New! View global litigation for patent families

US2902336A - Process for the production of amylose articles by extrusion of aqueous sodium hydroxide solution thereof into concentrated aqueous ammonium sulphate solution - Google Patents

Process for the production of amylose articles by extrusion of aqueous sodium hydroxide solution thereof into concentrated aqueous ammonium sulphate solution Download PDF

Info

Publication number
US2902336A
US2902336A US76807158A US2902336A US 2902336 A US2902336 A US 2902336A US 76807158 A US76807158 A US 76807158A US 2902336 A US2902336 A US 2902336A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
solution
amylose
bath
coagulation
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Inventor
Hiemstra Pieter
Muetgeert Johannes
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.)
AVEBE COOP VERKOOP PROD
COOPERATIEVE VERKOOP- EN PRODUCTIEVERENIGING VAN AARDAPPELMEEL EN DERIVATEN "AVEBE" GA
Original Assignee
AVEBE COOP VERKOOP PROD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR ARTIFICIAL THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments

Description

United States Patent Pieter Hiemstra, Veendam, and Johannes Muetgeert, Delft, Netherlands, assignors to Coiiperatieve Verkoopen Productievereniging Van Aardappelmeel en Derivaten Avebe G.A., Veendam, Netherlands Application October 20, 1958 Serial No. 768,071

Claims priority, application Netherlands October 22, 1957 3 Claims. (Cl. 18--54) No Drawing.

The invention relates to a process for the production of articles of manufacture, such as films and fibres, from amylose.

It is known that amylose films can be made by means of casting process. Processes of such a type, whereby an amylose solution is prepared by dissolving amylose in water e.g. with the aid of a complex forming agent or in an aqueous solution of an aldehyde such as for example formaldehyde, and wherein this solution is cast on a support on which it is dried, are relatively expensive, chiefly because the drying and coagulation rates are limited, and the process is consequently rather slow.

Attempts have been made at making fibres and films from an amylose solution by extrusion into a coagulation bath, but none of the attempts that have so far been made have yielded any useful results. In some cases, as for example by extruding amylose, which had been dissolved in an aqueous sodium hydroxide solution, into an acid bath as coagulation bath, a fibre or film was obtained by gelation, but the amylose film or fibre which had coagulated in this manner was so weak as to be practically untransportable.

It has now been found that amylose dissolved in an aqueous sodium hydroxide solution, when extruded into a concentrated aqueous ammonium sulphate solution, coagulates almost instantaneously, whereby a fairly strong, very resilient film or fibre is obtained, which is eminently free supporting and therefore very transportable.

As a measure for the coagulation rate the spinning rate may serve; for the coagulation rate is so high that it is hardly measurable in itself. In applying the process according to the invention spinning rates up to about 50 metres per minute were reached, whilst with casting processes rates of not more than 4 to 5 metres per minute could be reached.

Extrusion can be done through an opening of a round or rectangular or polygonal shape so that fibres or films and the like are formed.

The concentration of the ammonium sulphate in the coagulation bath is exceedingly important. With concentrations of 30 percent by weight and lower, the spinning rate is only a few metres a minute. With a concentration of 40%, however, this rate is already about 35 rn./minute, and in a saturated aqueous solution of ammonium sulphate spinning rates of up to 50 mjrninute could be realized.

Hereby a pH value of between 7.5 and 8.0 is automatically established in the coagulation bath. In extruding a solution of amylose in aqueous sodium hydroxide the following reaction takes place in the spinnnig bath:

ice

By the high concentration of NH,+ ions the dissociation of the NH OH which has been formed is pushed back and the above-mentioned pH value is reached automatically.

Attempts at accelerating the process by adding an acid to the coagulation bath did not bring about the desired result. It is true that coagulation in a bath of the type where acid is added is very swift, but the film or fibre thus obtained is very weak and its transportation and further working up is very difiicult. It would seem, therefore that a high H+-ion concentration is unfavourable for obtaining a strong amylose gel in the coagulation bath.

A very suitable extrusion bath contains NH OH and more than 30 percent by weight of ammonium sulphate.

