[go: up one dir, main page]

EP0522009A1 - Procede pour preparer des esters de cellulose - Google Patents

Procede pour preparer des esters de cellulose

Info

Publication number
EP0522009A1
EP0522009A1 EP19910907133 EP91907133A EP0522009A1 EP 0522009 A1 EP0522009 A1 EP 0522009A1 EP 19910907133 EP19910907133 EP 19910907133 EP 91907133 A EP91907133 A EP 91907133A EP 0522009 A1 EP0522009 A1 EP 0522009A1
Authority
EP
European Patent Office
Prior art keywords
anhydride
cellulose
amount
component
mixture
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.)
Ceased
Application number
EP19910907133
Other languages
German (de)
English (en)
Inventor
Charles Michael C/Oeastman Kodak Comp. Buchanan
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.)
Eastman Chemical Co
Original Assignee
Eastman Kodak Co
Eastman Chemical Co
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
Application filed by Eastman Kodak Co, Eastman Chemical Co filed Critical Eastman Kodak Co
Publication of EP0522009A1 publication Critical patent/EP0522009A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/08—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate

Definitions

  • This invention relates to preparation of cellulose esters by utilization of trifluoroacetic anhydride as an impelling agent in combination with certain acyl
  • Cellulose triesters with a degree of substitution (DS) of about 3 can be prepared as well as cellulose esters with a DS of less than about 3.
  • Cellulose esters are of great commercial interest. Cellulose acetates, for example, are used in cigarette filters and as photographic film base. Other cellulose esters, e.g., cellulose propionates, cellulose
  • Tedder J. Chem. Soc. 1949, 2976-2979 have disclosed the use of trifluoroacetic anhydride (TFAA) as an impelling reagent in the acetylation of cellulose and amylose with acetic acid.
  • TFAA trifluoroacetic anhydride
  • Tedder J. Chem. Soc. 1949, 2976-2979 have disclosed the use of trifluoroacetic anhydride (TFAA) as an impelling reagent in the acetylation of cellulose and amylose with acetic acid.
  • TFAA trifluoroacetic anhydride
  • the present invention is directed to a process for preparing a cellulose ester having a degree of substitution of about 3 comprising:
  • each of R and R 1 is, independently, H, a straight chain alkyl, a branched alkyl, aryl, or substituted aryl,
  • the cellulose triester formed by the above- described process is subjected to a second step
  • Another aspect of the present invention provides a process for directly preparing cellulose esters with a DS less than about 3.
  • This process (alternatively referred to herein as the "direct process") can be described as a process for preparing a cellulose ester having a degree of substitution of less than about 3 comprising:
  • each of R and R 1 is, independently, H, a straight chain alkyl, a branched alkyl, aryl or substituted aryl, and
  • Example 23 Figure 3 - The 400 MHz proton NMR spectrum of the methyl acetyl region of the cellulose diacetate obtained after treating the cellulose diacetate as shown in
  • R 2 , R 3 , and R 4 are selected independently from the group consisting of: hydrogen, straight chain alkanoyl, branched alkanoyl, aroyl, heteroaroyl,
  • acyloxy-(straight chain alkanoyl, branched alkanoyl, aroyl, heteroaroyl) alkyl ether or acyloxy-(straight chain alkanoyl, branched alkanoyl, aroyl, heteroaroyl) aroyl ether.
  • the alkanoyl, aroyl, heteroaroyl, acyloxy alkyl ether, and acyloxy aroyl ether moieties typically contain up to 20 carbon atoms.
  • the cellulose polymer used as a starting material for preparing the cellulose triester can be cellulose, a secondary cellulose ester, a cellulose hydroxy ether, a cellulose hydroxy alkyl ether, or a mixture thereof.
  • Examples of secondary cellulose esters include cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate, and are described in U.S. Patent 1,984,147.
