US3776994A - Method of manufacturing polyvinyl alcohol fiber of improved property - Google Patents

Method of manufacturing polyvinyl alcohol fiber of improved property Download PDF

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Publication number
US3776994A
US3776994A US00202384A US3776994DA US3776994A US 3776994 A US3776994 A US 3776994A US 00202384 A US00202384 A US 00202384A US 3776994D A US3776994D A US 3776994DA US 3776994 A US3776994 A US 3776994A
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acid
fiber
mol
spinning
polyvinyl alcohol
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US00202384A
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A Mizobe
Y Yoshioka
S Kobayashi
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Kuraray Co Ltd
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Kuraray Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

Definitions

  • polyvinyl alcohol fibers are improved by spinning polyvinyl alcohol containing boric acid or a borate into an alkaline spinning bath containing a conventional dehydrating salt and an additive comprising 4X10 to 9 x10 mol/l. of (a) an aminopolycarboxylic acid, or (b) a condensed phosphoric acid, or (c) a salt, e.g., sodium or potassium or ammonium salts of (a) or (b).
  • the present invention relates to a method of wet spinning polyvinyl alcohol (hereinafter abbreviated as PVA) fiber that contains boric acid or a borate and to spinning and manufacturing with high stability a 'PVA fiber of high strength and high modulus.
  • PVA polyvinyl alcohol
  • a PVA fiber can be produced by spinning a PVA spinning solution containing boric acid or a borate into an alkaline coagulation bath.
  • a fiber is formed by the PVA spinning solution making a gelatinizing reaction with the alkaline ingredients of the coagulation bath, a dehydro-coagulating reaction with the salt, and a cross linking reaction between PVA and boric acid in the fiber.
  • the spinning method of the type described above has been known for some time, and basic studies have been extensively made of the method. Accordingly, it is reported that the method can now provide a fiber of improved properties, but nevertheless it is certain that spinnability difficulties and instability of quality of the fibers have constituted some of the reasons that have so far hampered the industrial application of the method.
  • the present inventors in an effort to inquire into the factors causing instability of spinnability and properties of the fibers, particularly in conjunction with changes in the properties and the spinnability with the lapse of time, have found that scales adhered adjacent to the spinning nozzle holes form a main factor in the problem, and they have further found that the scales comprise metal salts such as iron and calcium salts.
  • the method of the present invention is the one of producing a PVA fiber of improved property by spinning of a PVA spinning solution containing boric acid or borate into an alkaline coagulation bath containing 4x10 to 9X10 mol/l. of a compound selected from aminopolycarboxylic acid or sodium and potassium salts (hereinafter abbreviated as salts thereof), and condensed phosphoric acid or sodium, potassium and ammonium salts (hereinafter abbreviated as salts thereof).
  • the formation of scales is completely prevented by spinning in the presence of 4X 10* to 9 x 10- mol/l. of a compound selected from aminopolycarboxylic acid or its salts, and condensed phosphoric acid or its salts in an alkaline coagulation bath.
  • the spinnability is highly stabilized with the result that the fiber obtained is entirely free from deterioration in quality due to lapse of time and has become well adapted for production on an industrial basis.
  • spinnability of the spinning solution got worse as time passed after the start of spinning, and the fiber obtained also has poor properties and the service life of the nozzle was at most less than five days.
  • the present invention makes it possible to spin with stabilized effectiveness for more than fifteen days, and also deterioration in the properties of the fiber obtained due to time lapse in the meantime is prevented.
  • the method of the present invention could produce a fiber far superior in such properties as strength, and initial modulus t0 the fiber produced from a coagulation bath to which aminopolycarboxylic acid, condensed phosphoric acid or a salt of either of these acids was not added.
  • the PVA used in the invention has a degree of polymerization of more than 500 and a degree of saponification of more than 98% (mol), preferably more than 99% (mol).
  • the spinning solution has a PVA concentration of preferably 10-30% by weight of aqueous solution, contains 0.55% by weight of boric acid or borate, and has a pH of 3.56.
  • the coagulation bath into which the PVA spinning solution is spun is an aqueous solution containing 5-200 g./l. of caustic alkali and 100 g./1. saturating concentration of a salt capable of dehydration in addition to aminopolycarboxylic acid, condensed phosphoric acid or salt thereof.
  • a salt capable of dehydration in addition to aminopolycarboxylic acid, condensed phosphoric acid or salt thereof.
  • sodium hydroxide or potassium hydroxide is used as caustic alkali
  • sodium sulfate, ammonium sulfate, sodium carbonate is used as the salt being capable of dehydration.
  • aminopolycarboxylic acid or its salts used in the invention are ethylenediaminetetraacetic acid and its mono-, di-, trior tetra-sodium salts or mono-, di-, tri-, or tetra-potassium salts and nitrilotriacetic acid and its mono-, di-, or tri-sodium salts, and mono-, di-, or tripotassium salts.
  • Another class of useful condensed phosphoric acids comprise polymetaphosphoric acids having a general formula of (HPO wherein n is 3-10, and preferred examples are trimetaphosphoric acid (11:3), tetrametaphosphoric acid (11:4), hexametaphosphoric acid (11:6), and salts thereof.
