WO2012107362A1 - Procédé de façonnage de carbamate de cellulose et produits fabriqués par ce procédé - Google Patents
Procédé de façonnage de carbamate de cellulose et produits fabriqués par ce procédé Download PDFInfo
- Publication number
- WO2012107362A1 WO2012107362A1 PCT/EP2012/051877 EP2012051877W WO2012107362A1 WO 2012107362 A1 WO2012107362 A1 WO 2012107362A1 EP 2012051877 W EP2012051877 W EP 2012051877W WO 2012107362 A1 WO2012107362 A1 WO 2012107362A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cellulose
- solvent
- carbamate
- swelling agent
- cellulose carbamate
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
-
- 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
- C08J2301/08—Cellulose derivatives
Definitions
- the present invention relates to a process for processing cellulose carbamate, wherein cellulose carbamate is mixed with a swelling agent or solvent. Furthermore, the invention relates to the use of this method obtainable body, for example as a single or multi-layer composite membranes. Finally, the invention relates to mixtures containing cellulose carbamate and a swelling agent or solvent.
- Cellulose carbamate is an alkali-soluble cellulose derivative, which is also referred to as cellulose aminomethanoate or cellulose amino formate.
- the carbamate group Upon dissolution in aqueous alkaline solutions, the carbamate group can be hydrolytically cleaved under suitable conditions and regenerated cellulose is formed. This process can be used to produce regenerated cellulose fibers.
- This process technology is considered to be an environmentally friendly alternative to the viscose spinning process (see for example WO 2007/135245, WO 2003/099871, US 2,134,825, US 4,999,425 and WO 2004/046198).
- the dissolution and shaping of the cellulose carbamate can also be used so that the carbamate group remains in the polymer and the formed cellulose carbamate is used without regeneration to cellulose.
- Examples of use for this are: Use as adsorbent in water treatment and heavy metal removal (JP 09099268A, US 2005/0035057), hygiene products, medical and health products (WO 2007/135245 AI).
- cellulose carbamate is used for sausage casings (EP 0 402 707 A1, EP 0 402 606 A2).
- the dissolution of cellulose carbamate has been extensively studied, various solvents have been proposed for this purpose. These include aqueous alkali solutions
- ionic liquids DE 10 2008 018 743, DE 10 2008 018 745, DE 10 2008 018 746
- NMMO N-methylmorpholine N-oxide
- the solutions are dissolved in a suitable e.g. coagulated acidic or alkaline precipitation bath. Additives can also be added to the precipitation bath. Depending on the process conditions, fibers, powders are formed in the precipitation bath, films are formed by casting (WO 2005/080660, JP 02227024).
- An improvement in the desired product properties can also be achieved by adding suitable additives to the carbamate solution, examples being Zn, Al, or Sn salts, and alkali metal salts can also be added (PL 168783, Halidan et al. Fangzhi Xuebao 2008 29 (1) 5-8).
- Flame retardant properties can be achieved by adding flame retardant chemicals containing P-N, e.g. l, 2-bis (2-oxo-5,5-dimethyl-l, 3,2-dioxyphosphacyclohexyl-2-imino) ethane (DDPN) to the carbamate solution are obtained (Cheng et al. Fangzhi Xuebao 2007 28 (4) 19 -21).
- cellulose carbamate solutions have also been proposed in the field of textile finishing for coating other materials, on the one hand to introduce the properties of the cellulose carbamate into the material and, on the other hand, to improve the biocompatibility of the materials (Hermanutz et al., Melliand Textilberichte 2004 85 (1-2 ) 68-72, EP 0 550 879).
- Blends of cellulose carbamate and cellulose have been dissolved in NMMO (EP 1 716 273) or other suitable solvents (Fibers & Textiles in Eastern Europe 2010 18 (2) 21-30) to produce regenerated fibers having enhanced water sorption properties therefrom.
- Object of the present invention is to eliminate the known problems in the shaping of cellulose or cellulose carbamate.
- This object is achieved by methods for processing cellulose carbamate, wherein cellulose carbamate is mixed with a swelling agent or solvent, which is characterized in that the mixture is brought by pressure and optionally temperature increase in a desired shape, wherein the amount of cellulose carbamate the maximum solubility of the Cellulosecarbamats in the swelling agent or solvent for the given physical conditions temperature, pressure and optionally available dissolution time by a factor of 1.5 to 6 exceeds.
- the present invention utilizes the swelling and dissolving behavior of the cellulose carbamate in suitable solvents and aqueous alkali.
