WO2010139426A1 - Solution contenant de la cellulose, procédé pour sa fabrication et utilisation de cette solution - Google Patents

Solution contenant de la cellulose, procédé pour sa fabrication et utilisation de cette solution Download PDF

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Publication number
WO2010139426A1
WO2010139426A1 PCT/EP2010/003255 EP2010003255W WO2010139426A1 WO 2010139426 A1 WO2010139426 A1 WO 2010139426A1 EP 2010003255 W EP2010003255 W EP 2010003255W WO 2010139426 A1 WO2010139426 A1 WO 2010139426A1
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WO
WIPO (PCT)
Prior art keywords
polar
cellulose
solution according
ionic liquids
ionic liquid
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PCT/EP2010/003255
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German (de)
English (en)
Inventor
Julia Schmidt
Armin Greiner
Gunter Scharfenberger
Original Assignee
Carl Freudenberg Kg
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 Carl Freudenberg Kg filed Critical Carl Freudenberg Kg
Publication of WO2010139426A1 publication Critical patent/WO2010139426A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids

Definitions

  • the present invention relates to solutions comprising cellulose and solvents, to processes for their preparation and to their use.
  • cellulose is one of the largest natural organic chemicals in the world and therefore of great importance as a renewable raw material.
  • Cellulose is a versatile raw material. Cellulose can be used unchanged or after physical or chemical treatment. For the last two cases, it is advantageous if cellulose is present in a melt or a solvent in as completely dissolved form as possible. However, cellulose is insoluble in most solvents. Therefore, as solvents for cellulose, the systems known in the literature inter alia as ionic liquid have been proposed.
  • Ionic liquids are liquids that contain only ions. These are liquid salts without having to dissolve the salts in a solvent such as water. Ionic liquids are characterized by a number of interesting properties. They are mostly thermally stable, not flammable, often have a very low vapor pressure and have very good dissolving properties for many substances.
  • US Pat. No. 1,943,176 describes the dissolution of cellulose into benzylpyridinium salts.
  • Benzylpyridinium chloride is a salt which, even at comparatively low temperatures, is in molten form and thus as a liquid.
  • the cellulose solution prepared in this way has a concentration of up to 11% by weight of cellulose.
  • ionic liquids Due to the good solvent properties of ionic liquids, their use for dissolving cellulose is also proposed in WO 03/029329 A2. It is proposed therein that the ionic liquid should consist of cations having a quaternary ammonium ion, which should be quaternized by alkyl groups, especially methyl.
  • the cellulose solution prepared in this way has a concentration of up to 25% by weight of cellulose.
  • EP 0 356 419 B1 describes a continuous process for the preparation of moldable cellulose solutions. There will be a
  • CMOS N-methyl-morpholine-N-oxide
  • the present invention has the object to provide a solution of dissolved cellulose, in particular thermoplastically processable cellulose, which shows improved properties, in particular allows a particularly high proportion of dissolved cellulose, and is suitable for multiple use. Furthermore, a particularly efficient and environmentally friendly method for the solution of cellulose should be specified.
  • the solution comprises cellulose and a homogeneous mixture of at least two compatible or non-chemically reacting with each other ionic liquids, wherein at least one ionic liquid is polar or strongly polar having a melting point of greater than 90 0 C, in particular to 300 0 C, and wherein at least one further ionic liquid is less polar or non-polar with a melting point of equal to or lower than 90 ° C., in particular to minus 30 ° C.
  • the weight ratio of the polar or strongly polar ionic liquid to the less polar or nonpolar ionic liquid is advantageously 1: 9 to 9: 1, more preferably 3: 7 to 1: 1.
  • the viscosity of the at least two ionic liquids mixed with cellulose at the processing temperature in the range of 50 Pas to 30000 Pas, more preferably in the range of 100 Pas to 2900 Pas and most preferably in the range of 150 Pas to 1400 Pas.
  • Polar ionic liquids provide a particularly good interaction between the cellulose and the ionic liquid. However, as the polarity increases, so does the melting point or viscosity of the ionic liquid. It follows that in strongly polar ionic liquids, although the cellulose can be dissolved particularly well, but that the solution is highly viscous. It has surprisingly been found that the particular combination of selected ionic liquids leads to a particularly low viscosity of the mixture with cellulose and thereby enables a particularly high concentration of cellulose.
