WO2014201480A1 - Nouveau procédé écologique de fabrication d'éponges et de toiles éponges en polysaccharides - Google Patents

Nouveau procédé écologique de fabrication d'éponges et de toiles éponges en polysaccharides Download PDF

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Publication number
WO2014201480A1
WO2014201480A1 PCT/AT2014/000121 AT2014000121W WO2014201480A1 WO 2014201480 A1 WO2014201480 A1 WO 2014201480A1 AT 2014000121 W AT2014000121 W AT 2014000121W WO 2014201480 A1 WO2014201480 A1 WO 2014201480A1
Authority
WO
WIPO (PCT)
Prior art keywords
glucan
shaped body
forming substance
porous
cellulose
Prior art date
Application number
PCT/AT2014/000121
Other languages
German (de)
English (en)
Inventor
Gregor Kraft
Gert Kroner
Thomas Röder
Original Assignee
Lenzing Ag
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 Lenzing Ag filed Critical Lenzing Ag
Publication of WO2014201480A1 publication Critical patent/WO2014201480A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085—Use of fibrous compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/044—Elimination of an inorganic solid phase
    • C08J2201/0444—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00

Definitions

  • the present invention relates to a process for the production of spongy moldings, which are prepared by means of a direct dissolving process in sodium hydroxide from a (1 -> 3) -glucan.
  • Solvent Conventional cellulosic starting materials such. B. Chemical pulps are only partially soluble due to their relatively high degree of polymerization in sodium hydroxide solution. By pre-switching corresponding
  • solubility of the cellulosic material used can be improved.
  • solubility-improving additives such as urea, thiourea or zinc oxide, in the dissolving process.
  • Freeze-drying corresponding, for example, crosslinked with glutaraldehyde solutions in aqueous urea-NaOH systems and subsequent neutralization with acetic acid are prepared.
  • No. 6,129,867 (A) deals in great detail with the production of sponges from cellulose dissolved in aqueous sodium hydroxide solution.
  • the cellulosic starting material may be subjected to a pretreatment, in particular a steam explosion or microfibrillation. According to the invention, however, the complete solution of the cellulose used is not a condition. In presence
  • pore-forming substances solids which melt under the precipitation conditions, sublimate or dissolve (eg ice or salt hydrates such as the sodium sulfate decahydrate, also called Glauber's salt, with melting points below 90 ° C.), furthermore solids or liquids which release a gas, polyelectrolytes or foaming bulking agents.
  • additives including pigments for coloring, biocides or fungicides to the
  • Cellulosic sponges give additional, functional properties.
  • the cellulosic mass loaded with pore formers is according to the
  • Moldings by extrusion by means of a nozzle or by coating of substances by means of rollers, processable.
  • gelation of the cellulose after deformation This can be effected by temperature change and / or by adding suitable substances, such as cellulose derivatives.
  • suitable substances such as cellulose derivatives.
  • the conditions in the subsequent last step of the process described must be chosen so that the cellulose is not only precipitated, but also to form the desired pore structure, such as by melting,
  • this sub-process comprises immersing the gelled mass in acid, preferably in sulfuric acid with
  • Acid treatment may involve further substeps such as precipitation of the cellulose with simultaneous melting of the pore former by hot water treatment or by heating without direct contact with heat transfer
  • Liquids e.g. B. in a microwave oven
  • a microwave oven Liquids, e.g. B. in a microwave oven
  • Sponge structures are obtained, wherein preferably first hot and then cold water is used as a washing liquid.
  • US Pat. No. 6,129,867 discloses a favorable and, compared to the viscose process, substantially more environmentally compatible process for the production of artificial sponge structures from cellulose.
  • the disadvantage is that the cellulose material used is generally only partially dissolved by the aqueous sodium hydroxide solution. Undissolved portions, especially if they are unevenly distributed and / or of varying size, affect the visual appearance of the final product. In the presence of larger agglomerates, negative effects on the strength of the final product are likely.
  • solubility-improving substances such as urea or zinc oxide
  • US 7,000,000 describes fibers obtained by spinning a solution of polysaccharides consisting essentially of hexose repeat units linked via a (1-3) glycosidic linkages. These polysaccharides can be prepared by contacting an aqueous solution of sucrose with glucosyltransferase (GtfJ) isolated from Streptococcus salivarius (Simpson et al.
  • the a (1 -> 3) -glucan is to be derivatized, preferably acetylated.
  • the solvent is preferably an organic acid, an organic halogen compound, a fluorinated alcohol or a
  • spongy, d. H. porous moldings consisting of a glucose-containing polysaccharide and a process for their preparation for
  • the polysaccharide raw material should be cheap and that
  • Structure-forming substance (1 -> 3) contains glucan, which consists of the following
  • Steps consists of: a. Preparation of an alkaline, a (1 -> 3) -glucan-containing
  • Additives e.g., biocides or reinforcing fibers
  • Shaping the mass e.g., by extrusion on perforated