  • a further class of useful condensed phosphoric acids comprises ultraphosphoric acids having a general formula of xH O-yP O wherein x/y is greater than and less than 1, and preferred examples are 2H O-3P O
  • the novel additive compound is added to a coagulation bath in the form of the acid or salt thereof and it is especially important to maintain its concentration within the specific range of 4X10- 9 10- mol/l. as shown in the following examples.
  • salt when used in reference to a salt of aminopolycarboxylic acid or of a condensed phosphoric acid is used in a broad sense to include a chelate compound, and thus this term includes a salt of an aminopolycarboxylic acid or of a condensed phosphoric acid with a metal having a smaller chelate formation constant than magnesium ion.
  • salts of sodium, potassium, and silver which are smaller in chelate formation constant than magnesium are included within this definition, and salt of iron, calcium, and copper which have larger chelate formation constants than magnesium are not included within this definition.
  • the concentration of either aminopolycarboxylic acid, or condensed phosphoric acid, or salts of the above in the coagulation bath is 4X to 9 10- mol/1., preferably 1.7 10- to 1.7 10- mol/l.
  • spinning of a PVA spinning solution containing boric acid or borate into an alkaline coagulation bath containing aminopolycarboxylic acid, condensed phosphoric acid or salts thereof can be carried out in accordance with an ordinary wet spinning method.
  • the fibers obtained can be further subjected to neutralization with acid, washing with water, drying, drawing, heat treatment and acetalizing treatment.
  • the PVA fiber obtained by the invention has excellent strength and initial modulus particularly at high temperatures, and is especially well suited for use as an industrial material in making tires and belts that are used under severe conditions.
  • Dry breaking tenacity This is a value of a sample fiber 20 cm. long being twisted 8 turns/ 10 cm. then dried for 3 hours at 105 C., measured in accordance with the Japanese Industrial Standards L 1070 by a tensile testing machine (constant rate of extension type) in which an elastie film (Lycra film made by Du Pont Company) is stuck to the jaw face of a chuck, and drawing the sample at a drawing speed of 10 cm. per minute.
  • Initial modulus This is a value measured on the basis of the stress-strain curve obtained by measuring the foregoing dry breaking tenacity in accordance with Japanese Industrial Standards L 1073. When the measurement is made at normal temperature, it is made in a room maintained at 20 C. and when the measurement is made at high temperatures, it is made by setting an electric heater so that the upper and lower chucks and the sample are maintained at C.
  • Example 1 A hundred kg. of PVA having a polymerization degree of 1,700 and a saponification degree of 99.9 mol percent were dissolved in water to obtain an aqueous solution containing 16 weight percent of PVA, and a spinning solution was prepared from the aqueous solution by adding 2.5 kg. of boric acid (2.5% by weight to PVA), and tartaric acid so as to obtain a pH of 4.5.
  • This spinning solution was extruded into a coagulation bath through a nozzle having 1000 holes each 0.06 mm. in diameter at an extrusion rate of 150 g. per minute and the product was removed from the bath at a speed of 8 111. per minute.
  • the coagulation bath contained 100 g./l. of sodium hydroxide, 150 g./l. of sodium sulfate, and 3.4 10 mol/l. of disodium ethylenediamine tetraacetate measured by titration with magnesium chloride.
  • the spun fiber was drawn with rollers at a ratio of 100%, thereafter sodium hydroxide adhered to the fiber was neutralized with sulfuric acid. Then the resulting fiber was wet hot drawn at a ratio of 100%, washed with water, dried, dry hot-drawn at a ratio of 250%, heat treated, taken up, and thereafter the properties of the fiber were measured.
  • Example 1 Aside from the fact that no disodium ethylenediamine tetraacetate was added to the coagulation bath, the treatment was essentially the same as that of Example 1. The results of Example 1 and Control Example 1 are shown in Table I and FIG. 1.
  • Examples 2-5 and Control Examples 2-3 A hundred kilograms of PVA having a polymerization degree of 1750 and a saponification degree of 98.5% were dissolved in water to obtain an 18% by weight aqueous solution, and a spinning solution was prepared by adding to the above solution 2.0 kg. of boric acid (2.0% by weight to PVA) and tartaric acid to obtain a pH of 4.0.
  • This spinning solution was spun through a nozzle having 800 holes each 0.10 mm. in diameter at an extrusion rate of g./min. into an aqueous coagulation bath to which 10 g./l. of sodium hydroxide, 500 g./l. of ammonium sulfide, and tetrasodium ethylenediamine tetra acetate were added, and the resulting fiber was removed from the bath at a speed of 8 m. per minute.
  • the concentration of ethylenediamine tetraacetate that can be quantitatively determined by magnesium chloride was 7 10- mol/l. (Example 2), 1.7 10 mol./l. (Example 3), 1.7 10- mol./l. (Example 4), 5x10" mol./l. (Example 2 1-0- mol/l. (Control Example 2) and 12 10- mol/l. (Control Example 3).
  • the spun fiber was subjected to a drawing ratio of 100% by rollers, and thereafter the adhered sodium hydroxide was neutralized. Then the resulting fiber was wet hot-drawn by 100%, washed with water, dried, and then dry hot drawn by 250%, heat treated and taken up on a bobbin.
  • Example 6 Instead of using disodium ethylenediamine tetraacefate in the coagulation bath as in Example 1, trisodium nitrilotriacetate was added in an amount of 3.4 10- mol/l. measured by the titration with magnesium chloride. The treatment was otherwise essentially the same as that of Example 1. The results of the spinning thus effected are shown in Table III.
