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EP1080114A1 - Procede pour la derivatisation de cellulose - Google Patents

Procede pour la derivatisation de cellulose

Info

Publication number
EP1080114A1
EP1080114A1 EP99919228A EP99919228A EP1080114A1 EP 1080114 A1 EP1080114 A1 EP 1080114A1 EP 99919228 A EP99919228 A EP 99919228A EP 99919228 A EP99919228 A EP 99919228A EP 1080114 A1 EP1080114 A1 EP 1080114A1
Authority
EP
European Patent Office
Prior art keywords
cellulose
oxide
water
dissolved
propanol
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.)
Withdrawn
Application number
EP99919228A
Other languages
German (de)
English (en)
Inventor
Thomas Wagner
Erik-Andreas Klohr
Wolfgang Koch
Klaus Szablikowski
Wolfgang Wagenknecht
Fritz Loth
Hendrik Wetzel
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.)
Dow Produktions und Vertriebs GmbH and Co OHG
Original Assignee
Wolff Walsrode AG
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 Wolff Walsrode AG filed Critical Wolff Walsrode AG
Publication of EP1080114A1 publication Critical patent/EP1080114A1/fr
Withdrawn legal-status Critical Current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
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/08—Alkali cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation

Definitions

  • the present invention relates to an activation process for cellulose and a process for the derivatization of the activated cellulose and those obtained thereby
  • Cellulose derivatives The products produced by these processes are characterized by advantageous properties, such as improved solubilities.
  • the accessibility and reactivity of cellulose is influenced by its super-molecular structure. This is due to the presence of zones of different degrees of crystalline order, fibrillar crystallites. as well as the number, size, distribution and availability of internal surfaces.
  • Cellulose is insoluble in common solvents such as water, dilute acids and alkalis and also in common organic solvents. Derivatizations in these solvents therefore take place at least at the start of the reaction under heterogeneous conditions.
  • the cellulose must first be activated in a suitable manner in order to increase the accessibility and reactivity of the cellulosic hydroxyl groups.
  • the known methods for activating cellulose are all aimed at opening or widening the (inner) surfaces, cleaving fibrillar aggregates, destroying crystalline regions and changing crystallite sizes and crystal modifications.
  • An activating effect on subsequent reactions of cellulose is, for example, by grinding, electron (DE 2,941,624), microwaves or ⁇ -radiation, hydrolysis, oxidation, thermal treatment, freeze-drying or
  • cellulose solvents are the tertiary amine oxides. From US Pat. No. 2,179,181 it is known that cellulose is of certain tertiary amine oxides. From US Pat. No. 2,179,181 it is known that cellulose is of certain tertiary amine oxides.
  • NMMNO-MH N-methylmorpholine-N-oxide monohydrate
  • the present invention was based on the object of developing a method for the activation and optionally subsequent derivatization of cellulose, which by reduced amounts of activating and
  • Derivatization reagents is marked and enables the economical presentation of products with improved solubility behavior (lower gel and fiber content, high clear solubility).
  • the present invention thus relates to a method for activating cellulose comprising the steps:
  • step b) optionally alkalizing the amorphous cellulose obtained in step b).
  • Chemical cellulose, cotton linters, softwood sulfite, softwood sulfate and / or hardwood cellulose of various degrees of polymerization are preferably used as the cellulose starting material for the process according to the invention.
  • Preferred water-containing tertiary amine oxides are amine oxides from the group
  • NMMNO N-methylmorpholine-N-oxide
  • NMMNO N-methyl-piperidine-N-oxide
  • N-methyl-pyrrolidine-N-oxide N-methyl-pyrrolidine-N-oxide
  • N, N-dimethylcyclohexylamine-N-oxide as well as N, N-dimethylethanolamine- N-oxide and triethylamine-N-oxide
  • water for example NMMNO-MH
  • dipolar aprotic compounds such as in particular dimethyl sulfoxide, N-methylpyrrolidone, dimethylacetamide or
  • the cellulose solutions are prepared in a known manner (US Pat. No. 4,145,532; US Pat. No. 4,196,282; EP 452,610; WO 95/1 1261) by dissolving the cellulose in a melt of NMMNO-MH at temperatures from 85 to 115 ° C.
  • the cellulose material is usually stirred into an aqueous solution of NMMNO at room temperature and water is distilled off in vacuo at 85 to 115 ° C.
  • concentration of cellulose is 2 to 20%, preferably 3 to 15%, depending on the degree of polymerization.
  • At least one stabilizer is advantageously added.
  • the stabilizers described in EP-A-047,929, in particular propyl gallic acid, are suitable.
  • the amount of stabilizer is preferably 1% by weight, based on the amount of cellulose.
