WO1999060026A1 - Solutions cellulosiques et leur utilisation - Google Patents

Solutions cellulosiques et leur utilisation Download PDF

Info

Publication number
WO1999060026A1
WO1999060026A1 PCT/GB1999/001566 GB9901566W WO9960026A1 WO 1999060026 A1 WO1999060026 A1 WO 1999060026A1 GB 9901566 W GB9901566 W GB 9901566W WO 9960026 A1 WO9960026 A1 WO 9960026A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
solution
solvent
oxide
solutions
Prior art date
Application number
PCT/GB1999/001566
Other languages
English (en)
Inventor
Peter George Urben
Original Assignee
Tencel Limited
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 Tencel Limited filed Critical Tencel Limited
Priority to AU39441/99A priority Critical patent/AU3944199A/en
Priority to EP99922339A priority patent/EP1086139A1/fr
Publication of WO1999060026A1 publication Critical patent/WO1999060026A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • 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
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids

Definitions

  • This invention relates to solutions of cellulose and to their uses, in particular in the manufacture of extruded cellulosic articles such as fibres and films.
  • amine oxides tertiary amine N- oxides
  • a preferred class of amine oxides comprises alicyclic mono (N-methylamine N-oxide) s, one such being N-methylmorpholine N-oxide (NMMO) .
  • Solutions containing by weight typically 5-20% cellulose, 5- 15% water and the balance NMMO have been extruded to yield shaped cellulosic articles such as fibres and films. True solutions are obtainable only within a limited region of the ternary phase diagram of these three components .
  • Solutions of cellulose in aqueous NMMO solidify below about 75°C (the freezing point of NMMO monohydrate) , and they may solidify even at somewhat higher temperatures . These solutions tend to decompose exothermically at temperatures above about 130°C. These solutions are very viscous. There is a need for cellulose solutions based on amine oxide solvents, which solutions exhibit depressed melting point, reduced viscosity and/or increased thermal stability.
  • US-A-3,508,941 discloses solutions of at least two different polymers, one of which may be cellulose, in solvents which comprise a cyclic mono (N-methylamine N-oxide), for example NMMO, and optionally a viscosity-reducing diluent such as dimethyl sulphoxide, N-methylpyrrolidone or sulpholane.
  • solvents which comprise a cyclic mono (N-methylamine N-oxide), for example NMMO, and optionally a viscosity-reducing diluent such as dimethyl sulphoxide, N-methylpyrrolidone or sulpholane.
  • US-A-4, 145, 532 discloses a process in which cellulose is dissolved in a solvent comprising an amine oxide and water in a very specifically defined critical range.
  • the amount of water is specific to each amine oxide and varies accordingly within the range from about 1.4 to about 29 percent by weight based on the weight of the solution.
  • the amount of cellulose dissolved in the solution may be varied from about 5 to about 35 percent by weight of the solution.
  • the amine oxide may be NMMO, in which case the amount of water in the solvent is preferably in the range from about 5.5 to about 18 percent by weight.
  • An organic co-solvent may be used in quantities up to about 25 percent by weight of the total solution as a less expensive diluent for the amine oxide or to lower the viscosity of the solution.
  • Any aprotic organic liquid non- solvent for cellulose which does not react chemically with the amine oxide nor cause degradation of the cellulose and which has a dipole moment greater than about 3.5 Debye will be suitable as co-solvent.
  • non-solvents include dimethylsulphoxide, dimethylformamide, dimethylacetamide, N- methylpyrrolidinone, hexamethylphosphoric triamide, acetonitrile and sulpholane.
  • US-A-4, 290, 815 discloses cellulose solvents which comprise an amine oxide, water and as co-solvent a compound containing primary, or combinations of primary and secondary, amino groups wherein the amino groups are bonded to alkyl, alicyclic, dialkyl ether or alkyl/alicyclic radical (s) and wherein the number of carbon atoms divided by the number of primary amino groups is approximately equal to or less than
  • the co-solvents increase the cellulose dissolution rate; lower the temperature necessary to reasonably form a solution; lower the viscosity of the solution; provide solutions with improved colour, amine oxide stability, and cellulose stability,- provide a solution with improved flow characteristics; increase solution processability, e.g. wet spinning; permit the replacement of amine oxides by a less expensive co-solvent; and are recoverable and reusable in cellulose dissolution and processing.
  • US-A-4, 324, 593 discloses cellulose solvents which comprise an amine oxide, an alkaline compound which increases the rate at which cellulose dissolves, and preferably a small amount of water.
  • alkaline compounds include alkali metal hydroxides, ammonia, primary, secondary and tertiary amines, and quaternary ammonium hydroxides.
  • CA-A-1, 251, 880 discloses the use as cellulose solvents of mixtures of two or more specific amine oxides containing a small proportion of water. Cellulose solutions which utilise these solvents have relatively low melting points in comparison to solutions utilising only one amine oxide, and some such solutions can be processed at room temperature.
  • US-A-5, 362, 867 discloses the use of mixtures of NMMO and recovered caprolactam as solvents for cellulose.
  • This recovered caprolactam is obtained by phosphoric acid-catalysed depolymerisation of waste nylon, and it may contain 25-50% of other substances, notably 6-methylvalerolactam.
  • Comminuted cellulose is added to a mixture of NMMO hydrate (63-67% by volume NMMO, balance water) and recovered caprolactam, and solution is effected by a three-stage heat treatment involving evaporation of water, reduction of cellulose D.P., and dissolution.
  • a preferred solution is said to comprise by weight 8-13% cellulose, 8-13% water, 47-52% NMMO and 32-37% recovered caprolactam.
  • EP-A-0, 686, 712 discloses solutions of cellulose in aqueous NMMO which include an additive such as an amine, amide or other amino group-containing compound. Examples of such compounds include urea, caprolactam, aminopropanol and amino acids .
  • the amount of compound in the solution is preferably in the range from 4 to 75 parts by weight on cellulose. These solutions can be spun to produce flexible cellulose fibres of relatively low modulus and degree of order.
  • a solution which comprises (a) cellulose, (b) a tertiary amine N-oxide solvent for the cellulose, and (c) a solution processability-enhancing amount of at least one co- solvent, miscible with the tertiary amine N-oxide, which is an amide selected from the group consisting of compounds of the formula R x CONHR 2 in which either (i) R 1 represents H or C x - C 3 alkyl and R 2 represents H or methyl or (ii) R 1 and R 2 together represent 1,3-propylene.
  • the solution of the invention may additionally comprise (d) a cellulose solubility-enhancing amount of water.
  • Preferred examples of the tertiary amine N-oxide solvent include N, N-dimethylcyclohexylamine N-oxide, N,N- dimethylethanolamine N-oxide and in particular NMMO.
