[go: up one dir, main page]

WO2000068271A1 - Procede pour la production d'une solution de filage de cellulose dans du n-methylmorpholine-n-oxyde monohydrate, solutions obtenues selon ce procede et fibres de cellulose regeneree obtenues par filage a partir de ces solutions - Google Patents

Procede pour la production d'une solution de filage de cellulose dans du n-methylmorpholine-n-oxyde monohydrate, solutions obtenues selon ce procede et fibres de cellulose regeneree obtenues par filage a partir de ces solutions Download PDF

Info

Publication number
WO2000068271A1
WO2000068271A1 PCT/EP2000/004136 EP0004136W WO0068271A1 WO 2000068271 A1 WO2000068271 A1 WO 2000068271A1 EP 0004136 W EP0004136 W EP 0004136W WO 0068271 A1 WO0068271 A1 WO 0068271A1
Authority
WO
WIPO (PCT)
Prior art keywords
pulp
cellulose
methylmorpholine
oxide
monohydrate
Prior art date
Application number
PCT/EP2000/004136
Other languages
German (de)
English (en)
Inventor
Ties Karstens
Original Assignee
Rhodia Acetow Gmbh
Ties Karstens
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 Rhodia Acetow Gmbh, Ties Karstens filed Critical Rhodia Acetow Gmbh
Priority to AU49183/00A priority Critical patent/AU4918300A/en
Publication of WO2000068271A1 publication Critical patent/WO2000068271A1/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

