WO2011116403A2 - Procédé de préparation d'un polysaccharide contenant de l'azote - Google Patents

Procédé de préparation d'un polysaccharide contenant de l'azote Download PDF

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Publication number
WO2011116403A2
WO2011116403A2 PCT/AT2011/000141 AT2011000141W WO2011116403A2 WO 2011116403 A2 WO2011116403 A2 WO 2011116403A2 AT 2011000141 W AT2011000141 W AT 2011000141W WO 2011116403 A2 WO2011116403 A2 WO 2011116403A2
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Prior art keywords
cellulose
salt
polysaccharide
amide
mixture
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PCT/AT2011/000141
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German (de)
English (en)
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WO2011116403A3 (fr
Inventor
Loan Thi To Vo
Barbora Siroka
Avinash P. Manian
Thomas Bechtold
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Universität Innsbruck
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Priority to EP11712745A priority Critical patent/EP2549965A2/fr
Publication of WO2011116403A2 publication Critical patent/WO2011116403A2/fr
Publication of WO2011116403A3 publication Critical patent/WO2011116403A3/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret

Definitions

  • the invention relates to a process for the preparation of a nitrogen-containing polysaccharide. Furthermore, the invention relates to a substance mixture for use in such a process. Finally, the invention relates to moldings and processes for the production of such moldings using nitrogen-containing polysaccharides and the use of these polysaccharides.
  • polysaccharides are the most commonly occurring.
  • Cellulose is the most widely used natural polymer ever, it has excellent properties and is used in a wide variety of applications. It is one of the main components of wood, of fibers such as flax, cotton and is formed as a bacterial cellulose by microbial processes. From wood, cellulose is made by different processes as pulp for a variety of applications, e.g. Fiber and foil production, paper production provided.
  • the potential of this polymeric material which is available from natural sources, is correspondingly great, but this can only be deformed and processed by complex processes. For deformation of the material e.g.
  • the cellulosic polymers are to be separated by suitable chemical concepts.
  • the very strong inter- and intramolecular hydrogen bonds between the cellulose chains can be opened by suitable methods and regenerated after the forming process, which explains the notion of cellulose regeneration.
  • the strong hydrogen bonds between the polymer chains are also the cause, therefore, a simple thermal deformation by heating, such as e.g. of synthetic polymers such as polypropylene or polyamide, or simply dissolving in a solvent are not suitable for the deformation of cellulose. Before the theoretical melting of the cellulose, a degradation reaction takes place with simultaneous destruction of the polymer chains.
  • swelling agents Solvents and mixtures of solutes that are only capable of swelling the polymeric polysaccharide matrix are referred to as swelling agents. Since such mixtures can not achieve complete dissolution of the polymers, but in particular penetrate into the low-order amorphous regions of a polysaccharide matrix, there is a reversible increase in volume of the undissolved matrix, which decreases again after removal of the swelling agent. For the expert are swelling agents therefore fundamentally different to solvents or solution systems for polysaccharides.
  • the swelling agent leads to an increase in volume of fibers and usually also to a significant change in the physical properties, e.g. Fiber strength, flexibility, elasticity, etc. From the physico-chemical state, the interactions between the macromolecules and the swelling agent are more favorable than the intermolecular forces between the macromolecules on the one hand and the swelling agent molecules on the other hand. The at least partial penetration of the swelling agent into the polymer structure (and thus the volume increase) is therefore energetically favored. (Source D. Klemm, B. Philipp, T. Heinze, U. Heinze, W. Wagenknecht, Comprehensive Cellulose Chemistry, Vol I and II, Wiley-VCH, 1998, ISBN 3- 527-29413-9, Vol. 1, Page 43, chapter 2.2 Swelling and Dissolution of Cellulose)
  • alkaline treatment solutions may contain alkali ions (Li, Na, K ions), as well as, for example, alkaline earth hydroxides and quaternary ammonium hydroxides are known.
  • alkali ions Li, Na, K ions
  • alkaline earth hydroxides alkaline earth hydroxides
  • quaternary ammonium hydroxides are known.
