US1683347A - Process of making chloroform-soluble cellulose acetate - Google Patents

Process of making chloroform-soluble cellulose acetate Download PDF

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US1683347A
US1683347A US21552027A US1683347A US 1683347 A US1683347 A US 1683347A US 21552027 A US21552027 A US 21552027A US 1683347 A US1683347 A US 1683347A
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cellulose
acid
mass
mixed
catalyst
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Harry Le B Gray
Cyril J Staud
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Eastman Kodak Co
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Eastman Kodak Co
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00Preparation of cellulose esters of organic acids
    • C08B3/06Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate

Description

Patented Sept. 4, 1928.

"UNITED STATES PATENT OFFICE.-

HARRY LE 13. GRAY AND CYRIL J. STAUD, OF ROCHESTER, NEW YORK. ASSIGNORS TO EASTMAN KODAK COMPANY, OF ROCHESTER, NEW YORK, A CORPORATION OF NEW YORK.

PROCESS OF MAKING CHLOROFORM-SOLUBLE GELL'ULOSE ACETATE.

No Drawing.

This invention relates to processes of making chloroform-soluble cellulose acetate, especially processes in which the cellulose is given a pretreatment prior to the main or final acetylation. One object of the invention is to provide a low cost process of this kind. which will yield cellulose acetate that can be made by subsequent operations into clear, flexible, transparent films. Another object is to provide a process of wide ap plicability to celluloses from different sources. Still another object is to provide a process in which an improved catalyst is used that stimulates acetylation without degrading the product and serves bothduring the pretreatment and the main or final acetylation. A further object is to provide a process in which the amount of cellulose sulf-acetates or other sulfur compounds in the product is reduced to the minimum. Other objects will hereinafter appear.

We have found that a process meeting the above requirements can be carried out by using a mixed catalyst of sulfuric acid and phosphoric acid in the right proportions, the same catalyst serving both for the pretreatment and for the final acetylation, an appreciable acetylation being accomplished during the pretreatment. The phosphoric acid is at least equal in weight to the sulfuric acid and may even weigh several times as much. We have found that this mixed catalyst functions better than sulfuric acid alone. The operations are under better control, the tendency to degrade the cellulose is less, the formation of sulf-acet-ates is minimized and the final transparent films are different temperatures, being shorter at the upper temperatures. The latter are preferably under (3., at which temperature pretreatments of 2 to 4 hours generally suffice.

In the'preferred form of our invention Application filed August 25, 1927. Serial No. 215,520.

mass before the acetic anhydrid is stirred into it. so that the heat evolved during such additionwill not raise the reaction mass to a dangerous temperature. The acetic anhy- (lrid may be added rapidly or slowly at intervals. For uniformity we prefer toadd it so that each part of the cellulosic' material will receive its quota of anhydrid at about the same time as every other part.

It is one of the features of our process that it may be applied successfully to manyv different kinds of cellulose, such as high grade clean cotton fibers, cotton fiber tissue paper, such as is especially prepared for esterification, surgical cotton wool, cotton linters, and even carefully prepared and bleached sulfite wood pulp.' These are merely illustrations of its Wide applicability.

e shall now give one specific example, but it will be understood that our invention is not limited to the details thus given, except as indicated in the appended claims. Fifty parts by weight of cellulose, say cotton linters which have been purified in the usual way, say by a boil in dilute caustic soda and a short bleach, are mixed with 490 parts of glacial acetic acid containing 3 parts of mixed catalyst. The latter is composed of 2.6 parts by Weight of phosphoric acid strength) and .9 parts of sulfuric acid (98% strength). The pretreatment mass, thus obtained, is kept at 38 C. for 4 hours. The ingredients may be brought to this temperature after mixing, or they may be preheated to this temperature and then mixed, the latter giving a more easily regula'table treatment.

At the end of the pretreatment the mass is brought to a lower temperature, say room temperature or even 15 C. This can be done by artificial cooling, or by allowing the heat from the mass to pass into the atmosphere. The time of cooling is not of critical importance and 2 0r 3 hours has been found convenient.

Into the cooled pretreatment mass there is next stirred 150 to 170 parts by weight of acetic anhydrid (85% strength). This cor responds to about 127 to 144 parts by weight of the actual anhydrid. The addition of the anhydrid causes the reaction mass to increase in temperature. This operation is conducted so that the reaction mass finally reaches a temperature within the range hereinabove named, say 42C. If the reaction mass does not reach the required temperature from the evolution of heat within, it may be heated by external means so as to bring the mass gradually up to the required point. The reaction, with the reagents kept thoroughly mixed, is carried out until the fibers disappear and a clear reaction solution or dope is obtained. Then a test is made of a sample to make certain that the product is fully soluble in chloroform.