  • the water-containing amine oxides can contain small amounts of basic compounds such as tertiary amines and / or alkali metal hydroxides.
  • Precipitants suitable for coagulating the dissolved cellulose are, in particular, organic solvents such as ethers, in particular dimethyl ether, ketones, in particular
  • Acetone alcohols with preferably 1-6 carbon atoms, especially methanol. - 5 -
  • the organic solvents can contain small amounts of basic-acting compounds such as tertiary amines and / or alkali metal hydroxides and / or quaternary ammonium bases.
  • the precipitant can be added to the cellulose solution both continuously and in stages, and is advantageously also used to wash out remaining amounts of amine oxide in the precipitated cellulose.
  • the activation process according to the invention leads to amorphous cellulose with increased reactivity and also allows direct derivatization without a previous alkalization step (eg esterification to cellulose acetate, nitrate or lactate, and or reaction with isocyanates), cellulose derivatives with improved solubility being obtained with improved yields.
  • a previous alkalization step eg esterification to cellulose acetate, nitrate or lactate, and or reaction with isocyanates
  • the present invention thus further relates to a process for the derivatization of cellulose comprising the steps:
  • step b) Derivatisiemng the amorphous cellulose obtained in step b) or c), optionally in the presence of a suitable solvent.
  • Cellulose derivatives are reaction products of cellulose with suitable derivatization reagents such as cellulose esters (e.g. cellulose acetates, cellulose lactates, cellulose nitrates), cellulose ether esters, cellulose carbamates and in particular water- and / or organo-soluble cellulose ethers such as carboxyalkyl celluloses (e.g. carboxyethylethyl cellulose), e.g.
  • suitable derivatization reagents such as cellulose esters (e.g. cellulose acetates, cellulose lactates, cellulose nitrates), cellulose ether esters, cellulose carbamates and in particular water- and / or organo-soluble cellulose ethers such as carboxyalkyl celluloses (e.g. carboxyethylethyl cellulose), e.g.
  • Hydroxypropyl celluloses examples include carboxyalkyl hydroxyalkyl celluloses (such as carboxymethyl hydroxyethyl, carboxymethyl hydroxypropyl cellulose), sulfoalkyl cellulose derivatives (e.g. sulfoethyl cellulose, sulfopropyl cellulose, methylsulfoethyl cellulose, methylsulfopropyl cellulose, carboxymethylsulfoethyl cellulose, carboxymethyl hydroxyl sulfyl ether)
  • carboxyalkyl hydroxyalkyl celluloses such as carboxymethyl hydroxyethyl, carboxymethyl hydroxypropyl cellulose
  • sulfoalkyl cellulose derivatives e.g. sulfoethyl cellulose, sulfopropyl cellulose, methylsulfoethyl cellulose, methylsulfopropyl cellulose, carboxymethylsulfoeth
  • Alkyl celluloses e.g. methyl cellulose, ethyl cellulose
  • alkyl hydroxyalkyl celluloses eg methylhydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, ethyl hydroxypropyl cellulose
  • alkylene celluloses such as allyl cellulose
  • alkylene alkyl celluloses eg allyl methyl cellulose, allyl ethyl cellulose
  • dialkylaminoalkyl celluloses eg diethylaminoethyl cellulose or ionic methylaminoethyl or cellulose hydroxylamino
  • dialkylaminoethylamino cellulose eg Cellulose ethers from the aforementioned functional groups.
  • the derivatization preferably takes place in the presence of the precipitant used to coagulate the dissolved cellulose.
  • Suitable precipitants are organic solvents such as 2-propanol, 2-methyl-2-propanol, acetonitrile, acetone.
  • the process according to the invention for the derivatization of cellulose is preferably carried out in such a way that
  • the dissolved cellulose is precipitated by adding organic solvents and is freed from adhering amine oxide by washing with the solvent used for the precipitation, and
  • step d) the amorphous cellulose thus obtained is reacted in the presence of the organic solvent used for the coagulation, step c) (alkalization) being omitted.
  • the cellulose derivatives produced by the derivatization process according to the invention are also the subject of the present invention. - 8th -
  • the cellulose derivatives according to the invention have an improved solubility and are largely free of fiber and gel particles. Even the cellulose derivatives according to the invention with low degrees of substitution still have excellent solubility in water and / or organic solvents.
  • the cellulose solution was mixed with stirring with 1500 ml of 2-propanol.
  • the precipitated cellulose was filtered off, washed free of NMMNO with 2-propanol and adjusted to a dry matter content of approx. 10% in a filter centrifuge.
  • the water retention capacity (WRV) of the activated cellulose is 3.30 cm 3 g " '.
  • the non-activated starting pulp had a WRV value of only 0.65 cm 3 g " '.
  • the activated celluloses were used in 2-propanol wet for the further reactions. - 10 -
  • the 2-propanol-moist activated cellulose (from Linters, DP C ⁇ on 560) was under

