US2909502A - Method of producing vinyl alcohol polymer fibers and products thereof - Google Patents

Method of producing vinyl alcohol polymer fibers and products thereof Download PDF

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Publication number
US2909502A
US2909502A US511408A US51140855A US2909502A US 2909502 A US2909502 A US 2909502A US 511408 A US511408 A US 511408A US 51140855 A US51140855 A US 51140855A US 2909502 A US2909502 A US 2909502A
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Prior art keywords
vinyl alcohol
water
fibers
alcohol
products
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Expired - Lifetime
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US511408A
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Matsumoto Masakazu
Osugi Tetsuro
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kurashiki Rayon Co Ltd
Airco Inc
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Kurashiki Rayon Co Ltd
Air Reduction Co Inc
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Priority to US511408A priority Critical patent/US2909502A/en
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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
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/12—Esters of monocarboxylic acids with unsaturated alcohols containing three or more carbon atoms
    • 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
    • D01F6/34—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 alcohols, acetals or ketals as the major constituent

Definitions

  • the invention relates to the manufacture of waters'oluble filaments, fibers, yarns, threads and the like.
  • polyvinyl alcohol fibers as obtained by spinning without after-treatment, are more or less water soluble. However, they have not sufficient strength to be useful for textile purposes and other industrial applications.
  • fibers which are soluble in water of 50 C. and below and have the strength required for textile manipulations are obtained from conjoint polymers of vinyl alcohol and allyl alcohol.
  • Such copolymers are best obtained by the saponification of the copolymers of organic vinyl esters with allyl esters or allyl alcohol.
  • Suitable esters are the esters of lower aliphatic acids, particularly of acetic acid, but the esters of formic acid, propionic acid, butyric acid and the like may also be used.
  • Such conjoint esters are readily prepared and saponified by conventional procedures.
  • the obtained polyvinyl alcohol-allyl alcohol copolymer dissolves in cold water and can be spun by the usual wet and dry spinning methods. In wet spinning, concentrated solutions with above two thirds of the saturated solubility of the coagulating salts, such as sodium sulphate or ammonium sulphate,
  • Patented Oct. 20, 1959 2 In wet spinning, a high allyl alcohol content of the conjoint polymer may atfect the speedy coagulation in a conventional spinning bath.
  • a preferred embodiment of the invention consists, therefore, in spinning together mixthe required minimum DP of the copolymer and its mixture with the homopolymer must be used above 250.
  • the table shows that in order to be soluble in water of 50 C. and below, the fibers must contain an allyl alcohol content of at least about 2 mole percent.
  • the upper limit is about 10 mol percent, as with higher proportions of allyl alcohol the tenacity of the fibers decreases to such an extent that the fibers are no longer suitable for textile purposes.
  • the optimum content will be about 2.5 to 5 mol percent of allyl alcohol.
  • fibersprepared from such mixtures have the required tenacity and water solubility.
  • the novel fibers are useful for specialty sewing threads, alone -or together with other fibers to obtain in woven material eifects which cannot be produced by other means. Twisted with cotton or nylon fibers, a sewing thread can be made which will shrink to a predetermined degree and When the novel fibers are twisted with a fully synthetic thermoplastic fiber, such as nylon, Dacron, and the like, a permanent twist can be applied to said thermoplastic fibers by first setting the twist and then washing out the polyvinyl alcohol-allyl alcohol fiber, thereby producing a permanently elastic fiber. Fabrics produced from the novel fiber are, for instance, useful for the manufacture of water soluble parachutes. As will be seen from the foregoing, the novel fiber opens up a vast field of new applications; for instance, in the manufacture of filter cloth, lace, knitted fabrics, and the like, effects can be obtained which cannot be produced by other means.
  • Example 1 291 parts of vinyl acetate and 9 parts of allyl acetate were mixed and polymerized in the presence of 0.6 part of benzoyl peroxide. After an about 5.0% polymerization was obtained, 100 parts of methanol were slowly added, and the polymerization was continued until after 20 hours, a polymer yield of was obtained. The copolymer was freed from unreacted monomers, dissolved in methanol and cold sa-ponified by adding a methanol solution of caustic soda to the methanol solution of the polymer. The polyvinyl alcohol-vinyl alcohol copolymer was obtained as a white powder containing 3 mol percent of allyl alcohol and having a DP of 1160.
  • the copolymer was dissolved in water to a 13% solution, which was spun into a saturated solution of Glauber salt.
  • the obtained white fibers had a tenacity of 3.3 g./d. and dissolved instantaneously in water of 23 C.
  • Example 2 A vinyl alcohol-allyl alcohol copolymer was prepared according to the procedure set forth in Example 1. It contained 4.4 mol percent of allyl alcohol, had an average DP of 700, and was soluble in water at 14 C. 60 parts of said copolymer were mixed with 40 parts of vinyl alcohol homopolymer having an average DP of 1630 and a saponification degree of 99.8, which was soluble in water at 70 C. The mixture was dissolved in water to a 15% solution, using the method described in Patent No. 2,642,333. The obtained fiber had, after drying, a tenacity of 3.0 g./d. and was soluble in water at 30 C.
  • Example 3 A 6% aqueous solution of a vinyl alcohol allyl-alcohol copolymer containing 3 mol percent of allyl alcohol and having an average DP of 930 was spun to filaments by extruding the solution through a spinneret into a column of hot air of l10120 C.
  • the solidified filaments had a tenacity of 1.5 g./ d. and Were soluble in Water at 22 C.
  • a fiber soluble in water at 50 C. and having a tenacity of at least about 1.5 g./d. comprising a vinyl alcohol-allyl alcohol copolymer containing 2 to 10 mol percent of allyl alcohol.