The chloroform-soluble cellulose acetate thus obtained may be hydrolyzed to the acetone-soluble formin any of the known ways, such as by adding a mixture of water, mineral acid and acetic acid to the reaction mass and allowing the hydrolysis to proceed at the appropriate temperatures, as is well known. Or the chloroform-soluble cellulose acetate may be obtained from the reaction mixture by precipitating in water and washing, or by spray drying methods; and then the solid chloroform-soluble cellulose acetate, thus obtained, may be hydrolyzed by treatment with appropriate aqueous acid solutions, ashitherto described in the art.

The films produced by subsequent hydrolysis of the chloroform-soluble cellulose acetate and final solution in acetone are strong, flexible and brilliantly transparent and their flexibility is very durable under prolonged tests at the usual testing temperatures. Analysis indicates that the amounts of cellulose sulf-acetate and other deleterious cellulose-sulfur compounds are very low in our product.

Having thus described our invention, what we claim as new and desireto secure by-"Letters Patent is:

1. In the process of making cellulose-acetate, prctreating the cellulose with glacial acetic acid containing a mixed catalyst of sulfuric and phosphoric acids in which the latter acid is at least equal to the weight of the former, mixing acetic anhydrid into the pretreated mass to complete the acetylation, and conducting the reaction until the product is chloroform-soluble, the same mixed catalyst serving both in the pretreatment and the final acetylation.

2. In the process of making cellulose acetate, pretreating the cellulose with glacial acetic acid containing a mixed catalyst of sulfuric and phosphoric acids in which the latter acid is from one to five times the weight of the former, said mixed catalyst being less'than 10% of the Weight of the cellulose, and said pretreatment being conducted until between 1 and 3.5% of acetyl has been combined with the cellulose, mixing acetic anhydrid with the pretreated mass to complete the acetylation, said acetylating reaction being carried on until the product is chloroform-soluble, the same mixed catalyst serving both in the pretreatment and the final acetylation.

3. In the process of making cellulose acetate, pretreating the cellulose with glacial acetic acid containing a mixed catalyst of sulfuric and phosphoric acids in which the latter acid is from one to five times the weight of the former, said mixed catalyst being less than 10% of the weight of the cellulose, and said pretreatment being conducted at a temperature below 40 C. until between 1 and 3.5% of acetyl has been combined with the cellulose, cooling the mass to at least room temperature, stirring in acetic anhydrid to complete the acetylation, said acetylation being conducted at a temperature between 35 and 60 C. until the product is chloroform-soluble, the same mixed catalyst serving both in the pretreatment and in the final acetylation.

Signed at Rochester, New York, this 19th day of Aug, 1927.

HARRY LE BpGrR/AY. CYBIL J. STAUD.

US1683347A 1927-08-25 1927-08-25 Process of making chloroform-soluble cellulose acetate Expired - Lifetime US1683347A (en)

