WO2014128128A1 - Fibres de cellulose régénérée, leur fabrication et leur utilisation - Google Patents

Fibres de cellulose régénérée, leur fabrication et leur utilisation Download PDF

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Publication number
WO2014128128A1
WO2014128128A1 PCT/EP2014/053151 EP2014053151W WO2014128128A1 WO 2014128128 A1 WO2014128128 A1 WO 2014128128A1 EP 2014053151 W EP2014053151 W EP 2014053151W WO 2014128128 A1 WO2014128128 A1 WO 2014128128A1
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WIPO (PCT)
Prior art keywords
cellulose
fibers
wet
emim
precipitation bath
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PCT/EP2014/053151
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German (de)
English (en)
Inventor
Denis INGILDEEV
Frank Hermanutz
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Deutsche Institute Für Textil- Und Faserforschung Denkendorf
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Publication of WO2014128128A1 publication Critical patent/WO2014128128A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D13/00—Complete machines for producing artificial threads
    • D01D13/02—Elements of machines in combination
    • 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
    • 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
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate

Definitions

  • the invention relates to cellulose regenerated fibers, to a process for their production by wet or dry-wet spinning and to their use for the production of cellulose regenerated fibers and textile structures.
  • a characteristic feature of these fibers is their pronounced tendency to fibrillate when wet.
  • the fibrillation tendency is the localized cleavage of the fibrillar elements on the fiber surface in the wet state, the is due to the morphology of the cellulose fibers.
  • This is a desired effect on the one hand; because this novel feel and effects can be achieved, on the other hand, the fibrillation also has disadvantages, such.
  • the reason for the fibrillation is believed that the application of the high stretching and the resulting high orientation of the polymer chains in the spinning process, the fiber consists of arranged in the fiber direction fibrils, between which only a small extent cross-linking is present.
  • the high degree of stretching defined by the difference in speed between the ejection and withdrawal speeds of the filaments, is necessary to achieve the required final filament fineness titers.
  • the cellulose solution leaving the spinneret orifices is pressed into a bath in which non-solvents such as e.g. As water are contained, is precipitated by the cellulose.
  • the solvent mixes with the non-solvent.
  • the non-solvent or non-solvent / ionic liquid mixtures alone can not be used as a spin bath because, due to the strong ionic character of the ionic liquids, the formation of thread runs too fast in the bundle of fibers that comes out of the nozzle. Such threads are highly swollen and have poor textile mechanical properties. This disadvantage can be reduced by the use of mixtures such.
  • the fibers In order for the fibers to have good mechanical properties, their structure must be as even and properly ordered as possible. For the uniformity of the fiber structure, two factors are decisive: the size, density and uniformity of the overmolecular structure as well as the orientation of the polymer chains in the direction of the fiber axis.
  • the supermolecular structure is dependent on the spinning conditions, the pulp yield, the solvent system and the cellulose concentration in the spinning solution.
  • the overall orientation of the polymer chains and the overmolecular structure are determined by the spinning and post-treatment conditions. In order to obtain fibers having the properties suitable for textile applications, it is necessary to stretch the filaments during their production.
  • the stretching is carried out between the spinning bath and the receiving device.
  • stretching the macromolecules are ordered in the direction of the fiber axis, which leads to an improvement of the mechanical fiber properties.
  • the orientation of the macromolecules is only possible under the action of the tensile forces applied during stretching when the thread is still in a certain plastic state, ie. H. when the interaction between the macromolecules is still small.
  • the interaction between the macromolecules or their aggregates increases steadily during coagulation.
  • the threads are less and less plastic until the forces that are usually applied during stretching, are no longer sufficient for orientation. Therefore, the spinning conditions and the composition of the spinning bath must be chosen so that even the outer layers of the filament are still in the plastic state when it leaves the spinning bath in the filament bundle.
  • the structure of the cellulosic fibers obtained using spunbonds of conventional composition is poorly oriented and uneven.
  • the macromolecule aggregates are poorly oriented in such fibers and packed more leaktightly than is necessary.
  • the fiber structure is usually the more uniform, the less swollen the filaments are on exit from the spinning bath.
  • the degree of swelling of the fibers as well as the thickness of the cladding layer depends on two factors: the composition of the spinning bath and the spinning solution, and the temperature of the spinning bath and the spinning solution. Most strongly, the coagulation or regeneration process or phase inversion process is influenced by the temperature and the composition of the spinning bath.
  • the use of the cellulose regenerated fibers prepared by the dry-wet spinning method according to the prior art is severely limited by the pronounced wet fibrillation tendency.
  • the fibrillation increases with increasing stretching of the filaments in the air gap and is due to the morphology of the cellulosic fiber. It is believed that the cellulosic fiber consists of fiber-directional fibrillar elements between which there is little cross-linking between them.