  • the treatment in solvent systems has also been described in the prior art. Strongly acidic swelling agents such as ortho-phosphoric acid and polyphosphoric acid have also been described as swelling agents.
  • swelling neutral solutions especially liquids from the classes of ionic liquids (eg 1-n-butyl-3-methylimidazolium chloride, 1-ally-3-methylimidazolium chloride or homologous substances or corresponding acetates), the organic swelling agent (for example, N-methyl-morpholine-N-oxide), the inorganic salts (eg CaCl 2 , ZnCl 2 , LiCl, NaSCN, MgCl 2 ) and more complex mixtures such as LiCl / N, N-dimethylacetamide, NH 4 Cl - sym-dimethylurea , NaCl / urea serve.
  • complex mixtures such as LiCl / N, N-dimethylacetamide, NH 4 Cl - sym-dimethylurea , NaCl / urea serve.
  • complexes between LiCl and urea is known in the art.
  • such solutions can be used as swelling agents for the treatment of cell
  • the cellulose is formed by dissolution in a suitable aqueous or nonaqueous solvent system, in which case, for example, NMMO N-methylmorpholine N-oxide or ionic liquids such as 1-n-butyl-3-methylimidazolium acetate important solvents for cellulose should be mentioned.
  • NMMO N-methylmorpholine N-oxide or ionic liquids such as 1-n-butyl-3-methylimidazolium acetate important solvents for cellulose should be mentioned.
  • the regeneration of the dissolved cellulose in the desired form is carried out here by extruding the viscous mass through spinnerets or slot dies, and washing out the solvent, whereby fiber or films of regenerated cellulose are obtained.
  • quaternary ammonium compounds such as N-alkylpyridinium halides are also suitable for dissolving cellulose, disadvantageously requiring high temperatures for producing a melt of these salts.
  • Alkali metal salts can also be used to dissolve cellulose using suitable solvents.
  • the system's corrosiveness and high cost have prevented a technical use for the formation of cellulose.
  • cellulose can be dissolved in solutions of LiCl in hexamethylphosphoramides or 1-methyl-2-pyrrolidinone (DD 214622 A1).
  • DD 214622 A1 1-methyl-2-pyrrolidinone
  • the known systems consisting of ethylenediamine or hydrazine and thiocyanates are to be regarded as anhydrous basic-reacting solvent systems (Xiao M, Cellulose, 16 (2009) 381-391).
  • Non-aqueous solvent systems rely on the use of mixtures of organic solvents, eg, DMSO (dimethyl sulfoxide) and SO 2 , to which amines are added (Heinze T., Koschella A., Polimeros: Ciencia e Tecnologia, 15 (2005) 84-90).
  • organic solvents eg, DMSO (dimethyl sulfoxide) and SO 2 , to which amines are added
  • alkaline aqueous solutions containing alkali metal hydroxides and other organic components such as urea or thiourea has also been described in the literature (Ruan, D., et al., Macromol Biosci., 2004, 4, 1105-1112).
  • Common to these methods is the disadvantage that regeneration of the polymer dissolved in the alkaline solution requires precipitation in acid to neutralize the caustic soda, otherwise technically unacceptable amounts of water would be required to wash out the caustic soda.
  • the non-derivatizing solvents include also the hydrate melts Lil.2 H 2 0 inorganic salts, LiN0 3l LiAcetat, LiCI0 4 .3 H 2 0, H 2 0 LiSCN.2, ZnCl 2 .4H 2 0, Zn (N0 3) 2 .x H 2 0, FeCl 3 .6H 2 0 and their mixtures with Mg salts Zn salts and thiocyanates and other perchlorates.
  • LiCl is described here merely as a swelling agent (Heinze T., Koschella A., Polimeros: Ciencia e Tecnologia, 15 (2005) 84-90, Leipner et al., Macromol. Chem. Phys., 201 (2000) 2041-2049 Fischer S., et al., Cellulose 10 (2003) 227-236). Due to the present in the melt water of crystallization these systems are added to the aqueous media.
  • Viscose fiber production by the xanthate method cellulose di- and triacetate, methyl cellulose, carboxymethyl cellulose.