  • Examples of cellulose hydroxy ethers include hydroxypropyl cellulose, hydroxyethyl cellulose, and hydroxypropylmethyl cellulose, and are described in U.S. Patent 3,278,520. Typical cellulose hydroxy alkyl ethers are also described in U.S. Patent 3,278,520.
  • the product cellulose esters produced by the process (es) of the present invention have at least 2 anhydroglucose rings and typically have between 2 and 5,000 anhydroglucose rings; also, such polymers typically have an inherent viscosity (I.V.) of about 0.2 to about 3.0
  • deciliters/gram as measured at a temperature of 25°C for a 0.25 gram sample in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane.
  • the DS of the cellulose polymer starting material for the triesterification process is preferably 0 to about 2.9.
  • the theoretical maximum DS for a cellulose ester is 3.
  • the maximum DS will vary experimentally, for example an error of plus or minus 3 percent is common.
  • this analytical error will be taken into account as well as minor actual deviations in the DS of the
  • acyl anhydride useful in the processes of the present invention is of the formula
  • each of R and R 1 is, independently, hydrogen, a straight chain alkyl, a branched chain alkyl, aryl or substituted aryl.
  • typical straight chain alkyl groups contain 1 to 20 carbon atoms
  • typical branched chain alkyl groups have 3 to 20 carbon atoms
  • typical aryl groups have 6 to 12 carbon atoms.
  • Substituted aryl groups are typically substituted with 1, 2 or 3 substituents such as lower alkyl (i.e., alkyl groups having 1 to 3 carbon atoms), halo (i.e., F, Br, Cl or I), and lower alkoxy (i.e., alkoxy groups having 1 to 3 carbon atoms).
  • the acyl anhydride is symmetrical, i.e., that R and R 1 are the same.
  • Suitable acyl anhydrides useful in the present invention include, but are not limited to, acetic anhydride, propionic anhydride, isobutyric anhydride, butyric anhydride, trimethylacetic anhydride valeric anhydride, hexanoic anhydride, nonanoic
  • acyl anhydrides are acetic anhydride, propionic anhydride, butyric anhydride, hexanoic
  • the trifluoroacetic anhydride (or TFAA) in the processes of the present invention is referred to herein as an "impelling agent" because it is not consumed but still promotes ester formation.
  • the amount of component (b) (i.e., the TFAA) is preferably about 0.076 to 2.3 equivalents per hydroxyl, more preferably about 0.5 to about 1 equivalent per hydroxyl; and the amount of component (c) is at least 1 equivalent per hydroxyl.
  • Conditions suitable for the formation of cellulose esters can vary widely. However, for preparing the cellulose triester, temperature typically varies from about 20 to about 60°C, preferably about 50 to about 60°C. Those skilled in the art readily recognize that contact times and cellulose morphology are interdependent. For example, while the contact time may extend up to 88 hours when acetylating ramie cellulose, the contact time will fall within the range of 1 to 10 hours when acetylating wood pulp. Accordingly, a broad contact time for the triesterification process of the invention is about 1 to about 90 hours, and a preferred contact time is about 1 to about 10 hours.
  • acylation of a dried wood pulp with acetic anhydride may require a contact time of about 6.5 hours.
  • Acylation of the same wood pulp under otherwise similar reaction conditions with hexanoic anhydride can require a contact time of about 65 hours.
  • anhydride used in the reaction will be interdependent. For example, acetylation of a given wood pulp using 0.76 eq of TFAA per hydroxyl may require about 1 hour to achieve complete esterification whereas, when 0.076 eq of TFAA per hydroxyl is utilized, about 168 hours may be required to achieve complete esterification.
  • equivalents of TFAA per hydroxyl is 1.0 to 0.5.
