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Process of making cellulosic esters containing halogen-substituted fatty-acid groups

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US1698049A
US1698049A US24774228A US1698049A US 1698049 A US1698049 A US 1698049A US 24774228 A US24774228 A US 24774228A US 1698049 A US1698049 A US 1698049A
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acid
halogen
substituted
fatty
cellulose
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Hans T Clarke
Carl J Malm
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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
    • C08B3/14Preparation of cellulose esters of organic acids in which the organic acid residue contains substituents, e.g. NH2, Cl

Description

Patented Jan. 8, 1929.

HANS T. CLARKE AND CARL J. MALM, or ROCHESTER, NEW Y RK, ASSIGNORS T0 EAST- MAN KODAK COMPANY, or ROCHESTER, new YORK, A coRroRA'rIoN OF NEW YORK.

PROCESS OF MAKING CELLULOSIG ESTEBS CONTAINING HALOGEN-SUBSTITUTED FATTY-ACID GROUPS.

No Drawing.

This invention relates to processes of making cellulosic esters containing halogen-substituted fatty acid groups. One object of the invention is to provide a simplified and relatively inexpensive process for making such esters by a single reaction. Other objects will hereinafter appear.

We have found that such esters may be made by subjecting cellulosic material to the coaction of a halogen-substituted fatty acid containing more than five carbon atoms and an organic acid anhydrid which impels this esterification but does not itself contribute any cellulose esterifying groups to the product. Moreover, the anhydrid is converted into an acid which does not contribute any groups to the ester.

The presence of substituted halogens in fatty acids either retards or prevents the formation of cellulose esters of such acids under conditions which will formuseful or substantially undegraded esters. When the fatty acid contains five, carbon atoms or less, the inhibiting effect of the halogen, whether the latter be in the alpha or other-position,

prevents esterification for all practical purposes But when the halogen-substituted fatty acids contain more than five carbon atoms, useful cellulose esters containing them can be prepared by our process by a single reaction. is thus the determining factor and not the alpha or other position of the halogen atoms. The greater the number of carbon atoms, provided there are more than five, the morev readily can the esterification be brought about in spite of the opposing effect of the halogen atoms. stearic acid is readily esterified with cellulose by our process, while halogen-substituted caproic acid is esterified more slowly. The intermediate members of the halogen-substituted fatty acid series, such as halogen-substituted heptylic, caprylic, pelargonic, capric, lauric, myristic, palmitic and margaric acids can be esterified with cellulose with intermediate ease of reaction. Of the halogen-substitutedhigher fatty acids which we can employ, we prefer to selectthe mono, di, tri or tetra brom or chlor members of the series. The correspondmg 1od1n'e compounds are expenslve.

The length of the carbon chain For example, halogen-substituted Application filed January 18, 1928. Serial No. 247,742.

,mixtures of them. The reaction can be-carried out using mono, di andtrichlor and brom propionic and butyric anhydrids. But they are relatively too expensive, without any compensating advantage. Likewise/the corresponding iodine-substituted acetic, propionic and butyric anhydrids cost too much. But anhydrids other than halogen-substituted .ones can also be employed, such as methoxy' acetic anhydrid and its higher alkyl homologues beginning with ethoxy acetic anhydrid. It is a characteristic of all of the above named anhydrids that they do not contribute groups to the ester. For example, the celluloseesters produced contain no chloracetic groups when chloracetic anhydrid is employed, nor any methoxy acetic groups when methoxy acetic anhydrid is used.

As the cellulosic materials to be esterified, we can use any customarily employed in the manufacture of the hitherto known cellulosic esters, For instance, cotton fiber tissue paper, clean cotton, surgical cotton wool, and even bleached sulfite wood pulp are useful .These materials, especially the cotton ones,

are sufficiently undegraded when they enter the reaction, so that they yield esters of good. flexibility. Of course, our ,process can be applied to the esterification of chemically affected cellulosic materials, such as so-called hydrocellulose, reverted cellulose from the viscose or cuprammonium processes, lower cellulose nitrates, lower ethyl celluloses, etc.