  • the following property-relevant factors and structural parameters are to be mentioned: degree of orientation of the components of the fiber with respect to the fiber axis (orientation of the polymer chains), the spatial arrangement and size of the cellulose molecules constituting the fiber within the morphological Structural elements (crystallite dimensions, crystallite orientation), morphological fiber structure (scanning electron microscopy) and textile-physical properties (tensile test, fibrillation tendency test).
  • degree of orientation of the components of the fiber with respect to the fiber axis orientation of the polymer chains
  • the spatial arrangement and size of the cellulose molecules constituting the fiber within the morphological Structural elements crystallite dimensions, crystallite orientation
  • morphological fiber structure scanning electron microscopy
  • textile-physical properties tensile test, fibrillation tendency test
  • the present invention seeks to propose cellulose regenerated fibers in the form of cellulose filaments, which have suitable fiber properties for textile applications and are also largely non-fibrillating.
  • the invention should propose a suitable direct production process, in particular for regenerated cellulose fibers in the established fineness range, as well as for micro- and super-microfilaments, wherein in comparison to the current technologies a wide range of variation in process control and thus the possibility should exist, the textile-fiber properties to vary in a large parameter range.
  • the invention is intended to provide not only satisfactorily non-fibrillating cellulosic filaments but also those in which the loss of wet tensile strength is improved over that in the dry state.
  • the above object is achieved by regenerated cellulose fibers in the form of non-fibrillating cellulose filaments, in particular a titer of 0.5 to 10.0 dtex, with a wet fibrillation grade of less than or equal to 2, a loss of tensile strength in the wet state compared to in the dry state, in each case measured according to DIN 53816, of less than 40%, in particular less than 30%.
  • the invention furthermore also relates to a process for the production of regenerated cellulose fibers, in particular cellulose regenerated fibers according to the invention.
  • generatfasern which is characterized in that cellulose is dissolved in a direct solvent for producing a spinning solution and this spinning solution in a precipitation bath wet or dry-wet spun, wherein the precipitation contains a non-solvent of the cellulose and a non-soluble carbohydrate and thereby delaying coagulation.
  • non-fibrillating in the context of the invention, it is to be understood that in combination with exposure to moisture, scrubbing becomes effective on the structural elements of the fiber and the fiber exerts little or no cleavage of the fibrils having the fiber surface, wherein in particular a Nassfibrillationsnote of less than or equal to 2, in particular 1, should be complied with.
  • the cellulose regenerate fibers according to the invention are thus referred to as “non-fibrillating" in this sense.
  • Lycocell fibers produced by the NMMO process have a round to oval fiber cross section and, in contrast to the viscose and modal fibers, have a pronounced fibrillar structure which is substantially homogeneous over the fiber cross section.
  • the fibers are separated from the sample material.
  • the fibers are placed straight on a slide and fixed at the ends with double-sided adhesive tape.
  • the fibers are cut to length of 2 cm by means of a scalpel on the slide.
  • the 8 fibers are filled with 4 ml of demineralized water in a 20 ml cylindrical glass jar (height 50 mm, diameter 30 mm).
  • the test tubes are clamped in a suitable shaking thermostat (eg B. Braun) and shaken for 9 hours at 160 rpm.
  • the fibers are transferred to a microscope slide, embedded in demineralized (DI) water and provided with a coverslip.
  • DI demineralized
  • the evaluation is carried out with a transmitted-light microscope (eg Zeiss Axioplan).
  • the cell ulcer regenerate fibers according to the invention are advantageously distinguished by the fact that their water retention capacity (according to DIN 53184) is between 60 and 150%, in particular between 70 and 120%.
  • the importance of this advantageous water retention property is that it is closely related to the amorphous contents and void system between the crystalline regions.
  • This pore system has a decisive influence on the sorption properties of the fibers and plays an important role in dyeing processes, for example.
  • the cellulose regenerated fibers according to the invention are advantageously distinguished by the fact that the non-fibrillating cellulose filaments have a titer of 0.8 to 3.5 dtex. Furthermore, it is preferred if the wet fibrillation grade is less than or equal to 2. Furthermore, special advantages are achieved if the loss of the mentioned tensile strength in the wet state compared to the dry state is less than 25%, in particular less than 20%. In addition, it is preferred according to the invention if the regenerated cellulose fibers according to the invention have a water retention capacity (according to DIN 53184) between 60 and 150%, in particular between 20 and 120%.
  • cellulose regenerated fibers according to the invention represent round fibers in which the roundness as the length / width (LJB) ratio is 0.6 to 1.0, in particular 0.7 to 0.9. wherein the range of 0.9 to 1.0 is particularly preferred and the most desirable value is about 1.0.
  • Cellulose fibers with perfect roundness show a high gloss, which is silk-like.
  • Very high quality yarns for textile use can be produced, since this roundness leads to a special yarn closure in secondary spinning to yarns. With it twisted threads can be made.
  • this exact roundness of the fibers results in high capillary action. When used as a precursor for carbon fibers, the exact roundness leads to particularly homogeneous carbonization, whereby particularly good carbon fiber can be produced.