  • the co-solvents used in the invention are amides and are not themselves solvents for cellulose.
  • Preferred examples of the co-solvent include acetamide, 2-pyrrolidinone, N- methylformamide, and in particular formamide.
  • the co-solvents used in the invention exhibit good thermal stability. Some of these co-solvents, including formamide, decompose endothermically . Accordingly, the solutions of the invention may exhibit enhanced thermal stability in comparison with solutions of cellulose in aqueous amine oxides.
  • the co- solvents used in the invention exhibit low toxicity. Use of primary amides such as formamide has the advantage that these amides scavenge nitrosating agents to produce nitrogen and the corresponding carboxylic acid, thereby reducing the risk of formation of toxic N-nitrosamines .
  • solutions of the invention freeze at lower temperatures than solutions of the same cellulose concentration in aqueous amine oxide.
  • the solutions of the invention are often found to supercool, solidifying only after prolonged storage at room temperature or below. Addition of the co-solvent to an aqueous amine oxide in the absence of cellulose also results in depression of freezing point.
  • phase diagrams may be obtained only in limited regions of the phase diagram of the various components of the solution, as is the case for other cellulose solvents including aqueous amine oxides. Such phase diagrams can be obtained by routine experimentation. Having regard to the foregoing comment on solution formation, as guidance the amount of cellulose in the solution may generally be in the range from 5 to 30 percent by weight, the amount of water in the solution may generally be in the range from 0 to 20 percent by weight, and the molar ratio of co-solvent to amine oxide may generally be in the range from 0.2:1 to 1.5:1.
  • the amine oxides and co-solvents may form relatively low- melting crystallisable complexes containing approximately equimolar amounts of the two components.
  • the solutions of the invention may include a small proportion of a stabiliser against thermal decomposition, for example a polyphenolic compound such as propyl gallate, preferably at an amount in the range from 0.01 to 0.5 percent by weight .
  • a stabiliser against thermal decomposition for example a polyphenolic compound such as propyl gallate, preferably at an amount in the range from 0.01 to 0.5 percent by weight .
  • solutions of the invention may be made by direct dissolution or by forming a mixture containing an excess of a volatile non-solvent for cellulose such as water and removing said excess by evaporation so that dissolution occurs.
  • the invention provides a method for the manufacture of a shaped cellulosic article comprising the steps of : (a) forming a solution according to the first aspect of the invention;
  • the shaped cellulose article may be a fibre or a film.
  • the coagulating bath may be aqueous, or it may comprise or consist of the co-solvent.
  • the co- solvents used in the invention are less expensive than amine oxides. This is advantageous in reducing running costs,- amine oxides can be recovered for re-use from coagulating baths with a high degree of efficiency, but some losses are inevitable.
  • the co- solvents used in the invention are of high boiling point.
  • water distils preferentially. This is advantageous, in that it enables uncomplicated recovery processes to be used.
  • dimethylformamide (DMF) distils preferentially from molten mixtures of NMMO, water and DMF.
  • Example 2 The invention is illustrated by the following Example, in which parts and proportions are by weight unless otherwise specified: - Example
  • Cellulose solvents may be investigated on small scale in preliminary fashion by mixing together cellulose, amine oxide hydrate and any co-solvent, and storing the resulting mixture under vacuum at about 90°C so that excess water evaporates and, desirably, dissolution occurs.
  • the possibility of direct dissolution in a solvent may be investigated by mixing amine oxide hydrate and co-solvent, removing excess water by evaporation under vacuum, and then adding cellulose to the concentrated mixture. Better results can be obtained by using finely-divided cellulose and by subjecting cellulose- containing mixtures to high shear. Preliminary experiments may be designed to test mixtures containing about 1 g cellulose and of 10 g total weight.
  • Rotary evaporation of equimolar amounts of NMMO monohydrate and formamide yielded a concentrate containing about 0.25 mole water per mole amine oxide or amide.
  • Rotary evaporation of equimolar amounts of NMMO monohydrate and N- methylformamide yielded a concentrate containing about 0.35 mole water per mole amine oxide or amide.
  • Cellulose was mixed into these concentrates for a few minutes at 45-50°C, and the resulting mixtures were stored at 70°C. The bulk of the cellulose dissolved within three hours without stirring, showing that these concentrates are direct solvents for cellulose. Improved solution was obtained by heating to 90 °C or by evaporation. These solutions were difficult to crystallise and were fibre-forming. Preliminary experiments indicated that the formamide-containing solution exhibited similar rheological properties at 90°C to those of a conventional solution containing the same percentage of cellulose in aqueous NMMO at 105°C.
  • Solutions containing over 20% cellulose could be obtained using the small scale technique, although they were of high viscosity: liquid in the technical sense at room temperature, but rubber .
  • a concentrated 1 : 1 molar mixture of NMMO and formamide was assessed as cellulose solvent on the l kg scale, using a jacketed Z-blade mixer. Much of the cellulose dissolved within a few minutes, by the time the temperature had been raised to 50-55°C. Solution was virtually complete within 2 hours, by which time the temperature was 90°C. It is thought that even more rapid solution could have been achieved with a more efficient mixer. The solution contained 15% cellulose, 62% NMMO and 23% formamide and was fibre-forming. Differential Scanning Calorimetry (DSC) revealed a small exothermic peak at 170°C and exothermic runaway at about 185°C.
  • DSC Differential Scanning Calorimetry
  • DSC of a conventional solution of cellulose in aqueous NMMO containing a small amount of propyl gallate stabiliser revealed exothermic peaks at 140°C and 175 °C (more pronounced than in the solution of the invention) and exothermic runaway at 190°C.
  • the solution of the invention appeared to decompose less violently and less completely at the runaway exotherm than did the comparative solution.
  • the solution of the invention may therefore be processable at higher temperatures than such comparative solutions .
  • Cellulose solutions of the invention such as those described in general or specifically above can be extruded through spinnerets into spin baths to form cellulosic fibres in a manner similar to known techniques.
  • Cellulosic films could be cast from the solutions of the invention by immersing in water glass plates coated with the solutions .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

