Otherwise specified.
the fibers (filaments) or films, cross-linking reaction proceeds EXAMPLE 1 when the acidic Substance is removed -S- y Washlhg- The 2Q Fifty parts of cow milk protein were dissolved in l ,940 parts tel'meleeulal' cross'lihkthg P Slowly at the room or of an aqueous solution of 60 percent zinc chloride. To this ma] temperature but Preeeecls p y at a higher temperature solution were added 123.75 parts of acrylonitrile (hereinafter Such 35 higher, Particularly at higheh referred to as AN) and 1.25 parts (corresponding to 1.0 per- It is preferable to stretch the formed fibers or films in order cent on h tote] amount f the monomers) f 2- |1 i to improve the mechanical properties- However it is dimeult 25 4,6-dichloro-s-triazine (referred to as AAT). While the soluto effect the stretching after the cross-linking has considerably tion was kept at a temperature f 10 and was being Slowly proceeded. Therefore, in this invention, it is preferable that Stirred parts f an aqueous solution f 60 percent i the stretching is conducted while the cross-linking has not yet chloride containing L0 percent ammonium pawn-ate and proceeded or h proceeded only to a very small extent and 250 parts of an aqueous solution of 60 percent zinc chloride that the cross-linking is substantially proceeded during or after containing 1.0 percent Sodium sulfite were added to the solu the Stretching Thus for example the formed filaments or tion. The polymerization was conducted under stirring at 10 films are stretghed before the bove me mtio,m?d C. for 2 hours. The viscosity of the resulting polymer solution stance thereon is removed or while the said acidic substance IS was 250 poises at 0 The polymerization conversion rate being removed. Alternatively, the acidic substance is first was 488 Percent (Na removed, and immediately thereafter or after travelling in an The Same procedures were repeated except that AAT was of the normal temperature for a Very Short period of time added in an amount of 3.0 percent on the total amount of the the filaments or films are stretched. In order to complete the monomers (Na 2) and that AAT was not added (Nov intermolecular cross-linking reaction, it is preferable to heat Each of the polymer Sotutions thm obtained was filtered the filaments or films; dunng or after thestretchmg a and deaerated, and then extruded through a spinnerette into perature of from 50 to h melung Polm It h an aqueous solution of 28 percent zinc chloride kept at 2 to preferable to first remove the acidic substance by washing, C. The formed coagulated filaments were washed with and immediately thereafter or after travelling in an air of the water and stretched l 5 times the length in steam at to normal or for a Short period Oftime to obtain fibers of a silky luster. The properties, dry and wet, of i l stretching m a heme? Steam hot water or hot bath 45 the fibers are shown in table 1. Their load-elongation curves in taming salt(s) such as sodium sulfate. hot water at are shown in FKL L TABLE 1 Dry state Wet state Inltlal Initial modulus modulus Elongaof elas- Elongaof elas- Strength tion ticity Strength tion tlcity (g./d.) (percent) (g./d.) (g./d.) (percent) (g./d.)
The reason why the acrylic fibers or films produced by the A5 pp from table. 1, as compared with the Control present invention show an excellent hot water-resistance is fibers the fibers (Noe 1 and 2) of the invention were that an intermolecular cross-linkage is formed due to the reachigher the Strength and t l modhlus of elastieity- A5 tion f the hebgenated s triazihyl group or halogenated shown in FIG. 1, the fibers of this invention (Nos. 1 and 2) are pyrimidihfl group in the Shaped article with the active remarkably superior particularly in strength and elongation in hydrogen-containing group in the protein or/and the group hot Watercontaining active hydrogen, group capable of forming active EXAMPLE 2 hydrogen, pyridyl group, pyrazinyl group or quinolyl group in the monomer B. within the fibers or films. Further, n the Fifty parts of gelatin were dissolved in 2,000 parts of a 60 present invention, the halogeno-s-triazinyl group or percent aqueous solution of zinc chloride. To this solution halogenopyrimidinyl group in the monomer A mp n nt were added 115 parts of AN, 6 parts of methyl methacrylate shows no reactivity in an acidic medium so that the cross-linkd 3 75 rt f z-( -vin l anilino)-4,6-di hl ropyrimidine ing reaction does not substantially proceed during the (referred to as VAP). Then the solution was irradiated with polymerizing reaction and up to the formation of the fibers or gamma rays of I00 curies of Co at an intensity of l.0Xl0 films. Therefore, the viscosity of the polymer solution is very r./hr. at 30 C. for 3 hours to effect the polymerization. There stable foralong time. was obtained a polymer solution (No. 4) with a polymeriza tion conversion rate of 99.3 percent and a viscosity of 290 poises at 30 C.
The same procedure was repeated except that VAP was not added to obtain a polymer solution (No.