  • the process according to the invention is a direct dissolution process in sodium hydroxide solution.
  • a shaped body having a sponge structure can be produced, wherein ⁇ (1 ⁇ 3) -glucan-containing sodium hydroxide solution instead of a
  • the term “sponge” can also be used for shaped bodies having a porous structure, and such a porous structure can therefore also be termed "sponge-like".
  • structure-forming substance is to be understood as meaning the homogeneous, solid material of the molding material surrounding the pores
  • Embodiments of the invention still contain reinforcing materials such as fibers or fabrics, but for the purposes of this invention these reinforcing materials should not be included in the structure-forming substance.
  • the a (1-3) glucan can be prepared by contacting an aqueous solution of sucrose with glucosyltransferase (GtfJ) isolated from Streptococcus salivarius (Simpson et al., Microbiology, vol 41, pp 1451-1460 (1995) )).
  • the a (1-3) -glucan consists of at least 90% hexose units and at least 50% of the hexose units are linked by cx (1-> 3) -glycosidic bonds.
  • the structure-forming substance contains between 20 and 100% by weight of a (1-3) -glucan.
  • a (1-3) -glucan in addition to the a (1 - 3) -glucan, in step a. solution also contain cellulose. Pulp is preferably used as cellulosic raw material. But in principle, any other cellulosic raw material suitable for direct dissolving processes in caustic soda solution is also suitable.
  • the structure-forming substance contains 100% by weight of a (1-3) -glucan.
  • the concentration of the structure-forming substance in the polymer solution may be between 4 and 15% by weight; preferably 5.5 to 12 wt .-%.
  • the concentration of sodium hydroxide in the polymer solution may be between 2 and 10% by weight; from 4.0 to 5.5% by weight are preferred.
  • the degree of polymerization of the cx (1-3) glucan used in the process according to the invention expressed as weight average DP W , can be between 200 and 2000; values between 800 and 1500 are preferred.
  • step b a filtration and / or venting of the polysaccharide solution take place.
  • Glauber's salt sodium or potassium chloride, magnesium or sodium sulfate, other readily soluble or meltable substances, including water-soluble polymers or at elevated temperatures soluble, gel-like particles, such as gelatin, propellant such.
  • gas-forming substances such as aluminum powder or gases are used. The resulting pore structure and thus ultimately the density of the sponges obtained depend essentially on the particle size and the particle size distribution of the salts used.
  • a preferred pore-forming agent is Glauber's salt.
  • the porous shaped body according to the invention may contain a reinforcing material to improve its properties.
  • Reinforcing material may be made of fibers, for example
  • Short cut fibers which are the polysaccharide solution in
  • inventive method are added. This gives a shaped body in which the reinforcing fibers are distributed throughout the structure-forming material.
  • a variant of this embodiment is to apply the polysaccharide solution so that the planar
  • Reinforcing material is located inside the porous molding.
  • the textile fabric can be, for example, a dry or wet-laid paper or another nonwoven, but also a woven, knitted or knitted fabric. Basically, of course, foils or thicker, rigid plates of almost any materials as a flat
  • the invention also relates to a porous shaped body, as
  • structure-forming substance contains a (1- »3) -glucan.
  • This shaped body can also be referred to as a sponge.
  • the structure-forming substance contains between 20 and 100% by weight, preferably 100% by weight of a (1-3) -glucan.
  • At least 90% of the ct (1-> 3) -glucan consists of hexose units and at least 50% of the hexose units are linked by a (1- »3) -glycosidic bonds.
  • the shaped body contains cellulose as further structure-forming substance.
  • Shaped body a reinforcing material, as already described above.
  • the shaped bodies according to the invention can be used as sponges or
  • Sponge cloths of all kinds are used.
  • the degree of polymerization of the a (1-3) -glucans was determined by GPC in
  • Gluecangehalt added and mixed.
  • the sponge raw material was poured into a mold, coagulated with an acidic sodium sulfate solution (400 g / l Na 2 SO 4) and a temperature> 95 ° C and regenerated. During coagulation and regeneration, the Glauber's salt is partially melted and washed out. Thereafter, the sponge-like structure was washed and dried.
  • an acidic sodium sulfate solution 400 g / l Na 2 SO 4
  • the sponge raw material was extruded on a fine-meshed grid, coagulated with hot water (97 ° C) and then regenerated with glacial acetic acid. During coagulation and regeneration or the washing steps, the Glauber's salt is partially melted and washed out. Thereafter, the sponge-like structure was washed and dried.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention concerne un procédé de dissolution directe dans de la lessive de soude pour la fabrication de corps moulés poreux contenant du α(1→3)-glucane comme substance structurante, ainsi que les corps moulés poreux fabriqués selon ce procédé.
PCT/AT2014/000121 2013-06-19 2014-06-13 Nouveau procédé écologique de fabrication d'éponges et de toiles éponges en polysaccharides WO2014201480A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA526/2013A AT514472B1 (de) 2013-06-19 2013-06-19 Neues umweltschonendes Verfahren zur Herstellung von Schwämmen und Schwammtüchern aus Polysacchariden
ATA526/2013 2013-06-19