  • said solvent is typically a carboxylic acid having 1 to 20 carbon atoms, dimethylformamide, dimethylsulfoxide, or a mixture thereof; however, excess acyl anhydride can be used as solvent.
  • the carboxylic acid can optionally be substituted with halogen atoms such as F, Br, and Cl; an example of such a substituted carboxylic acid is trifluoroacetic acid.
  • Preferred is a carboxylic acid, especially the particular carboxylic acid corresponding to the acyl anhydride(s) employed, or, in the case of mixed esters, corresponding to the least reactive acyl anhydride.
  • the acid can contribute to the reaction (i.e., act as a reactant) if the particular carboxylic acid used has a corresponding anhydride that is more reactive than the acyl anhydride employed as reactant (c).
  • the reactive hydrolysis solvent for the hydrolysis step is typically a polar solvent such as an n-alkanol having 1 to 4 carbon atoms, water, a branched chain alkanol having 3 to 4 carbon atoms, an aromatic alcohol having 6 to 12 carbon atoms, and a mixture thereof.
  • a polar solvent such as an n-alkanol having 1 to 4 carbon atoms, water, a branched chain alkanol having 3 to 4 carbon atoms, an aromatic alcohol having 6 to 12 carbon atoms, and a mixture thereof.
  • Preferred reactive hydrolysis solvents include methanol, ethanol, n-propanol, n-butanol, isopropyl alcohol, benzyl alcohol, water, or a mixture thereof; most preferred are methanol, water, or a mixture thereof
  • the amount of reactive hydrolysis solvent is from about 1 volume % to that amount which results in the desired product precipitating from solution. It is more
  • the amount of reactive hydrolysis solvent is from about 5 to about 15 volume %.
  • Preferred reaction conditions for the hydrolysis step include a temperature of about 20°C to about 70°C and a reaction time of about 0.5 to about 100 hours. More preferred are a temperature of about 50°C to about 60°C and a reaction time of about 0.5 to about 44 hours.
  • the cellulose triester formed by the triesterification process can be isolated and/or purified by conventional means known in the art such as by
  • the cellulose triester can be hydrolyzed directly in the reaction medium without the need for any special purification or isolation steps.
  • the desired cellulose ester can be isolated and purified by conventional means known in the art such as by a nonsolvent precipitation, distillation, or by spray drying.
  • trifluoroacetic acid as well as TFAA, is present in the reaction medium after the desired product is formed.
  • the trifluoroacetic acid can be formed, for example, by reaction of TFAA with residual water present in the cellulose polymer starting material or by means of a transesterification mechanism in the conversion of the cellulose polymer to a cellulose ester. Therefore, it is also preferable to isolate
  • hydrolysis step Such isolation can be accomplished by distillation or by use of a spray drying process.
  • the direct process of the present invention can include the additional step of isolating, after reaction, TFAA, trifluoroacetic acid, or a mixture thereof, by distillation or by a spray drying process. Also the direct process of the
  • inventions can include the additional step of isolating, after reaction, the desired product by the addition of a precipitating amount of a nonsolvent, by distillation, or by spray drying.
  • Typical nonsolvents for the desired product (s) include water, an n-alkanol having 1 to 4 carbon atoms, a branched alkanol having 3-4 carbon atoms, or a mixture thereof.
  • the desired cellulose ester product (which is typically acetone insoluble) can optionally be dissolved in a carboxylic acid corresponding to an acyl group bonded to the cellulose polymer (e.g., acetic acid corresponding to acetyl) wherein the carboxylic acid contains sufficient H 2 SO 4 (e.g., at least about 0.05 weight %, preferably about 0.1 weight % ) to promote migration of the bonded acyl group so that a cellulose ester is obtained which is substantially acetone soluble.
