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WO2018137757A1 - Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé - Google Patents

Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé Download PDF

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Publication number
WO2018137757A1
WO2018137757A1 PCT/EP2017/051419 EP2017051419W WO2018137757A1 WO 2018137757 A1 WO2018137757 A1 WO 2018137757A1 EP 2017051419 W EP2017051419 W EP 2017051419W WO 2018137757 A1 WO2018137757 A1 WO 2018137757A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
spinning solution
carbamate
spinning
filaments
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/EP2017/051419
Other languages
German (de)
English (en)
Inventor
André Lehmann
Robert Protz
Gerd Weidel
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.)
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten 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 Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Priority to EP17704403.9A priority Critical patent/EP3574137A1/fr
Priority to PCT/EP2017/051419 priority patent/WO2018137757A1/fr
Publication of WO2018137757A1 publication Critical patent/WO2018137757A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/22—Cellulose xanthate
    • 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
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives

Definitions

  • the present invention relates to a spinning solution which contains or consists of cellulose carbamate and cellulose xanthogenate and also a suitable solvent.
  • the cellulose carbamate and the cellulose xanthate are dissolved in the solvent.
  • the present invention relates to the production of a shaped body, in particular a filament by means of a shaping process, in particular a spinning process of the aforementioned spinning solution.
  • the invention also relates to a correspondingly produced shaped body, in particular a filament, which contains or consists of cellulose carbamate and cellulose xanthogenate.
  • Synthetic fibers from regenerated cellulose are currently produced at a production volume of about 5 million t / a, with more than 90% being produced by the viscose process.
  • CS 2 carbon disulfide
  • the molded bodies produced, in particular Spun fibers produced therefrom have a different spectrum of the textile-physical characteristics and, in particular, exhibit a high tendency to fibrillate due to the high orientation of the amorphous regions of the semicrystalline cellulose polymer.
  • Synthetic fibers produced by the viscose process thus differ from synthetic fibers produced after the carbamate process in terms of their structure and their superior mechanical properties.
  • the object of the present invention to provide a spinning solution, a process for producing a shaped body, in particular staple fibers and a shaped body, in particular staple fibers, wherein the physical-chemical properties of the produced Form body not at all or only slightly different from the physico-chemical properties of moldings, which were produced by the viscose process.
  • the spinning solution according to the invention or the production process should make it possible to work for the viscose process while minimizing carbon disulfide in the comparison.
  • it is an object of the present invention to provide new structure-property relationships in the moldings produced enable.
  • the spinning solution according to the invention according to claim 1 contains cellulose carbamate and cellulose xanthate, which are dissolved in a suitable solvent.
  • solvent in this case comprises a single suitable solvent and mixtures of a number of suitable solvents
  • the spinning solution may alternatively also be formed from the abovementioned substances, ie cellulose carbamate, cellulose xanthate and solvent, so that, if appropriate, no further additives are present.
  • the spinning solution according to the invention is in particular free of externally added carbon disulfide.
  • the particular advantage of the spinning solution according to the invention is that it has a shaping process, for example, a spinning process can be subjected, while maintaining the xanthate polyelectrolyte structure of the cellulosic material to be formed during the spinning process.
  • This makes it possible to influence the diffusion processes and the coagulation rate by salts contained in the spinning bath during the regeneration of the dissolved cellulosic polymers.
  • structural parameters such as crystallite size and orientation, degree of crystallinity and overall orientation of the cellulosic polymer chains can be varied over a larger range than is possible, for example, in the lyocell or carbamate process alone (compare characteristic values for the elongation Ex. 1 and Ex. 3) ,
  • the spinning solution according to the invention can be prepared by dissolving cellulose carbamate and cellulose xanthogenate in the solvent by stirring or kneading.
  • the dissolution process is preferably carried out at temperatures below 10 ° C, more preferably below 0 ° C.
  • a preferred embodiment provides that the cellulose carbamate and / or the cellulose xanthate a DP CU oxam (determined according to SCAN-CM 15:99) of 150 to 750, preferably from 250 to 550.
  • the cellulose has a degree of substitution of carbamate (DP rbamat Ca) of 0.1 to 1, preferably from 0.2 to 0.6.
  • the cellulose xanthate can be prepared prior to introduction into the spinning solution by reaction of cellulose with CS 2 analogously to the viscose process.
  • the cellulose xanthate preferably has a fresh y value (determined by Fock, Svensk Papperstidn, 60 (1957), 911-912) of 100 to 30, preferably 60 to 40.
  • the cellulosic solids content ie the total weight of cellulose carbamate and cellulose xanthogenate of the spinning solution of 4 to 15 wt .-%, preferably from 6 to 10 wt .-%.
  • the spinning solution preferably has a content of cellulose carbamate of 1 to 15 wt .-%, preferably from 2 to 8 wt .-% and / or cellulose xanthate from 1 to 15 wt .-%, preferably from 2 to 8 wt .-% to.
  • the weight ratio of cellulose carbamate to cellulose xanthogenate is from 5:95 to 95: 5, preferably from 60:40 to 85:15, particularly preferably from 65:35 to 70:30.
