EP1427778A1 - Eponge de cellulose et son procede de fabrication - Google Patents

Eponge de cellulose et son procede de fabrication

Info

Publication number
EP1427778A1
EP1427778A1 EP02757951A EP02757951A EP1427778A1 EP 1427778 A1 EP1427778 A1 EP 1427778A1 EP 02757951 A EP02757951 A EP 02757951A EP 02757951 A EP02757951 A EP 02757951A EP 1427778 A1 EP1427778 A1 EP 1427778A1
Authority
EP
European Patent Office
Prior art keywords
weight
cellulose
mixture
water
amine oxide
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.)
Withdrawn
Application number
EP02757951A
Other languages
German (de)
English (en)
Inventor
Eduard Mülleder
Heinrich Firgo
Olivier Bedue
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.)
Financiere Elysees Balzac SA
Original Assignee
Financiere Elysees Balzac SA
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 Financiere Elysees Balzac SA filed Critical Financiere Elysees Balzac SA
Publication of EP1427778A1 publication Critical patent/EP1427778A1/fr
Withdrawn legal-status Critical Current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
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • 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
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • tertiary amine oxides in particular NMMO
  • swelling and solvent are well known and is used industrially for the production of fibers and other cellulosic moldings.
  • a method for producing a cellulose sponge from a solution of cellulose in NMMO is described in WO 97/23552.
  • WO 98/28360 describes the production of a cellulose sponge which is coagulated from a cellulose solution, the cellulose having an average degree of polymerization which does not exceed 800.
  • WO 99/27835 describes a cellulose-based sponge cloth, wherein a solution of cellulose in aqueous amine oxide solution is produced, which is then mixed with at least one pore former and fibers. This mixture is spread on a conveyor belt, which is then passed through a coagulation bath, the temperature of which is so high that the pore former melts and is released.
  • the process usually consists of:
  • c C ell 34.69-1.695 * c H2 o + 0.81 * where cceii the concentration of cellulose (% by weight) in the three-substance mixture and C H2O the concentration of water (% by weight) in the three-substance mixture.
  • the upper limit for the possible cellulose concentration given by this formula includes the so-called confidence range. This means that if the concentration of cellulose is less than the value given by the right part of the formula, there is a 95% chance that a solution will result.
  • a mixture of cellulose and other ingredients such as pore formers (gas, salt or blowing agent) is produced in an aqueous tertiary amine oxide, which mixture contains undissolved and / or highly swollen cellulose, and the mixture shaped and coagulated.
  • shape is understood by the person skilled in the art to shape the mixture into a sponge cloth or into a block sponge according to methods known per se.
  • the aqueous tertiary amine oxide is preferably N-methyl-morpholine-N-oxide and is the expression in the mixture A> 34.69-1.695 * B + 0.81 * V1i, 65 + 0.1 * (B-12.76)
  • A is the proportion of cellulosic material in the mixture (wt.%>), Based on the sum of the proportions by weight of cellulosic material, water and amine oxide in the mixture and B the water proportion in the mixture (wt.%>), Based on the sum is the weight fraction of cellulosic material, water and amine oxide in the mixture.
  • the proportion of cellulosic material based on the proportion of the three-substance mixture of cellulosic material, water and amine oxide in the mixture is preferably outside the range given by US Pat. No. 4,196,282.
  • the result of this is that - unless special measures are taken in accordance with DD 226 573 or EP 0 452 610 - at least some of the cellulosic material is undissolved.
  • cellulosic material means the sum of cellulosic materials in the mixture, namely on the one hand the cellulose (for example cellulose) which is used to produce the mixture and on the other hand cellulosic reinforcing fibers which are optionally additionally used according to a preferred embodiment of the invention ,
  • the process according to the invention consists in the use of NMMO in a concentration which is preferably capable of dissolving a certain amount of cellulose, but not the entire amount of cellulose.
  • the water content of the NMMO used for the preparation can be from 15% by weight to 30% by weight, preferably from 17% by weight to 26% by weight, particularly preferably from 19% by weight to 24% by weight, most preferably 22% by weight.
  • the proportion of cellulosic material can, however, also be within the range defined by US Pat. No. 4,196,282 if the components are mixed in such a way that no dissolution occurs. This can be achieved by adjusting the mixing time, temperature and the shear rates used accordingly.
  • This mixture is thermally far more stable than a complete cellulose solution, so that in the process according to the invention, in particular when using NMMO with a high water content and when processing at low temperatures, numerous complex safety measures, such as e.g. elaborate designs to minimize dead spaces, the provision of rupture disks or the use of stabilizers can be dispensed with.
  • the favorable temperature range for producing and shaping the mixture can easily be determined by the person skilled in the art depending on the respective components. In particular, it should be noted that any reinforcing fibers that are used do not come loose at the temperatures used.
  • the lower limit for the temperature is usually the respective melting point of the amine oxide / water mixture given by the water content of the amine oxide.
  • the upper limit of 105 ° C has proven to be favorable.
  • the temperature for producing and shaping the mixture is preferably from 80 ° C. to 100 ° C.