Naturally, the films and fibres obtained by coagulation, can be freed of the inorganic compounds they had taken up, by washing with a suitable solvent, in which the amylose is not soluble, as for example a mixture of water and alcohol or more generally mixtures of water and organic water soluble substances, and subsequently dried.

Amylose films have the advantage of consisting of easily digestible material, and are therefore eminently suitable for packing food, as these films can be consumed with the packed product.

Example 224 g. of air-dry commercial amylose in powder form (moisture content 12% by weight) was dispersed in 1070 g. of air-free distilled water at a temperature of 20 C. whilst stirring vigorously. To the viscous mass thus obtained a solution of 50 g. of sodium hydroxide in 156 g. of air-free distilled water was added whilst stirring vigorously. After three more hours of stirring a solution was obtained, in which no undissolved amylose had been left.

The solution was subsequently filtered over a vacuum filter through filtering cloth with a high mesh-number. This solution was kept in vacuum for 24 hours, in order to remove dissolved gases if any.

The solution thus obtained was optically void and contained 13.2% by weight of amylose and 3.3% by weight of NaOH, and had a viscosity of 10002000 centipoises.

The solution was extruded from a spinnerette of platinum rhodium with 30 apertures, each of which having a diameter of 0.100 mm., into a spinning bath of 30 C., consisting of a solution of ammonium sulphate in distilled water, which solution contained 43-44% by weight of (NH SO The fibres which were formed were led through the bath for about 2 seconds and subsequently wound on a bobbin (at a rate of about 45 m./ minute) The closing of the spinning solution was 3.8 cm. a minute; the filaments obtained had, after washing and drying, a denier of 3.3.

If, instead of a spinnerette with round apertures, a slot having a width of 0.1 mm. is used for extruding the spinning solution, an amylose film can be produced at approximately the same rate.

Impurities may influence the properties of the fibres and films obtained to a large extent. In order to obtain the greatest possible strength, ammonium sulphate should be removed as completely as possible. This can be done by thorough washing.

It proved to be possible, however, to replace part of the amylose by amylopectin without exerting a distinctly unfavourable influence on the properties of the films.

What we claim is:

1. In a process for the production of articles of manufacture such as fibres and films from amylose, the step of dissolving amylose in an aqueous sodium hydroxide solution and extruding this solution into a concentrated aqueous ammonium sulphate'solution.

2. The process according to claim 1, wherein the coagulation bath, in addition to more than 30% sy Weight of '(NH )2SO also contains 'NH OH.

3. The process according to claim 1 wherein the coagulation bath has a pH value of 7.5-8.

References Cited in the file of this patent UNITED STATES PATENTS Levey Nov. 15, 1938 Reid et a1. Jan. 31, 1950 Horsak Oct. 9, 1951 Wolfi et a1 Sept. 2, 1952 Muetgurt et al Feb. 11, 1958 Wimmer Sept. 23, .1958

Claims (1)

1. IN A PROCESS FOR THE PRODUCTION OF ARTICLES OF MANUFACTURE SUCH AS FIBRES AND FILMS FROM AMYLOSE, THE STEP OF DISSOLVING AMYLOSE IN AN AQUEOUS SODIUM HYDROXIDE SOLUTION AND EXTRUDING THIS SOLUTION INTO A CONCENTRATED AQUEOUS AMMONIUM SULPHATE SOLUTION.
US2902336A 1957-10-22 1958-10-20 Process for the production of amylose articles by extrusion of aqueous sodium hydroxide solution thereof into concentrated aqueous ammonium sulphate solution Expired - Lifetime US2902336A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
NL2902336X 1957-10-22

Publications (1)

Publication Number Publication Date
US2902336A true US2902336A (en) 1959-09-01

Family

ID=19876242

Family Applications (1)

Application Number Title Priority Date Filing Date
US2902336A Expired - Lifetime US2902336A (en) 1957-10-22 1958-10-20 Process for the production of amylose articles by extrusion of aqueous sodium hydroxide solution thereof into concentrated aqueous ammonium sulphate solution