  • the invention also makes it possible to deviate from the round cross-section:
  • the nozzles in the case of wet spinning consist of small cones of noble metal alloys of gold, platinum, iridium, rhodium in certain proportions.
  • Essential for spinning are the diameter of the spinning holes, their shape and the shape of the hole channel.
  • the openings of most nozzles have a round cross-section.
  • one sets for the production of profile fibers spinnerets with "Y", cross-shaped, triangular, star-shaped or otherwise designed spinning openings.
  • the profile fibers have certain properties depending on the cross-sectional shape.
  • Y- and star-shaped fibers have a particularly high surface area per fineness stite, and hollow fibers increase thermal insulation. Due to the particular coagulation conditions which are adhered to in the method according to the invention and which are described in detail below, it is now possible to produce profiled fibers, such as those with a Y cross-section. These were previously not accessible due to a rapid diffusion of the non-solvent into the fiber inside when entering the spun yarn into the coagulation and the resulting strong swelling of the filaments.
  • Particularly advantageous regenerated cellulose fibers which can be assigned to the invention and are advantageously preparable by the process according to the invention described below, are based on cellulose, characterized in that they have (a) a tensile strength (according to DIN 53816) of 15 to 80 cN / tex , in particular from 20 to 60 cN / tex, (b) an elongation at break (according to DIN 53816) of 2 to 30%, in particular of 5 to 25%, (c) an E modulus (measured according to BISFA at an elongation of 0, 2 to 4%) from 500 to 2500 cN / tex, in particular from 700 to 2000 cN / tex, (another corresponding indication is an E modulus measured according to BISFA at 5% elongation of 1 to 20 cN / tex, in particular of 2 to 15 cN / tex), and / or (d) have a density of 1.48 to 1.54 g / cm 3 , in particular from
  • the cellulosic regenerated fibers according to the invention are obtained by targeted control of the coagulation behavior of the threads in the precipitation bath, which consequently makes it possible to produce the regenerated cellulose fibers according to the invention with particularly advantageous properties.
  • the cellulose regenerated fibers according to the invention are suitable as carbon fiber precursor for the production of carbon fibers by carbonation, optionally with subsequent graphitization.
  • the invention also provides the process according to the invention for the production of advantageous cell uloseregenerate fibers, in particular cellulose regenerated fibers according to the invention, according to which the filaments formed in the precipitation bath are preferably stretched in the manner described below, optionally followed by washing.
  • An essential idea of the process according to the invention is the incorporation of a soluble carbohydrate into the precipitation bath, this in admixture with, inter alia, rem the non-solvent.
  • carbohydrates in particular mono-, di-, tri-, tetra-, oligo- and / or polysaccharides, both branched and straight-chain, with the precipitating bath, whereby also isomers in Can consider.
  • carbohydrates represents a collective term for the polyhydroxy aldehydes (aldoses) and polyhydroxy ketones (ketones), which are very widespread as natural substances, and also compounds of higher molecular weight which can be converted by hydrolysis into such compounds.
  • the macromolecular carbohydrates are polysaccharides. Frequently, the mono- and oligosaccharides are also summarized as "sugars" and compared with the polysaccharides.
  • Monosaccharides At first important are pentoses and hexoses.
  • the most important pentoses include L (+) - arabinose, D (-) - arabinose, D (+) - xylose and D (-) - ribose among the important hexoses D (+) - glucose, D (+) - Mannose, D (+) - galactose, D (-) - fructose and L (-) sorbose.
  • Also suitable would be derivatives thereof, such as deoxysugars in the form of 2-deoxy-D-ribose and L (+) rhamnose, and also amino sugars, in particular D-glucosamine and D-galactosamine.
  • Disaccharides include, in particular, sucrose, trehalose, milk sugar (lactose), maltose (maltose), derivatives, in particular cellobiose, dentiobiose and meleobiose, rutinose.
  • Trisaccharides Here, raffinose is to be mentioned as advantageous. Tetrasaccharides and oligosaccharides can also be used, but are less suitable because of their poor solubility in water.
  • Polysaccharides The most important polysaccharides include starch of plant and animal origin, such as glycogen.
  • starch In the case of starch, it must be stated that in order to achieve the required solution in the precipitation bath, it must be dissolved in it, which applies, for example, to the media water and / or alcohol, if appropriate sufficiently heated.
  • the mixing ratio of non-solubilizers of the cellulose to the carbohydrates is not critical. However, it is preferred that, based on the mixture of non-solubilizers of the cellulose and carbohydrates, the carbohydrates be present in an amount of from 20 to 90% by weight, in particular in an amount of from 40 to 70. It should be noted that the indicated amounts are especially valid for sucrose. Optimal adaptation can also be carried out professionally for other carbohydrates or cellulose concentrations. In any case, it is desirable that a "soft precipitation" or slow diffusion is achieved, ie, the highest possible concentration of, for example, sucrose in the precipitation bath is present. The chemical structure and the temperature in the precipitation bath has a Auswir ⁇ effect.