- composite material in the present application follows the usual definition for such materials
- Composite materials often abbreviated as “composites” are engineered or natural materials of two or more materials that have distinctly different physical or chemical properties and are microscopic or macroscopically separated in the finished structure (http://en.wikipedia.org/wiki/Composite_material).
- a swelling agent is a substance which is able to penetrate into the cellulosic structure at least locally and thus cause an increase in the volume of the cellulose structure.
- the swelling agent thus leads to an increase in volume and usually also to a significant change in the physical properties, e.g. Fiber strength, flexibility, elasticity, etc.
- the interactions between the macromolecules and the swelling agent are more favorable than the intermolecular forces between the macromolecules on the one hand and the swelling agent molecules on the other hand.
- the at least partial penetration of the swelling agent into the polymer structure (and thus the volume increase) is therefore energetically favored.
- the ability to form cellulose carbamate without the dissolution of the polymer has not previously been described.
- the process is characterized by the small amounts of source / Solvents that are required to perform simply and inexpensively, and by the ability to incorporate other polymers into the swollen matrix of carbamate allows for the production of a variety of product variants.
- the materials that can be produced by the process according to the invention are also environmentally friendly and resources can be produced gently.
- the simple process management also allows the simple integration of the process in today's textile production processes.
- materials or combinations of materials containing cellulose carbamate are treated with a swelling / solvent whereby the cellulose carbamate is converted into a moldable state.
- the materials are molded, then washed and optionally neutralized. This will remove the source / solvent. Subsequently, the drying of the material takes place.
- fiber-reinforced composites with membrane properties can be produced by this process technology.
- the material e.g. Tissue retains the original structure, but the pores between the binding sites are largely closed and the materials have membrane properties.
- the membranes produced according to the invention have low air permeability, high water penetration resistance and further membrane-characteristic properties.
- the invention relates to uses of such products made from cellulose carbamate.
- Suitable source / solvents for the procedure according to the invention are conventional solvents for cellulose carbamate, for example aqueous alkali solutions, ionic liquids, concentrated salt solutions, for example ZnCl 2 .
- a dissolution of the material to be treated is to be avoided, as this causes the basic structure (fabric, knitted fabric, non-woven, paper) to be disadvantageously lost.
- the ratio of cellulose carbamate to swelling solvent is therefore to be chosen so that the maximum solubility of the cellulose carbamate in the swelling / solvent is significantly exceeded by the amount present and cellulose carbamate. This maximum solubility is easily determined by preliminary tests for the dissolution of cellulose carbamate in a particular liquid.
- the amount of swelling / solvent to be used in the process according to the invention should be selected so that for a given solvent and fixed experimental conditions (time, temperature) the amount of cellulose carbamate used is 1.5 to 6 times greater than the maximum solubility of the cellulose carbamate ,
- the method differs from the prior art methods which suggest for the preparation and processing of liquid crystalline solutions a content of 20-50% by weight of cellulose carbamate in a solvent, which is in the range of solubility for cellulose carbamate and for the selected working conditions remains below the value of maximum solubility (DE 10 2005 029 793, US 2009/0258227 AI).
- additional components e.g., fabrics, yarns, fibers, powders
- various novel materials can be produced.
- cellulose carbamate is used in the form of woven fabrics, nonwovens, knits, cellulose nonwovens or combinations thereof.
- at least one further material is added, which is substantially insoluble in the solvent or swelling agent, this material being molded simultaneously with the cellulose carbamate.
- the at least one further material is a polymer in order to combine advantageous material properties of other polymers with those of cellulose carbamate.
- Advantageous is the use of natural polymers such as cellulose, cellulose derivatives, polysaccharides or mixtures thereof. Natural fibers are also advantageous. Of course, synthetic polymers such as polyester, polyamide or the like. Possible. It is advantageous if the at least one further material in the form of fabrics, nonwovens, knits, cellulose nonwovens or combinations thereof is present.
- An advantageous embodiment may consist in that at least two layers of material have been combined to form a composite.
- substances dissolved or dispersed in the solvent or swelling agent are added prior to the formation of the carbamate so that at least some of these added substances are incorporated into the carbamate or optionally into the further material. It is particularly advantageous if the solvent or swelling agent inorganic salts, flame retardant chemicals, pigments, dyes, other colorants or mixtures thereof are added.
- the swelling agent or solvent is an aqueous alkali metal hydroxide solution, an ionic liquid or NMMO.
- Fig. 2 schematically illustrates the inventive method according to a variant embodiment
- Fig. 3 schematically illustrates the inventive method according to another
- Variant (variant C), 4 shows a tensile force length change curves of viscose CV (- -),
- Cellulose carbamate CC and (c) cellulose carbamate treated in 2.5 M NaOH and 1 bar squeezing pressure (top row: 65 ⁇ , scale 200 ⁇ - bottom: 250 ⁇ , scale 100 ⁇ ).