Each of the polymer solutions was formed into filaments which were stretched under the same conditions as in example 1 to obtain fibers having a silky luster. The properties of the fibers thus obtained are shown in table 2.
EXAMPLE 4 Twenty two and a half parts of dried cow milk protein were added and dissolved into 277.5 parts of anhydrous dimethyl sulfoxide. A small amount of acetic acid was added to the solution to adjust the pH to about 3.5. Then 49.5 parts of AN, 0.5 parts of AAT (corresponding to 1.0 percent on the total weight of the monomers) and 0.75 part of ammonium per- As evident from table 2, as compared with the control fibers (No. 5), the fibers (No. 4) of the present invention were higher in the strength both in dry and wet state and were remarkably superior particularly in the strength and elongation and in the dimensional stability in hot water.
EXAMPLE 3 Fifty parts of soybean protein were dissolved in 1,940 parts of an aqueous solution containing 55 percent zinc chloride and 5 percent sodium chloride. 0 this solution were added 115 parts of AN, 6.25 parts of acrylamide (referred to as AAM hereinafter) and 3.75 parts of 2-amino-4-allyloxy-6- chloro-s-triazine (hereinafter referred to as AAOT). While the solution was kept at 8 C. and slowly stirred, 125 parts of an aqueous solution of 60 percent zinc chloride containing 1.0 percent ammonium persulfate and 250 parts of an aqueous solution of 60 percent zinc chloride containing 1.0 percent sodium sulfite were added to the solution and the polymerization was proceeded under stirring for 3 hours to obtain a polymer solution (No. 6) of a polymerization conversion rate of 96.5 percent and a viscosity of2 l5 poises at C.
sulfate were added to the solution. The polymerization was conducted at 30 C. under a reduced pressure for 12 hours to obtain a polymer solution (No. 8) ofa polymerization conversion rate of 94.8 percent.
The same procedures were repeated except that AAT was added in an amount of 3.0 percent on the total weight of the monomers (No. 9) and that, as a control, no AAT was added (No. 10).
Each of the three polymer solutions thus obtained was extruded through a spinnerette into an aqueous solution of 50 percent dimethyl sulfoxide of a pH adjusted to 3.51 with acetic acid. The formed filaments were well washed with water and were stretched 13 times the length in hot water at 90 C. to obtain white fibers ofa silky luster. The properties of the fibers are shown in table 4.
As evident from table 4, as compared with the control fibers (No. 10), the fibers (Nos. 8 and 9) of the invention were higher in the strength and initial modulus of elasticity both in dry and wet, and were remarkably superior particularly in strength and elongation in hot water at 90 C.
TABLE 4 Dry state Wet state In hot water at 90 C.
Elonga- Initial modu- Elonga- Initial modu- El0nga- Strength tion lus of elastic- Strength tion lus of elastic- Strength tion (g./d.) (percent) lty (g./d.) (g./d.) (percent) ity (g./d.) (g./d.) (percent) 3. 92 lb. 6 52. 5 3. 17. 2 39. 9 l. 60. 3 4. 33 14. 9 70. 0 3. 58 16. 0 45. 2 2. 13 42. 9 3. 89 16.9 45. 6 3. 23 18. 8 33. 4 1.18 80. 9
The same procedure was repeated except that AAOT was EXAMPLE 5 not added to obtain a polymer solution (No. 7).
Each of these polymer solutions was extruded through a spinnerette into an aqueous coagulating bath containing 21 percent zinc chloride and 7 percent sodium chloride. The formed filaments were treated in the same manner as in example l to obtain fibers having a silky luster. The properties of the fibers thus obtained are shown in table 3.
Twenty two and half parts of dried gelatin were dispersed and heated at 120 C. to be dissolved in 277.5 parts of an- 60 acrylonitrile, 1.5 parts of methyl methacrylate and 1.5 parts of As evident from table 3, as compared with the control fibers (No. 7), the fibers (No. 6) of the invention were higher in the strength both in dry and wet, and were remarkably superior particularly in strength and elongation in hot water at 90 C.
2-(P-vinylanilino)--dichloro-pyrimidine (hereinafter referred to as VAP). To this solution was further added 0.75 part of azobisisobutylonitrile. The polymerization was conducted at 50 C. under a reduced pressure for 24 hours. The
polymerization conversion rate in this example was 93.4 per- TABLE 7 (Nu AN MA AAT AA Total For comparison, the same procedure was repeated except that VAP was not added to obtain a control polymer solution 1 3 100 (No. 12 5 g g 1% Each of these polymer solutions was formed into filaments n 100 under the same conditions as in example 4 to obtain fibers having a silky luster. The properties of the fibers thus obtained are shown in table 5. l 0
TABLE 5 Dry state Wet state hot water at 90 C.