The temperature at which our process .is conducted must obviously be above the melting point of the ingredients of the esterifying" bath, but it should not rise to a point where, the products are degraded, as indicated by the poor quality of ,films prepared from the resulting esters. The melting points of the esterifying baths are lower than the melting strong splvent action upon the acids which are employed, thus tending to insure good working baths. It is convenient, although not essential, to have an additional solvent present which will not enter into the reaction. We have found monochloraoetic acid to be useful for this purpose. And as the reaction proceeds, further amounts of monochlorace'tic acid are formed and likewise add to the fluidity of the bath Under these circumstances, temperatures between 50 C. and 80 C. are satisfactory, to C. being preferred.

The reaction can be hastened and more thorough results obtained when a catalyst is present- We may use any of the customary esterifying catalysts, but we prefer the milder ones, such as the perchlorates disclosed in United States Patent No. 1,645,915, Carl J. Malm, October 18, 1927, process of making cellulose esters of organic acids. Zinc chlorid is likewise usable, as well as the red phosphorus and chlorine of United States Patent N 0. 1,591,590, William R. lVebb and Carl J. Malm, July 6, 1926. y I

We shall now describe several examples of our invention, but it will be understood that the latter is not limited to the illustrative details thus set forth, except as indicated in the appended claims. A reaction bath is prepared by warming at 60 to 65 C. for 1 to 2 'hours the following mixture,8 parts by weight. of cellulose, 40 parts by weight of chloracetic anhydrid, 20 parts by weight of chloracetic acid and .05 parts by weight of magnesium perchlorate trihydrate. For conveniencewe shall hereinafter refer to this as the standard bath. Into this bath there are thoroughly stirred 15part's by weight of alpha bromo stearic acid and 4 parts by weight .of acetic acid. By maintaining a temperature between 60 and 65 0., a clear dope forms in about 6 hours, indicating the completion of the reaction. The product is isolated by pouring intomethyl alcohol and washing the precipitate with this same liquid. The cellulose-aceto-alpha-bromo-stearate thus produced contains 11.3% of bromine I and is soluble in acetone, chloroform, benzene,

or mixtures of these, and can be deposited from its solutions in the form of transparentflexible films which are substantially noninflamma'ble,that is, will not burn with a sustained flame when held in the presence of an igniting flame.

In another example of our invention there are stirred into the standard bath hereinabove described 17 parts by weight of 9-l0-dibromo stearic acid and 7 parts by weight of acid).- 'After about 6 hours at 60 to 65 C.

acetic acid (this halogen-substituted stearic acid is readily prepared by brominating oleic the reaction is complete, as indicated by the formation ofv a clear homogeneous dope, which is precipitated in methyl alcohol and the product washed with the-same substance.

The product contains 23% of bromine, is

soluble in acetone, in chloroform and in benzone, or mixtures of these liqulds, andde- 'of dichloro stearic' acid (obtained by chlorinating oleic acid) and 5 parts by weight of acetic acid. After 6 hours at 60 to 65 C. the clear dope is poured into methyl alcohol with vigorous stirring and the precipitate washed until purified. It contains 8.5% of chlorine and is soluble in acetone and in chloroform, or mixtures of them; but isinsoluble in benzene. It yields flexible, transparent films.

In yet a different example of our invention there are added to the standard bath hereinabove described 14 parts by weight of tetrachloro steario acid'and 5 parts by weight of acetic acid (the first-named acid may be prepared by adding chlorine to the acid formed upon sap'onification of linseed oil). After 6 hours at 60 to 65 C. the solution becomes clear enough and is poured with agitation into methyl alcohol and the precipitate washed with said alcohol. The cellulose aceto-tetrachloro stearate 'thus produced contains 14% of chlorine and is soluble in acetone and chloroform or mixtures of them, but not in benzene. It forms flexible, transparent films'of very low inflammability.

