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WO2001058960A1 - Procede pour la production et le traitement d'une solution cellulosique - Google Patents

Procede pour la production et le traitement d'une solution cellulosique Download PDF

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Publication number
WO2001058960A1
WO2001058960A1 PCT/DE2001/000445 DE0100445W WO0158960A1 WO 2001058960 A1 WO2001058960 A1 WO 2001058960A1 DE 0100445 W DE0100445 W DE 0100445W WO 0158960 A1 WO0158960 A1 WO 0158960A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
nmmo
solution
solvent
pyrrolidonate
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
PCT/DE2001/000445
Other languages
German (de)
English (en)
Inventor
Bernd Riedel
Eberhard Taeger
Markus Eilers
Horst Kramer
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.)
Thueringisches Institut fuer Textil und Kunststoff Forschung eV
Original Assignee
Thueringisches Institut fuer Textil und Kunststoff Forschung eV
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 Thueringisches Institut fuer Textil und Kunststoff Forschung eV filed Critical Thueringisches Institut fuer Textil und Kunststoff Forschung eV
Priority to AU39157/01A priority Critical patent/AU3915701A/en
Publication of WO2001058960A1 publication Critical patent/WO2001058960A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/096—Nitrogen containing compounds
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • the invention relates to a simplified method for producing and processing a cellulose solution, which is obtained by dissolving the cellulose in a tertiary amine oxide pyrrolidonate, preferably NMMO pyrrolidonate.
  • cellulose which is obtained from plants, has been used to produce textile moldings, e.g. B. fibers, filaments or foils.
  • textile moldings e.g. B. fibers, filaments or foils.
  • processes dominated in which the cellulose had to be chemically modified before it went into solution, extruded through appropriate molding tools and then chemically converted again.
  • the most widely used process was the viscose process, in which a large number of environmentally harmful chemicals, by-products and waste products as well as resource-intensive process design play a role.
  • people were looking for suitable direct solvents for cellulose.
  • Such a system which has also been used industrially, is an aqueous solution of a tertiary amine oxide, e.g. B.
  • N-methylmorpholine-N-oxide, further NMMO (z. B. US 4324593, US 4290815, DD 218104).
  • the fibers spun using such processes were given the generic term LYOCELL.
  • a key disadvantage of this system is the relatively high viscosity of the spinning masses, which only allows transport within a process under defined, technically difficult conditions.
  • the dissolving process requires an exact temperature control, which is complex to implement to be able to set the residual water content determining the dissolving process (EP 0668941, EP 0662204).
  • the aim of the invention is to eliminate these disadvantages of cellulose solutions.
  • cellulose dissolves in tertiary amine oxide pyrrolidonates, preferably NMMO pyrrolidonates, and that molded articles can be produced from these advantageous solutions by shaping, coagulation and subsequent removal of the solvent.
  • tertiary amine oxide pyrrolidonates preferably NMMO pyrrolidonates
  • molded articles can be produced from these advantageous solutions by shaping, coagulation and subsequent removal of the solvent.
  • This advantage is evidently due to the fact that the pyrrolido- nate causes a more favorable internal structure of the cellulose solution.
  • the solutions are characterized by a lower freezing temperature and, as a result of the larger molecular volume of the pyrrolidonates in comparison and the associated greater distance between the solvated cellulose molecules, by a lower shear thinning viscosity.
  • Pyrrolidone is an amphiprotic solvent which forms an integer defined and isolable 1: 1 complex as well as fractional complexes, which are not individually isolable, via hydrogen bonds with tertiary amine oxides. These complexes, which are thermally stable up to 150 ° C, are called pyrrolidonates.
  • pyrrolidonates For their preparation, water-containing NMMO is mixed with pyrrolidone and the water is drawn off from the solution in vacuo via an interposed column while adding heat. When cooling, the NMMO pyrrolidonate crystallizes out and can be purified by recrystallization from benzene.
  • the cellulose can be dissolved by a) defined pyrrolidonate or defined pyrrolidonate mixtures, produced from aqueous NMMO and pyrrolidone by distilling off the water and purification by recrystallization, b) pyrrolidonate mixtures, produced from aqueous NMMO and pyrrolidone by distillation of the water until a soldering quality sufficient for cellulose is achieved.
  • the pyrrolidonate or the pyrrolidonate mixtures can contain diluents.
  • the diluents which may still be present in the solutions can be aprotic organic solvents, such as z. B. dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and dimethylacetamide, or amphiprotic solvents, such as. B. the pyrrolidone and / or water and / or lower alcohols, or the tertiary amine oxide itself. Due to the boiling point of the pyrrolidone compared to water, which is more than 140 ° C, the composition of the pyrrolidonate can be realized technically safely.