Elonga- Elonga- Elonga- Stren th tion Strength tion Strength tlon (git) (percent) (g./d.) (percent) (g./d.) (percent) As evident from table 5, as compared with the control fibers (No. 12), the fibers (No. 11) of the present invention were higher in the strength both in dry and wet state and were remarkably superior particularly in the strength and elongation in hot water at 90 C.
EXAMPLE 6 Twenty two and a half parts of dried soybean protein were dispersed and heated at 120 C. to dissolve in 277.5 parts of anhydrous dimethyl sulfoxide. Then formic acid was added to the solution to adjust the pH to 3.0. To this solution were added 47 parts of acrylonitrile, 1.5 parts of vinyl acetate and l .5 parts of 2-amino-4-allyloxy-6-chloro-s-triazine (hereinafter referred to as AAOT). To this solution was further added 0.75 part of ammonium persulfate. The polymerization was conducted at C. under a reduced pressure for 18 hours. The polymerization conversion rate in this example was 96.8 percent (No. 13).
For comparison, the same procedure was repeated except that AAOT was not added, to obtain a control polymer solution (No. 14).
Each of these two polymer solutions was formed into fibers under the same conditions as in Example 4 to obtain fibers of a silky luster. The properties of the fibers thus obtained are shown in table 6.
As evident from table 7, the ratio of AN/MA in Nos. 1 to 4 was fixed at 95/5.
One hundred parts of the total monomers were added to 895 parts of an aqueous solution of 60 percent zinc chloride kept at l5 C. in the case of Nos. 15 to 17 or 20 C. in the case of No. 18. Then I35 parts of an aqueous solution of zinc chloride containing l.67 percent sodium sulfite and 80 parts of an aqueous solution of 60 percent zinc chloride containing 1.25 percent ammonium persulfate'were added to the solution under stirring. Further, after 30 minutes, 40 parts of the same aqueous solution of ammonium persulfate and zinc chloride were added thereto and the polymerization was conducted with stirring for 2 hours. The polymer solution was deaerated under a reduced pressure at C. In any case the polymerization conversion rate was 99 to 100 percent. The viscosity at 30 C. was 30 poises in Nos. l5, l7 and 18 and 250 poises in No. 16.
Each of these polymer solutions was extruded through a spinnerette into an aqueous solution of 28 percent zinc chloride. The formed filaments were washed with water and then stretched 15 times the length in boiling water at 100" C. The properties of the fibers, in dry and wet states, are shown in the table 8 and their load-elongation curves in hot water at 90 C. are shown in FIG. 2.
TABLE 6 Dry state Wet state In hot water at 90 C.
Elonga- Elonga- Elonga- Strength tion Strength tion Strength tion ./d (percent) (g./d.) (percent) (g./d.) (percent) As evident from table 6, as compared with the control fibers TA 3 Dry Wet (No. 14), the fibers (No. 13) of the present invention were Elonger higher in the strength, lower in the elongation and higher in Strength tion Strength Elongation the dimensional stability particularly in hot water (percent) (pmmt) EXAMPLE 7 3.98 17.2 3. 49 21. 0 $4. 22 15. g g8 0 .13 25. .9 By using AN, AAT, methyl acrylate (hereinafter referred to 3' 18 3 3 33 22 3 as MA) and allylamine (hereinafter referred to as AA) in various proportions, the polymerization was conducted at a total monomer concentration of 8 percent by weight in an aqueous solution of 60 percent zinc chloride (Nos. 15 and 16). In this example, AA was used in the form of a hydrochloride.
For comparison, the same procedure was repeated except that no AAT was used (No. 17) and that neither of AAT and AA was used (No. 18).
The monomer compositions were as in table 7.
polymerization was conducted at a total monomer concentration of 8 percent by weight in an aqueous solution of 60 percent zinc chloride at C. The polymerizing catalyst and other polymerizing conditions were the same as in example 7 (but the polymerizing temperature in No. 24 was C.). The monomer compositions, polymerization conversion rates and the viscosities (poises at C.) of the polymer solutions were as shown in table I l.
TABLE 11 Total Polymeriza- Viscosity 01? tion conof monoversion polymer AN MA AAT AOH rners rate solution EXAMPLE 8 With the monomers in various proportions as in table 9, the polymerization was conducted in the same manner as in exam- Each of the polymer solutions was deaerated and was then extruded through a spinnerette into an aqueous solution of 28 percent zinc chloride. The formed filaments were washed with ple 7 in an aqueous solution of 60 percent zinc chloride at 15 2 5 water Stretched times the length in a glycerm bath at 12c C. The viscosity (centipoises at 30 C.) of the thus obtained polymer solution is also given in table 9.
C. and were then dried. The properties of the fibers are shown in table 12.
TABLE 12 Dry Wet In hot water at 90 C.