On décrit des solutions qui comprennent (a) de la cellulose; (b) un solvant N-oxyde d'amine tertaire pour la cellulose; (c) une quantité d'au moins un cosolvant capable d'améliorer la transformabilité, et miscible avec le N-oxyde d'amine tertaire, lequel est un amide sélectionné dans le groupe constitué par de composés de la formule R1CONHR2 dans laquelle (i) R1 est H ou alkyle C¿1?-C3 et R?2¿ est H ou méthyle, ou (ii) R1 et R2 forment ensemble 1,3-propylène; et au besoin, (d) une quantité d'eau pouvant améliorer la solubilité de la cellulose. On décrit en outre des procédés de fabrication d'articles cellulosiques formés à partir desdites solutions.
PCT/GB1999/001566 1998-05-19 1999-05-17 Solutions cellulosiques et leur utilisation WO1999060026A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU39441/99A AU3944199A (en) 1998-05-19 1999-05-17 Cellulosic solutions and their uses
EP99922339A EP1086139A1 (fr) 1998-05-19 1999-05-17 Solutions cellulosiques et leur utilisation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9810778.2 1998-05-19
GBGB9810778.2A GB9810778D0 (en) 1998-05-19 1998-05-19 Cellulosic solutions and their uses

Publications (1)

Publication Number Publication Date
WO1999060026A1 true WO1999060026A1 (fr) 1999-11-25

Family

ID=10832347

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/001566 WO1999060026A1 (fr) 1998-05-19 1999-05-17 Solutions cellulosiques et leur utilisation

Country Status (4)