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WO2014201480A1 true WO2014201480A1 (fr) 2014-12-24

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10059778B2 (en) 2014-01-06 2018-08-28 E I Du Pont De Nemours And Company Production of poly alpha-1,3-glucan films
US10106626B2 (en) 2014-01-17 2018-10-23 Ei Du Pont De Nemours And Company Production of poly alpha-1,3-glucan formate films
US10731297B2 (en) 2015-10-26 2020-08-04 Dupont Industrial Biosciences Usa, Llc Water insoluble alpha-(1,3-glucan) composition
US10738266B2 (en) 2015-06-01 2020-08-11 Dupont Industrial Biosciences Usa, Llc Structured liquid compositions comprising colloidal dispersions of poly alpha-1,3-glucan
US10800859B2 (en) 2014-12-22 2020-10-13 Dupont Industrial Biosciences Usa, Llc Polymeric blend containing poly alpha-1,3-glucan
US10822574B2 (en) 2015-11-13 2020-11-03 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10844324B2 (en) 2015-11-13 2020-11-24 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10876074B2 (en) 2015-11-13 2020-12-29 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10895028B2 (en) 2015-12-14 2021-01-19 Dupont Industrial Biosciences Usa, Llc Nonwoven glucan webs
US11230812B2 (en) 2015-10-26 2022-01-25 Nutrition & Biosciences Usa 4, Inc Polysaccharide coatings for paper
US11351104B2 (en) 2015-02-06 2022-06-07 Nutrition & Biosciences USA 4, Inc. Colloidal dispersions of poly alpha-1,3-glucan based polymers