Country Status (1)

Country Link
US (1) US2902336A (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999032A (en) * 1958-01-29 1961-09-05 Vasco Ind Corp Process for the preparation of amylose solutions
US3030667A (en) * 1959-10-05 1962-04-24 American Viscose Corp Method of preparing amylose film, tubing, and the like
US3108891A (en) * 1961-04-24 1963-10-29 Owens Corning Fiberglass Corp Amylaceous forming size compositions
US3188237A (en) * 1960-12-29 1965-06-08 American Machinery And Foundry Activation of amylose
DE2713311A1 (en) * 1976-03-25 1977-09-29 Nat Starch Chem Corp A process for the production of paper, cardboard or paperboard
US4139699A (en) * 1976-03-25 1979-02-13 National Starch And Chemical Corporation Water insensitive starch fibers and a process for the production thereof
US4243480A (en) * 1977-10-17 1981-01-06 National Starch And Chemical Corporation Process for the production of paper containing starch fibers and the paper produced thereby
US4340442A (en) * 1978-11-06 1982-07-20 Champion International Corporation Starch fibrids useful in enhancing the physical properties of paper, and process of preparing same
US4755397A (en) * 1986-12-24 1988-07-05 National Starch And Chemical Corporation Starch based particulate encapsulation process
US4812445A (en) * 1987-02-06 1989-03-14 National Starch And Chemical Corporation Starch based encapsulation process
US4853168A (en) * 1987-12-23 1989-08-01 National Starch And Chemical Corporation Process for spinning starch fibers
US5430140A (en) * 1992-07-16 1995-07-04 Ems-Inventa Ag Starch intermediate product, a process for producing a starch intermediate product, and a process for further processing of a starch intermediate product
US5866251A (en) * 1992-10-16 1999-02-02 Eridania Beghin-Say Device and process for the production of fibrious starch materials
US20030203196A1 (en) * 2000-11-27 2003-10-30 Trokhan Paul Dennis Flexible structure comprising starch filaments
US6709526B1 (en) 1999-03-08 2004-03-23 The Procter & Gamble Company Melt processable starch compositions
US6723160B2 (en) 2002-02-01 2004-04-20 The Procter & Gamble Company Non-thermoplastic starch fibers and starch composition for making same
US20040183238A1 (en) * 2001-09-06 2004-09-23 James Michael David Process for making non-thermoplastic starch fibers
US6811740B2 (en) 2000-11-27 2004-11-02 The Procter & Gamble Company Process for making non-thermoplastic starch fibers
US6955850B1 (en) 2004-04-29 2005-10-18 The Procter & Gamble Company Polymeric structures and method for making same
US20050244635A1 (en) * 2004-04-29 2005-11-03 The Procter & Gamble Company Polymeric structures and method for making same
US7029620B2 (en) 2000-11-27 2006-04-18 The Procter & Gamble Company Electro-spinning process for making starch filaments for flexible structure

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2137171A (en) * 1936-09-25 1938-11-15 Harold A Levey Composite carbohydrate films
US2495767A (en) * 1946-08-09 1950-01-31 Reid John David Preparation of fibers from carboxymethylcellulose
US2570449A (en) * 1946-01-19 1951-10-09 Horsak Drahomir Method of production of synthetic material from starch or starch containing substances
US2608723A (en) * 1950-08-01 1952-09-02 Ivan A Wolff Process for the production of amylose films
US2822581A (en) * 1954-04-22 1958-02-11 Avebe Coop Verkoop Prod Amylose films
US2853414A (en) * 1953-12-02 1958-09-23 American Sugar Refining Co Water-insoluble complex of quaternary ammonium salt, a heavy-metal oxide, and an organic colloid and method of preparing same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2137171A (en) * 1936-09-25 1938-11-15 Harold A Levey Composite carbohydrate films
US2570449A (en) * 1946-01-19 1951-10-09 Horsak Drahomir Method of production of synthetic material from starch or starch containing substances
US2495767A (en) * 1946-08-09 1950-01-31 Reid John David Preparation of fibers from carboxymethylcellulose
US2608723A (en) * 1950-08-01 1952-09-02 Ivan A Wolff Process for the production of amylose films
US2853414A (en) * 1953-12-02 1958-09-23 American Sugar Refining Co Water-insoluble complex of quaternary ammonium salt, a heavy-metal oxide, and an organic colloid and method of preparing same
US2822581A (en) * 1954-04-22 1958-02-11 Avebe Coop Verkoop Prod Amylose films