  • An optimization of the process conditions can also be achieved by the temperature control of the precipitation bath. It is expedient that the tempera ture ⁇ of the precipitation bath to 10 to 100 ° C, it is in particular adjusted with water as non-solvent. The optimum temperature can be expertly determined depending on the substances used. This also addressed the preferred non-solvent in the precipitation bath with water. In general, it is preferred that protic solvents, in particular water and / or alcohols, and mixtures thereof are used as the non-solvent in the precipitation bath. Among the alcohols, methanol, ethanol and / or isopropanol are particularly preferred.
  • the coagulated filaments precipitated in the precipitation bath by the process according to the invention are preferably stretched, with washing being able to follow.
  • stretching can be done directly in the precipitation bath by the filaments withdrawn faster than initiated.
  • the temperature in the precipitation bath for optimum stretching depends on various conditions. These can be purely professionally depending on the composition of the coagulation bath carbohydrate / neutralizer /
  • Direct solvent for example ionic liquids.
  • the stretching described above may, as already mentioned, be followed by a washing. This allows the recovery of valuable solvents, in particular the ionic liquids, but also the carbohydrates used, such as sugar. After stretching or washing, the resulting filaments can be dried.
  • a downstream stretching section for example in a heating channel or in a stretching bath. It is advantageous to stretch the coagulated, d. H. swollen filaments at a temperature between 40 ° C and 220 ° C, in particular between 80 ° C and 180 ° C, in particular in a heating channel, which may have usual configurations.
  • the stretching can take place in one or more stages.
  • the stretching can take place up to 200%, in particular up to 100% and very particularly preferably up to 50%.
  • the range of 20 to 80% is considered to be particularly preferred.
  • degree of stretching reference is made to the above statements.
  • the cellulose regenerated fibers according to the invention in particular in the form of micro- or super-microfilaments, can be prepared in particular after direct wet or dry-wet spinning, the following steps being expediently included: (a) dissolving the cellulose in a solvent to produce a spinning solution and (b) direct wet or dry-wet spinning of the spinning solution using a spinneret and the spinning solution precipitated in a coagulation bath to non-fibrillating cellulosic filaments.
  • the terms "precipitation bath”, “coagulation bath” and “spinning bath” are to be understood as conceptual.
  • the present invention is not subject to any significant limitations. It is preferably present as fibrous cellulose, in particular wood pulp, linters, paper, and / or in the form of other natural cellulose fibers.
  • natural cellulose fibers adhesive, coconut, jute, bamboo and / or sisal fibers may be found to be advantageous.
  • the cellulose is partially derivatized. It is preferred if the derivatives are present as esters or ethers.
  • esters may, for example, be phosphoric acid and / or nitrogen-containing esters, such as cellulose carbamate or -allophonat, Cellullosecarboxylate, such as cellulose acetate, cellulose propionate and cellulose butyrate, and in the ethers to carboxymethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose or z.
  • cellulose derivatives are also suitable.
  • DP> 800 molecular weight cellulose
  • improved advantageous product properties such as strength, modulus of elasticity and rigidity are achieved.
  • the mixing of the cellulose starting material in the respective solvent is preferably carried out under the action of high shear forces, in particular by means of an extruder.
  • a twin-screw extruder has proved to be particularly advantageous.
  • the dissolution is further favored by simultaneously irradiated with microwaves during mixing, in particular ultrasound comes to act.
  • the dissolution of the cellulose is promoted by raising the temperature of the solution system.
  • the elevated temperature is 20 to 150 ° C, in particular 30 to 120 ° C.
  • the resulting solution is heated during further processing for carrying out the regeneration measures, in particular at 85 to 120 ° C., and / or the precipitation bath mentioned later is adjusted in particular to a temperature of 20 to 100 ° C. becomes .
  • These measures have the advantage that a preferred viscosity of the solution is set and the solvent is advantageously washed out. Accordingly, it can be seen that in order to optimize the idea of the invention in the regeneration of cellulose particularly advantageous when using cellulose as starting material, attention must also be paid to the viscosity of the spinning solution.
  • the spinning solution containing the cellulose has a viscosity of 10 to 2000 Pa.s, in particular 20 to 1500 Pa.s, in the wet-spinning process, and a viscosity of 100 to 15000 Pa.s in the dry-wet spinning process, especially 100 to 8000 Pa.s, wherein the range of 200 to 20,000 Pa.s can still provide a desired result. This is the so-called zero viscosity.
  • a rheometer SR500 from Rheometrics was used, which is not based on any standard. The measurements are absolute measurements. In this case, the temperature and occasionally also the measuring geometry is indicated. For the measurement, a plate-plate measurement geometry with a diameter of 25 mm was used. The measuring temperature at the rheometer for recording the master curves was 30 to 100 ° C, with a reference temperature of 80 ° C. Consequently, the particularly preferred viscosity values of the respective spinning solutions used according to the invention can be determined expertly.