  • aprotic organic solvents such as z. B. dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and dimethylacetamide
  • amphiprotic solvents such as. B. the pyrrolidone and / or water and / or lower alcohols, or the tertiary amine oxide itself. Due to the boiling point of the pyrrolidone compared to water,
  • Cellulose materials that are used in the process are preferably chemical fiber pulp, cotton linters, softwood sulfite, softwood sulfate and or hardwood pulps from the sulfite or sulfate digestion process of different degrees of polymerization.
  • the pulp can be used in one or in the form of mixtures of different degrees of polymerization. Pulps treated with pressure explosion technology, electron beams or enzymes can also be used.
  • a particularly advantageous embodiment (b) will further describe how a cellulose solution is produced, shaped into fibers, the cellulose is regenerated by the action of a coagulation medium, and the solvent is washed out and recovered.
  • NMMO is used as the tertiary amine oxide.
  • the starting point is pulp, as they were called in the section described above.
  • the pulp is subjected to a pretreatment to ensure better access to the solvent or its precursor.
  • the pulp can be shredded mechanically using shredders or mills and added in this form.
  • Another variant of the pretreatment of the pulp is that it is crushed in an aqueous solution by intensive shearing and the resulting pulp is then dewatered to a defined moisture level. content is set before it comes into contact with the solvent system.
  • the pulp In the phase of the aqueous treatment, the pulp can be treated with chemicals (lyes, acids, surfactants) or enzymes that promote the digestion and accessibility of cellulose.
  • a mash is produced by continuously or discontinuously mixing the components water, NMMO, pyrrolidone and cellulose.
  • the cellulose concentration of the mash is usually between 4 and 23% (mass).
  • other soluble or insoluble, organic or inorganic compounds such as pigments, dyes, ion exchangers, reactive resins, carbon black, stabilizers, ceramic powders, can be added.
  • the resulting mash is sheared in an evaporator by applying a vacuum with appropriate temperature control. It is irrelevant whether the apparatus is designed according to the principle of a thin layer or other wave apparatus. According to the invention, temperatures between 60-140 ° C, preferably 80-130 ° C, and pressures of 30-150 mbar can be used.
  • the cellulose concentration in the solution is between 5 and 25%.
  • stabilizers such as. B. gallic acid propyl ester, preferably up to a content of 1% based on cellulose, in the spinning solution.
  • the spinning solution obtained is pressed through a temperature-controlled transport line with the aid of a pump through a filter element and then fed directly into a precipitation bath via a molding tool or through an air gap.
  • the subsequent washing of the adhering solvent NMMO / pyrrolidone shoots with water, which controls the concentration of the spinning bath in the countercurrent principle.
  • a customary post-treatment procedure known for cellulosic fibers / filaments follows [finishing, drying, if necessary (in between) bleaching and cutting].
  • the precipitation bath consisting of NMMO, pyrrolidone and water and / or low molecular weight alcohols as the direct coagulation medium, is given for reprocessing.
  • the reprocessing includes the processes of removing undissolved foreign matter via filters and of dissolved foreign matter via anion and cation exchange resins as well as the concentration using evaporator systems.
  • the regenerated mixture obtained in this way can in turn be made available to the stage of the mash production in the required concentration.
  • the resulting concentrate from the coagulant evaporation stage is also recycled to the wash stage after the coagulation bath.
  • the described cycle management makes it possible to maintain the recovery rate for NMMO and pyrrolidone at> 99.5%.
  • 370 g of pulp are homogenized with a Cuoxam DP of 520 in a mixture of 1830 g of NMMO, 530 g of pyrrolidone and 720 g of water.
  • the temperature of the mixture is 50 ° C.
  • the resulting homogeneous mash is treated with shear, the application of heat and a vacuum until a homogeneous solution of the cellulose is observed.
  • the process ran at a final vacuum of 30 mbar and a temperature of the reaction mass of max. 95 ° C.
  • the solution obtained was pressed through a spinneret at a temperature of 80 ° C. and spun through an air gap into a precipitation bath of water.
  • the hole diameter of the nozzle bores was 75 ⁇ m, the spinning speed 36 m / min.
  • the resulting fiber cable was washed out, cut and prepared.
  • the textile-physical values were measured as follows:
  • a cellulose solution was prepared analogously to Example 1, but without the pyrrolidone component.
  • the mixture was homogenized into a mash: 370 g of cellulose, 2240 g of NMMO and 800 g of water.
  • the evaporation conditions corresponded to those of Example 1; 440 g of water were evaporated.
  • Example 1 350 g cellulose, Cuoxam DP 500, 1150 g NMMO, 500 g water, 840 g pyrrolidone, 2 g propyl gallic acid. The subsequent treatment of the homogenized mash under the conditions of Example 1 was carried out until 500 g of water had been distilled off.
  • Viscosity 4520 Pa s