  • the invention relates to a method for producing a spinning solution of cellulose in N-methylmorpholine-N-oxide monohydrate. the solutions available with them and the regenerated cellulose fibers obtainable therefrom by spinning.
  • N-methylmorpholine-N-oxide is a non-derivatizing pulp solvent which, in the form of its monohydrate, has gained outstanding importance for pulp deformation in recent years.
  • the dissolution of the pulp in the solvent N-methylmorpholine-N-oxide / water is a purely physical process. It can be assumed that in a first step the intermolecular hydrogen bonds are destroyed and the isolated cellulose chains are stabilized by solvation. It has been demonstrated that in addition to the required dissolving properties, the solvent molecule must meet geometric requirements and must not exceed a diameter of 0.515 ran.
  • the dissolution process corresponds to a competitive reaction between the solvent N-methylmorpholine-N-oxide and the non-solvent water.
  • the rate of dissolution depends on the mechanical degree of comminution of the pulp, the dissolving temperature, the ratio of N-methylmorpholine-N-oxide / water, the ratio of pulp / N-methylmorpholine-N-oxide / water, the degree of polymerization of the pulp and the shear field.
  • the procedure is that crushed, cracked or ground pulp is mixed in 60% N-methylmorpholine-N-oxide solution. The excess water is then removed in suitable devices with heating and, if appropriate, in vacuo.
  • N-meth ⁇ lmorpholm-N-o ⁇ id is already industrial for the production of new cellulose fiber materials. Lyocell fibers are used, the dissolving mechanism and the loose structures in the cellulose / N-methylmorphohn-N-oxide monohydrate system have not yet been fully clarified. In contrast to many other solvents, the dissolution in N-methylmorphohn-N- oxide monohydrate does not require a "pre-activation" of cellulose
  • Activation leads to changes in the molecular, supermolecular and morphological structure of the pulp, as a result of which the accessibility of the pulp to the solvent is significantly improved.
  • the most important methods include inter- and intra-stable swelling processes and mechanical disaggregation.
  • the activation is for a number of solvents indispensable prerequisite for pulp dissolving Furthermore, the speed of the dissolving process can be increased
  • the prior art attempts, inter alia, to improve the accessibility of the pulp to the solvent N-methylene morpholine-N-oxide by subjecting the pulp to an enzymatic pretreatment.
  • This procedure is not only due to the relatively dilute suspension in which the pulp is treated, expensive, but also very expensive because of the high costs of the enzymes.
  • it is therefore not possible to start from the N-methylmorphohn-N-oxide monohydrate but from a strong water-containing N-methylmorphohn-N-oxide solution
  • the batch temperature must be kept low on the one hand for safety reasons and on the other hand in order to preferably remove the water from the pulp / N-methylmorphol-N-oxide / water system
  • the invention is therefore based on the object of providing a method in which the disadvantages of the prior art mentioned are largely avoided.
  • the method should make it possible to generally improve the dissolution of pulp in N-methylmorphol-N-oxide -
  • the production of pulp / N-methylmorphohn-N-oxide monohydrate solutions is carried out in a shorter time, with less energy consumption and in better quality.
  • the effort involved in processing and spinning for economic and quality reasons should be kept as low as possible
  • the gel content should be as low as possible
  • the above object is achieved by a process for the preparation of a spinning solution of pulp in N-methylmorphohn-N-oxide monohydrate, in which (a) the pulp is preactivated with liquid ammonia at a starting pressure which is higher than atmospheric pressure and (b) the preactivated pulp is dissolved in N-methylmorphohn-N-oxide monohydrate with heating
  • the pulp is first pressurized with liquid ammonia. After the desired exposure time, the pulp activated in this way can then be dissolved directly in N-methylmorpholine-N-oxide * H: O; ie it is not necessary to use dilute N-methylmorpholine-N-oxide while evaporating the water from the solution.
  • step (b) part of the N-methylmorpholine-N-oxide monohydrate used in step (b) is already added in step (a), so that the liquid ammonia already contains NMMO monohydrate used as solvent.
  • the liquid ammonia also transports the N-methylmorpholine-N-oxide * H2 ⁇ into the crystalline areas of the pulp, which leads to a "spacer" effect. This means a spreading or spatial expansion of the molecular structure of the pulp, whereby the activation or Accessibility compared to the solvent N-methylmorpholine-N-oxide * H 2 O.
  • the mass ratio of pulp to N-methylmorpholine-N-oxide monohydrate is preferably about 20: 1 to about 1: 1.
  • the treatment of the pulp with liquid ammonia at an initial pressure which is higher than atmospheric pressure in the form of a “preactivation” of the pulp after process step (a) can be carried out by any known activation process.
  • the pulp is preferably brought into contact with the liquid ammonia, the amount of the liquid ammonia at least is sufficient for wetting the surface of the mixture and the volume available to the cellulose / liquid ammonia system is increased explosively while lowering the pressure, whereby the preactivated cellulose is obtained.
  • the cellulose / liquid ammonia system is preferably available here Volume explosively increased by lowering the pressure by at least 5 bar. At least about 0.5 parts by mass, preferably at least about 1 part by mass, in particular about 2 parts by mass, of liquid ammonia are used for 1 part by mass of cellulose
  • the explosion-like volume increase takes place within a time of less than one second.
  • the pulp is preferably brought into contact with the liquid ammonia in a pressure device and the pulp with the liquid ammonia Ammonia released by transfer to an explosion chamber with a larger volume than the pressure device.