Elonga- Elonga- Elonga- Strength tion Strength tion Strength tlon (g./ (percent) (g./d.) (percent) (g./d.) (percent) TABLE 9 AA (AA Viscosity hydro- Total of of polymer AN AAT chloride) monomers solution Each of the polymer solutions was deaerated and then extruded through a spinnerette into an aqueous solution of 28 percent zinc chloride. The formed coagulated filaments were washed with water and then stretched 12 times the length in boiling water and were then dried. The properties of the fibers thus obtained are shown in table i0.
As evident from table 12, as compared with the control fibers (Nos. 23 and 24), the fibers (No. 22) of the present invention were superior particularly in the strength and elongation in hot water at 90 C.
EXAMPLE 10) TABLE 10 Dry Wet In hot water at 90 C.
Elonga- Elonga- Elonga- Stren th tion Strength tion Strength tion (g. d.) (percent) (g./d.) (percent) (g./d.) (percent) No.:
As evident from table l0, as compared with the control fibers (No. 21), the fibers (Nos. 19 and 20) of the present invention were higher in the strength and smaller in the elongation and were remarkably superior particularly in the strength TABLE 13 and elongation in hot water at C. Viscosity N M A T v H 1 Total of of DOPglGl' A A A P 'P C no ers so u on EXAMPLE 9 l No.: By using AN, MA, AAT and allyl alcohol (hereinafter 89.3 4.7 3 3 (4- 7) 1 2 26. 5 0 0 303 referred to as AOH) as monomers m various proportions, the 75 Each of the polymer solutions was deaerated and was then extruded through a spinnerette into an aqueous solution of 28 percent zinc chloride. The formed filaments were washed with water, then stretched times the length in a glycerin bath at 120 C. and were dried. The properties of the fibers thus obtained are shown in table 14.
TABLE 17 AN AAM AAOT AA (AA H01) Total 29.... 89.3 4.1 a s 4.9 100 30.... 92.15 4.85 0 a 4.9 100 31.-.. 9s a 0 o 100 TABLE 14 Dry Wet In hot water at 90 C.
Elonga- Elonga- Elonga- Strength tion Strength tion Strength tion (g./d.) (percent) (g./d.) (percent) (g./d..) (percent) As evident from table 14, as compared with the control fibers (No. 26), the fibers (No. 25) of the present invention were superior particularly in strength and elongation in hot water at 90 C.
The properties of the fibers obtained from the polymer solutions in the same manner as in example 9 are shown in table 18.
EXAMPLE 1 1 By using AN, MA, 2-allylaminc-4,6-dichloro-pyrimidine (referred to as AAP) and AA as monomers in various proportions the polymerization was conducted at C. for No 27 and at C. for No. 28 in an aqueous solution of 60 percent zinc chloride and otherwise under the same conditions as in example 7. The monomer compositions and the viscosities (poises at C.) of the obtained polymer solutions were as shown in table 15.
TABLE 16 Viscosity Total of of polymer AN MA AAP AA (AA HCl) monomers solution Each of the polymer solutions was spun and the filaments were stretched and dried in the same manner as in example 7. The properties of the fibers are shown in table 16.
As evident from table 18, as compared with the control fibers (Nos. 30 and 31), the fibers (No. 29) of the present invention were superior particularly in the strength and elongation in hot water at 90 C.
EXAMPLE l3 By using various monomers as shown in table 19. the polymerization was conducted in a nonuniform system at a total monomer concentration of 8.7 percent by weight in deoxygenated water adjusted to a pH of 1.5 with sulfuric acid.
TABLE 19 AN MA AAT AA (AA CH1) Total Thus, 100 parts of the total monomers (AA was added in the form of a hydrochloride) were added into 1040 parts of deoxygenated water of a pH of L5 kept at 35 C. for No. 32
TABLE 16 Dry Wet In hot water at 90 C.
Elonga- Elonga- Elonga- Strength tion Strength tlon Strength tlon (g./ (percent) (g./d.) (percent) (g./d.) (percent) As evident from table 16, as compared with the control fibers (No. 28), the fibers (No. 27) of the present invention were superior particularly in the strength and elongation in hot water at 90 C.