  • the mass preferably contains cellulose outside the usual dissolution diagram according to US Pat. No. 4,196,282
  • a premix consisting of cellulose, aqueous amine oxide and optionally a stabilizer is prepared.
  • the aqueous tertiary amine oxide is preferably N-methyl-morpholine-N-oxide and is the expression in the premix
  • Bl is the water content in the mixture (% by weight), based on the sum of the weight proportions of cellulose, water and amine oxide in the premix.
  • the proportion of cellulose (e.g. cellulose) in the three-component mixture of cellulose, water and amine oxide in the mixture in the premix is preferably outside the range given by US Pat. No. 4,196,282. The result of this is that at least part of the cellulose is also undissolved in the premix.
  • the cellulose / NMMO mixture is preferably only heated, but no water is evaporated.
  • a further preferred embodiment of the present invention is characterized in that the dissolved cellulose concentration in the premix is less than 7% by weight of cellulose, preferably 2 to 6% by weight of cellulose, particularly preferably 3 to 4% by weight of cellulose, based on the total of Is by weight of cellulose, water and amine oxide.
  • a concentration range of less than 7%> dissolved cellulose based on the total premix has proven to be an advantage in terms of product quality.
  • the water retention capacity of sponges made from premixes with a low cellulose concentration showed a higher value than with more highly concentrated premixes.
  • the NMMO concentration can be kept low compared to the conventional amine oxide process, in particular if the amount of cellulose provided for the production of the premix is advantageously less than 7%.
  • the mixture contains undissolved reinforcing fibers. These reinforcing fibers can preferably be added to the premix.
  • the reinforcing fibers can be synthetic fibers and / or cellulosic fibers, but also inorganic fibers such as e.g. Be glass fibers.
  • the reinforcing fibers should preferably be insoluble or at least sparingly soluble in the environment of the mixture or the premix.
  • Preferred cellulosic reinforcing fibers are cotton fibers, flax fibers and / or crosslinked man-made cellulose fibers, such as e.g. cross-linked lyocell fibers.
  • Polyester, polyamide, polypropylene, polyethylene and / or polyacrylic fibers are preferably used as synthetic reinforcing fibers.
  • the total proportion of cellulosic material in the mixture is preferably less than 12% by weight, based on the sum of the proportions of cellulosic material, amine oxide and water in the mixture.
  • the type and amount of the reinforcing fibers can be determined by the person skilled in the art depending on the desired product properties, but also on the properties of the starting material.
  • the further ingredients such as pore formers (gas, salt or blowing agent) are preferably added to the premix.
  • pore formers gas, salt or blowing agent
  • the mixture preferably contains a salt as a pore former.
  • salts as pore formers for sponges is known from the prior art.
  • Sodium chloride, sodium sulfate, potassium chloride and potassium sulfate are known from the prior art.
  • the ratio of the proportion by weight of salt to the sum of the proportions by weight of cellulosic material, amine oxide and water can be 2: 1 to 8: 1, preferably 3: 1 to 7: 1, particularly preferably 4: 1 to 7: 1 be.
  • the salt preferably has, at least in part, a grain size of 0.1 to 2 mm. Furthermore, the salt at least partially has a grain size of more than 3 mm.
  • the strength of block sponges produced according to the invention increases if the mixture is pressed after filling into a mold with pressures of typically 20 to 40 bar.
  • the strength of the sponges obtained increases if the mixture is cooled before coagulating or washing out. This effect is particularly pronounced when the mixture is cooled to room temperature or even to temperatures below 0 ° C '.
  • the properties of the sponges according to the invention can also be influenced by the fact that the mixture contains ingredients which impart functional properties to the sponge.
  • reinforcing fibers that may be used may themselves be chemically functionalized, i.e. functional groups with e.g. wear biocidal, fungicidal, antibacterial, absorptive function etc.
  • Processing is preferably carried out in a single apparatus, which means that the pore formers, such as gas-propelling organic or inorganic substances, salts or gases, and reinforcing materials - cellulosic and non-cellulosic materials - are mixed in one and the same apparatus and at the same time part of the cellulosic materials dissolved by the amine oxide present.
  • the pore formers such as gas-propelling organic or inorganic substances, salts or gases
  • reinforcing materials - cellulosic and non-cellulosic materials - are mixed in one and the same apparatus and at the same time part of the cellulosic materials dissolved by the amine oxide present.
  • the apparatus used for this purpose is preferably a combination of mixer-kneader and optionally an extruder.
  • a typical process for producing cellulose sponges according to the present invention therefore comprises the following steps:
  • Steps 1 and 2 are preferably carried out in an aggregate without evaporation of water - the use of mixer-extruder apparatuses such as those offered by List or Buss is particularly advantageous, for example “List ORP, List CRP apparatus ", which are particularly well suited for highly viscous, crusting (salt as porophore) materials.
  • liquid and / or supercritical carbon dioxide can also be mixed in as the propellant.
  • the present invention also relates to a cellulose sponge which can be obtained by the process according to the invention.
  • the cellulose sponge is preferably in the form of a block sponge.
  • the procedure for producing block sponges from cellulose solutions or according to the viscose process is known to the person skilled in the art.