  • the outlet pressure is preferably between about 5 and 46 bar. It is even more advantageous to set a minimum pressure drop of 5 bar, since this gives the best results.
  • the temperature of about 25 is correct with the specified pressure frame up to 85 ° C or 55 to 65 ° C.
  • the explosion preferably takes place in an explosion space which is kept under vacuum. The explosion space must be chosen large enough to be able to achieve the desired defibrillation or defibrillation into the large volume
  • the ammonia explosion can be carried out discontinuously or continuously. It should be noted here that the valve has a large clear opening when open so that the pulp does not jam during the explosion process and not only ammonia escapes. The procedure is then that of opening The contents of the pressure reactor can suddenly escape from a ball valve.
  • the expansion tank has a multiple volume compared to the pressure tank. For example, the volume of the pressure tank is 1 1 and the volume of the expansion tank is 30 1.
  • the contact time between the liquid ammonia and the other starting materials within the pressure vessel is not critical. It is usually about 20 minutes.
  • the N-methylmorpholine-N-oxide monohydrate is preferably completely embedded in the pulp after the ammonia explosion.
  • a pulp in the form of plates, rolls, bales or sheets can be assumed.
  • softwood or hardwood pulp is used as pulp.
  • the pulp is preferably mechanically fiberized before treatment with liquid ammonia after process step (a). This can be done in any way known to the person skilled in the art.
  • the dissolving of the preactivated pulp after process step (b) is then preferably carried out at a temperature of about 80 to 130 ° C., in particular a temperature of more than about 85 ° C., in N-methylmorpholine-N-oxide monohydrate.
  • the N-methylmorpholine-N-oxide monohydrate used can be used both in the form of a melt and in an aqueous solution. A dissolution can be observed from a content of approximately 79% N-methylmorpholine-N-oxide.
  • the monohydrate is preferably used in an at least about 86% N-methylmorpholine-N-oxide solution.
  • the N-methylmorpholine-N-oxide dihydrate in a 76.5% aqueous solution is a non-solvent.
  • the invention also relates to the solution of preactivated cellulose in N-methylmorpholine-N-oxide monohydrate. available according to the above described drive the invention.
  • Such solutions are characterized by a very high quality or quality, which is particularly reflected in the processing products. This is shown by a lower content of undissolved or poorly dissolved constituents of the pulp, which is reflected in an improved solution structure, lower particle density and smaller aggregates.
  • the invention further relates to regenerated cellulose fibers obtainable by spinning the solution according to the invention.
  • the invention is therefore characterized by numerous advantages.
  • the pulp solution produced in the process according to the invention can be produced directly without complex intermediate steps.
  • the cellulose can be preactivated with liquid ammonia in any manner, which allows a wide range of variations.
  • the additional enzymatic pretreatment of the pulp which is complex and very expensive according to the prior art and which leads to relatively dilute suspension, is not necessary.
  • the process according to the invention makes it possible for the first time to start from N-methylmorpholine-N-oxide monohydrate, so that the disadvantages of a more water-containing N-methylmorpholine-N-oxide solution are avoided.
  • the teaching according to the invention allows the production of N-methylmorpholine-N-oxide monohydrate solutions in a shorter time, with less energy expenditure and in better quality than according to the methods from the prior art.
  • the process according to the invention enables a very cost-effective and simplified production process for pulp solutions on a large industrial scale. In addition to a reduced risk potential, a significantly shorter dissolving time, significantly improved solution structure, lower particle density and smaller aggregates are achieved.
  • the method according to the invention thus leads to a relatively homogeneously pulped pulp material. It can be much more uniform in N-methylmorpholine-N-oxide Monohydrate are dispersed than in the case of untreated cellulose, which ensures better access of the solvent to the individual cellulose fibers; the cellulose activated according to the invention is dissolved significantly faster than the untreated cellulose
  • the softwood sulfate pulp Buckeye was used for the investigations. hereinafter referred to as reference sample "V60", used.
  • the untreated cellulose has a viscosimetric Cuoxam-DP of 535
  • This reference sample V60 was defibrated with the aid of a pin mill, after which it still contained residues of the cellulose sheet. This sample was then activated in suspension with liquid ammonia by means of a so-called “ammonia explosion”. This gave the sample “V60A” to be examined, ie a Cellulose activated with liquid ammonia according to the invention.
  • the Cuoxam-DP of the activated cellulose V60A was 485 N-methylmorphohn-N-oxide monohydrate (hereinafter abbreviated as “NMMO-MH”) was a chemically pure industrial product with a melting point of 72-73 ° C.
  • the softwood cellulose BUCKEYE V60 was subjected to a further treatment, after which NMMO-MH was added to the liquid ammonia during activation, which was completely stored in the cellulose after the “explosion” was.
  • an amount of 20 g NMMO-MH was applied to 120 g pulp.
  • V60AM a portion of the N-methylmorpholine-N-oxide monohydrate being added during the ammonia activation, is referred to below as "V60AM”.
  • the DP of the cellulose i V60AM activated according to the invention was not redetermined - it is based on the known value for V60A of 485.
  • the solutions were filtered at 90 ° C. through a heated glass frit with a pore diameter of 16 ⁇ m and each filled into a 10 ml ampoule and sealed melted. With the solutions prepared in this way, light scatter measurements were carried out.