  • Viscose has been used for a long time with great commercial success for producing regenerated cellulose.
  • cellulose is treated with NaOH and CS 2 to obtain cellulose xanthate, which in turn is dissolved in a weak NaOH solution to finally obtain the viscose.
  • this process is accompanied by the use and emergence of environmentally problematic chemicals such as CS 2 , H 2 S and heavy metals.
  • a particular method of derivatization is the preparation of cellulose carbamates which have increased solubility in alkaline solutions.
  • Cellulose carbamates are also known as cellulose aminomethanates, cellulose aminomethanoates or cellulose aminoformates.
  • Cellulose carbamates are advantageous compared to cellulose xanthate because they are more stable and can be transported in a dried state while cellulose xanthogenate is not even transportable in solution.
  • the formation of alkali-soluble cellulose carbamates by reacting urea with alkali-activated cellulose has been extensively described in the literature (US 4,999,425, WO 2004/046198, WO 2003/099871).
  • alkaline swelling agents The preliminary treatment in alkaline swelling agents leads to an improved conversion / but the use of alkaline media is cumbersome and requires a subsequent neutralization.
  • alkaline swelling agents alkali metal hydroxides or liquid ammonia have been proposed in the literature (CN 1687137, EP 282 881, DE 19635707, EP 57 105). task This additional swelling pretreatment is to improve the accessibility of the undissolved cellulose structure.
  • a combination of alkaline activation with the simultaneous use of inert solvents e.g. 1-methyl-2-pyrrolidone, alcohols or polyethylene glycol as urea solvent is proposed, for example, in WO 2003/054023 and DE 19940393 for the production of cellulose by cellulose pulp.
  • the reaction mixture can also be processed simultaneously by extrusion into fibers, films and other shaped articles (WO 2003/099872).
  • the disadvantageous use of alkaline solutions can not be circumvented according to WO 2003/099872.
  • the object of the present invention is therefore to remedy this situation and to provide a method and means for carrying out the method so that it is better to make cellulose thermally deformable.
  • This object is achieved by a method for producing a nitrogen-containing polysaccharide, which is characterized in that the polysaccharide is reacted with an amide in the presence of a salt and a polyol at a temperature of at least 90 ° C.
  • the process can be carried out using a mixture of substances comprising:
  • the method according to the invention now provides a possibility for the deformation of cellulose which dispenses with the use of concentrated alkaline or acidic aqueous solutions and allows the formation of the cellulosic matrix in a single-stage treatment process.
  • the above-mentioned composition contains an amide as a derivatizing agent for the polysaccharide, an ionic component (the salt) as a swelling agent, and a polyol having two objects of serving as a co-solvent for the amide and as a plasticizer for the polysaccharide.
  • an amide as a derivatizing agent for the polysaccharide
  • an ionic component the salt
  • a polyol having two objects of serving as a co-solvent for the amide and as a plasticizer for the polysaccharide.
  • the mixtures according to the invention are not stable at room temperature, but at least one component crystallizes out at room temperature owing to the limited solubility.
  • the water content is less than 10% by weight.
  • the content of salt is between 10 and 35% by weight, preferably between 10 and 30% by weight, of amide between 10 and 80% by weight and of polyol between 1 and 50% by weight.
  • the salt may e.g. be selected from the group of alkali salts, alkaline earth salts or mixtures thereof.
  • organic salts When using organic salts, the following conditions and amounts have proved to be advantageous: It is advantageous if the content of salt is between 10 and 35% by weight, preferably between 20 and 30% by weight, of amide between 50 and 70% by weight. and on Polyol between 4 and 20 wt.% Is.
  • Preferred organic salts are salts of carboxylic acids. Preferred examples have the general formula (R 1 - COO) n M.
  • the amide is a carboxylic acid amide, preferably urea or an N-substituted urea. It has turned out to be particularly advantageous if the polyol is also a polyether. In such compounds at least two -OH groups are provided which are in position 1 and TO, i. located at the first and last carbon atom.
  • polyol selected from the group of polyethylene glycols, the polypropylene glycols, copolymers of ethylene glycol and propylene glycol or mixtures thereof selected. Polyols of different chain lengths can be used.