  • the solution of the invention contains cellulose with more than 1 wt .-% up to 50 wt .-%, preferably up to 40 wt .-%, based on the total weight of the solution.
  • a preferred combination of at least two ionic liquids comprises at least one polar or highly polar ionic liquid, preferably hard bases or hard bases as defined by RG Pearson (so-called HSAB concept, hard and soft acids and bases). having.
  • Preferred anions in this regard are hydroxide, fluoride, chloride, acetate, carbonate, phosphate, trifluoroacetate and / or bicarbonate.
  • the cationic component of the ionic liquid or of the salt preferably has short and / or small radicals, such as aliphatic radicals having two to six carbon atoms, in particular ethyl radicals.
  • a preferred combination of at least two ionic liquids comprises at least one less polar or nonpolar ionic liquid having soft anions or soft bases as defined by R. G. Pearson (so-called HSAB concept, hard and soft acids and bases).
  • the cationic component of the less polar or nonpolar ionic liquid or of the salt preferably has long and / or large radicals, such as aliphatic radicals having from 2 to 25 carbon atoms combined with aromatic or cyclic structures or alternatively only aliphatic radicals having from 6 to 25 ° C. -atoms.
  • the cationic component of the polar and / or non-polar ionic liquid or salt ammonium, choline, guanidinium, imidazolium, phosphonium, pyrazolium, pyridinium, pyrrolidinium, benzimidazolium, pyrazolidinium, pyridazinium, pyrimidinium , Pyrazimium-, piperazinium and / or sulfonium salts used.
  • the polar ionic liquid used is preferably tributylmethylammonium chloride (BMNCI) and / or triethylmethylammonium chloride (EMNCI).
  • BMNCI tributylmethylammonium chloride
  • EMNCI triethylmethylammonium chloride
  • the less polar ionic liquid used is preferably 1-ethyl-3-methylimidazolium chloride (EMIMCI) and / or 1-ethyl-3-methylimidazolium acetate (EMIMCH 3 COO).
  • EMIMCI 1-ethyl-3-methylimidazolium chloride
  • EMIMCH 3 COO 1-ethyl-3-methylimidazolium acetate
  • Preferred combinations of two ionic liquids are a mixture of tributylmethylammonium chloride (BMNCI) and 1-ethyl-3-methylimidazolium chloride (EMIMCI) or of triethylmethylammonium chloride (EMNCI) and 1-ethyl-3-methylimidazolium chloride (EMIMCI)
  • the solution preferably one or more additives are added, in particular low molecular weight compounds such as water and / or dimethyl sulfoxide (DMSO), surfactants, synthetic polymers such as polyolefins, polyvinyl alcohols (PVA), polyethers, for example on the basis of polyethylene glycol (PEG) and / or polyoxymethylene, polyesters, polyamides and / or biopolymers, such as proteins, such as silk.
  • DMSO dimethyl sulfoxide
  • surfactants synthetic polymers such as polyolefins, polyvinyl alcohols (PVA), polyethers, for example on the basis of polyethylene glycol (PEG) and / or polyoxymethylene, polyesters, polyamides and / or biopolymers, such as proteins, such as silk.
  • synthetic polymers such as polyolefins, polyvinyl alcohols (PVA), polyethers, for example on the basis of polyethylene glycol (PEG) and / or polyoxymethylene,
  • polyvinylpyrrolidone polyvinylamine, chitosan, peptides, such as Collagen, polyhydroxy fatty acid, such as polyhydroxybutyric acid, polyglycolic acid, dextrins, polyvinylpyridine, polyhydroxyethylmethylacrylate, polyacrylamide, xanthan, lignin, dendrimers, pectin, agar, guar gum, hyaluronate, alginate, casein, polyurethane, polyacrylate, polyethyleneimine, dyes, active ingredients, in particular medicaments, antibacterial preparations, fertilizers, etc., flame retardants, foam additives and / or other biodegradable polymers, such as polycaprolactone and / or polylactide.
  • polyhydroxy fatty acid such as polyhydroxybutyric acid, polyglycolic acid, dextrins
  • polyvinylpyridine polyhydroxyethylmethylacrylate
  • polyacrylamide polyacrylamide
  • xanthan
  • polyvinyl alcohol can improve water absorption compared to pure cellulose.
  • Polyvinyl alcohols, polyethylene glycol and water for example, reduce the surface tension or the viscosity of the melt, so that processing at lower temperatures makes it possible to protect the substances.
  • the solution is low-viscosity, that is, wherein the solution at the processing temperature has a viscosity in the range of 50 Pas to 30000 Pas, preferably in the range of 100 Pas to 2900 Pas , more preferably in the range of 150 Pas to 1500 Pas.
  • the method preferably comprises the steps of a) adding cellulose to a homogeneous mixture of at least two compatible or non-chemically reactive ionic liquids, wherein at least one ionic liquid is polar or strongly polar with a melting point of greater than 90 0 C, in particular bis 300 0 C, and wherein at least one further ionic liquid is less polar or nonpolar having a melting point of equal to or less than 90 0 C, in particular to minus 30 0 C, and b) mixing until the cellulose is completely dissolved.