EXAMPLE 12 and at 40 C. for No. 33. Then, 5.8 parts of an aqueous solution of l2 percent sodium sulfite and 5.8 parts of an aqueous solution of 8 percent ammonium persulfate were further added thereto with stirring in a nitrogen atmosphere and the polymerization was conducted for 4 hours. The formed polymer precipitate was separated, washed several times with lN hydrochloric acid, and once with water and dehydrated with a centrifugal separator. The polymer (moisture content of 30 percent) was directly added into a solvent consisting of 55 percent nitric acid, 20 percent zinc nitrate and 25 percent water so as to produce a polymer concentration of 13 percent by weight. The mixture was stirred at 10 C. to dissolve the polymer. The resulting polymer solution was deaerated while being kept at C. and was extruded through a spinnerette into an aqueous solution of 35 percent nitric acid at 10 C. The formed coagulated filaments were washed with water, stretched 7 times their length in boiling water and were dried.
polymerization was conducted at a total monomer concentration of 14.5 percent by weight in an aqueous solution of 94 percent ethylene carbonate in a nitrogen atmosphere at 50 C. for 20 hours. The resulting polymer solution was of a viscosity The properties of the obtained fibers are shown in table 20. 5 f 705 poises at 50 and a polymer conversion rate f 395 TABLE 20 Dry Wet In hot water at 90 C.
Elonga- Elonga- Elonga- Stren th tion Strength tion Strength tion (g. d.) (percent) (g. /d.) (percent) (g./d.) (percent) As evident from table 20, even in case the polymerization percent (No. 36).
EXAMPLEM With the same monomers as in example 13, the polymerization was conducted at a total monomer concentration of about 20 percent by weight in dimethyl sulfoxide at a temperature of C. adjusted to a pH of 1.2 with sulfuric acid.
Thus 100 parts of the total monomers were added to 395 parts of dimethyl sulfoxide of a pH of 1.2. Further, 0.3 part of azobisisobutylonitrile and 0.1 to 0.3 part of dodecylmercaptan were added thereto and the polymerization was conducted with stirring at C. for 40 hours in a nitrogen atmosphere. The resulting polymersolution was deaerated and was then extruded through a spinnerette into an aqueous solution of 82 For comparison, the same procedure was repeated except that AAT and AA were not added to obtain a polymer solution (No. 37) ofa viscosity of 730 poises and a polymerization conversion rate of 88.0 percent.
Each of the polymer solutions was deaerated and was then extruded through a spinnerette into an aqueous coagulating bath at 30 C., adjusted to a pH of 1.8 with hydrochloric acid. The formed filaments were waterwashed then stretched 7 times their length in boiling water and were dried. The monomer compositions employed are shown in table 22 and the properties of the obtained fibers: are shown in table 23.
As evident from table 23, as compared with the control fibers (No. 37), the fibers (No. 36) of the present invention were remarkably superior particularly in the strength and elongation in hot water at 90 C.
percent dimethylsulfoxide at 40 C. The formed coagulated 35 TABLE 22 filaments were stretched 7 times their length in a glycerin bath AN MA AAT AA (AA H01) Total at 120 C., washed well with water, tlren passed as tensioned through a boiling water bath at 100 G. and finally dried. The 3 26.213) properties of the obtained fibers are shown in table 21.
TABLE 23 Dry Wet 1n hot water at 90 C.
Elonge- Elongu- Elonga- Stren tll tion Stren th tion Strength tion (g. (1.) (percent) (g. d.) (percent) (g./d.) (percent) 36 2. 62 8 2. 52 25. (i l. 28 42. U 37 2. 23 27. 6 2. 09 29. 1 0. 87 73. 2
TABLE 21 Dry Wet In hot water at 90 C.
Elonga Elonga- Elonga- Strength tion Strength tion Strength tion (g./d.) (percent) (g./d.) (percent) (g./d.) (percent) As evident from table 21, as compared with the control EXAMPLE 1'5 fibers (No. 35), the fibers of the present invention were superior particularly in the strength and elongation in hot water at 90 C.
EXAMPLE 15 By using AN, MA, AAT and AA as monomers in various proportions and using azoisobutylonitrile as a catalyst, the
Each of the polymers obtained in. example 13 was added and dissolved with stirring into dimethyl acetamide adjusted to a pH of 1.2 with sulfuric acid, so as to produce a polymer concentration of 20 percent. The polymer solution was filtered, deaerated and then extruded through a spinnerette into an aqueous solution of 55 percent dimethyl acetamide at 20 C.
The formed filaments were washed with water, then stretched 6 times their length in boiling water at 95 to I C. and were dried. The properties of the obtained fibers are shown in table 24.
water content of 28 percent. The hydrous polymer was processed in the same manner as in example 17 to obtain fibers having a silky luster (No. 42).
For comparison, the same procedure was repeated except As evident from table 24, as compared with the control fibers (No. 39), the fibers (No. 38) of the present invention were remarkably superior particularly in the strength and elongation in hot water at 90 C.