  • the goniometer SLS-2 from SLS-Systemtechnik was used for the light scatter measurements.
  • the device is equipped with a He-Ne laser with a wavelength of 632.8 ⁇ m and enables measurements in the angular range from 15 ° to 145 ° and at temperatures from 0 ° C to 150 ° C.
  • the software allows evaluation according to the procedures of ZIMM, BERRY and GUINIER.
  • the method according to the invention accordingly leads to a relatively homogeneously pulped pulp material. It can be dispersed in NMMO-MH much more uniformly than the untreated cellulose, which ensures better access of the solvent to the individual cellulose fibers. As a result, the activated pulp dissolves much faster than the untreated pulp.
  • V60A pulp according to the invention activated with ammonia explosion and
  • n * can be estimated from the quotient of the measured and the "theoretical" molecular weight. It is 445 for the sample V60, 95 for the sample V60A and 63 for the sample V60AM.
  • the particle size or the weight-average molar mass Mw of the non-activated cellulose is approximately 4.5 times larger than Mw of the cellulose V60A according to the invention and approximately 7.5 times larger than Mw of the cellulose V60AM according to the invention. Accordingly, a larger radius of inertia is found for V60 than for V60A and V60AM.
  • the second virial coefficient A is larger in the case of the activated sample V60A compared to the untreated sample V60, which indicates a thermodynamically better solution.
  • the radii of inertia Ro match for the two pulp samples within the error limits.
  • the A 2 value for all of the samples listed is very small, so that it can be set to approximately zero.
  • the smaller particles in solutions of samples V60A and V60AM differ only slightly in size. Overall, the cellulose activation carried out according to the invention leads to solutions which contain significantly smaller cellulose particles than those of the untreated sample V60.
  • Absolute molar masses cannot be determined with this method.
  • the calculated values are provided with a factor c, which stands for the proportion of the corresponding particles.
  • the size of the factor must be determined using other investigation methods.
  • Table 2 shows the results that follow from the scattering curve decomposition. The sizes of the molar masses and radii of inertia obtained are comparable to the values obtained with the normal GUINIER application.
  • the small particles in solutions of samples V60A and V60AM differ only slightly in size. In turn, lower densities for the particles in the V60A and V60AM solutions result.
  • Index 1 stands for large and index 2 for small particles
  • V60A pulp according to the invention activated with ammonia explosion and V60AM .. pulp according to the invention, addition of NMMO to the ammonia explosion.
  • the form factor function determined from the measured values was fitted with various models. Combinations of hard spheres, microgels and homogeneously branched structures were considered. The best results are achieved if the form factor for microgels is used for the large particles; the model was varied for the small particles.
  • Table 3 contains the radii of inertia of the pulp particles and the proportion of large particles calculated for the examined form factor decomposition models.
  • the method according to the invention with cellulose activation leads to a cellulose material with a uniformly shredded morphological structure. No statements can be made here about changes in the super-molecular structure.
  • the accessibility of the cellulose for the solvent NMMO-MH is improved.
  • the cellulose activated according to the invention can be significantly faster be dissolved as the untreated pulp
  • Preactivation can increase the accessibility of the pulp and the solvent can penetrate deeper into the pulp structure.
  • the particles in the activated pulp solutions are significantly smaller and more swollen than in untreated, i.e. unactivated, pulp solutions.There are at least two different solutions in the solutions Types of particles before The larger particles can be described as microgels. They are probably the remains of the crystalline areas of the pulp. phen areas and split chains.
  • This example relates to the production of pulp loaded with NMMO * HzO (NMMO monohydrate).
  • NMMO monohydrate 6 g are placed in an autoclave provided with a magnetic stirring fish. Then 200 g of liquid ammonia are transferred from a steel bottle to this pressure-resistant batch container at room temperature using an ammonia metering pump. The NMMO monohydrate instantly dissolves in the liquid ammonia, which is easy to follow visually through the inspection window in the lid of the autoclave. The solution of the NMMO monohydrate in the liquid ammonia is then pumped into the reaction autoclave, which has already been filled with about 100 g of pulp that has been torn into small, postage-sized pieces. This is heated to 60 ° C after filling, which causes the internal pressure to rise to 20 bar. The ball valve is then opened towards the collecting container. The entire content of the reaction autoclave suddenly discharges with the evaporation of the liquid ammonia. The analysis of the pulp freed from ammonia shows a concentration of 6% by mass of NMMO monohydrate. Sample 2
  • the pulp used has a DP (Cuoxam) of 535.
  • DP Cuoxam
  • the sample V60 was fiberized with a pin mill; it served as a reference.
  • Sample V60W had been swollen in water at room temperature for 16 hours.
  • the V60AM sample is one prepared according to Example 1, i.e. , sample containing NMMO monohydrate in liquid ammonia (sample 2).
  • the molar mass, the number of aggregations, the particle density and the radius of inertia were determined from the scattered light measurements. Table 4 below gives values standardized to the reference (V60) in order to achieve better comparability.
  • RG radius of inertia.