  • the spinning temperature during spinning is not subject to any relevant limitation. Conveniently, it is between 10 and 90 ° C, in particular between 20 and 60 ° C, wherein the choice of a temperature of 20 ° C (room temperature) is particularly advantageous in many cases. About the selected spinning temperature, it is possible to adjust the advantageous for the inventive method viscosity values.
  • the desirable viscosity of the spinning solution can also be adjusted by a targeted concentration adjustment of the dissolved cellulose.
  • the cellulose in the respective direct solvent in an amount of 1 to 35 wt .-%, in particular in an amount of 8 to 20 wt .-%, is used. If the value falls below 1% by weight, then the desirable cost-effectiveness of the process according to the invention does not arise.
  • the spinning solution can also be optimized by being filtered before use, especially under pressurization or vacuum. Thus, it may be advantageous to degas the spinning solution prior to further processing for regenerating the cellulose, wherein the degassing is preferably carried out with stirring and under vacuum.
  • additives are carbohydrates, especially those that have been treated above. These are both linear (unbranched) and branched. The solubility of the carbohydrates decreases with increasing polymer chain length and the degree of branching. For this reason, mono- and disaccharides are particularly preferred. Also, as already mentioned, isomeric carbohydrates can be used, such as inositol (cyclohexanehexol).
  • the processing of cellulose solutions with the aid of the wet-spinning method is greatly influenced by the diffusion processes at the nozzle exit, that is to say when it comes into contact with the precipitation bath. Therefore, the stretching of the filaments is severely limited, inter alia, by the rapid diffusion of the precipitation bath into the fiber interior.
  • Cellulose solutions in the concentration range between about 4 and 16, in particular between about 6 and 14% by weight of cellulose in the direct solvent, in particular in the ionic liquids can be processed in the above-mentioned molecular weight range of the cellulose-based polymers.
  • the driving force of the spontaneously occurring diffusion is the difference between the chemical potentials of the cellulose solution and the precipitation bath.
  • Non-solvent molecules diffuse in the direction of their lower chemical potential (in the not yet formed polymer thread).
  • the mixing process resulting from this movement reduces the Gibbs energy (or free enthalpy) of the whole system, so the process is voluntary. Since the viscosities of the cellulose solvent, the non-solvent and the polymer solution functions of Temperature, the dependence of the diffusion coefficient on the temperature is not linear.
  • the particle current density (flux) J (mol m “2 s " 1 ) is proportional to the concentration gradient opposite to the diffusion direction 3c / 3x ( ⁇ ⁇ 4 ).
  • the proportionality constant is the diffusion coefficient D (m 2 )
  • the particle current density makes a quantitative statement about the (statistical average) directed movement of particles, i. H. How many particles of a substance amount move per unit of time through a surface unit, which is perpendicular to the direction of diffusion, net.
  • the equation given also applies to the general case that the diffusion coefficient is not constant, but depends on the concentration.
  • Spinning higher-concentration solutions can be carried out with advantage also after the dry-wet spinning process.
  • cellulose solutions in the concentration range between in particular about 8 and 20% by weight polymer, in particular between about 10 and 18, in the direct solvents, in particular in ionic liquids can be processed with this process.
  • the filaments exiting the die may preferably pass through an air gap of up to 10 cm, in particular about 1 to 10 cm, before they are precipitated in an underlying precipitation bath. It is expedient that the air gap is at least about 1 mm.
  • the phase inversion can be decisively delayed and a homogeneous regeneration of the cellulose can be achieved. Furthermore, these conditions prevent the formation of the fibrillar fiber structure and thus reduce the fibrillation tendency of the air-gap spun fibers.
  • additives may be added to the precipitation bath, the spinning solution containing the cellulose, and / or in a subsequent step, for example in a modifying medium.
  • the additives may be, for example, microcapsules, pore formers, plasticizers, matting agents, marking agents, flame retardants, bactericides, crosslinking agents, water repellents, antistatic agents and / or colorants.
  • Precipitation in the precipitation bath is generally not affected by any particular limitations on its flexibility. It is particularly preferred if water is used as the precipitation bath, in particular with an included amount of a solvent which optimizes the coagulation rate.
  • an adapted amount of direct solvent in particular an ionic liquid or N-oxide, in particular NMMO hydrate, remains in the precipitation bath, in particular in an amount of from 1 to 90% by weight, in particular 10 to 80 wt .-%, wherein the range of 20 to 60 wt .-% is particularly advantageous.
  • the cellulose filaments drawn off from the precipitation bath are dried, in particular in a circulating air oven.
  • the filaments can also be cut, washed and dried directly after stretching or after each further step to staple fibers. In principle, however, the filaments formed in the precipitation bath can be stretched, if appropriate with subsequent washing.
  • an ionic liquid is used as a direct solvent in the context of the invention, it is particularly advantageous to recover them from the precipitation bath used, in particular with regard to the economy of the method according to the invention.