In another example of our invention 10 parts by weight of alpha bromo caproic acid and 4 parts by weight of acetic acid are stirred intothe standard bath hereinabove described." This is heated at 60 to 65 C.

produced by our process yield flexible films or filaments without softeners or plastifiers, but chloroform-soluble or acetone-soluble plastifiers or softeners heretofore used with cellulose acetates may be employed with them, triphenyl and tricresyl phosphates being examples of the large number that can be employed. Our compounds can be mixed or laminated with cellulose nitrate or acetate by means of acommon solvent. Films of them can be backed with a cellulose acetate layer or with hygroscopic nitrocellulose coatings to prevent static, or nitrocellulose or acetate films may be backed with thin layers of our compounds. In short, our process can produce products of technical importance in thepreparation of films for photographic purposes, filaments for rayon, lacquers, artificial leather, moldable plastics, etc.

Having thus described ourinvention, What we claim as new and desire to secure by Letters Patent is:

1. In the process of making cellulosic esters containing halogen-substituted fatty acid groups, subjecting cellulosic material to the ooaction of a halogen substituted fatty acid containing more than five carbon atoms and an organic acid anhydrid which impels such .esterification but is free from celluloseesterifying groups and during the esterification is converted into a compound that is also free from cellulose-esterifying groups.

2. In the processof making cellulosic esters containing halogen-substituted fatty acid grou s, treating cellulosic material with an esteri ying bath containing a halogensubstituted fatty acid having more than live carbon atoms and a halogen-substituted fatty acid anhydrid having less than ten carbon atoms.

3. In the process of making cellulose esters containing halogen-substituted fatty acid groups, treating cellulosic material with an esterifying bath containing a halogen-substituted fatty acid having'more than five carbon atoms, and chloracetic anhydrid.

4. In the process of making cellulosic esters containing a halogen-substituted stearic acid group, subjecting cellulosic material to the coaction'of a corresponding halogen-substituted stearic acid and a halogensubstituted fatty acid anhydrid having "less than ten carbon atoms.

5. In the process of making a cellulose est-er containing a brom-substituted stearic acid group, treating cellulosic material in a bath.

containing brom-substituted stearic acid and chloracetic anhydrid. Signed at Rochester, New York,-this 10th day of January, 1928.

HANS T. CLARKE. CARL. J. MALM.

US1698049A 1928-01-18 1928-01-18 Process of making cellulosic esters containing halogen-substituted fatty-acid groups Expired - Lifetime US1698049A (en)

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2980491A (en) * 1955-06-15 1961-04-18 Segal Leon Textile fibers comprising perfluoroalkanoyl esters of cellulose and process of making the same
US3409386A (en) * 1964-10-01 1968-11-05 Universal Oil Prod Co Reaction of halocycloalkenyl acyl halide with polyesters, polyamides and textiles
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
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
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
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
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
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
US9708475B2 (en) 2011-12-07 2017-07-18 Eastman Chemical Company Cellulose esters in highly-filled elastomeric systems

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2980491A (en) * 1955-06-15 1961-04-18 Segal Leon Textile fibers comprising perfluoroalkanoyl esters of cellulose and process of making the same
US3409386A (en) * 1964-10-01 1968-11-05 Universal Oil Prod Co Reaction of halocycloalkenyl acyl halide with polyesters, polyamides and textiles
US5599858A (en) * 1990-11-30 1997-02-04 Eastman Chemical Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US5446079A (en) * 1990-11-30 1995-08-29 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
US5900322A (en) * 1990-11-30 1999-05-04 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
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
US20030199087A1 (en) * 1999-02-10 2003-10-23 Eastman Chemical Company Methods of separating a corn fiber lipid fraction from corn fiber
US20030188340A1 (en) * 1999-02-10 2003-10-02 Eastman Chemical Company Methods of separating a corn fiber lipid fraction from corn fiber
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
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
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
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
US9273195B2 (en) 2010-06-29 2016-03-01 Eastman Chemical Company Tires comprising cellulose ester/elastomer compositions
US9200147B2 (en) 2010-06-29 2015-12-01 Eastman Chemical Company Processes for making cellulose ester 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
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
US9708472B2 (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

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