  • Control Example 4 Aside from the fact that the concentration of 3.4x l0" mol/l. of the trisodium nitrilotriacetate in Example 6 was substituted by 12 10- mol/1., spinning was carried out under the same conditions as in Example 6. The results obtained are shown in Table III in comparison with the results of Example 6.
  • Example 7 100 kg. of PVA having a polymerization degree of 1,700 and a saponification degree of 99.9 mol percent were dissolved in water to form an aqueous solution containing 16 weight percent of PVA, and a spinning solution was prepared from the aqueous solution by adding 2.5 kg. of boric acid (2.5% by weight to PVA) and tartaric acid in an amount to obtain a pH of 4.5.
  • This spinning solution was extruded into a coagulation bath through a nozzle having 1000 holes each 0.06 mm. in diameter at an extrusion rate of 150 g./min., and removed from the bath at a speed of 8 ml. per minute.
  • the coagulation bath contained 100 g./l.
  • the spun fiber was drawn with rollers at a ratio of 100%. Thereafter, the sodium hydroxide adhered to the fiber was neutralized with sulfuric acid. Then the resulting fiber was wet hot-drawn at a ratio of washed with water, dry hot-drawn at a ratio of 250%, heat treated, taken up on a bobbin. Thereafter the properties of the fiber were measured.
  • Example 5 Aside from the fact that no triphosphoric acid was added to the coagulation bath, the treatment was essen tially the same as that of Example 7. The results of Example 7 and Control Example 5 are shown in Table IV:
  • Examples 8-11 and Control Examples 6-7 100 kg. of PVA having a polymerization degree of 1750 and a saponification degree of 98.5% was dissolved in water to obtain an aqueous solution containing 18 wt. percent PVA, and a spinning solution was prepared from the aqueous solution by adding 4.0 kg. of boric acid (4.0% by weight to PVA) and suflicient tartaric acid to bring the pH to 4.0.
  • This spinning solution was extruded into a coagulation bath through a nozzle having 800 holes each 0.10 mm. in diameter at an extrusion rate of g./min., and the fibers were removed from the bath at a. speed of 8 m. per minute.
  • the coagulation bath contained 10 g./l.
  • Example 12 Instead of using triphosphoric acid in the coagulation bath as in Example 7, sodium hexametaphosphate was added to the bath in an amount of 3.4 10- mol/1., and spinning was carried out under the same conditions as in Example 7. The results obtained are shown in Table VI.
  • Dr('y llreaking tenacity at room temperature 1st day 4th day.- 7th day th day.
  • the improvement comprising improving the spinnability of said spinning solution and producing a polyvinyl alcohol fiber having increased strength and initial modulus by wet-spinning said spinning solution into a coagulating bath consisting essentially of, in addition to said (a) and (b), from about 4X10 to 9 l0- mole/liter of solution of a compound selected from the group consisting of an aminopolycarboxylic acid, a condensed phosphoric acid and salts thereof.
  • a method according to claim 1, wherein said compound is selected from the group consisting of ethylenediaminetetraacetic acid and its mono-, di-, trior tetrasodium salts or mono-, di-, trior tetra-potassium salts; nitrilotriacetic acid and its mono-, di-, or tri-sodium salts, and mono-, di-, or tri-potassium salts; and trimethylenediaminetetraacetic acid, methylaminediacetic acid, or 1,2- cyclohexylaminetetraacetic acid, and their sodium or potassium salts.
  • salts of said compound are the sodium, potassium or ammonium salts thereof.
  • a method according to claim 2, wherein said compound is selected from the group consisting of: (1) polyphosphoric acids of the formula H P O wherein n is 2-100; (2) polymetaphosphoric acids of the formula (HPO wherein m is 3-10; (3) ultraphosphoric acids of the formula xH O-yP O wherein x/y is greater than 0 but less than 1; and (4) the sodium, potassium or ammonium salts thereof.
  • polyvinyl alcohol has a degree of polymerization of more than 500 and a degree of saponification of more than 98 mole percent.
  • a method according to claim 1 wherein the concentration of the polyvinyl alcohol in said spinning solution is from 10 to 30% by weight, based on the weight of the spinning solution, and wherein the pH of said spinning solution varies from 3.5 to 6.
  • said polyphosphoric acid is selected from the group consisting of pyrophosphoric acid wherein n is 2, triphosphoric acid wherein n is 3, tetraphosphoric acid wherein n is 4 and Grahams Salt wherein n varies from 30 to wherein said polymetaphosphoric acid is selected from the group consisting of trimetaphosphoric acid wherein m is 3, tetrametaphosphoric acid wherein m is 4 and hexametaphosphoric acid wherein m is 6; and wherein said x and said y in the general formula for said ultraphosphoric acid are 2 and 3, respectively.
  • alkaline compound is selected from the group consisting of sodium hydroxide and potassium hydroxide.
  • said dehydrating salt is selected from the group consisting of sodium sulfate, ammonium sulfate, and sodium carbonate.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
US00202384A 1970-11-27 1971-11-26 Method of manufacturing polyvinyl alcohol fiber of improved property Expired - Lifetime US3776994A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3987140A (en) * 1972-04-11 1976-10-19 Kuraray Co., Ltd. Method of preparing polyvinyl alcohol fibers having improved properties
US4029725A (en) * 1976-04-02 1977-06-14 Dow Badische Company Nonoxidative process for purifying aqueous inorganic salt solutions employed in the wet spinning of filamentary vinyl polymers
US4612157A (en) * 1984-01-31 1986-09-16 Kuraray Company, Limited Method for production of high-tenacity, fine-denier polyvinyl alcohol fiber
US20100059155A1 (en) * 2008-09-09 2010-03-11 Walter Kevin Westgate Pneumatic tire having a high strength/high modulus polyvinyl alcohol carcass ply
WO2018187710A1 (en) 2017-04-07 2018-10-11 North Carolina State University Additive for fiber strengthening
US12098481B2 (en) 2018-10-05 2024-09-24 North Carolina State University Cellulosic fiber processing