  • a simultaneous or subsequent stretching can be considered.
  • the solvents used in the process according to the invention are direct solvents, in particular molten ionic liquids, which will be discussed in detail below, and / or an N-oxide.
  • N-methylmorpholine N-oxide examples include N-methylmorpholine N-oxide (NMMO).
  • N-oxides can be used with advantage: ⁇ , ⁇ , ⁇ - Trimethylamine N-oxide, N, N-dimethylcyclohexylamine-N-oxide, N-methylpiperidine-N-oxide, N-methylazacycloheptane-N-oxide, N-methylpyrrolidine-N-oxide, N, N-dimethylbenzylamine-N-oxide , N, N dimethylethanolamine N-oxide.
  • NMMO N-methylmorpholine N-oxide
  • radicals R 1 , R 2 , R 3 , R 4 or the radicals R 1 to R 8 in the formulas (I) to (VI), independently of one another, are linear, cyclic, branched, saturated or unsaturated alkyl radicals, mono- or polycyclic, aromatic or heteroaromatic radicals or derivatives of these radicals substituted by further functional groups, where R 1 , R 2 , R 3 and R 4 may be linked to one another, wherein the anion [Z] n "is in the form of a carboxylate, halide, pseudohalide, amide, in the form of phosphorus bonds or nitro compounds.
  • the abovementioned alkyl radical in the form of a Ci-Ci 8 - alkyl radical in particular an alkyl radical having 1 to 4 carbon atoms, preferably ⁇ before a methyl, ethyl, 1-propyl, 2-propyl, 1- butyl, or 2-butyl group is present
  • the cyclic alkyl group is present 0 i -cycloalkyl radical, and in particular in the form of a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radical in the form of a C 3, the alkyl radical unsaturated in the form of a vinyl, 2 Propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl radical is present, the aromatic radical in the form of a phenyl or naphthyl radical is present, having 1 to 3 halogen atoms, alkyl radicals having 1 to 4 Carbon atoms or
  • the ionic liquids designated below prove to be particularly suitable for the process according to the invention:
  • Imidazolium carboxylates in the form of [EMIM] [acetate], [EMIM] [propionate], [EMIM] [butyrate], [EMIM] [pentanoate], [EMIM] [hexanoate], [EMIM] [heptanoate], [EMIM] [octanoate], [EMIM] [nonanoate], [EMIM] [decanoate] and / or imidazolium phosphates [MMIM] [DMP], [MMIM] [DEP], [EMIM] [DEP].
  • EMIM means l-ethyl-3-methylimidazolium, [MMIM] 1,3-dimethylimidazolium, [DEP] diethyl phosphate and [DMP] dimethyl phosphate.
  • the molten ionic liquid has a melting point of -100 to + 150 ° C, in particular from -30 to + 130 ° C, with the range of -30 to 100 ° C being particularly preferred is. In the majority of cases it is advantageous not to exceed this maximum value.
  • the person skilled in the art can carry out suitable optimizations here, for example by varying the cations and anions of the ionic liquid, which favors the resulting structural parameters and the further properties of the cellulose regenerated fibers.
  • the invention can be achieved in an optimal form by the use of certain ionic liquid, in particular, the thread formation process at the nozzle or in the air gap is optimally controlled.
  • different desirable properties of the cellulose regenerated fibers can be obtained by favorably controlling the diffusion processes in the regeneration / coagulation of the thread and the stretching conditions.
  • a spinneret having circular holes is normally used to obtain coagulated fibers having a circular or circular cross-sectional shape.
  • Coagulated fibers having a cross-sectional shape other than a circle such as a cross-sectional shape of a triangle, quadrangle, or multilobal cross-sectional shapes can be obtained by using differently profiled nozzle bores, as discussed above.
  • the regenerated cellulose fibers of the invention can be used for a variety of purposes, not only those in textile materials such as threads, yarns, threads and the like, as well as fabrics, in particular woven, knitted, knitted, laid, nonwoven and wadding. These textiles, and in particular the fibers or yarns, are advantageous as reinforcing materials in fiber-based composite materials.
  • the cellulose regenerated fibers according to the invention are then carbonized and, if necessary, graphitized to obtain carbon fibers.
  • carbonization which occurs at gradually increasing temperatures between about 300 and 1500 ° C in the nitrogen atmosphere, the carbon content steadily increases and reaches about 95%.
  • the carbon content of the fibers can be increased to about 99%.
  • the graphitization is carried out by a thermal treatment at about 1500 to 2800 ° C in a protective gas atmosphere.
  • the graphitized fibers have a higher modulus than conventionally carbonized fibers.
  • the method according to the invention therefore, the underlying objective of the production for textile and technical applications of optimal cellulose regenerated fibers is achieved.
  • the method according to the invention also provides advantageous control options, in particular all final measures of stretching.