  • the polysaccharide is reacted with a mixture of substances according to the aforementioned type at a temperature of at least 90 ° C.
  • the deformation of the cellulose can take place in the temperature range in which the preparation remains homogeneous. This temperature range is 90-260 ° C, and in a preferred embodiment, temperatures of 140-230 ° C are used.
  • the preferred polysaccharide is cellulose, in which the process works particularly well, and adaptation and optimization of the conditions for other polysaccharides (eg chitosan, alginate, xanthan, pectin) is readily reasonable to one of ordinary skill in the art.
  • polysaccharides eg chitosan, alginate, xanthan, pectin
  • both natural and regenerated, in particular fibrous celluloses can be used.
  • the main task of the process is to increase the nitrogen content of the polysaccharide, ie, if there is still no nitrogen, to bind it chemically or if nitrogen is already present in the polysaccharide, to increase the content of nitrogen.
  • Such modified polysaccharides are well applicable in the textile industry, so that one embodiment may provide that the polysaccharide is a textile or part of a textile. It is then particularly preferred for the textile to contain cotton.
  • amides in particular carboxylic acid amides preferably urea or an N
  • novel findings prove to be advantageous for the initial formation of a polysaccharide, preferably of cellulose, wherein the polysaccharide is subjected to a process of the aforementioned type and simultaneously brought into the desired shape.
  • novel findings also prove to be advantageous for the production of a shaped body, wherein a polysaccharide is reacted with an amide in the presence of a salt and a polyol at a temperature of at least 90 ° C and is brought into the desired shape.
  • the shaping may be e.g. by pressing, extrusion, pressing with rollers or the like.
  • the degree of substitution is the number of hydroxyl groups substituted by carbamate per monosaccharide unit.
  • the DS can vary and reach at most the number of OH groups per monosaccharide unit.
  • the maximum DS 3.
  • a suitable and sufficient DS for the present invention depends on the mode of application and can be changed by selecting the saccharide substrate and the reaction temperature and reaction time.
  • the invention relates to shaped articles containing a nitrogen-containing polysaccharide prepared by a process of the aforementioned kind.
  • Another aspect of the invention relates to the use of a nitrogen-containing polysaccharide prepared by a process of the aforementioned type as an adsorbent. It has been found that such modified polysaccharides have good Adsorptionseigeschaften for liquids and other substances.
  • a mixture prepared by the process according to the invention preferably contains an ionic component as the swelling agent in a concentration of 10-35% by weight and an amide or urea derivative with 10-80% by weight as derivatizing agent, and a polyol as co-solvent in an amount of 1-10% by weight , The proportion of water in the mixture remains below 10 percent by weight.
  • the blend contains 20-30 percent by weight of the ionic component, and a urea derivative of 50-70 percent by weight, and a polyol of 4-20 percent.
  • the softening conditions for the polymer depend on the cellulose used, the comminution of the material and the composition of the preparation used.
  • the time to complete melt may be between 1 minute and 20 hours, in a preferred embodiment the time being between 1 and 60 minutes.
  • Urea is preferably used as the amide component, but after appropriate optimization of the formulation it is also possible to use substituted urea derivatives and other carboxamides.
  • Polyethylengylcole can be used with different chain length, also short-chain polyalcohols, polypropylene glycols and block copolymers of propylene glycol and Polyethylengylcol are used.
  • the added salt component is preferably selected from the group of ionic components which act as swelling agents, alkali or alkaline earth salts being used in one form.
  • ionic components which act as swelling agents, alkali or alkaline earth salts being used in one form.
  • either LiCl or CaCl 2 is used as the ionic component in the preparation.
  • the derivatizing melt thus produced can now be processed into shaped articles by the usual methods, e.g. by extrusion through nozzles or dissolution of the cellulosecarbamat conceptionigen polymer in sodium hydroxide solution and precipitation in an aqueous precipitation bath. If the cellulose carbamate solution is introduced directly into an aqueous solution, cellulose carbamate in amorphous form is obtained.
  • aqueous solutions or organic solvents e.g. serve alcohols.