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3987140A (en) * 1972-04-11 1976-10-19 Kuraray Co., Ltd. Method of preparing polyvinyl alcohol fibers having improved properties
US4029725A (en) * 1976-04-02 1977-06-14 Dow Badische Company Nonoxidative process for purifying aqueous inorganic salt solutions employed in the wet spinning of filamentary vinyl polymers
US4612157A (en) * 1984-01-31 1986-09-16 Kuraray Company, Limited Method for production of high-tenacity, fine-denier polyvinyl alcohol fiber
US20100059155A1 (en) * 2008-09-09 2010-03-11 Walter Kevin Westgate Pneumatic tire having a high strength/high modulus polyvinyl alcohol carcass ply
WO2018187710A1 (en) 2017-04-07 2018-10-11 North Carolina State University Additive for fiber strengthening
CN110678515A (zh) * 2017-04-07 2020-01-10 北卡罗莱纳州立大学 用于纤维强化的添加剂
JP2020516711A (ja) * 2017-04-07 2020-06-11 ノース カロライナ ステイト ユニヴァーシティ 繊維強化のための添加剤
EP3606994A4 (en) * 2017-04-07 2021-01-06 North Carolina State University ADDITIVE FOR FIBER REINFORCEMENT
US11560461B2 (en) 2017-04-07 2023-01-24 North Carolina State University Additive for fiber strengthening
US12098481B2 (en) 2018-10-05 2024-09-24 North Carolina State University Cellulosic fiber processing

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DE2158501A1 (de) 1972-06-22
NL7116126A (enrdf_load_stackoverflow) 1972-05-30

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