  • at least two ionic liquids having the properties mentioned and having particularly low processing temperatures, in particular for protecting the substances it is possible to achieve particularly high concentrations of cellulose, in particular due to the particularly low viscosity of the mixture. Due to the particular choice of ionic liquids, in particular with regard to their melting points, mixing ratios and / or their viscosity, the method according to the invention is particularly energy-efficient and environmentally friendly, which, for example, also permits processing at particularly low pressure.
  • cellulose is converted into xanthogenates or carbamates in many established processes, especially in the first step.
  • the cellulose is not chemically altered, but merely dissolved.
  • the inventive method is particularly simple and efficient.
  • the present invention has also set itself the task of providing a solution of dissolved cellulose, which is suitable for multiple use.
  • the inventive solution without chemical reaction from the melt use for thermoplastic processing, in particular at 25 0 C to 300 0 C, preferably at 100 0 C to 280 ° C, more preferably to 160 0 C, in particular to fibers, nonwovens, films, and / or other moldings, such as tablets.
  • the solution according to the invention is preferably used for the production of raw materials, in particular fibers, nonwovens and / or sponges, for packaging, hygiene or household products, in particular cleaning utensils, and / or in the medical field, in particular for wound dressings. Furthermore, the solution according to the invention is preferably used for filters, films, insulating materials and / or carrier materials, in particular for catalysts, furniture, clothing, for example as intermediate lining or liner (interlinings), for sound and / or heat protection.
  • a salt mixture of 70 wt .-% 1-ethyl-3-methylimidazoliumchlorid (EMIMCI) having a melting point of 87 ° C and 30 wt .-% tributylmethylammonium chloride (BMNCI) having a melting point of 110 0 C is mixed with cellulose and mixed homogeneously, wherein 80 wt .-% of ionic Liquids and 20 wt .-% cellulose are used. At 85 ° C, this mixture has a viscosity of 280 Pas.
  • the mixture of cellulose and the ionic liquids EMIMCI and BMNCI is heated for 1, 5 hours at 100 0 C, then melted at 130 0 C and processed into a molding, for example, to a tablet. Fibers and films are also made.
  • EMIMCI 1-ethyl-3-methylimidazoliumchlorid
  • BMNCI tributylmethylammonium chloride
  • the mixture of cellulose and the ionic liquids EMIMCI and BMNCI is heated for 1, 5 hours at 100 0 C, then melted at 16O 0 C and processed by means of a hot press to form a cellulose film. Fibers and tablets are also made.
  • a salt mixture of 70% by weight of 1-ethyl-3-methylimidazolium chloride (EMIMCI) having a melting point of 87 ° C. and 30% by weight of triethylmethylammonium chloride (EMNCI) having a melting point of 282 ° C. is added with cellulose and mixed homogeneously, wherein 80 wt .-% of ionic liquids and 20 wt .-% cellulose are used. At 85 ° C, this mixture has a viscosity of 1006 Pas.
  • the mixture of cellulose and the ionic liquids EMIMCI and EMNCI is heated for 1, 5 hours at 100 0 C, then melted at 120 0 C and processed by means of a hot press to form a cellulose film. Fibers and tablets are also made.
  • the ionic liquids are finally completely washed out with water, which is confirmed by gravimetric investigations.
  • Optional can be reduced as well as their thermal stability are improved by the addition of water as an additive, the melting point of the above-mentioned mixtures of cellulose and ionic liquid to about 110 ° C to 100 0 C.
  • both low molecular weight compounds such as water and / or dimethyl sulfoxide (DMSO), surfactants, as well as various synthetic polymers, such as, for example, polyolefins, polyvinyl alcohols (PVA), polyethers (for example based on polyethylene glycol (PEG), polyoxymethylene), polyesters, polyamides and / or biopolymers, such as, for example, protein, such as silk.
  • DMSO dimethyl sulfoxide
  • surfactants as well as various synthetic polymers, such as, for example, polyolefins, polyvinyl alcohols (PVA), polyethers (for example based on polyethylene glycol (PEG), polyoxymethylene), polyesters, polyamides and / or biopolymers, such as, for example, protein, such as silk.
  • additives are polyvinylpyrrolidone, polyvinylamine, chitosan, collagen, pectin, agar, guar gum, hyaluronate, alginate, casein, polyurethane, polyacrylate, polyethyleneimine, dyes, active ingredients, in particular Medicines, antibacterial preparations, fertilizers, etc., flame retardants, foam additives and other biodegradable polymers, such as polycaprolactone and / or polylactide.