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

Abstract

L'invention concerne un procédé simplifié pour la production et le traitement d'une solution cellulosique qui est produite par dissolution de la cellulose dans un aminoxyde pyrrolidonate tertiaire, de préférence du NMMO pyrrolidonate. La cellulose est dissoute dans des aminoxyde pyrrolidonates tertiaires, de préférence des NMMO pyrrolidonates, et des corps moulés sont produits par façonnage, coagulation, puis élimination du solvant. Grâce à l'ajout de composés organiques et inorganiques, on obtient des applications du corps moulé cellulosique pour la formation de caractéristiques spéciales. Les étapes du processus comprennent la préparation du matériau de départ, le mélange et l'homogénéisation dans une phase préalable de solvant, l'élimination de l'eau, le transport et le filtrage de la solution, l'extrusion à travers un outil de moulage, le lavage pour éliminer le solvant, l'application, la purification et l'augmentation de concentration du bain de précipitation.
PCT/DE2001/000445 2000-02-08 2001-02-06 Procede pour la production et le traitement d'une solution cellulosique Ceased WO2001058960A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39157/01A AU3915701A (en) 2000-02-08 2001-02-06 Method for producing and processing a cellulose solution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2000105163 DE10005163A1 (de) 2000-02-08 2000-02-08 Verfahren zur Herstellung und Verarbeitung einer Celluloselösung
DE10005163.4 2000-02-08

Publications (1)

Publication Number Publication Date
WO2001058960A1 true WO2001058960A1 (fr) 2001-08-16

Family

ID=7629980

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2001/000445 Ceased WO2001058960A1 (fr) 2000-02-08 2001-02-06 Procede pour la production et le traitement d'une solution cellulosique

Country Status (3)