  • the supermolecular structure of a regenerated cellulose fiber can be selectively controlled by stretching the filaments on the die needed to achieve the desired fineness titer, and this control can be effectively performed if the stretching does not provide a particular one , for each direct solvent characteristic value exceeds.
  • the supermolecular structure determines the fibrilization in such a way that a high orientation of the polymer chains, high crystal
  • low orientation of the polymer chains, low crystallinity, and short crystalline domains give a fiber with correspondingly lower fibrillation tendency.
  • cellulose-based micro- and superfibre fibers can be further processed using web and knitting technology. This allows the development of new fiber reinforced composites with special properties, such.
  • the particularly advantageous idea of the present invention is the use of special additives in the form of carbohydrates in the precipitation bath.
  • This makes it possible to advantageously stretch the filaments during their production in order, in particular, to obtain cellulose regenerated fibers with very satisfactory textile-mechanical properties, in particular by means of the technology using ionic liquids, as described above.
  • the phase invasion (coagulation) is slowed down in an advantageous manner and, in addition, time is gained to stretch the filaments more strongly. This then leads to an improved tensile strength and a reduction of the elongation at break. This increases a maximum attainable degree of stretching of the still plastic filaments.
  • the above-mentioned effects are achieved particularly well when monomeric or oligomeric carbohydrates are used in the precipitation bath.
  • Simple carbohydrates are generally very soluble in water because of the larger number of hydroxyl groups. However, as the molecular weight increases and branching increases, the solubility decreases greatly. The degree of hydration of a strongly swollen filament and thus also its swelling in the precipitation bath is the lower the more carbohydrate compounds the precipitation bath contains.
  • Cotton interlens having an average degree of polymerization of 500 was used to obtain a spinning solution in [EMIM] [OAc] at a concentration of 12% by weight.
  • the resulting spinning solution was spun at a controlled 100 ° C using a spinneret with 1000 holes, each with a diameter of 0.05 mm.
  • the conveying volume of the spinning solution was 3.9 cm 3 / min, the extrusion speed was 2.0 m / min and the drawing speed was 3.5 m / min.
  • the resulting filaments were coagulated in a precipitation bath filled with sucrose / water mixture (65/35 wt.%) And heated to 70.degree. C., stretched in the hot air duct, washed and washed in 90.degree. C. water in two baths.
  • the fracture surface of the resulting fibers was observed by SEM.
  • the structure of the fiber cross-section is very homogeneous and when looking at the fracture surface no prominent fibril bundles can be seen here.
  • the textile mechanical properties of this fiber were: tensile strength 27.6 cN / tex, ultimate elongation 4.0% and modulus of elasticity (0.2-0.4% elongation) 1860 cN / tex. Furthermore, the regenerated cellulose fibers produced show no fibrillation tendency when wet scrubbed.
  • Cotton interlens having an average degree of polymerization of 900 was used to obtain a spinning solution in [EMIM] [OAc] at a concentration of 10% by weight.
  • the resulting spinning solution was spun at a controlled 100 ° C using a spinneret with 1000 holes, each with a diameter of 0.04 mm.
  • the conveying volume of the spinning solution was 5.6 cm 3 / min, the extrusion speed was 4.5 m / min and the take-off speed was 6.5 m / min.
  • the resulting filaments were coagulated in a precipitation bath filled with sucrose / water mixture (65/35 wt.%) And heated to 68.degree. C., stretched in the hot air duct, washed and washed in 90.degree. C.
  • the textile mechanical properties of this fiber were: tensile strength 21.1 cN / tex, elongation at break 10.2% and modulus of elasticity (0.2-0.4% elongation) 1320 cN / tex. Furthermore, the cellulose regenerated fibers produced show no fibril tendency when scrubbed in the wet state.
  • Cotton interlens having an average degree of polymerization of 900 was used to obtain a spinning solution in [EMIM] [OAc] at a concentration of 10% by weight.
  • the resulting spinning solution was spun at a controlled 100 ° C using a spinneret with 1000 holes, each with a diameter of 0.04 mm.
  • the conveying volume of the spinning solution was 1.4 cm 3 / min, the extrusion speed was 1.1 m / min and the drawing speed was 1.6 m / min.
  • the filaments obtained were coagulated in a precipitation bath filled with sucrose / water mixture (60/40 wt.%) And heated to 70.degree. C., stretched in the hot air duct, washed and washed in 90.degree. C. water in two baths.
  • the fracture surface of the resulting fibers was observed by SEM.
  • the structure of the fiber cross-section is very homogeneous and when looking at the fracture surface no prominent fibril bundles can be seen here.
  • the textile mechanical properties of this fiber were: tensile strength 20.5 cN / tex, breaking elongation 10.6% and modulus of elasticity (0.2-0.4% elongation) 1320 cN / tex.
  • the cellulose regenerated fibers produced show no fibril tendency when scrubbed in the wet state.
  • Cotton interlens having an average degree of polymerization of 900 was used to obtain a spinning solution in [EMIM] [OAc] at a concentration of 10% by weight.