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

Abstract

Le but de l'invention est d'obtenir une solution de cellulose dissoute, en particulier une cellulose pouvant être traitée à façon des thermoplastiques, qui présente de meilleures propriétés, en particulier la possibilité d'obtenir un pourcentage particulièrement élevé de cellulose dissoute et qui peut être fabriqué de façon simple et dans des conditions respectueuses de l'environnement. A cet effet, selon l'invention, la solution contient de la cellulose et un mélange homogène composé d'au moins deux liquides ioniques compatibles entre eux ou qui ne réagissent pas chimiquement entre eux, au moins un liquide ionique étant soit polaire ou très polaire, avec un point de fusion supérieur à 90°C, en particulier pouvant atteindre jusqu'à 300°C, et au moins un autre liquide ionique étant moins polaire ou non polaire et présentant un point de fusion inférieur ou égal à 90°C, en particulier pouvant atteindre jusqu'à moins 30°C.
PCT/EP2010/003255 2009-06-02 2010-05-28 Solution contenant de la cellulose, procédé pour sa fabrication et utilisation de cette solution WO2010139426A1 (fr)

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DE102009023458A DE102009023458A1 (de) 2009-06-02 2009-06-02 Lösung, umfassend Cellulose, Verfahren zu deren Herstellung sowie deren Verwendung
DE102009023458.6 2009-06-02

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN102329422A (zh) * 2011-08-24 2012-01-25 华南理工大学 离子液体中壳聚糖接枝聚乳酸的制备方法
CN103418021A (zh) * 2013-08-08 2013-12-04 四川大学 一种原位交联i型胶原电纺纤维膜敷料及其制备方法
JP2016138339A (ja) * 2015-01-26 2016-08-04 国立大学法人高知大学 湿潤強度を有する紙の製造方法
CN109337094A (zh) * 2018-04-20 2019-02-15 西北大学 一种离子液体辅助酶解法制备水凝胶的方法
CN110964205A (zh) * 2018-09-30 2020-04-07 天津大学 壳聚糖胍阳离子水性聚氨酯在制备抗菌涂层中的应用
CN113322186A (zh) * 2021-06-21 2021-08-31 昆明理工大学 一种离子液体快速采收微藻的方法
CN114957196A (zh) * 2022-05-06 2022-08-30 哈尔滨工业大学（威海） 一种离子液体类似物催化合成双酯基环酯的方法

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CN101492837A (zh) * 2009-03-03 2009-07-29 江苏盛丰登泰生物技术有限公司 一种高聚合度细菌纤维素纤维的制备方法

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329422A (zh) * 2011-08-24 2012-01-25 华南理工大学 离子液体中壳聚糖接枝聚乳酸的制备方法
CN102329422B (zh) * 2011-08-24 2013-06-12 华南理工大学 离子液体中壳聚糖接枝聚乳酸的制备方法
CN103418021A (zh) * 2013-08-08 2013-12-04 四川大学 一种原位交联i型胶原电纺纤维膜敷料及其制备方法
JP2016138339A (ja) * 2015-01-26 2016-08-04 国立大学法人高知大学 湿潤強度を有する紙の製造方法
CN109337094A (zh) * 2018-04-20 2019-02-15 西北大学 一种离子液体辅助酶解法制备水凝胶的方法
CN110964205A (zh) * 2018-09-30 2020-04-07 天津大学 壳聚糖胍阳离子水性聚氨酯在制备抗菌涂层中的应用
CN113322186A (zh) * 2021-06-21 2021-08-31 昆明理工大学 一种离子液体快速采收微藻的方法
CN113322186B (zh) * 2021-06-21 2023-05-26 昆明理工大学 一种离子液体快速采收微藻的方法
CN114957196A (zh) * 2022-05-06 2022-08-30 哈尔滨工业大学（威海） 一种离子液体类似物催化合成双酯基环酯的方法
CN114957196B (zh) * 2022-05-06 2023-11-14 哈尔滨工业大学（威海） 一种离子液体类似物催化合成双酯基环酯的方法

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