Description

United States Patent IVIETHOD OF PRODUCING VINYL ALCOHOL POLYMER FIBERS AND PRODUCTS THEREOF Masakazu Matsumoto, Masayasu Maeda, and Tetsuro Osugi, Kurashiki-shi, Japan, assignors, by direct and mesne assignments, of three-fourths to Kurashiki Rayon (30., Ltd., Kurashiki-shi, Japan, a corporation of Japan, and one-fourth to Air Reduction Company, gfnctirporated, New York, N.Y., a corporation of New No Drawing. Application May 26, 19-55 Serial No. 511,408
. 3 Claims. 01. rat-"45.5
The invention relates to the manufacture of waters'oluble filaments, fibers, yarns, threads and the like.
It is known that polyvinyl alcohol fibers as obtained by spinning without after-treatment, are more or less water soluble. However, they have not sufficient strength to be useful for textile purposes and other industrial applications.
It is a principal object of the invention to provide a fiber on polyvinyl alcohol basis, which is useful as a textile fiber.
It is another object of the invention to provide a method for preparing water soluble fibers on polyvinyl alcohol basis which have increased mechanical strength.
Other objects and advantages will be apparent from a consideration of the specification and claims.
According to the invention, fibers which are soluble in water of 50 C. and below and have the strength required for textile manipulations are obtained from conjoint polymers of vinyl alcohol and allyl alcohol. Such copolymers are best obtained by the saponification of the copolymers of organic vinyl esters with allyl esters or allyl alcohol. Suitable esters are the esters of lower aliphatic acids, particularly of acetic acid, but the esters of formic acid, propionic acid, butyric acid and the like may also be used. Such conjoint esters are readily prepared and saponified by conventional procedures. The obtained polyvinyl alcohol-allyl alcohol copolymer dissolves in cold water and can be spun by the usual wet and dry spinning methods. In wet spinning, concentrated solutions with above two thirds of the saturated solubility of the coagulating salts, such as sodium sulphate or ammonium sulphate,
Patented Oct. 20, 1959 2 In wet spinning, a high allyl alcohol content of the conjoint polymer may atfect the speedy coagulation in a conventional spinning bath. A preferred embodiment of the invention consists, therefore, in spinning together mixthe required minimum DP of the copolymer and its mixture with the homopolymer must be used above 250.
must be used. The cold water solubility of the obtained Mol percent Allyl Al hol co 0 0.5 0.9 1. 8 2. 2 2. 6 3 3. 5 4.4 Dissolving Temp., O. 70 61 54 30 23 20 17 14 Tenacity, g./d 3.4 3.3 2.5 2.0 3.0 3.0 2.0 2.5 2.9
The table shows that in order to be soluble in water of 50 C. and below, the fibers must contain an allyl alcohol content of at least about 2 mole percent. The upper limit is about 10 mol percent, as with higher proportions of allyl alcohol the tenacity of the fibers decreases to such an extent that the fibers are no longer suitable for textile purposes. Generally, the optimum content will be about 2.5 to 5 mol percent of allyl alcohol.
prevent the obnoxious puckering of seams.
Also, fibersprepared from such mixtures have the required tenacity and water solubility.
The novel fibers are useful for specialty sewing threads, alone -or together with other fibers to obtain in woven material eifects which cannot be produced by other means. Twisted with cotton or nylon fibers, a sewing thread can be made which will shrink to a predetermined degree and When the novel fibers are twisted with a fully synthetic thermoplastic fiber, such as nylon, Dacron, and the like, a permanent twist can be applied to said thermoplastic fibers by first setting the twist and then washing out the polyvinyl alcohol-allyl alcohol fiber, thereby producing a permanently elastic fiber. Fabrics produced from the novel fiber are, for instance, useful for the manufacture of water soluble parachutes. As will be seen from the foregoing, the novel fiber opens up a vast field of new applications; for instance, in the manufacture of filter cloth, lace, knitted fabrics, and the like, effects can be obtained which cannot be produced by other means.
The following specific examples are given to illustrate the invention but they are not intended to limit it thereto; the parts are by Weight.
Example 1 291 parts of vinyl acetate and 9 parts of allyl acetate were mixed and polymerized in the presence of 0.6 part of benzoyl peroxide. After an about 5.0% polymerization was obtained, 100 parts of methanol were slowly added, and the polymerization was continued until after 20 hours, a polymer yield of was obtained. The copolymer was freed from unreacted monomers, dissolved in methanol and cold sa-ponified by adding a methanol solution of caustic soda to the methanol solution of the polymer. The polyvinyl alcohol-vinyl alcohol copolymer was obtained as a white powder containing 3 mol percent of allyl alcohol and having a DP of 1160. The copolymer was dissolved in water to a 13% solution, which was spun into a saturated solution of Glauber salt. The obtained white fibers had a tenacity of 3.3 g./d. and dissolved instantaneously in water of 23 C.
Example 2 A vinyl alcohol-allyl alcohol copolymer was prepared according to the procedure set forth in Example 1. It contained 4.4 mol percent of allyl alcohol, had an average DP of 700, and was soluble in water at 14 C. 60 parts of said copolymer were mixed with 40 parts of vinyl alcohol homopolymer having an average DP of 1630 and a saponification degree of 99.8, which was soluble in water at 70 C. The mixture was dissolved in water to a 15% solution, using the method described in Patent No. 2,642,333. The obtained fiber had, after drying, a tenacity of 3.0 g./d. and was soluble in water at 30 C.
:3 Example 3 A 6% aqueous solution of a vinyl alcohol allyl-alcohol copolymer containing 3 mol percent of allyl alcohol and having an average DP of 930 was spun to filaments by extruding the solution through a spinneret into a column of hot air of l10120 C. The solidified filaments had a tenacity of 1.5 g./ d. and Were soluble in Water at 22 C.
As various embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.
We claim:
1. A fiber soluble in water at 50 C. and having a tenacity of at least about 1.5 g./d. comprising a vinyl alcohol-allyl alcohol copolymer containing 2 to 10 mol percent of allyl alcohol.
2. A fiber soluble in water at 50 C. and having a tenacity of at least about 1.5 g./ d. consisting essentially of a mixture of a vinyl alcohol-allyl alcohol copolymer References Cited in the file of this patent UNITED STATES PATENTS 2,236,061 Izard et al. Mar. 25, 1941 2,332,896 DAlelio Oct. 26, 1943 2,424,838 Moffett'et al. July 29, 1947 2,611,754 Rudofi? Sept. 23, 1952 OTHER REFERENCES Elvanol,- copyright, 1947, E. I. du Pont, pages 37-38.