EXAMPLE l7 Four parts of soybean protein were dissolved in 180 parts of formic acid. Then 15.5 parts of AN, 0.5 part of AAT and 0.6 part of aa-azoisobutylonitrile were added thereto and the mixture was polymerized at 60 C. under a reduced pressure for 6 hours (No. 40). Then, the resulting reaction mixture was put into 500 parts of water and was dehydrated with a centrifugal separator to obtain 23.4 parts of a hydrous polymer of a moisture content of 30 percent. This hydrous polymer was added and dissolved with stirring into an aqueous solution of 60 percent zinc chloride to obtain a solution of a polymer concentration of 8 percent. The polymer solution was filtered and deaerated and was then extruded through a spinnerette into an aqueous solution of 28 percent zinc chloride at 0 C. The formed filaments were washed with water, then stretched l times their length in steam at l C. and were dried to obtain fibers having a silky luster.
The same procedure was repeated except that AAT was not added (No. 41).
The properties of the fibers thus obtained are shown in table that AAT was not added (No. 43).
The properties of the fibers thus obtained are shown in table 26.
As evident from table 26, as compared with the control fibers (No. 43), the fibers (No. 42) of the present invention were remarkably superior particularly in their strength and elongation in hot water at 90 C.
EXAMPLE l9 Five parts of corn protein were added to 80 parts of dimethyl formamide adjusted to a pH of 2.0 with phosphoric acid and were dissolved therein with stirring at the room temperature. Then, to this solution were added 14.85 parts of AN and 0.l5 part of ATT and, as catalysts, 0.006 part of cupric nitrate and 0.225 part of potassium persulfate. The mixture was polymerized with stirring in a nitrogen gas current for 5 hours (No. 44). The polymerization conversion rate was 94.3 percent.
The same procedure was repeated except that AAT was added in an amount of 3.0 percent based on the total monomers (No. 45) and that no AAT was added (No. 46).
Each of the three polymer solutions was extruded through a spinnerette into a hot air spinning tube at 200 to 250 C. and the formed filaments were taken at a velocity of 1 l0 m./min. The filaments were then stretched 5 times their length in hot 25. water at 100 C. and were dried to obtain fibers having a silky TABLE 25 Dry Wet In hot water at 90 C.
Elonga- Elonga- Elonga- Strength tlon Strength tion Strength tion (g.s/d.s) (percent) (g.s/d.s) (percent) (g.s/d.s) (percent) No.:
TABLE 27 Dry Wet ln hot water at 90 C.
Elonga- Elonga- Elonga- Strength tion Strength tlon Strength tion (g.s/d.'s) (percent) (g.s/d.s) (percent) (g.s/d.s) (percent) As evident from table 25, as compared with the control fibers (No. 41), the fibers (No. 40) of the present invention were remarkably superior particularly in their strength and elongation in hot water at 90 C.
EXAMPLE 18 Four parts of cow milk casein were dissolved in 190 parts of an aqueous solution of percent urea adjusted to a pH of 6.01 with hydrochloric acid. To this solution were added 15.5 parts of AN, 0.5 part of ATT and 1 part of a,a-azoisobutylonitrile. The mixture was polymerized at C. for 6 hours (No. 42). Then the polymer precipitate was centrifugally separated, washed with water adjusted to a pH of 6 and was luster. The properties of the fibers thus obtained are shown in table 27.
As evident from table 27, as compared with the control EXAMPLE 20 A polymer solution obtained in the same manner as in example l was extruded through a slit l.5 mm. wide and l m. long into an aqueous solution of 35 percent zinc chloride at 0 C. and was made to slide down, while being slowly coagulated dehydrated to obtain 21.7 parts of a hydrous polymer of a at a velocity of IO m./min., on a flat plate inclined by 15 771 degrees within coagulating bath. Then, the coagulated film rated monomer containing a group selected from the was transferred to a water-washing bath, and was then class consisting of amin imin an hydroxyl gr p stretched 5 times their length in one direction in hot water to glycidyl groups, pyridyl, pyrazinyl groups and quinolyl obtain a stretched transparent film (No. 47). groups and (d) protein and mixtures of (c) and (d) and In the same manner films were prepared from the polymer 5 extruding an acidic solution of the polymer in the forms wherein the amount of AAT was 3.0 percent based on the of filaments into an acid or neutral coagulating bath or total amount of the monomers (No. 48) and also from the a hot almosphere' Stremhlng the formed filaments polymer not t i i at (N() 49), 9 wherein cross-linkage is caused to occur in the filaments The physical properties in the stretching direction of the dunng or after the.stretchm.g' films are Shown in table 28 lo 2. A process according to claim 1 wherein the polymeriza- TABLE 28 Dry Wet In hot water at 90 0.