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)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne un procédé pour la production d'une solution de filage de cellulose dans du N-méthylmorpholine-N-oxyde monohydraté, dans lequel (a) on pré-active la cellulose avec de l'ammoniac liquide sous une pression initiale supérieure à la pression atmosphérique et (b) on dissout la cellulose pré-activée par chauffage dans du N-méthylmorpholine-N-oxyde monohydraté. L'invention concerne également une solution obtenue selon le procédé, ainsi que les fibres de cellulose régénérée obtenues par filage à partir de cette solution. L'invention est caractérisée en ce qu'on exclut un déroulement explosif de la dissolution et qu'on obtient simultanément une qualité améliorée de la solution de cellulose. On constate cette amélioration de qualité, par exemple, au temps de dissolution considérablement réduit, à la structure de solution améliorée, aux densités de particules moindres, ainsi qu'aux plus petits agrégats obtenus.
PCT/EP2000/004136 1999-05-11 2000-05-09 Procede pour la production d'une solution de filage de cellulose dans du n-methylmorpholine-n-oxyde monohydrate, solutions obtenues selon ce procede et fibres de cellulose regeneree obtenues par filage a partir de ces solutions WO2000068271A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49183/00A AU4918300A (en) 1999-05-11 2000-05-09 Method for producing a spinning solution of cellulose in n-methylmorpholin-n-oxide-monohydrate, solutions thus obtained and regenerated cellulose fibers obtained therefrom by spinning