Claims (1)

  1. 2. A FIBER SOLUBLE IN WATER AT 50*C. AND HAVING A TENACITY OF AT LEAST ABOUT 1.5 G./D. CONSISTING ESSENTIALLY OF A MIXTURE OF A VINYL ALCOHOL-ALLYL ALCOHOL COPOLYMER WITH VINYL ALCOHOL HOMOPOLYMER AND CONTAINING 2 TO 10 MOL PERCENT OF ALLYL ALCOHOL.
US511408A 1955-05-26 1955-05-26 Method of producing vinyl alcohol polymer fibers and products thereof Expired - Lifetime US2909502A (en)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3211685A (en) * 1959-03-20 1965-10-12 Kurashiki Rayon Co Production of polyvinyl alcohol having improved dyeability and composition therefor including polyvinyl alcohol basic nitrogen-containing derivatives
US3548031A (en) * 1967-10-21 1970-12-15 Kuraray Co Shapable polyvinyl alcohol composition
US5019609A (en) * 1988-08-02 1991-05-28 Aicello Chemical Co., Ltd. Films easily soluble in cold water
US5070126A (en) * 1988-08-02 1991-12-03 Aicello Chemical Co., Ltd. Films easily soluble in cold water
FR2675161A1 (en) * 1991-04-10 1992-10-16 Isolyser Co METHOD FOR REMOVING CLOTHING ARTICLES IN A SOLUBLE ETOFFE IN HOT WATER
US5238995A (en) * 1990-01-22 1993-08-24 Kuraray Company Limited Polyvinyl alcohol fiber
US5470653A (en) * 1994-08-05 1995-11-28 Isolyser Company, Inc. Disposable mop heads
US5620786A (en) * 1993-04-29 1997-04-15 Isolyser Co. Inc. Hot water soluble towels, sponges and gauzes
US5650219A (en) * 1991-04-10 1997-07-22 Isolyser Co. Inc. Method of disposal of hot water soluble garments and like fabrics
US5661217A (en) * 1994-08-05 1997-08-26 Isolyser Company, Inc. Method of manufacturing monolithic structures from polyvinyl alcohol
US5707731A (en) * 1996-05-09 1998-01-13 Isolyser Company, Inc. Disposable cleaning articles
US5871679A (en) * 1991-04-10 1999-02-16 Isolyser Company, Inc. Method of producing hot water soluble garments and like fabrics
US5885907A (en) * 1993-04-29 1999-03-23 Isolyser Company, Inc. Method of disposal of hot water soluble garments and like fabrics
US5891812A (en) * 1996-10-11 1999-04-06 Isolyser Company, Inc. Liquid absorbable non-permeable fabrics and methods of making, using, and disposing thereof
US6048410A (en) * 1991-04-10 2000-04-11 Isolyser Company, Inc. Method of disposal of hot water soluble garments and like fabrics
US20100005575A1 (en) * 2005-05-18 2010-01-14 Eye Safety Systems, Inc. Goggles with removable frame and methods of making and using the same
US9758601B2 (en) 2013-12-26 2017-09-12 Kuraray Co., Ltd. Modified polyvinyl alcohol and production method therefor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2236061A (en) * 1937-05-27 1941-03-25 Du Pont Method of making films, threads, and the like
US2332896A (en) * 1940-05-29 1943-10-26 Gen Electric Synthetic composition comprising hydrolyzed acetalized copolymers of vinyl esters and unsaturated organic esters
US2424838A (en) * 1940-04-05 1947-07-29 Pittsburgh Plate Glass Co Conjoint polymerization products
US2611754A (en) * 1948-11-30 1952-09-23 Shawinigan Resins Corp Vinyl acetate-allyl acetate copolymer emulsion

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2236061A (en) * 1937-05-27 1941-03-25 Du Pont Method of making films, threads, and the like
US2424838A (en) * 1940-04-05 1947-07-29 Pittsburgh Plate Glass Co Conjoint polymerization products
US2332896A (en) * 1940-05-29 1943-10-26 Gen Electric Synthetic composition comprising hydrolyzed acetalized copolymers of vinyl esters and unsaturated organic esters
US2611754A (en) * 1948-11-30 1952-09-23 Shawinigan Resins Corp Vinyl acetate-allyl acetate copolymer emulsion

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3211685A (en) * 1959-03-20 1965-10-12 Kurashiki Rayon Co Production of polyvinyl alcohol having improved dyeability and composition therefor including polyvinyl alcohol basic nitrogen-containing derivatives
US3548031A (en) * 1967-10-21 1970-12-15 Kuraray Co Shapable polyvinyl alcohol composition
US5019609A (en) * 1988-08-02 1991-05-28 Aicello Chemical Co., Ltd. Films easily soluble in cold water
US5070126A (en) * 1988-08-02 1991-12-03 Aicello Chemical Co., Ltd. Films easily soluble in cold water
US5238995A (en) * 1990-01-22 1993-08-24 Kuraray Company Limited Polyvinyl alcohol fiber
US5650219A (en) * 1991-04-10 1997-07-22 Isolyser Co. Inc. Method of disposal of hot water soluble garments and like fabrics
FR2675161A1 (en) * 1991-04-10 1992-10-16 Isolyser Co METHOD FOR REMOVING CLOTHING ARTICLES IN A SOLUBLE ETOFFE IN HOT WATER
US5871679A (en) * 1991-04-10 1999-02-16 Isolyser Company, Inc. Method of producing hot water soluble garments and like fabrics
US6048410A (en) * 1991-04-10 2000-04-11 Isolyser Company, Inc. Method of disposal of hot water soluble garments and like fabrics
US5620786A (en) * 1993-04-29 1997-04-15 Isolyser Co. Inc. Hot water soluble towels, sponges and gauzes
US5885907A (en) * 1993-04-29 1999-03-23 Isolyser Company, Inc. Method of disposal of hot water soluble garments and like fabrics
US5470653A (en) * 1994-08-05 1995-11-28 Isolyser Company, Inc. Disposable mop heads
US5661217A (en) * 1994-08-05 1997-08-26 Isolyser Company, Inc. Method of manufacturing monolithic structures from polyvinyl alcohol
US5707731A (en) * 1996-05-09 1998-01-13 Isolyser Company, Inc. Disposable cleaning articles
US5985443A (en) * 1996-05-09 1999-11-16 Isolyser Company, Inc. Method of disposing of a mop head
US5891812A (en) * 1996-10-11 1999-04-06 Isolyser Company, Inc. Liquid absorbable non-permeable fabrics and methods of making, using, and disposing thereof
US20100005575A1 (en) * 2005-05-18 2010-01-14 Eye Safety Systems, Inc. Goggles with removable frame and methods of making and using the same
US9758601B2 (en) 2013-12-26 2017-09-12 Kuraray Co., Ltd. Modified polyvinyl alcohol and production method therefor

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