  • This acetone soluble product can then be optionally processed by the
  • the amount of component (b) is about 0.07 to about 2.3 equivalents per hydroxyl; the amount of component (c) is about 0.07 to about 1.0 equivalents per hydroxyl; and the amount of component (d) is about 5 to about 10 parts dry cellulose.
  • the DS of the cellulose polymer starting material for the direct process is less than about 2.85, more preferably less than about 2.5.
  • the most preferred cellulose polymer starting material for the direct process is cellulose.
  • Typical desired products produced by either the hydrolysis step or the direct process have a DS of about 0.5 to about 2.85, more typically about 1.75 to about 2.85.
  • the solvents and other conditions for the direct process are about the same as can be used for the triesterification process.
  • the materials employed were loaded into a flask equipped for mechanical stirring.
  • the reactor was then heated to 50 to 60°C.
  • the reaction mixture was stirred until a clear solution was obtained which is the indicated reaction time for the triesters.
  • the reaction mixture was filtered before the products were isolated by the addition of a non-solvent.
  • the impelling reagent, the carboxylic acid, and the anhydride can be recovered from the reaction mixture before precipitation or from the filtrate following precipitation by distillation
  • the impelling reagent, the carboxylic acid, the acid anhydride, and the product ester can be isolated by spray drying techniques familiar to those skilled in the art. The results in the examples
  • the products were typically characterized by proton NMR spe ⁇ troscopy, intrinsic viscosity, gel permeation chromatography, differential scanning
  • This example differs from the standard procedure in the following way: Acetic anhydride was omitted and enough acetic acid was employed so that the total solid/liquid ratio remained the same relative to
  • Trichloroacetic anhydride (TCAA) was substituted for trifluoroacetic anhydride.
  • the materials employed (60 g of cellulose, 0.76 eq of TFAA, 2.1 eq of AC 2 O, and 360 g of AcOH) were loaded into a flask equipped for mechanical stirring. The reactor was then heated to 55°C and the reaction mixture was stirred until a clear solution was obtained (2.5 h). An aliquot was removed before adding 700 g of AcOH and 208.5 g of water to the homogeneous solution. The reaction was stirred at 50°C with aliquots being removed at the following indicated times. All aliquots were processed by the standard procedure and analyzed by the standard methods.
  • cellulose acetate is acetone soluble and has the same acetyl distribution as conventional acetone soluble CDA (see Figures 2 and 3).
  • TFAA promotes the synthesis of cellulose acetate propionates with a degree of substitution of less than three from cellulose.
  • this example also demonstrates that high molecular weight, high hydroxyl mixed cellulose esters can be obtained.
  • TFAA promotes the synthesis of cellulose acetate butyrates with a degree of substitution of less than three from cellulose.
  • this example also demonstrates that high molecular weight, high hydroxyl mixed cellulose esters can be obtained.
  • This example differs from the standard procedure in that a reactive solvent was added to the homogeneous reaction mixture at the triester stage to promote hydrolysis of the triester to a cellulose acetate with a degree of substitution of less than three.
  • TFAA promotes the synthesis of cellulose acetates with a degree of substitution less than three from cellulose. Furthermore, this example also demonstrates that high molecular weight, high hydroxyl cellulose acetates can be