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999032A (en) * 1958-01-29 1961-09-05 Vasco Ind Corp Process for the preparation of amylose solutions
US3030667A (en) * 1959-10-05 1962-04-24 American Viscose Corp Method of preparing amylose film, tubing, and the like
US3188237A (en) * 1960-12-29 1965-06-08 American Machinery And Foundry Activation of amylose
US3108891A (en) * 1961-04-24 1963-10-29 Owens Corning Fiberglass Corp Amylaceous forming size compositions
JPS6035480B2 (en) * 1976-03-25 1985-08-14 Nashonaru Sutaachi Ando Chem Corp
DE2713311A1 (en) * 1976-03-25 1977-09-29 Nat Starch Chem Corp A process for the production of paper, cardboard or paperboard
US4139699A (en) * 1976-03-25 1979-02-13 National Starch And Chemical Corporation Water insensitive starch fibers and a process for the production thereof
JPS52118009A (en) * 1976-03-25 1977-10-04 Nat Starch Chem Corp Process for making paper admixed with starch fiber and paper made thereof
US4243480A (en) * 1977-10-17 1981-01-06 National Starch And Chemical Corporation Process for the production of paper containing starch fibers and the paper produced thereby
US4340442A (en) * 1978-11-06 1982-07-20 Champion International Corporation Starch fibrids useful in enhancing the physical properties of paper, and process of preparing same
US4755397A (en) * 1986-12-24 1988-07-05 National Starch And Chemical Corporation Starch based particulate encapsulation process
US4812445A (en) * 1987-02-06 1989-03-14 National Starch And Chemical Corporation Starch based encapsulation process
US4853168A (en) * 1987-12-23 1989-08-01 National Starch And Chemical Corporation Process for spinning starch fibers
US5430140A (en) * 1992-07-16 1995-07-04 Ems-Inventa Ag Starch intermediate product, a process for producing a starch intermediate product, and a process for further processing of a starch intermediate product
US5514790A (en) * 1992-07-16 1996-05-07 Ems-Inventa Ag Starch intermediate product, a process for producing a starch intermediate product, and a process for further processing of a starch intermediate product
US5866251A (en) * 1992-10-16 1999-02-02 Eridania Beghin-Say Device and process for the production of fibrious starch materials
US7041369B1 (en) 1999-03-08 2006-05-09 The Procter & Gamble Company Melt processable starch composition
US6709526B1 (en) 1999-03-08 2004-03-23 The Procter & Gamble Company Melt processable starch compositions
US8168003B2 (en) 1999-03-08 2012-05-01 The Procter & Gamble Company Fiber comprising starch and a surfactant
US20040132873A1 (en) * 1999-03-08 2004-07-08 The Procter & Gamble Company Melt processable starch compositions
US7938908B2 (en) 1999-03-08 2011-05-10 The Procter & Gamble Company Fiber comprising unmodified and/or modified starch and a crosslinking agent
US7704328B2 (en) 1999-03-08 2010-04-27 The Procter & Gamble Company Starch fiber
US8764904B2 (en) 1999-03-08 2014-07-01 The Procter & Gamble Company Fiber comprising starch and a high polymer
US7666261B2 (en) 1999-03-08 2010-02-23 The Procter & Gamble Company Melt processable starch compositions
US7524379B2 (en) 1999-03-08 2009-04-28 The Procter + Gamble Company Melt processable starch compositions
US9458556B2 (en) 1999-03-08 2016-10-04 The Procter & Gamble Company Fiber comprising polyvinylpyrrolidone
US20030203196A1 (en) * 2000-11-27 2003-10-30 Trokhan Paul Dennis Flexible structure comprising starch filaments
US6811740B2 (en) 2000-11-27 2004-11-02 The Procter & Gamble Company Process for making non-thermoplastic starch fibers
US7029620B2 (en) 2000-11-27 2006-04-18 The Procter & Gamble Company Electro-spinning process for making starch filaments for flexible structure
US20040183238A1 (en) * 2001-09-06 2004-09-23 James Michael David Process for making non-thermoplastic starch fibers
US7276201B2 (en) 2001-09-06 2007-10-02 The Procter & Gamble Company Process for making non-thermoplastic starch fibers
US7025821B2 (en) 2002-02-01 2006-04-11 The Procter & Gamble Company Non-thermoplastic starch fibers and starch composition for making same
US20040149165A1 (en) * 2002-02-01 2004-08-05 The Procter & Gamble Company Non-thermoplastic starch fibers and starch composition for making same
US20050076809A1 (en) * 2002-02-01 2005-04-14 Mackey Larry Neil Non-thermoplastic starch fibers and starch composition for making same
US6723160B2 (en) 2002-02-01 2004-04-20 The Procter & Gamble Company Non-thermoplastic starch fibers and starch composition for making same
US6802895B2 (en) 2002-02-01 2004-10-12 The Procter & Gamble Company Non-thermoplastic starch fibers and starch composition for making same
US7744791B2 (en) 2004-04-29 2010-06-29 The Procter & Gamble Company Method for making polymeric structures
US7754119B2 (en) 2004-04-29 2010-07-13 The Procter & Gamble Company Method for making polymeric structures
US6955850B1 (en) 2004-04-29 2005-10-18 The Procter & Gamble Company Polymeric structures and method for making same
US6977116B2 (en) 2004-04-29 2005-12-20 The Procter & Gamble Company Polymeric structures and method for making same
US8623246B2 (en) 2004-04-29 2014-01-07 The Procter & Gamble Company Process of making a fibrous structure
US20050244634A1 (en) * 2004-04-29 2005-11-03 The Procter & Gamble Company Polymeric structures and method for making same
US9017586B2 (en) 2004-04-29 2015-04-28 The Procter & Gamble Company Polymeric structures and method for making same
US20050244635A1 (en) * 2004-04-29 2005-11-03 The Procter & Gamble Company Polymeric structures and method for making same