Tensile Elonga- Tensile Elonga- Tensile Elongastrength tion strength tion strength tion Shrinkage (kg/111. (percent) (kg/ml) (percent) (kg/m2) (percent) (percent) 3. 18 22 2. 68 24 O. 9 40 4. 2 3. 33 19 3. 23 l. 3 83 1. l 2. 72 24 2. 46 26 0. 4 99 8. 0
As evident from table 28, as compared with the control film tion of monomers (a) and (b) takes place in the presence of a (No. 49), the films of the present invention (Nos. 47 and 48) 'protein selected from the group consisting of cow milk casein, were remarkably superior particularly in the strength, elongayeast protein, gelatin, corn protein, soybean protein, tlon and shrinkage in hot water at 90 C. 25 cyanoethylated protein or carbamylethylated protein.
3. A process as claimed in claim 1 wherein the polymeriza- EXAMPLE 21 ble unsaturated monomer having halogenated s-triazinyl Films were formed under the same conditions as in example group l"9' f? except that polymer solutions obtained in the same manner lymiy'aghlomis'mazme z'w'vlnylamlmij)'4''dlchlor9's' as in example 7 were used. The physical properties of the films F aery oyloxyeithylene zlmmodl6'(llclilro-s'mazm? in the stretching direction are shown in table 29 wherein Nos. T z g g. is l or 24pm 50 to 53 correspond respectively to Nos. 1 5 to 18 in table 7. p enoxy) lc oro'smazme' TABLE 29 Dry Wet In hot water at 90 C.
Tensile Elon a- Tensile Elon e- Tensile Elongastrength t on strength t on strength tion Shrinkage (kg/m!) (percent) (kg/m!) (percent) (kg/m!) (percent) (percent) As evident from table 29, as compared with the control 4. A process according to claim 1 wherein the polymerizafilms (Nos. 52 and 53), the films of the present invention ble unsaturated monomer having halogenated pyrimidinyl (Nos. and 51) were remarkably superior particularly in the group is 2-allylamino-4,6-dichloropyrimidine, 2-amino-4-alstrength, elongation and shrinkage in hot water at 90 C. lyloxy-6chloropyrimidine, 2-( p vinylanilino)-4,6- What is claimed is: dichloropyrimidine, OO-acryloyloxyethylene amino-4,6- 1. A process for producing acrylic fibers characterized by dichloropyrimidine, 2-vinyloxyethylene amino-4,6- polymerizing, in an acidic medium, (a) a vinyl monomeric 50 dichloropyrimidine or 2-(p-vinylphenoxy)-4,6- material consisting mainly of acrylonitrile and (b) a dichloropyrimidine. polymerizable unsaturated monomer having a group selected 5. A process according to claim 1 wherein the protein is f h class consisting f h l d i i groups f selected from the class consisting of natural proteins, modified the general formula: proteins and synthetic proteins.
55 6. A process according to claim 1 wherein the polymeriza- Xl ble unsaturated monomer having a group containing active N l hydrogen, a group capable of forming active hydrogen, a N pyridyl group, pyrazinyl group or quinolyl group is ailylamine,
methallylamine, allylmethylamine, allylethylamine, l-(N- X2 ethylamino)-3-butene, ,B-aminoethyl acrylate, ,B-aminoethyl mHhfimMWm' methacrylate, fl-(N-methylamino)ethyl acrolate, B-(N- and halogenated pyrimidinyl groups of the general formula: ethylamlno) ethyl ylate, B'( l' methacrylate, B-(Nethylamino)ethyll methacrylate, p-
aminostyrene, allyl alcohol, -aminoethyl methallyl alcohol, 3-
f butene-l-Ol, 3-butene2-ol, 4-pentene-2-ol, B-hydroxyethyl N acrylate, B-hydroxyethyl methacrylate, glycidyl methacrylate,
glycidyl acrylate, ethylene glycol monovinyl ether. diethylene i glycol monovinyl ether, 2,3-dihydroxypropyl methacrylate, l-
methacryloyl-D-glucose, l-o-methacryloyl-D-galactose, 6-0- wherein each f X, n X is a halogen, hydrogen. alkyl methacryloyl-D-galactose, Z-N-methacryloyl glucosamine, 1- group, amino group, hydroxyl group, mercapto group, or acrylamide-l-dioxy-glucitol, l-o-p-vinylphenyl glucose, pcarboxyl group, and wherein at least one of X and X hydroxystyrene, vinyl pyridine, 2-methyl-5-vinyl pyridine, must be a halogen, in the presence of a material selected vinyl pyrazine, or 2-vinyl-quinoline.
from the group consisting of(c)apolymerizable unsatu- 7. A process according to claim 1 wherein the vinyl component havin a group containing active lydrogen, a group capable of ormmg active hydrogen, a pyrl yl group, a
pyrazinyl group or a quinolyl group is 0.3 to l percent by weight on the polymer.
11. A process according to claim 1 wherein the acidic medium is an aqueous solution of more than 40 percent by weight zinc chloride.