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention concerne un procédé pour préparer des esters de cellulose en utilisant un anhydride acylique et un anhydride trifluoroacétique en tant qu'agent agitateur. L'invention comprend la formation d'un triester de cellulose suivi ou non d'une phase d'hydrolyse. En outre, on peut préparer directement un ester de cellulose ayant un degré de substitution pratiquement inférieur à 3, en utilisant, en plus, un acide trifluoroacétique.
EP19910907133 1990-03-19 1991-03-13 Procede pour preparer des esters de cellulose Ceased EP0522009A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US49518690A 1990-03-19 1990-03-19
US495186 1990-03-19

Publications (1)

Publication Number Publication Date
EP0522009A1 true EP0522009A1 (fr) 1993-01-13

Family

ID=23967619

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910907133 Ceased EP0522009A1 (fr) 1990-03-19 1991-03-13 Procede pour preparer des esters de cellulose

Country Status (4)

Country Link
EP (1) EP0522009A1 (fr)
JP (1) JPH05506046A (fr)
CA (1) CA2070390C (fr)
WO (1) WO1991014709A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110506061A (zh) * 2017-03-29 2019-11-26 伊士曼化工公司 区域选择性取代的纤维素酯

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2186784C2 (ru) * 2000-05-25 2002-08-10 Алтайский государственный технический университет им. И.И.Ползунова Способ получения сложного эфира целлюлозы
CN104277122B (zh) * 2013-07-11 2016-08-10 南通醋酸纤维有限公司 溶于丙酮的纤维素酯的直接合成方法及其产品
CN105199001B (zh) * 2014-06-19 2019-01-01 南通醋酸纤维有限公司 一种纤维素长链脂肪酸酯或长短链混合酸酯的制备方法
ES2677547T3 (es) * 2015-03-05 2018-08-03 Lanxess Deutschland Gmbh Preparaciones de éster de celulosa ignífugas
KR102158917B1 (ko) * 2017-12-04 2020-09-22 주식회사 엘지화학 기체 분리막 활성층 형성용 조성물의 제조방법, 이에 의해 제조된 기체 분리막 활성층 형성용 조성물, 기체 분리막의 제조방법 및 기체 분리막
FR3136465A1 (fr) * 2022-06-14 2023-12-15 Université De Lorraine Procédé de préparation d’un matériau cellulosique thermoplastique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2581565A (en) * 1952-01-08 Cellulose vestoees
US2629716A (en) * 1948-07-07 1953-02-24 Du Pont Preparation and hydrolysis of esters
JPS6017441B2 (ja) * 1981-07-10 1985-05-02 ダイセル化学工業株式会社 新規なセルロ−スアセテ−トの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9114709A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110506061A (zh) * 2017-03-29 2019-11-26 伊士曼化工公司 区域选择性取代的纤维素酯

Also Published As

Publication number Publication date
WO1991014709A1 (fr) 1991-10-03
CA2070390C (fr) 1999-03-30
CA2070390A1 (fr) 1991-09-20
JPH05506046A (ja) 1993-09-02

Similar Documents

Publication Publication Date Title
Heinze et al. 4.2 Chemical characteristics of cellulose acetate
US4278790A (en) Novel cellulose solutions
EP0893451B1 (fr) Modification de polysaccharide dans un fluide densifié
EP0590401B1 (fr) Procédé de préparation d'un ester d'acide gras de cellulose
EP0074631B1 (fr) Procédé pour la préparation d'un sel alcalin de carboxyméthylcellulose
WO1991016359A1 (fr) Compositions d'ester de cellulose et leur procede de preparation
Labafzadeh et al. Reactive dissolution of cellulose and pulp through acylation in pyridine
JPH0632801A (ja) セルロースエステルの製造方法
EP0522009A1 (fr) Procede pour preparer des esters de cellulose
EP0800538B1 (fr) Procede de preparation d'esters cellulosiques a l'aide d'un catalyseur de resine d'acide sulfonique
EP0477347B1 (fr) Procede de preparation d'esters de cellulose a l'aide d'acides carboxyliques
EP0525082A1 (fr) Preparation d'esters de cellulose de faible poids moleculaire
US2629716A (en) Preparation and hydrolysis of esters
EP0895514B1 (fr) Procede de preparation d'alcanoates d'acetoacetate de cellulose
JP2001213901A (ja) 酢酸セルロースの製造方法
Hall et al. Preparation of cellulose triacetate and cellulose tricarbanilate by nondegradative methods
US5770726A (en) Process for preparing a cellllose acetoacetate alkanoates
JPH0433901A (ja) セルロース誘導体及びコーテイング材料
US2048685A (en) Process of making cellulose esters and the products resulting therefrom
US2300213A (en) Boron fluoride complex as catalyst for the esterification of cellulose
US2000602A (en) Process for the fibrous esterification of cellulose
US2828305A (en) Manufacture of hydroxyalkyl
US1946632A (en) Manufacture of mixed esters of cellulose
CN119930846A (zh) 一种羟丙基纤维素的均相制备方法
US1836689A (en) Process for esterification of cellulose and products resulting therefrom

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19921010

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19930924

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EASTMAN CHEMICAL COMPANY

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19950203