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999121755 DE19921755A1 (de) 1999-05-11 1999-05-11 Verfahren zur Herstellung einer Spinnlösung von Zellstoff in N-Methylmorpholin-N-oxid-Monohydrat, die damit erhältlichen Lösungen sowie die daraus durch Verspinnen erhältlichen Regeneratcellulosefasern
DE19921755.6 1999-05-11

Publications (1)

Publication Number Publication Date
WO2000068271A1 true WO2000068271A1 (fr) 2000-11-16

Family

ID=7907747

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/004136 WO2000068271A1 (fr) 1999-05-11 2000-05-09 Procede pour la production d'une solution de filage de cellulose dans du n-methylmorpholine-n-oxyde monohydrate, solutions obtenues selon ce procede et fibres de cellulose regeneree obtenues par filage a partir de ces solutions

Country Status (3)

Country Link
AU (1) AU4918300A (fr)
DE (1) DE19921755A1 (fr)
WO (1) WO2000068271A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2830685A1 (de) * 1977-07-26 1979-02-15 Akzona Inc Verfahren zur herstellung einer loesung von zellulose in einem aminoxyd
WO1995011261A1 (fr) * 1993-10-19 1995-04-27 Lenzing Aktiengesellschaft Procede pour la preparation de solutions de cellulose
WO1996030411A1 (fr) * 1995-03-25 1996-10-03 Rhone-Poulenc Rhodia Aktiengesellschaft Procede permettant d'activer des polysaccharides, polysaccharides obtenus selon ledit procede et leur utilisation
WO1999016793A1 (fr) * 1997-09-26 1999-04-08 Rhodia Acetow Gmbh Procede pour activer des polysaccharides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2830685A1 (de) * 1977-07-26 1979-02-15 Akzona Inc Verfahren zur herstellung einer loesung von zellulose in einem aminoxyd
WO1995011261A1 (fr) * 1993-10-19 1995-04-27 Lenzing Aktiengesellschaft Procede pour la preparation de solutions de cellulose
WO1996030411A1 (fr) * 1995-03-25 1996-10-03 Rhone-Poulenc Rhodia Aktiengesellschaft Procede permettant d'activer des polysaccharides, polysaccharides obtenus selon ledit procede et leur utilisation
WO1999016793A1 (fr) * 1997-09-26 1999-04-08 Rhodia Acetow Gmbh Procede pour activer des polysaccharides

Also Published As

Publication number Publication date
AU4918300A (en) 2000-11-21
DE19921755A1 (de) 2000-11-16

Similar Documents

Publication Publication Date Title
DE2249604C2 (de) Synthetische Pulpe zur Papierherstellung sowie Verfahren zu deren Herstellung
EP0817803B1 (fr) Procede permettant d'activer des polysaccharides, polysaccharides obtenus selon ledit procede et leur utilisation
DE69024284T2 (de) Feinteilige Zellulosematerialsuspension und Verfahren zu ihrer Herstellung
DE69300823T2 (de) Verfahren zur herstellung von mikrokapseln oder liposomen definierter grösse.
DE19839214C1 (de) Verfahren zur Herstellung von sphärischen Mikropartikeln mit glatter Oberfläche, die ganz oder teilweise aus mindestens einem wasserunlöslichen linearen Polysaccharid bestehen, sowie mit diesem Verfahren erhältliche Mikropartikel und deren Verwendung
DE3823729A1 (de) Verfahren zur herstellung eines harzes mit einem hohen wasserabsorptionsvermoegen
DE3338169C2 (fr)
DE69105367T2 (de) Verfahren zur Herstellung eines metallischen Hydroxidpulvers und auf diese Weise hergestellte Pulver.
EP0631984B1 (fr) Hydroxide de magnésium et procédé pour son préparation
DE4439149C2 (de) Verfahren zur Herstellung einer homogenen Celluloselösung
DE69414104T2 (de) Karrageenan enthaltendes produkt und verfahren zu dessen herstellung
DE4439149C9 (de) Verfahren zur Herstellung einer homogenen Celluloselösung
DE3872346T2 (de) Ionenaustauscher aus basis von vernetztem glukomannan.
DE2023195A1 (de) Verfahren zur Behandlung roher kaolinitischer Tone
WO2007023002A1 (fr) Production de purs metaux, de melanges metalliques et/ou d'alliages metalliques se presentant sous la forme de nanoparticules et nanostructures par adsorption sur des fibres de cellulose
DE69609738T2 (de) Verfahren zur Herstellung von Xanthangummi, löslich in einer Salzlösung
DE2008643A1 (de) Kationische synthetische Latices und Verfahren zu deren Herstellung
WO2000068271A1 (fr) Procede pour la production d'une solution de filage de cellulose dans du n-methylmorpholine-n-oxyde monohydrate, solutions obtenues selon ce procede et fibres de cellulose regeneree obtenues par filage a partir de ces solutions
DE19707387C1 (de) Verfahren zur Herstellung von Viskose
DE2321829B2 (de) Verfahren zur herstellung von viskose
DE3590071C2 (de) Verfahren zur Herstellung von Kapseln
DE69606041T2 (de) Verfahren zur herstellung einer zelluloseformiatelösung durch imprägnierung und kneten von zelluloseplatten
DE2603313C3 (de) Aluminiumpulver für schlammförmige Explosiv- und Sprengstoffe und Verfahren zu dessen Gewinnung
DE2112231A1 (de) Verfahren zur Herstellung eines Polymerpulvers
DE2145090A1 (de) Verfahren zur Herstellung von Kieselsäure mit hohem Porenvolumen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM DZ 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 MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ 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 TZ 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

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

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP