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WO2014201479A1 - 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
WO2014201479A1
WO2014201479A1 PCT/AT2014/000120 AT2014000120W WO2014201479A1 WO 2014201479 A1 WO2014201479 A1 WO 2014201479A1 AT 2014000120 W AT2014000120 W AT 2014000120W WO 2014201479 A1 WO2014201479 A1 WO 2014201479A1
Authority
WO
WIPO (PCT)
Prior art keywords
glucan
shaped body
forming substance
porous
viscose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AT2014/000120
Other languages
German (de)
English (en)
Inventor
Gregor Kraft
Gert Kroner
Thomas Röder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser 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, Chemiefaser Lenzing AG filed Critical Lenzing AG
Publication of WO2014201479A1 publication Critical patent/WO2014201479A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • 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
    • 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 preparation of
  • Viscous method of a (1 - 3) -glucan be prepared.
  • Viscose process is done by mixing the alkaline
  • Cellulose xanthate solution with at least one pore-forming agent.
  • water-soluble salts such as sodium or potassium chloride or magnesium or sodium sulfate have proven particularly useful, the resulting pore structure and thus also the density of the obtained
  • Sponges are essentially determined by the grain size and the particle size distribution of the salts used.
  • the decahydrate of sodium sulfate also called Glauber's salt, is used particularly frequently. This decomposes at 32 ° C with elimination of its water of crystallization, in which dissolves the sodium sulfate. This process is optically called melting of the
  • gelatin JP2000186166 (A)
  • propellant z. B.
  • JP2001 139718 (A) has the production of cellulosic sponges by introducing air bubbles in viscose and subsequent heating to the content.
  • the shaping can be carried out continuously by extruding the viscose
  • Viscose pastes can also be thermally, for example by heating by means of alternating current or by treatment with hot liquids, for. B.
  • Hot water or sodium sulfate-containing solutions to be regenerated describes such a process, wherein in a first step the Glauber's salt crystals contained in the viscose mass are melted by passage of alternating current. Subsequently, the cellulose is completely regenerated by treatment with a hot liquid, preferably by spraying with hot acidic solution.
  • Block sponges are prepared in a batchwise manner by filling any shaped article with the viscous masses.
  • the regeneration of the molding compositions is possible in a similar manner as in the above-outlined continuous process, namely by chemical means, for.
  • acid treatment or by microwave heating, as described in KR830001030 (A).
  • a treatment with aqueous, acidic solution can be connected in this process variant. Any existing salt-form pore formers can be removed by washing with water or appropriate washing solutions.
  • textile reinforcing fibers including natural cellulosic fibers such as hemp, jute or cotton or man-made cellulosic fibers such as lyocell or viscose fibers, or the introduction of textile fabrics such as fabrics or nets, improve the mechanical properties of regenerated cellulose sponges. It is also possible to dye the viscose composition, for example by mixing in color pigments.
  • DE103391 13 (A1) describes, with the aid of reactive dyes, uniformly dyed sponge cloths which are distinguished by the same coloration of the regenerated cellulose and the cotton fibers used for reinforcement. Furthermore, processes for the modification of cellulose sponges are known with the aim to give them additional functional properties.
  • the cx (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 mixture of such components. These solvents are expensive and expensive to regenerate.
  • the object was over this prior art is spongy, d. H. porous moldings consisting of a glucose-containing polysaccharide, as well as to provide an environmentally improved process for their preparation.
  • the polysaccharide raw material should be cheap and that
  • Additives e.g., biocides or reinforcing fibers
  • Shaping the mass e.g., by extrusion on perforated
  • the process according to the invention is a modified viscose process.
  • the devices suitable for carrying out these steps and the general process conditions are in principle known to the person skilled in the art from US Pat
  • a porous shaped body having a sponge structure can be produced, wherein a (1 ⁇ 3) -glucan-containing sodium hydroxide solution is mixed only with small amounts of carbon disulfide (CS2).
  • CS2 carbon disulfide
  • inventive method can be significantly lower than in the
  • 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 are not to 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)).
  • At least 90% of the a (1 ⁇ 3) -glucan consists of hexose units and at least 50% of the hexose units are linked by a (1 ⁇ 3) -glycosidic bonds.
  • the structure-forming substance contains between 20 and 100% by weight of a (1- »3) -glucan.
  • the in step a. solution also contain cellulose.
  • Pulp is preferably used as cellulosic raw material. However, in principle any other cellulosic raw material suitable for viscose processes is suitable for this purpose, for example cotton linters, recycled old textiles, waste paper or the like.
  • the structure-forming substance contains 100% by weight of (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 degree of polymerization of the ⁇ (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 short Nachreife, filtration and / or venting of the polysaccharide solution.
  • certain salts such as Glauber's salt, sodium or potassium chloride, magnesium or sodium sulfate, other readily soluble or meltable substances, including water-soluble polymers or gelatinous particles soluble at elevated temperatures, for example 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 depends essentially on the grain 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
  • the structure-forming substance u (1 -> 3) -glucan.
  • This shaped body can also be referred to as a sponge.
  • the structure-forming substance contains between 20 and 100 wt .-%, preferably 100 wt .-% ⁇ x (1 -> 3) -glucan.
  • At least 90% of the a (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 a (1 -> 3) -glucans was determined by GPC in
  • the viscose thus prepared contained 8.9 wt .-% structure-forming material, 4.6 wt .-% NaOH and 1, 1 wt .-% sulfur. This viscose solution was 900 wt .-%
  • Glauber's salt based on glucan content, added and mixed.
  • the solution as reinforcing fibers was still 25 wt .-% Lyocell fibers, based on glucan content, added with a cut length of 2-3 mm.
  • the sponge raw material was extruded on a fine-meshed grid, coagulated with hot water (97 ° C) and then with a
  • the viscose thus prepared contained 9.3 wt .-% structure-forming material and 4.6 wt .-% NaOH and 1, 4 wt .-% sulfur. 500% by weight Glauber's salt, based on glucan content, was added to this viscose solution and mixed in.
  • the sponge raw material was extruded onto a fine-meshed grid, coagulated with an acidic sodium sulfate solution (400 g / l Na 2 SO 4) and at a temperature> 95 ° C and regenerated. During coagulation and

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

Abstract

La présente invention concerne un procédé viscose modifié 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/AT2014/000120 2013-06-19 2014-06-13 Nouveau procédé écologique de fabrication d'éponges et de toiles-éponges en polysaccharides Ceased WO2014201479A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA497/2013A AT514473B1 (de) 2013-06-19 2013-06-19 Neues umweltschonendes Verfahren zur Herstellung von Schwämmen und Schwammtüchern aus Polysacchariden
ATA497/2013 2013-06-19

Publications (1)

Publication Number Publication Date
WO2014201479A1 true WO2014201479A1 (fr) 2014-12-24

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AT (1) AT514473B1 (fr)
WO (1) WO2014201479A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT518612A1 (de) * 2015-02-06 2017-11-15 Chemiefaser Lenzing Ag Polysaccharid-Suspension, Verfahren zu ihrer Herstellung und ihre Verwendung
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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT517822B1 (de) 2015-10-12 2021-09-15 Dr Oberascher Leonhard Vorrichtung zum Mischen farbiger Lichtstrahlen

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1005569A (en) 1961-05-04 1965-09-22 Lipaco Sa Process for making cellulose sponge
DE1569226A1 (de) 1964-10-30 1969-06-26 Novacel S A Nouvelles Applic C Verfahren zur Herstellung von kuenstlichen Schwaemmen aus regenerierte Cellulose
GB1278586A (en) 1968-09-13 1972-06-21 Sponcel Ltd Improvements in and relating to the production of regenerated cellulose sponge material
US4306059A (en) * 1977-09-30 1981-12-15 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Shaped products of alpha-glucan
KR830001030A (ko) 1979-08-14 1983-04-29 헨리 바뚜렐 액체 조성물로 직물의 실패를 함침시키는 방법
JPH11279323A (ja) 1998-03-31 1999-10-12 Hokuetsu Paper Mills Ltd 溶媒再生セルローススポンジ成型体及びその製造方法
KR20000033143A (ko) 1998-11-20 2000-06-15 안효근 고흡수성 세루로스 스폰지 제조방법
JP2000186166A (ja) 1998-12-21 2000-07-04 Rengo Co Ltd セルロ―ス多孔体の製造方法
US6129867A (en) * 1996-05-06 2000-10-10 Financiere Elysees Balzac Method for manufacturing alveolate cellulosed products
JP2001139718A (ja) 1999-11-19 2001-05-22 Nisshinbo Ind Inc セルローススポンジの製造方法
DE10339113A1 (de) 2003-08-22 2005-03-10 Kalle Gmbh & Co Kg Eingefärbtes Schwammtuch und Verfahren zu dessen Herstellung
US7000000B1 (en) 1999-01-25 2006-02-14 E. I. Du Pont De Nemours And Company Polysaccharide fibers
US7189667B1 (en) 1997-12-03 2007-03-13 Kalle Gmbh & Co. Kg Sponge towel based on cellulose and a method for producing the same
AT502363A1 (de) 2004-07-07 2007-03-15 Chemiefaser Lenzing Ag Verfahren zur herstellung eines celluloseschwammes
JP2007197649A (ja) 2006-01-26 2007-08-09 Omikenshi Co Ltd 多糖物質からなるスポンジ
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

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1005569A (en) 1961-05-04 1965-09-22 Lipaco Sa Process for making cellulose sponge
DE1569226A1 (de) 1964-10-30 1969-06-26 Novacel S A Nouvelles Applic C Verfahren zur Herstellung von kuenstlichen Schwaemmen aus regenerierte Cellulose
GB1278586A (en) 1968-09-13 1972-06-21 Sponcel Ltd Improvements in and relating to the production of regenerated cellulose sponge material
US4306059A (en) * 1977-09-30 1981-12-15 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Shaped products of alpha-glucan
KR830001030A (ko) 1979-08-14 1983-04-29 헨리 바뚜렐 액체 조성물로 직물의 실패를 함침시키는 방법
US6129867A (en) * 1996-05-06 2000-10-10 Financiere Elysees Balzac Method for manufacturing alveolate cellulosed products
US7189667B1 (en) 1997-12-03 2007-03-13 Kalle Gmbh & Co. Kg Sponge towel based on cellulose and a method for producing the same
JPH11279323A (ja) 1998-03-31 1999-10-12 Hokuetsu Paper Mills Ltd 溶媒再生セルローススポンジ成型体及びその製造方法
KR20000033143A (ko) 1998-11-20 2000-06-15 안효근 고흡수성 세루로스 스폰지 제조방법
JP2000186166A (ja) 1998-12-21 2000-07-04 Rengo Co Ltd セルロ―ス多孔体の製造方法
US7000000B1 (en) 1999-01-25 2006-02-14 E. I. Du Pont De Nemours And Company Polysaccharide fibers
JP2001139718A (ja) 1999-11-19 2001-05-22 Nisshinbo Ind Inc セルローススポンジの製造方法
DE10339113A1 (de) 2003-08-22 2005-03-10 Kalle Gmbh & Co Kg Eingefärbtes Schwammtuch und Verfahren zu dessen Herstellung
AT502363A1 (de) 2004-07-07 2007-03-15 Chemiefaser Lenzing Ag Verfahren zur herstellung eines celluloseschwammes
JP2007197649A (ja) 2006-01-26 2007-08-09 Omikenshi Co Ltd 多糖物質からなるスポンジ
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SIMPSON ET AL., MICROBIOLOGY, vol. 41, 1995, pages 1451 - 1460

Cited By (14)

* 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
AT518612B1 (de) * 2015-02-06 2019-03-15 Chemiefaser Lenzing Ag Polysaccharid-Suspension, Verfahren zu ihrer Herstellung und ihre Verwendung
AT518612A1 (de) * 2015-02-06 2017-11-15 Chemiefaser Lenzing Ag Polysaccharid-Suspension, Verfahren zu ihrer Herstellung und ihre Verwendung
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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