Country Link
EP (1) EP1086139A1 (fr)
AU (1) AU3944199A (fr)
GB (1) GB9810778D0 (fr)
WO (1) WO1999060026A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10005163A1 (de) * 2000-02-08 2001-08-16 Thueringisches Inst Textil Verfahren zur Herstellung und Verarbeitung einer Celluloselösung
DE10016307C2 (de) * 2000-03-31 2002-05-08 Thueringisches Inst Textil Verfahren zur Herstellung und Verarbeitung einer Celluloselösung
WO2017211798A1 (fr) * 2016-06-07 2017-12-14 Universität Regensburg Procédé de préparation d'un produit à base de cellulose

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0047929A2 (fr) * 1980-09-13 1982-03-24 Akzo GmbH Masses à mouler et à filer à base de cellulose ayant une faible teneur en produits de dégradation à bas poids moléculaire, procédé pour leur préparation et leur application comme objets moulés
EP0662283A2 (fr) * 1994-01-10 1995-07-12 Viskase Corporation Procédé de préparation d'enveloppes en cellules pour aliments
EP0686712A2 (fr) * 1994-06-10 1995-12-13 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Fibres cellulosiques flexibles avec module et RMN-caractéristiques réduits et procédé pour leur fabrication

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0047929A2 (fr) * 1980-09-13 1982-03-24 Akzo GmbH Masses à mouler et à filer à base de cellulose ayant une faible teneur en produits de dégradation à bas poids moléculaire, procédé pour leur préparation et leur application comme objets moulés
EP0662283A2 (fr) * 1994-01-10 1995-07-12 Viskase Corporation Procédé de préparation d'enveloppes en cellules pour aliments
EP0686712A2 (fr) * 1994-06-10 1995-12-13 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Fibres cellulosiques flexibles avec module et RMN-caractéristiques réduits et procédé pour leur fabrication

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10005163A1 (de) * 2000-02-08 2001-08-16 Thueringisches Inst Textil Verfahren zur Herstellung und Verarbeitung einer Celluloselösung
DE10016307C2 (de) * 2000-03-31 2002-05-08 Thueringisches Inst Textil Verfahren zur Herstellung und Verarbeitung einer Celluloselösung
WO2017211798A1 (fr) * 2016-06-07 2017-12-14 Universität Regensburg Procédé de préparation d'un produit à base de cellulose

Also Published As

Publication number Publication date
GB9810778D0 (en) 1998-07-15
EP1086139A1 (fr) 2001-03-28
AU3944199A (en) 1999-12-06

Similar Documents

Publication Publication Date Title
CA1079005A (fr) Solutions de cellulose et produits qui en derivent
CA1215802A (fr) Mise en solution du carbamate de cellulose
US4255300A (en) Composition and process for making precipitated cellulose-polyvinyl alcohol biconstituent composition
US4256613A (en) Composition and process for making precipitated nylon-cellulose biconstituent composition
KR20020093866A (ko) 셀룰로오스 용액의 제조 및 가공방법
CN111621875A (zh) 一种以pet为岛组分的海岛纤维及其制备方法和由其形成的超细纤维
US5362867A (en) Method of making cellulose yarn solution
EP1086139A1 (fr) Solutions cellulosiques et leur utilisation
CN113785007B (zh) 回收利用方法
JP3267781B2 (ja) 再生セルロース成形品の製造方法
JPS6136083B2 (fr)
DE19961818C2 (de) Flüssiginitiator zur beschleunigten Durchführung der anionischen Lactampolymerisation, Verfahren zu dessen Herstellung und Verwendung
CN111676546A (zh) 改性共聚酯作为海岛纤维的海材料的用途
KR910004467B1 (ko) 방향족 폴리아미드섬유와 그의 제조방법
Chacko et al. Melting transition in the leucoemeraldine form of polyaniline
CN111704745B (zh) 一种海岛纤维中海材料的回收方法
KR910004705B1 (ko) 방향족 폴리아미드섬유와 그의 제조방법
US4435547A (en) Stabilized polypyrrolidone end capped with alkanolamine and process for preparing
US4247688A (en) Composition and process for making precipitated hydroxyethylcellulose
US4261881A (en) Poly-2-pyrrolidone composition having improved stability and method of extruding
DE2632416C2 (de) Verfahren zur Herstellung von Poly-p-phenylenterephthalamid oder seiner Copolymere
GB2337990A (en) Process for shaping cellulose
CA2037317A1 (fr) Utilisation d'un solvant pour la formation in-situ de fibres de renfort d'un elastomere
JP2581853B2 (ja) ポリ−γ−グルタミン酸エステル繊維およびその製造法
KR960012441B1 (ko) 셀룰로오스를 주성분으로 하는 압출 및 방사 용액

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1999922339

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: KR

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999922339

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1999922339

Country of ref document: EP