  • the resulting spinning solution was spun at a controlled 100 ° C using a spinneret with 4000 holes, each with a diameter of 0.04 mm.
  • the conveying volume of the spinning solution was 5.6 cm 3 / min, the extrusion speed was 1.1 m / min and the take-off speed was 1.6 m / min.
  • the resulting filaments were coagulated in a precipitation bath filled with sucrose / water mixture (65/35 wt.%) And heated to 70.degree.
  • the fracture surface of the resulting fibers was observed by SEM.
  • the structure of the fiber cross-section is very homogeneous and when looking at the fracture surface no prominent fibril bundles can be seen here.
  • the textile mechanical properties of this fiber were: tensile strength 21.2 cN / tex, breaking elongation 8.1% and modulus of elasticity (0.2-0.4% elongation) 790 cN / tex. Furthermore, the regenerated cellulose fibers produced show no fibrillation tendency when wet scrubbed.

Abstract

L'invention concerne des fibres de cellulose régénérée sous la forme de filaments de cellulose non fibrillants, en particulier ayant un titre de 0,5 à 10,0 dtex, avec une note de fibrillation humide égale à 1 ou 2, une perte de résistance à la traction à l'état humide, mesurée suivant DIN 53816, inférieure à 40%, en particulier inférieure à 30% par rapport à l'état sec. L'invention concerne en outre un procédé de fabrication de fibres de cellulose régénérée, en particulier du type précité, dans lequel la cellulose est dissoute dans un solvant direct afin de produire une solution de filage et cette solution de filage est filée par voie humide-humide ou sec-humide dans un bain de régénération. Le bain de régénération contient un non-solvant de la cellulose ainsi qu'un hydrate de carbone soluble dans ledit non-solvant, ce qui a pour effet de retarder la coagulation. Les fibres de cellulose régénérée décrites et obtenables par ce procédé peuvent être employées dans de multiples applications, par exemple dans des structures textiles et pour fabriquer des fibres de carbone.
PCT/EP2014/053151 2013-02-19 2014-02-18 Fibres de cellulose régénérée, leur fabrication et leur utilisation WO2014128128A1 (fr)

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EP3536832A1 (fr) * 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Fibre lyocell présentant des propriétés de désintégration améliorées
CN113354850A (zh) * 2021-06-04 2021-09-07 东华大学 一种纤维素/淀粉复合物的制备方法
CN113493934A (zh) * 2020-04-01 2021-10-12 苏州合祥纺织科技有限公司 一种琼胶纤维的制备方法

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WO2019122648A1 (fr) * 2017-12-18 2019-06-27 Association Pour Le Développement De L'enseignement Et Des Recherches Auprès Des Universités, Des Centres De Recherche Et Des Entreprises D'aquitaine (Adera) Procédé de fabrication d'une fibre de carbone à partir de coton recyclé et utilisation de la fibre ainsi obtenue pour la formation d'un article en matériau composite
CN111936680A (zh) * 2017-12-18 2020-11-13 阿基坦大学、研究中心和企业教学和研究发展协会 (Adera) 由回收棉生产碳纤维的方法及由此获得的纤维用于形成由复合材料制成的制品的用途
JP2021507139A (ja) * 2017-12-18 2021-02-22 アソシアシオン・プール・ル・デベロップマン・ドゥ・ランセニュマン・エ・デ・ルシェルシュ・オープレ・デ・ユニヴェルシテ・デ・サントル・ドゥ・ルシェルシュ・エ・デ・ザントルプリーズ・ダキテーヌ・（アーデーエーエルアー） リサイクル綿から炭素繊維を生産する方法、及びこの方法で得られた繊維の、複合材料から物品を形成するための使用
US11578433B2 (en) 2017-12-18 2023-02-14 Association Pour Le Développement De L'enseignement Et Des Recherches Auprès Des Universitès. Des Centres De Recherche Et Des Entreprises D'aqitaine (Adera) Method for producing a carbon fibre by recycling cotton
JP7368923B2 (ja) 2017-12-18 2023-10-25 アソシアシオン・プール・ル・デベロップマン・ドゥ・ランセニュマン・エ・デ・ルシェルシュ・オープレ・デ・ユニヴェルシテ・デ・サントル・ドゥ・ルシェルシュ・エ・デ・ザントルプリーズ・ダキテーヌ・（アーデーエーエルアー） リサイクル綿から炭素繊維を生産する方法、及びこの方法で得られた繊維の、複合材料から物品を形成するための使用
EP3536832A1 (fr) * 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Fibre lyocell présentant des propriétés de désintégration améliorées
WO2019170715A1 (fr) 2018-03-06 2019-09-12 Lenzing Aktiengesellschaft Fibre lyocell présentant des propriétés de désintégration améliorées
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CN113354850A (zh) * 2021-06-04 2021-09-07 东华大学 一种纤维素/淀粉复合物的制备方法

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