- the cellulose carbamate (1) is passed through the swelling / solvent (2), and e.g. compressed by a squeezing (3).
- the result is compacted materials with a compact structure, so for example, when using a tissue structure, a membrane-like material.
- a component (4) is added to the swelling / solvent during the molding process to the swelling / solvent (2), dissolved or dispersed therein and processed together with the carbamate during the molding process.
- This component may be dissolved or undissolved.
- this component is introduced into the moldable carbamate and fixed. This results Functional materials that have special properties due to the fixed component, eg flame-retardant properties.
- the procedures A and B are combined and at the same time functional elements and structural elements are combined to form a functional multi-layer material, e.g. Fiber reinforcement (variant 1) and color pigments embedded in the cellulose carbamate (variant 2). This procedure is shown in FIG.
- Suitable swelling / solvents can be selected from the known solvents for cellulose carbamate, eg aqueous alkali metal hydroxide solutions (eg NaOH), NMMO, ionic liquids (eg [Bmim] Ac) or concentrated metal salt solutions and melts (eg ZnCl 2 ).
- the application can be carried out by the usual methods for liquid application, for example, be: spray, dive and squeeze, imprint and auftakeln.
- the pressure required for deformation is between 0.5 and 5 bar, preferably between 1 and 3 bar.
- the processing temperature is between -25 ° C and 160 ° C, with the solvent used setting the preferred temperature range. In a particularly advantageous embodiment, the application temperature is defined by the maximum dissolving power of the swelling agent / solvent.
- the processing time depends on the material properties and the process conditions temperature, time, processing pressure and solvent and can be between 30 s and 24 hours.
- Suitable cellulose carbamate different cellulose polymers can be used with different degrees of substitution, a characterization can be done by the nitrogen content.
- Suitable polymers may have different average degrees of polymerization, different material structures may be used, eg, nonwoven fabrics, fibers, yarns, nonwovens, knits, fabrics.
- the mechanical properties of the membranes produced depend not only on the processing conditions but also on the starting material. Therefore, the mechanical properties can be changed by selecting appropriate structuring materials in a wide range and adapted to a particular application. In the mode of operation according to variant A, different solid materials can also be incorporated into the cellulose carbamate structure.
- the supplied solid component may have different structure and consist for example of fibers, yarns or textile surfaces (nonwovens, fabrics, knits) and there are composites.
- the polymer material conventional materials may be used, for example, cellulose, cellulose carbamate, cellulose derivatives, polyesters, polyamide or mixtures thereof.
- the procedure B embedding of materials in the deformable cellulose carbamate matrix can be achieved.
- the source / solvent dispersed materials may be polysaccharides, natural fibers or colored pigments, solutes which are incorporated into the cellulose carbamate may e.g. its inorganic salts, flame retardants, dyes, organic functional chemicals (antimicrobial additives).
- the amount of substances to be incorporated is determined by the required final properties of the composites.
- novel membrane composites which can be prepared according to the invention can have a multiplicity of functional properties, for example by the production technique. antimicrobial properties, flame retardant properties, high moisture and water absorption, heavy metal absorption.
- the membranes can have high air permeability, high swelling capacity and high water passage resistance.
- the extraordinarily advantageous properties of the composite materials allow their use for a variety of applications, of which examples are given: waterproof membranes with high vapor permeability, water-absorbing layers in high-performance textiles, membranes as separators and filter media.
- a particular advantage of the technology results from the cost-effective production, which does not require high investments, and the high flexibility of the technology, so that a wide range of composite materials can be produced for many different applications.
- the technology is useful for:
- cellulose carbamate composites which additionally contain other polymers (for example cellulose, PES, PA, PUR, PP),
- the process according to the invention is environmentally friendly and energy-saving. Therefore, by the described procedure, a new hitherto unknown access to products with improved properties is possible, which are produced from renewable polymers.
- the general mode of operation of the process technology can be used a variety of natural sources of cellulose, as examples of raw materials are: cotton, bamboo fibers, sugar cane, sisal, coconut, pineapple, straw (rice, wheat, corn), poplar wood, spruce wood, Cellulose.
- a tissue of cellulose carbamate (degree of substitution 0.25) is impregnated by a pad with 2.5 mol / 1 sodium hydroxide solution at room temperature.
- the contact pressure at the padder is set to 1, 2, 3 bar and an operating speed of 1 m / min is set.