Similar Documents

Publication Publication Date Title
US3141875A (en) Crystallite aggregates disintegrated in acid medium
US3014024A (en) Collagen film
US2978446A (en) Level-off d.p. cellulose products
Liebert Cellulose solvents–remarkable history, bright future
US4674519A (en) Cohesive tobacco composition
US4161544A (en) Process for making a pourable material for chewing gum
US2831852A (en) Water-soluble thermoplastic cellulose ethers
Yackel et al. The oxidation of cellulose by nitrogen dioxide
US2627477A (en) Higher alkyl ketene dimer emulsion
US4166173A (en) Process for phosphorylating starch in alkali metal tripolyphosphate salts
US2368527A (en) Treatment of cellulosic pulp
US5762846A (en) Dispersion spinning process for polytetrafluoroethylene and related polymers
US2171976A (en) Process of manufacturing stabilized
US4063016A (en) Chitin complexes with alcohols and carbonyl compounds
US3072635A (en) Readily dissolving cellulose derivatives and process therefor
US3388119A (en) Non-fibrous particulate cellulose and method of making same
US4141746A (en) Cellulose sulfate esters
US2879268A (en) Methods of improving the dissolution of high-molecular substances
US3974251A (en) Production of flameproof fibers of regenerated cellulose
US2645576A (en) Purifying wood pulp
US5693279A (en) Starch acetate and blends thereof with metal chelates
WO2007076979A1 (en) Solvent system based on molten ionic liquids, its production and use for producing regenerated carbohydrates
US3900463A (en) Process for preparing alkali carboxymethyl cellulose
CN1851063A (en) Method for preparing cellulose fiber using ion liquid as solvent
US4216310A (en) Continuous process for phosphorylating starch