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4480090A (en) * 1983-10-21 1984-10-30 Eastman Kodak Company Process for esterification of cellulose using as the catalyst the combination of sulfuric acid, phosphoric acid and a hindered aliphatic alcohol
US5446079A (en) * 1990-11-30 1995-08-29 Eastman Chemical Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US5545681A (en) * 1993-12-20 1996-08-13 The Procter & Gamble Company pH-Modified polymer compositions with enhanced biodegradability
US5594068A (en) * 1993-05-28 1997-01-14 Eastman Chemical Company Cellulose ester blends
US6193841B1 (en) 1998-11-30 2001-02-27 Eastman Chemical Company Shaped, plastic articles comprising a cellulose fiber, a cellulose ester, and a non-ionic surfactant
US6228895B1 (en) 1996-10-11 2001-05-08 Eastman Chemical Company Method for plasticizing a composition comprised of cellulose fiber and a cellulose ester
US6352845B1 (en) 1999-02-10 2002-03-05 Eastman Chemical Company Corn fiber for the production of advanced chemicals and materials: separation of monosaccharides and methods thereof
US20030171458A1 (en) * 2002-01-16 2003-09-11 Buchanan Charles M. Novel carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
US20040181009A1 (en) * 2003-03-14 2004-09-16 Shelton Michael Charles Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
US20060267243A1 (en) * 2005-05-26 2006-11-30 Debra Tindall Method for compounding polymer pellets with functional additives
EP2279725A2 (en) 2003-02-05 2011-02-02 Corium International Hydrogel compositions for tooth whitening
US8039531B2 (en) 2003-03-14 2011-10-18 Eastman Chemical Company Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
US8124676B2 (en) 2003-03-14 2012-02-28 Eastman Chemical Company Basecoat coating compositions comprising low molecular weight cellulose mixed esters
WO2012177482A1 (en) 2011-06-23 2012-12-27 Eastman Chemical Company Filters having improved degradation and methods of making them
WO2012177483A1 (en) 2011-06-23 2012-12-27 Eastman Chemical Company Cellulose esters having mixed-phase titanium dioxide particles for improved degradation
US8461234B2 (en) 2003-03-14 2013-06-11 Eastman Chemical Company Refinish coating compositions comprising low molecular weight cellulose mixed esters
EP2601939A2 (en) 2003-09-12 2013-06-12 Corium International, Inc. Hydrogel compositions with an erodible backing member
WO2014099468A1 (en) 2012-12-20 2014-06-26 Eastman Chemical Company Surface attachment of particles to cellulose ester fibers
US9068063B2 (en) 2010-06-29 2015-06-30 Eastman Chemical Company Cellulose ester/elastomer compositions
US9273195B2 (en) 2010-06-29 2016-03-01 Eastman Chemical Company Tires comprising cellulose ester/elastomer compositions
US9624311B2 (en) 2011-10-25 2017-04-18 VTIP Intellectual Properties, Inc. Regioselectively substituted cellulose esters and efficient methods of preparing them
WO2017117554A1 (en) 2015-12-30 2017-07-06 Corium International, Inc. Systems and methods for long term transdermal administration
US9708473B2 (en) 2011-12-07 2017-07-18 Eastman Chemical Company Cellulose esters in pneumatic tires
WO2018089573A1 (en) 2016-11-11 2018-05-17 Eastman Chemical Company Cellulose ester and impact modifier compositions and articles made using these compositions
WO2018089610A1 (en) 2016-11-11 2018-05-17 Eastman Chemical Company Polymer-based resin compositions derived from cellulose and articles made using these compositions
WO2018089575A1 (en) 2016-11-11 2018-05-17 Eastman Chemical Company Cellulose ester and ethylene vinyl acetate compositions and articles made using these compositions