  • the solvent is selected from the group consisting of
  • Alkali solutions in particular sodium hydroxide solution or potassium hydroxide solution, wherein preferably the concentration of alkali in the alkali metal hydroxide solution is 4 to 12% by weight, preferably 5 to 10% by weight, particularly preferably 6 to 9% by weight.
  • spinning aids in particular inorganic spinning aids, such as, for example, can be used.
  • the present invention also relates to processes for producing a shaped body, in particular a filament, a bead, a sponge, a film of a spinning solution according to the invention, wherein the spinning solution by means of a shaping step in a molded body, transferred and during and / or after the forming Step, the solvent is removed from the molding.
  • the process according to the present invention relates to the production of filaments, in which case a spinning solution according to the invention is spun into filaments by means of a spinneret and the filaments produced are introduced into a coagulation bath.
  • the coagulation bath preferably contains water, and dissolved therein at least one component selected from the group consisting of inorganic acids, such as sulfuric acid; Salts, such as sodium sulfate; as well as organic liquids, for example glycerol or is formed therefrom.
  • the spinning solution is freshly prepared in the solvent before the shaping step, in particular spinning by dissolving the cellulose carbamate and the cellulose xanthate and then ripened, the tire preferably over a period of 1 to 72 hours, more preferably from 5 to 36 hours, more preferably 12 to 24 hours and / or at temperatures of the spinning solution of -10 to +50 ° C, preferably 0 to 30 ° C, particularly preferably 15 to 25 ° C is performed.
  • the coagulation bath to a temperature of 10 to 90 ° C, preferably 20 to 70 ° C, particularly preferably 30 to 50 ° C tempered.
  • the filaments After removal from the coagulation bath, the filaments can be fed to a stretching bath and stretched there, preferably with a stretching factor of 1.1 to 4, in particular 1.5 to 2.5.
  • the aforementioned stretching bath in this case is preferably an aqueous solution of an inorganic acid, which in particular includes sulfuric acid and / or at temperatures of 50 to 99 ° C, preferably from 60 to 90 ° C, more preferably 75 to 85 ° C tempered.
  • an inorganic acid which in particular includes sulfuric acid and / or at temperatures of 50 to 99 ° C, preferably from 60 to 90 ° C, more preferably 75 to 85 ° C tempered.
  • these are preferably drawn off from the spinneret with a nozzle delay of 0.3 to 2.0, preferably 0.5 to 1.5, in particular 0.6 to 0.8.
  • the resulting shaped articles, in particular filaments, are preferably finally washed, in particular with water or, in particular, subsequently dried.
  • the invention additionally relates to a shaped body, in particular filament, pearl, sponge, foil, containing or consisting of cellulose carbamate and cellulose xanthogenate.
  • the shaped body described above is preferably produced or producible by a process according to the invention.
  • the present invention will be further illustrated by the following examples, without limiting the invention thereto.
  • the measured values determined in the examples became as follows
  • the spinning solution thus produced was at a temperature of +5 ° C by means of a spinning pump to the spinneret (300 hole, 70 ⁇ ), which in a 40 ° C tempered, aqueous spinning bath of 80 g / l sulfuric acid and 240 g / l sodium sulfate, promoted ,
  • the coagulated filaments were drawn off by means of a nozzle delay of 0.7 and further in a stretching bath (stretching factor 1.15, 80 ° C, 20 g / l H 2 S0 4 ) and then the laundry (60 ° C, distilled water) supplied before they were dried isometrically at 80 ° C using dry palettes and finally wound up as filament yarn.
  • the filaments thus produced had a tensile strength of 17 cN / tex, an elongation of 6% and an elastic modulus of 1020 cN / tex.
  • the spinning solution thus produced was fed to the spinning nozzle at a spinning-y value of 38 at a temperature of +10 ° C. by means of a spinning pump (300 hole,
  • the filaments thus produced had a tensile strength of 17 cN / tex, an elongation of 18% and an E modulus of 780 cN / tex.
  • Na cellulose xanthate (CX, DP CuO x: 340, fresh y value: 52.4) was dissolved in caustic at 5 ° C to realize cellulose content of 8.8% by weight and an alkali content of 7.0% by weight , Further, cellulose carbamate (CC, DPcuox: 258, N content 2.2%) was dissolved in a 7 wt% sodium hydroxide aqueous solution in the cold at -4 ° C with stirring within 90 minutes to give a CC concentration of 9.5 % to realize.
  • the thus produced low-viscosity spinning solution was after maturity (20h at 22 ° C) at a temperature of +5 ° C by means of a spinning pump to the spinneret
  • the filaments thus produced had a tenacity of 17 cN / tex, an elongation of 12% and a modulus of 970 cN / tex.
  • Example 3 Analogously to Example 3, to the solution of cellulose carbamate in 7% by weight of alkali, the solution of CX was added with stirring and a ratio of CC: CX of 33:67 was set, the final resulting cellulose concentration being 8.5% by weight and that of the alkali 7% by weight.
  • the low-viscosity spinning solution was after maturity (20h at 22 ° C) at a temperature of +5 ° C by means of a spinning pump to the spinneret (300 holes, 70 ⁇ ), which in a 40 ° C tempered aqueous spinning bath of 80 g / l
  • the filaments thus produced had a tensile strength of 17 cN / tex, an elongation of 17% and a modulus of 890 cN / tex.
  • Example 5 Analogously to Example 3, to the solution of cellulose carbamate in 7% by weight
  • the filaments thus produced had a tensile strength of 32 cN / tex, an elongation of 6% and a modulus of 1200 cN / tex.
  • Example 4 The procedure was as in Example 4 and made of the spinning solution at -2 ° C, a mixture with cotton fibers and sodium carbonate. 0.5 parts were added per 1 part of cellulose in the form of the dissolved cellulose derivatives