  • molding methods can be used by injection molding.
  • the plasticizing components remain in the molding and are no longer washed out.
  • the inventive method thus represents a one-step method for the production and deformation of cellulosic materials, wherein when using urea as the amide component at the same time an efficient method for the production of cellulose carbamate is provided.
  • the process can be applied to pulp of various origins, in a preferred embodiment the process is applied to cellulosic textile fabrics applied, in particular textiles are mentioned, which contain at least one cellulose regenerated fiber as a blend component.
  • the following recipe examples show exemplary composition of suitable treatment mixtures and experimental results on their behavior.
  • the cellulosic material used was a fabric of viscose material.
  • a water-diluted mixture of PEG 2000 (a polyethylene glycol) urea and LiCl was applied to the fabric with a padder.
  • PEG 2000 polyethylene glycol
  • LiCl LiCl
  • reaction mixtures of the following composition:
  • the deformation of the materials takes place by the action of heat and pressure.
  • the material samples described below were treated at a pressure of around 1.0 bar for a period of 30 seconds to 2 minutes at temperatures of 150 ° C to 220 ° C.
  • the formation of the cellulose carbamate can be confirmed on the basis of the N content and the IR spectrum, wherein the nitrogen content increases with the use of said formulations with increasing treatment temperature and treatment time up to about 2 wt.% N from the weight of the material.
  • N about 1% by weight of N is obtained after treatment at 190 ° C. for 2 minutes or 220 ° C. for 30 seconds; for a treatment at 220 ° C. for 2 minutes, formulations 1 1, 6 Wt.% N and in formulation 3 2.0 wt.% N bound in the polymer (this corresponds to a degree of substitution DS of 0.2-0.25).
  • the deformability of the polymer can be detected and confirmed under the microscope on the change in the fiber and fabric structure as well as on fiber deformations.
  • Fig. 1 shows the steps of carbamation.
  • Fig. 2 shows the nitrogen content in wt.% Of the treated cellulose
  • Fig. 3 shows a FTIR-ATR spectrum of (a) untreated cellulose and (b)
  • the treating solution was prepared by mixing polyethylene glycol (20% by weight), urea (60% by weight) and sodium acetate (20% by weight). The molecular weight of polyethylene glycol was varied from 4000 to 6000 from 2000. A sufficient amount of deionized water was added. Viscose fabric stored under standard conditions (20 +/- 2 ° C, 65 + 1-2% RH) for at least 48 hours was impregnated with a pad at the above solution at room temperature under 1 bar pressure at a speed of 1 m / min. Thereafter, the textile was dried in a tenter dryer at 105 ° C for 40 seconds to remove water. Thereafter, the dried textile was treated at 1 bar pressure for 2 min at 100 ° C to 250 ° C.
  • the nitrogen content was determined between 0.1 wt.% To about 2 wt.%, Corresponding to a degree of substitution DS of 0.02 to 0.25. The DS increased to 220 ° C and then again slightly to 250 ° C, due to onset of decomposition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un mélange de substances contenant de 10 à 80 % en poids d'au moins un amide, de 10 à 80 % en poids d'au moins un sel et de 1 à 80 % en poids d'au moins un polyol. Elle concerne en outre l'utilisation de ce mélange de substances pour préparer un polysaccharide contenant de l'azote à partir d'un polysaccharide, ainsi que diverses utilisations des produits ainsi fabriqués.
PCT/AT2011/000141 2010-03-23 2011-03-22 Procédé de préparation d'un polysaccharide contenant de l'azote WO2011116403A2 (fr)

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Application Number Priority Date Filing Date Title
EP11712745A EP2549965A2 (fr) 2010-03-23 2011-03-22 Procédé de préparation d'un polysaccharide contenant de l'azote

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ATA464/2010 2010-03-23
AT4642010A AT509621B1 (de) 2010-03-23 2010-03-23 Verfahren zur herstellung eines stickstoffenthaltenden polysaccharids

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WO2011116403A2 true WO2011116403A2 (fr) 2011-09-29
WO2011116403A3 WO2011116403A3 (fr) 2011-11-24

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