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 d'activation pour la cellulose, ainsi qu'un procédé pour la dérivatisation de cellulose activée, et les dérivés cellulosiques ainsi obtenus, l'étape d'activation s'effectuant en présence d'oxydes d'amine tertiaires.
EP99919228A 1998-04-20 1999-04-13 Procede pour la derivatisation de cellulose Withdrawn EP1080114A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1998117454 DE19817454A1 (de) 1998-04-20 1998-04-20 Verfahren zur Aktivierung und Derivatisierung von Cellulose
DE19817454 1998-04-20
PCT/EP1999/002472 WO1999054361A1 (fr) 1998-04-20 1999-04-13 Procede pour l'activation et la derivatisation de cellulose

Publications (1)

Publication Number Publication Date
EP1080114A1 true EP1080114A1 (fr) 2001-03-07

Family

ID=7865108

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99919228A Withdrawn EP1080114A1 (fr) 1998-04-20 1999-04-13 Procede pour la derivatisation de cellulose

Country Status (6)

Country Link
EP (1) EP1080114A1 (fr)
JP (1) JP2002512271A (fr)
AU (1) AU3707599A (fr)
DE (1) DE19817454A1 (fr)
PL (1) PL343492A1 (fr)
WO (1) WO1999054361A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL336363A1 (en) * 1999-10-29 2001-05-07 Inst Wlokien Chem Method of obtaining a modified cellulose pulp
JP5265124B2 (ja) * 2006-08-01 2013-08-14 日本製紙株式会社 非結晶セルロース誘導体
JP5237618B2 (ja) * 2007-12-12 2013-07-17 花王株式会社 ヒドロキシプロピルセルロースの製造方法
JP5237612B2 (ja) * 2007-11-08 2013-07-17 花王株式会社 セルロース誘導体の製造方法
WO2009054373A1 (fr) * 2007-10-25 2009-04-30 Kao Corporation Procédé de fabrication d'un dérivé d'éther de cellulose
JP5237609B2 (ja) * 2007-10-25 2013-07-17 花王株式会社 カチオン化セルロースの製造方法
JP2009120716A (ja) 2007-11-14 2009-06-04 Kao Corp ヒドロキシエチルセルロースの製造方法
JP5352179B2 (ja) * 2007-12-26 2013-11-27 花王株式会社 ヒドロキシエチルセルロースの製造方法
JP5193637B2 (ja) * 2008-03-17 2013-05-08 花王株式会社 メチルセルロースの製造方法
US8440817B2 (en) 2007-12-27 2013-05-14 Kao Corporation Method for producing methyl cellulose
EA022464B1 (ru) * 2012-11-23 2016-01-29 Сумгаитский Государственный Университет Способ активации целлюлозы
CN104045720B (zh) * 2014-07-01 2016-07-06 东华大学 一种纤维素经过尿素改性后的低温溶解方法
CN109790226B (zh) * 2016-09-29 2022-05-03 住友精化株式会社 水溶性羟乙基纤维素的制造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3447939A (en) * 1966-09-02 1969-06-03 Eastman Kodak Co Compounds dissolved in cyclic amine oxides
DE3034685C2 (de) * 1980-09-13 1984-07-05 Akzo Gmbh, 5600 Wuppertal Cellulose-Form- und Spinnmasse mit geringen Anteilen an niedermolekularen Abbauprodukten
DE19730090A1 (de) * 1997-07-14 1999-01-21 Wolff Walsrode Ag Neuartige Celluloseether und Verfahren zu deren Herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9954361A1 *

Also Published As

Publication number Publication date
AU3707599A (en) 1999-11-08
PL343492A1 (en) 2001-08-27
DE19817454A1 (de) 1999-10-21
JP2002512271A (ja) 2002-04-23
WO1999054361A1 (fr) 1999-10-28

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