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US4306059A (en) * 1977-09-30 1981-12-15 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Shaped products of alpha-glucan
EP0147634A2 (fr) 1983-12-26 1985-07-10 Asahi Kasei Kogyo Kabushiki Kaisha Solution de cellulose, procédé de préparation et méthode d'application
FI980008A (fi) 1991-02-28 1998-01-02 Tampereen Teknillinen Korkeako Menetelmä alkaliliukoisen selluloosan valmistamiseksi ja menetelmä kuitujen, kalvojen ja muiden tuotteiden valmistamiseksi liukoisesta selluloosasta
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JP2007197649A (ja) 2006-01-26 2007-08-09 Omikenshi Co Ltd 多糖物質からなるスポンジ
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WO2008087026A1 (fr) 2007-01-17 2008-07-24 Carl Freudenberg Kg Procédé de fabrication d'un tissu-éponge en cellulose, tissu-éponge ainsi obtenu et son utilisation
CN101569757A (zh) 2008-12-31 2009-11-04 褚加冕 一种医用生物海绵的制备方法
CN101792538A (zh) 2010-04-02 2010-08-04 山东海龙股份有限公司 一种采用离子液体生产纤维素海绵的方法
CN102504327A (zh) 2011-10-22 2012-06-20 桂林理工大学 利用剑麻废弃物麻糠和麻头制备纤维素海绵的方法

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US4306059A (en) * 1977-09-30 1981-12-15 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Shaped products of alpha-glucan
EP0147634A2 (fr) 1983-12-26 1985-07-10 Asahi Kasei Kogyo Kabushiki Kaisha Solution de cellulose, procédé de préparation et méthode d'application
FI980008A (fi) 1991-02-28 1998-01-02 Tampereen Teknillinen Korkeako Menetelmä alkaliliukoisen selluloosan valmistamiseksi ja menetelmä kuitujen, kalvojen ja muiden tuotteiden valmistamiseksi liukoisesta selluloosasta
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EP1693407A2 (fr) 2005-02-17 2006-08-23 Kalle GmbH Eponge, son procédé de préparation et son utilisation
JP2007197649A (ja) 2006-01-26 2007-08-09 Omikenshi Co Ltd 多糖物質からなるスポンジ
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CN101792538A (zh) 2010-04-02 2010-08-04 山东海龙股份有限公司 一种采用离子液体生产纤维素海绵的方法
CN102504327A (zh) 2011-10-22 2012-06-20 桂林理工大学 利用剑麻废弃物麻糠和麻头制备纤维素海绵的方法

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10059778B2 (en) 2014-01-06 2018-08-28 E I Du Pont De Nemours And Company Production of poly alpha-1,3-glucan films
US10106626B2 (en) 2014-01-17 2018-10-23 Ei Du Pont De Nemours And Company Production of poly alpha-1,3-glucan formate films
US10800859B2 (en) 2014-12-22 2020-10-13 Dupont Industrial Biosciences Usa, Llc Polymeric blend containing poly alpha-1,3-glucan
US11351104B2 (en) 2015-02-06 2022-06-07 Nutrition & Biosciences USA 4, Inc. Colloidal dispersions of poly alpha-1,3-glucan based polymers
US11918676B2 (en) 2015-02-06 2024-03-05 Nutrition & Biosciences USA 4, Inc. Colloidal dispersions of poly alpha-1,3-glucan based polymers
US10738266B2 (en) 2015-06-01 2020-08-11 Dupont Industrial Biosciences Usa, Llc Structured liquid compositions comprising colloidal dispersions of poly alpha-1,3-glucan
US10731297B2 (en) 2015-10-26 2020-08-04 Dupont Industrial Biosciences Usa, Llc Water insoluble alpha-(1,3-glucan) composition
US11230812B2 (en) 2015-10-26 2022-01-25 Nutrition & Biosciences Usa 4, Inc Polysaccharide coatings for paper
US10822574B2 (en) 2015-11-13 2020-11-03 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10844324B2 (en) 2015-11-13 2020-11-24 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10876074B2 (en) 2015-11-13 2020-12-29 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
US10895028B2 (en) 2015-12-14 2021-01-19 Dupont Industrial Biosciences Usa, Llc Nonwoven glucan webs

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AT514472A1 (de) 2015-01-15

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