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AU (1) AU3915701A (fr)
DE (1) DE10005163A1 (fr)
WO (1) WO2001058960A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004088010A1 (fr) * 2003-04-01 2004-10-14 Zimmer Aktiengesellschaft Procede et dispositif pour produire des fils de cellulose post-etires
US7204265B2 (en) 2002-02-13 2007-04-17 Zimmer Aktiengesellschaft Bursting insert
US7364681B2 (en) 2002-01-08 2008-04-29 Stefan Zikeli Spinning device and method having cooling by blowing
WO2009098073A1 (fr) 2008-02-08 2009-08-13 List Holding Ag Procédé et dispositif de production de corps moulés
WO2009111836A1 (fr) * 2008-03-14 2009-09-17 Zeo Ip Pty Ltd Procédé de granulation de fibres de cellulose
US7614864B2 (en) 2002-01-28 2009-11-10 Stefan Zikeli Ergonomic spinning system
EP2484820A4 (fr) * 2009-09-30 2013-06-26 Shanghai Lyocell Fibre Dev Co Ltd Fibre de bambou filée avec solvant présentant un module à l'état humide élevé et son procédé de production
US9555558B2 (en) 2010-04-08 2017-01-31 List Holding Ag Process for producing a product

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10331342B4 (de) * 2003-07-11 2009-03-12 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Thermostabile Form- oder Spinnmasse
DE102014220289B4 (de) 2014-10-07 2016-12-29 Bundesdruckerei Gmbh Verfahren zur Herstellung von modifizierter Regeneratcellulose und deren Verwendung
WO2017211798A1 (fr) * 2016-06-07 2017-12-14 Universität Regensburg Procédé de préparation d'un produit à base de cellulose
CN115369505B (zh) * 2022-07-08 2024-05-03 株洲时代新材料科技股份有限公司 一种多级分散盘沉析成型装置及成型工艺、沉析纤维沉析纯化装置及其工艺

Citations (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
US4324593A (en) * 1978-09-01 1982-04-13 Akzona Incorporated Shapeable tertiary amine N-oxide solution of cellulose, shaped cellulose product made therefrom and process for preparing the shapeable solution and cellulose products
GB2337990A (en) * 1998-06-03 1999-12-08 Courtaulds Fibres Process for shaping cellulose

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9810778D0 (en) * 1998-05-19 1998-07-15 Courtaulds Plc Cellulosic solutions and their uses

Patent Citations (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
US4324593A (en) * 1978-09-01 1982-04-13 Akzona Incorporated Shapeable tertiary amine N-oxide solution of cellulose, shaped cellulose product made therefrom and process for preparing the shapeable solution and cellulose products
GB2337990A (en) * 1998-06-03 1999-12-08 Courtaulds Fibres Process for shaping cellulose

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7364681B2 (en) 2002-01-08 2008-04-29 Stefan Zikeli Spinning device and method having cooling by blowing
US7614864B2 (en) 2002-01-28 2009-11-10 Stefan Zikeli Ergonomic spinning system
US7204265B2 (en) 2002-02-13 2007-04-17 Zimmer Aktiengesellschaft Bursting insert
WO2004088010A1 (fr) * 2003-04-01 2004-10-14 Zimmer Aktiengesellschaft Procede et dispositif pour produire des fils de cellulose post-etires
CN100410430C (zh) * 2003-04-01 2008-08-13 齐默尔股份公司 用于制造后拉伸的纤维素长丝的方法和设备
WO2009098073A1 (fr) 2008-02-08 2009-08-13 List Holding Ag Procédé et dispositif de production de corps moulés
US9206528B2 (en) 2008-02-08 2015-12-08 List Holding Ag Method and device for the production of molded bodies
WO2009111836A1 (fr) * 2008-03-14 2009-09-17 Zeo Ip Pty Ltd Procédé de granulation de fibres de cellulose
EP2484820A4 (fr) * 2009-09-30 2013-06-26 Shanghai Lyocell Fibre Dev Co Ltd Fibre de bambou filée avec solvant présentant un module à l'état humide élevé et son procédé de production
US9555558B2 (en) 2010-04-08 2017-01-31 List Holding Ag Process for producing a product

Also Published As

Publication number Publication date
DE10005163A1 (de) 2001-08-16
AU3915701A (en) 2001-08-20

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