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4480090A (en) * 1983-10-21 1984-10-30 Eastman Kodak Company Process for esterification of cellulose using as the catalyst the combination of sulfuric acid, phosphoric acid and a hindered aliphatic alcohol
US5446079A (en) * 1990-11-30 1995-08-29 Eastman Chemical Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US5900322A (en) * 1990-11-30 1999-05-04 Eastman Chemical Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US5559171A (en) * 1990-11-30 1996-09-24 Eastman Chemical Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US5580911A (en) * 1990-11-30 1996-12-03 Eastman Chemical Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US5599858A (en) * 1990-11-30 1997-02-04 Eastman Chemical Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US6342304B1 (en) 1990-11-30 2002-01-29 Eastman Chemical Company Aliphatic aromatic copolyesters
US5594068A (en) * 1993-05-28 1997-01-14 Eastman Chemical Company Cellulose ester blends
US6313202B1 (en) 1993-05-28 2001-11-06 Eastman Chemical Company Cellulose ester blends
US5545681A (en) * 1993-12-20 1996-08-13 The Procter & Gamble Company pH-Modified polymer compositions with enhanced biodegradability
US6228895B1 (en) 1996-10-11 2001-05-08 Eastman Chemical Company Method for plasticizing a composition comprised of cellulose fiber and a cellulose ester
US6268028B1 (en) 1996-10-11 2001-07-31 Eastman Chemical Company Composition and paper comprising cellulose ester, alkylpolyglycosides, and cellulose
US6309509B1 (en) 1996-10-11 2001-10-30 Eastman Chemical Company Composition and paper comprising cellulose ester, alkylpolyglycosides, and cellulose
US6193841B1 (en) 1998-11-30 2001-02-27 Eastman Chemical Company Shaped, plastic articles comprising a cellulose fiber, a cellulose ester, and a non-ionic surfactant
US20030199087A1 (en) * 1999-02-10 2003-10-23 Eastman Chemical Company Methods of separating a corn fiber lipid fraction from corn fiber
US6388069B1 (en) 1999-02-10 2002-05-14 Eastman Chemical Company Corn fiber for the production of advanced chemicals and materials:arabinoxylan and arabinoxylan derivatives made therefrom
US6586212B1 (en) 1999-02-10 2003-07-01 Eastman Chemical Company Corn fiber for the production of advanced chemicals and materials: derivatizable cellulose and cellulose derivatives made therefrom
US6589760B1 (en) 1999-02-10 2003-07-08 Eastman Chemical Company Methods of separating a corn fiber lipid fraction from corn fiber
US6352845B1 (en) 1999-02-10 2002-03-05 Eastman Chemical Company Corn fiber for the production of advanced chemicals and materials: separation of monosaccharides and methods thereof
US20030188340A1 (en) * 1999-02-10 2003-10-02 Eastman Chemical Company Methods of separating a corn fiber lipid fraction from corn fiber
US6977275B2 (en) 2002-01-16 2005-12-20 Eastman Chemical Company Carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
US20030171458A1 (en) * 2002-01-16 2003-09-11 Buchanan Charles M. Novel carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
US20050228084A1 (en) * 2002-01-16 2005-10-13 Buchanan Charles M Novel carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
US7276546B2 (en) 2002-01-16 2007-10-02 Eastman Chemical Company Carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
EP2279725A2 (en) 2003-02-05 2011-02-02 Corium International Hydrogel compositions for tooth whitening
US8461234B2 (en) 2003-03-14 2013-06-11 Eastman Chemical Company Refinish coating compositions comprising low molecular weight cellulose mixed esters
US20040181009A1 (en) * 2003-03-14 2004-09-16 Shelton Michael Charles Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
US7585905B2 (en) 2003-03-14 2009-09-08 Eastman Chemical Company Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
US7893138B2 (en) 2003-03-14 2011-02-22 Eastman Chemical Company Low molecular weight carboxyalkylcellulose esters and their use as low viscosity binders and modifiers in coating compositions
EP2301973A2 (en) 2003-03-14 2011-03-30 Eastman Chemical Company Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
US8003715B2 (en) 2003-03-14 2011-08-23 Eastman Chemical Company Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
US8039531B2 (en) 2003-03-14 2011-10-18 Eastman Chemical Company Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
US8124676B2 (en) 2003-03-14 2012-02-28 Eastman Chemical Company Basecoat coating compositions comprising low molecular weight cellulose mixed esters
EP2601939A2 (en) 2003-09-12 2013-06-12 Corium International, Inc. Hydrogel compositions with an erodible backing member
US20060267243A1 (en) * 2005-05-26 2006-11-30 Debra Tindall Method for compounding polymer pellets with functional additives
US9068063B2 (en) 2010-06-29 2015-06-30 Eastman Chemical Company Cellulose ester/elastomer compositions
US9200147B2 (en) 2010-06-29 2015-12-01 Eastman Chemical Company Processes for making cellulose ester compositions
US9273195B2 (en) 2010-06-29 2016-03-01 Eastman Chemical Company Tires comprising cellulose ester/elastomer compositions
WO2012177483A1 (en) 2011-06-23 2012-12-27 Eastman Chemical Company Cellulose esters having mixed-phase titanium dioxide particles for improved degradation
WO2012177482A1 (en) 2011-06-23 2012-12-27 Eastman Chemical Company Filters having improved degradation and methods of making them
US9624311B2 (en) 2011-10-25 2017-04-18 VTIP Intellectual Properties, Inc. Regioselectively substituted cellulose esters and efficient methods of preparing them
US9708474B2 (en) 2011-12-07 2017-07-18 Eastman Chemical Company Cellulose esters in pneumatic tires
US9708472B2 (en) 2011-12-07 2017-07-18 Eastman Chemical Company Cellulose esters in highly-filled elastomeric systems
US9708473B2 (en) 2011-12-07 2017-07-18 Eastman Chemical Company Cellulose esters in pneumatic tires
US9708475B2 (en) 2011-12-07 2017-07-18 Eastman Chemical Company Cellulose esters in highly-filled elastomeric systems
WO2014099468A1 (en) 2012-12-20 2014-06-26 Eastman Chemical Company Surface attachment of particles to cellulose ester fibers
WO2017117554A1 (en) 2015-12-30 2017-07-06 Corium International, Inc. Systems and methods for long term transdermal administration
WO2018089599A1 (en) 2016-11-11 2018-05-17 Eastman Chemical Company Polymer-based resin compositions derived from cellulose and articles made using these compositions
WO2018089573A1 (en) 2016-11-11 2018-05-17 Eastman Chemical Company Cellulose ester and impact modifier compositions and articles made using these compositions
WO2018089610A1 (en) 2016-11-11 2018-05-17 Eastman Chemical Company Polymer-based resin compositions derived from cellulose and articles made using these compositions
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