- the fabric After squeezing, the fabric is washed with warm water and neutralized in a neutralizing bath with 1 mol / 1 acetic acid for 4 hours and then washed with cold water. The completeness of the washout process is checked by pH measurement in the wash water. The drying is done on a tenter at 105 ° C carried out within 3 min, then the samples are stored at room temperature for 24 h. The treatment gives a single-layer cellulose carbamate membrane.
- the tensile force-elongation curves show the solidification of the material in Fig. 4, wherein the tensile force (strength) is plotted as a function of the elongation (Elongation).
- Environmental Scanning Electron Microscope images (ESEM, Fig. 5) confirm the membrane structure of the treated material. Elemental analysis (N content) and FTIR-ATR analysis confirm that the carbamate group was not removed by the treatment. With tests to measure air permeability, swellability and water tightness, the membrane properties can be confirmed.
- Two tissues of cellulose carbamate (degree of substitution 0.25) are impregnated by a padder with 2.5 mol / 1 sodium hydroxide solution at room temperature.
- the contact pressure at the padder is set to 1, 2, 3 bar and an operating speed of 1 m / min is set.
- the fabric After squeezing, the fabric is washed with warm water and neutralized in a neutralizing bath with 1 mol / 1 acetic acid for 4 hours and then washed with cold water. The completeness of the washout process is checked by pH measurement in the wash water. The drying is carried out on a tenter at 105 ° C within 3 min, then the samples are stored at room temperature for 24 h. Through the treatment, the two layers are connected together and it forms a two-layer cellulose carbamate membrane.
- the tensile force-length change curves show the solidification of the material (Fig. 5).
- Environmental Scanning Electron Microscope Images confirm the membrane structure of the treated material. Elemental analysis (N content) and FTIR-ATR analysis confirm that the carbamate group was not removed by the treatment.
- Application example 3 A fabric of cellulose carbamate (degree of substitution 0.25) and a viscose fabric are impregnated by a pad with 2.5 mol / 1 sodium hydroxide solution at room temperature.
- the contact pressure at the padder is set to 1, 2, 3 bar and an operating speed of
- the fabric After squeezing, the fabric is washed with warm water and neutralized in a neutralizing bath with 1 mol / 1 acetic acid for 4 hours and then washed with cold water. The completeness of the washout process is checked by pH measurement in the wash water. The drying is carried out on a tenter at 105 ° C within 3 min, then the samples are stored at room temperature for 24 h. Through the treatment, the two layers are connected together and it forms a two-layer cellulose / cellulose-carbamate composite membrane. The tensile force-length change curves show the solidification of the material.
- Environmental Scanning Electron Microscop images confirm the membrane structure of the treated material. Elemental analysis (N content) and FTIR-ATR analysis confirm that the carbamate group was not removed by the treatment. With tests to measure air permeability, swellability and water tightness, the membrane properties can be confirmed.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
L'invention concerne un procédé de traitement de carbamate de cellulose, consistant à mélanger du carbamate de cellulose avec un agent gonflant ou un solvant. Une forme désirée est conférée au mélange par application de pression et éventuellement par augmentation de la température, la quantité de carbamate de cellulose étant 1,5 à 6 fois supérieure à la solubilité maximale du carbamate de cellulose dans l'agent gonflant ou le solvant pour les conditions physiques prédéfinies en termes de température, de pression et de temps de dissolution disponible.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12703762.0A EP2673135A1 (fr) | 2011-02-08 | 2012-02-03 | Procédé de façonnage de carbamate de cellulose et produits fabriqués par ce procédé |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ATA163/2011 | 2011-02-08 | ||
AT1632011A AT511002A1 (de) | 2011-02-08 | 2011-02-08 | Verfahren zur verformung von cellulosecarbamat und produkte, die nach diesem verfahren hergestellt werden |
Publications (1)
Publication Number | Publication Date |
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WO2012107362A1 true WO2012107362A1 (fr) | 2012-08-16 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2012/051877 WO2012107362A1 (fr) | 2011-02-08 | 2012-02-03 | Procédé de façonnage de carbamate de cellulose et produits fabriqués par ce procédé |