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

Abstract

La présente invention concerne une solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose ainsi qu'un solvant approprié ou constituée de ceux-ci. Le carbamate de cellulose et le xanthogénate de cellulose sont présents sous forme dissoute dans le solvant. La présente invention concerne en outre la fabrication d'un corps façonné, en particulier d'un filament, au moyen d'un procédé de façonnage, en particulier d'un procédé de filage à partir de la solution de filage susmentionnée. L'invention concerne en outre un corps façonné fabriqué selon ledit procédé, en particulier un filament qui contient du carbamate de cellulose et du xanthogénate de cellulose ou qui est constitué de ceux-ci.
PCT/EP2017/051419 2017-01-24 2017-01-24 Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé Ceased WO2018137757A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP17704403.9A EP3574137A1 (fr) 2017-01-24 2017-01-24 Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé
PCT/EP2017/051419 WO2018137757A1 (fr) 2017-01-24 2017-01-24 Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2017/051419 WO2018137757A1 (fr) 2017-01-24 2017-01-24 Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé

Publications (1)

Publication Number Publication Date
WO2018137757A1 true WO2018137757A1 (fr) 2018-08-02

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PCT/EP2017/051419 Ceased WO2018137757A1 (fr) 2017-01-24 2017-01-24 Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé

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EP (1) EP3574137A1 (fr)
WO (1) WO2018137757A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2805119A (en) * 1954-01-12 1957-09-03 Schweizerische Viscose Alkali cellulose xanthates
PL168080B1 (pl) * 1992-01-20 1995-12-30 Inst Wlokien Chem Modyfikowane włókna wiskozowe o podwyższonej sorpcji wilgoci i sposób wytwarzania modyfikowanych włókien wiskozowych o podwyższonej sorpcji wilgoci
WO1997004148A1 (fr) * 1995-07-20 1997-02-06 Lenzing Aktiengesellschaft Fibres de cellulose
DE60123377T2 (de) 2000-06-12 2007-08-23 Instytut Biopolimerow I Wlokien Chemicznych Verfahren zur herstellung von fasern, filmen und anderen produkten aus modifizierter löslicher zellulose
US20120088686A1 (en) 2010-10-08 2012-04-12 Nan Jiang Methods of array data wave correction
WO2014162062A1 (fr) 2013-04-04 2014-10-09 Aalto University Foundation Procédé pour la production d'articles formés en cellulose
WO2014201483A1 (fr) * 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide et leur procédé de production

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2805119A (en) * 1954-01-12 1957-09-03 Schweizerische Viscose Alkali cellulose xanthates
PL168080B1 (pl) * 1992-01-20 1995-12-30 Inst Wlokien Chem Modyfikowane włókna wiskozowe o podwyższonej sorpcji wilgoci i sposób wytwarzania modyfikowanych włókien wiskozowych o podwyższonej sorpcji wilgoci
WO1997004148A1 (fr) * 1995-07-20 1997-02-06 Lenzing Aktiengesellschaft Fibres de cellulose
DE60123377T2 (de) 2000-06-12 2007-08-23 Instytut Biopolimerow I Wlokien Chemicznych Verfahren zur herstellung von fasern, filmen und anderen produkten aus modifizierter löslicher zellulose
US20120088686A1 (en) 2010-10-08 2012-04-12 Nan Jiang Methods of array data wave correction
WO2014162062A1 (fr) 2013-04-04 2014-10-09 Aalto University Foundation Procédé pour la production d'articles formés en cellulose
WO2014201483A1 (fr) * 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide et leur procédé de production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FOCK, SVENSK PAPPERSTIDN, vol. 60, 1957, pages 911 - 912

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Publication number Publication date
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