12. A process according to claim 1 wherein said acidic medium is dimethyl sulfoxide, dimethyl formamide, ethylene carbonate, an aqueous solution of ethylene carbonate, deoxygenated water, a concentrated aqueous solution of urea, or formic acid, all being adjusted to a pH not higher than 6.
13. A process according to claim 1 wherein the coagulating bath is adjusted to a pH not higher than 6.
14. A process according to claim 1 wherein the stretching is conducted in heated steam, hot water or a hot bath containing sodium sulfate, after an acidic substance in the fibers or films has been removed by washing.
t t l

Claims (13)

  1. 2. A process according to claim 1 wherein the polymerization of monomers (a) and (b) takes place in the presence of a protein selected from the group consisting of cow milk casein, yeast protein, gelatin, corn protein, soybean protein, cyanoethylated protein or carbamylethylated protein.
  2. 3. A process as claimed in claim 1 wherein the polymerizable unsaturated monomer having halogenated s-triazinyl group is 2-allylamino-4,6-dichloro-s-triazine, 2-amino-4-allyloxy-6-chloro-s-triazine, 2-(p-vinylanilino)-4,6-dichloro-s-triazine, 2-acryloyloxyethylene amino-4,6-dichloro-s-triazine, 2-vinyloxyethylene amino-4,6-dichloro-s-triazine or 2-(p-vinylphenoxy)-4,6-dichloro-s-triazine.
  3. 4. A process according to claim 1 wherein the polymerizable unsaturated monomer having halogenated pyrimidinyl group is 2-allylamino-4,6-dichloropyrimidine, 2-amino-4-allyloxy-6chloropyrimidine, 2-(p-vinylanilino)-4,6-dichloropyrimidine, 2-acryloyloxyethylene amino-4,6-dichloropyrimidine, 2-vinyloxyethylene amino-4,6-dichloropyrimidine or 2-(p-vinylphenoxy)-4,6-dichloropyrimidine.
  4. 5. A process according to claim 1 wherein the protein is selected from the class consisting of natural proteins, modified proteins and synthetic proteins.
  5. 6. A process according to claim 1 wherein the polymerizable unsaturated monomer having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, pyrazinyl group or quinolyl group is allylamine, methallylamine, allylmethylamine, allylethylamine, 1-(N-ethylamino)-3-butene, Beta -aminoethyl acrylate, Beta -aminoethyl methacrylate, Beta -(N-methylamino)ethyl acrylate, Beta -(N-ethylamino) ethyl acrylate, Beta -(N-methylamino)ethyl methacrylate, Beta -(N-ethylamino)ethyl methacrylate, p-aminostyrene, allyl alcohol, methallyl alcohol, 3-butene-1-o1, 3-butene-2-ol, 4-pentene-2ol, Beta -hydroxyethyl acrylate, Beta -hydroxyethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, 2,3-dihydroxypropyl methacrylate, 1-o-methacryloyl-D-glucose, 3-o-methacryloyl-D-glucose, 6-o-methacryloyl-D-glucose, 1-o-methacryloyl-D-galactose, 6-o-methacryloyl-D-galactose, 2-N-methacryloyl glucosamine, 1-acrylamide-1-dioxy-glucitol, 1-o-p-vinylphenyl glucose, p-hydroxystyrene, vinyl pyridine, 2-methyl-5-vinyl pyridine, vinyl pyrazine, or 2-vinyl-quinoline.
  6. 7. A process according to claim 1 wherein the vinyl monomeric material contains at least 70 percent by weight acrylonitrile.
  7. 8. A process according to claim 1 wherein the content of the unsaturated monomer component having a group selected from halogenated s-triazinyl group and halogenated pyrimidinyl group in the resulting polymer is 0.03 to 10 percent by weight.
  8. 9. A process according to claim 1 wherein the content of the protein in the resulting acrylic polymer is 5- 50 percent by weight.
  9. 10. A process according to claim 1 wherein the content, in the resulting Acrylic polymer, of said unsaturated monomer component having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or a quinolyl group is 0.3 to 10 percent by weight on the polymer.
  10. 11. A process according to claim 1 wherein the acidic medium is an aqueous solution of more than 40 percent by weight zinc chloride.
  11. 12. A process according to claim 1 wherein said acidic medium is dimethyl sulfoxide, dimethyl formamide, ethylene carbonate, an aqueous solution of ethylene carbonate, deoxygenated water, a concentrated aqueous solution of urea, or formic acid, all being adjusted to a pH not higher than 6.
  12. 13. A process according to claim 1 wherein the coagulating bath is adjusted to a pH not higher than 6.
  13. 14. A process according to claim 1 wherein the stretching is conducted in heated steam, hot water or a hot bath containing sodium sulfate, after an acidic substance in the fibers or films has been removed by washing.
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