Country Status (3)
Country | Link |
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EP (1) | EP2673135A1 (fr) |
AT (1) | AT511002A1 (fr) |
WO (1) | WO2012107362A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104045720A (zh) * | 2014-07-01 | 2014-09-17 | 东华大学 | 一种纤维素经过尿素改性后的低温溶解方法 |
CN104163872A (zh) * | 2014-06-13 | 2014-11-26 | 天津工业大学 | 一种阻燃纤维素衍生物的制备方法 |
US20190100739A1 (en) * | 2012-11-21 | 2019-04-04 | Ipsen Bioinnovation Limited | Methods for the manufacture of proteolytically processed polypeptides |
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US4906521A (en) * | 1986-12-31 | 1990-03-06 | Neste Oy | Non-woven fibre product |
WO2002097175A2 (fr) * | 2001-05-30 | 2002-12-05 | Deutsche Institute für Textil- und Faserforschung Stuttgart | Materiau a base de cellulose adapte a une coloration peu saline et a une impression a hauts rendements de couleur et a hautes solidites de couleur, a une impression par des procedes a jet d'encre et a une impression par transfert a l'etat humide |
US20080038979A1 (en) * | 2004-02-17 | 2008-02-14 | Peter Weigel | Method For The Production Of Non-Woven, Non-Woven, And Use Thereof |
US20090258561A1 (en) * | 2008-04-14 | 2009-10-15 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Cellulose carbamate spinning solution, method for producing a cellulose carbamate nonwoven, and use of the same |
Family Cites Families (5)
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DE19910105C2 (de) * | 1999-03-08 | 2003-12-04 | Fraunhofer Ges Forschung | Verfahren zur Herstellung einer porösen Cellulose-Matrix |
DE10203005A1 (de) * | 2002-01-26 | 2003-08-07 | Juergen Wack | Verfahren zur Herstellung einer Cellulosecarbamatlösung |
DE102004007616B4 (de) * | 2004-02-17 | 2005-12-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung von Fasern und anderen Formkörpern aus Cellulosecarbamat und/oder regenerierter Cellulose |
DE102005029793B4 (de) * | 2005-06-27 | 2007-04-26 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Vliesstoffe, Verfahren zu deren Herstellung sowie deren Verwendung |
DE102008018745A1 (de) * | 2008-04-14 | 2009-10-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Cellulosecarbamat-Spinnlösung, Cellulosecarbamat-Blasfolie sowie Verfahren zu deren Herstellung und Verwendungsmöglichkeiten |
-
2011
- 2011-02-08 AT AT1632011A patent/AT511002A1/de not_active Application Discontinuation
-
2012
- 2012-02-03 EP EP12703762.0A patent/EP2673135A1/fr not_active Withdrawn
- 2012-02-03 WO PCT/EP2012/051877 patent/WO2012107362A1/fr active Application Filing
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US4906521A (en) * | 1986-12-31 | 1990-03-06 | Neste Oy | Non-woven fibre product |
WO2002097175A2 (fr) * | 2001-05-30 | 2002-12-05 | Deutsche Institute für Textil- und Faserforschung Stuttgart | Materiau a base de cellulose adapte a une coloration peu saline et a une impression a hauts rendements de couleur et a hautes solidites de couleur, a une impression par des procedes a jet d'encre et a une impression par transfert a l'etat humide |
US20080038979A1 (en) * | 2004-02-17 | 2008-02-14 | Peter Weigel | Method For The Production Of Non-Woven, Non-Woven, And Use Thereof |
US20090258561A1 (en) * | 2008-04-14 | 2009-10-15 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Cellulose carbamate spinning solution, method for producing a cellulose carbamate nonwoven, and use of the same |
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AMARASEKARA A S ET AL: "Homogeneous phase synthesis of cellulose carbamate silica hybrid materials using 1-n-butyl-3-methylimidazolium chloride ionic liquid medium", CARBOHYDRATE POLYMERS, APPLIED SCIENCE PUBLISHERS, LTD. BARKING, GB, vol. 78, no. 3, 15 October 2009 (2009-10-15), pages 635 - 638, XP026824618, ISSN: 0144-8617, [retrieved on 20090606] * |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190100739A1 (en) * | 2012-11-21 | 2019-04-04 | Ipsen Bioinnovation Limited | Methods for the manufacture of proteolytically processed polypeptides |
US10808236B2 (en) * | 2012-11-21 | 2020-10-20 | Ipsen Bioinnovation Limited | Methods for the manufacture of proteolytically processed polypeptides |
US11441141B2 (en) | 2012-11-21 | 2022-09-13 | Ipsen Bioinnovation Limited | Methods for the manufacture of proteolytically processed polypeptides |
CN104163872A (zh) * | 2014-06-13 | 2014-11-26 | 天津工业大学 | 一种阻燃纤维素衍生物的制备方法 |
CN104045720A (zh) * | 2014-07-01 | 2014-09-17 | 东华大学 | 一种纤维素经过尿素改性后的低温溶解方法 |
Also Published As
Publication number | Publication date |
---|---|
AT511002A1 (de) | 2012-08-15 |
EP2673135A1 (fr) | 2013-12-18 |
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