  • the mixture can also be processed into a sponge cloth in a manner known per se.
  • Block sponges according to the invention are preferably of a density of 20 to 60 kg / m 3 , preferably of 25 to 45 kg / m 3 , an absorption capacity of 10 to 40 times, preferably 15 to 30 times their own weight and one Strength of 0.5 to 5 daN / cm 2 (dekaNewton) marked.
  • a cellulose solution with the following composition was prepared in a manner known per se by heating, evaporating water and applying shear force: NMMO 75.3% by weight cellulose (type Solucell, viscosity SCAN 400,
  • the cellulose is completely dissolved.
  • NaCl with a grain size of 0.1 to 1 mm was added to this solution in a weight ratio of 6.1: 1.
  • the mixture obtained was placed in a mold for the production of block sponges and coagulated or washed out with water at 50 ° C. for 11 hours and then at 25 ° C. for 2 days.
  • the dimension (volume) of the wet sponge and the mass of the dry sponge are determined.
  • the density (volume weight) results from the quotient of the mass of the dry sponge and the volume of the wet sponge.
  • the sponge that has never dried or, in the case of sponges that have already dried, a sponge that has been moistened again is removed from the water, stripped and weighed. After drying in a drying cabinet at 60 ° C, the sponge is weighed again.
  • the water content in the sponge results from the difference between the mass in the moist state and the mass in the dry state. This proportion of water will divided by the mass in the dry state. The resulting quotient (ie x times its own weight when dry) is the WRV.
  • a test specimen is clamped in and the force until the test specimen tears.
  • the cross section of the test specimen is measured beforehand.
  • the measured maximum force before tearing is divided by the cross-sectional area and thus gives the strength, which is expressed in daN (decaNewton) / cm 2 .
  • a cellulose solution was prepared as in Comparative Example 1, but the cellulose solution had the following composition:
  • NaCl with a grain size of 0.1 to 1 mm was added to this solution in a weight ratio of 6.1: 1.
  • the mixture obtained was placed in a mold for the production of block sponges and coagulated or washed out with water at 50 ° C. for 2 days.
  • the cellulose content is within the dissolving range given by US Pat. No. 4,196,282. However, part of the cellulose was undissolved because the premix had been stirred too briefly to bring about a complete solution.
  • Salt was added to this premix at a ratio of 5.3: 1.
  • the mixture obtained was cooled to room temperature, placed in a mold for the production of block sponges and coagulated or washed out with water at 50 ° C. for 48 hours.
  • the mixture thus obtained is placed in a mold for the production of block sponges and coagulated in water or washed free of NMMO and salt.
  • the resulting block sponge has the following properties when never dried: Density 37.2 g / 1
  • the resulting block sponge has the following properties when never dried:
  • Examples 9 and 10 show how the person skilled in the art can control the properties of the resulting sponge over a wide range, inter alia on the basis of the selection of the type and amount of the starting materials.
  • sponges produced according to the invention are compared, in which flax was used as reinforcing fibers in one case and polyester as reinforcing fibers in the other case.
  • the NMMO is introduced and then preheated to 78 ° C. Then the roughly torn pulp is added in sheet form and mixed at the same temperature. After adding the proportion of flax or polyester fibers, the mixture is mixed at 72 ° C. for a further 7 minutes and heated to 78 ° C. After this temperature has been reached, mixing is continued for a further 5 minutes.
  • the apparatus is emptied and in the emptied apparatus in Example 11 0.623 kg and in Example 12 0.723 kg of the premix obtained and 6 kg each of NaCl with a grain size fraction of 0.5-1 mm and a grain size fraction of> 3 mm are filled.
  • the ratio of the grain size fraction of 0.5 - 1 mm to the grain size fraction of> 3mm was 7: 3.
  • First the salt is introduced and then the calculated amount of premix is added.
  • the salt was preheated to 80 ° C. before the addition.
  • the mixture is kneaded at 85 ° C. for a further 15 minutes, the mass is removed and manually introduced into a rectangular shape. After cooling to room temperature, the mass is coagulated or washed with water at 50 ° C. for 12 hours.
  • NMMO monohydrate, 78% NMMO and stabilizer were initially introduced into a kneader of the Werner-Pfleiderer type and stirred at 60.degree. Then the pulp, the flax fibers and the glass fibers were added. The mixture was stirred at about 100 ° C for about 10 minutes.
  • Salt was then added gradually: first the salt with a grain size of 0.5 - 1 mm, then the salt with a grain size of less than 25 ⁇ m and finally the salt with a grain size of> 4 mm. In between, the mixture was stirred at about 95 ° C. for about 5 minutes. The salt fractions were preheated to approx. 55-60 ° C each.
  • the resulting mixture was placed in a mold for the production of block sponges and coagulated or washed out with water at about 90 ° C. for 48 hours.
  • the block sponge obtained had the following properties when never dried:
  • the sponge also shows abrasive properties.
  • Examples 14 to 16 (according to the invention):
  • NMMO 50% NMMO were placed in a kneader and cotton fibers were added. The mixture was impregnated at 250 mbar for 30 minutes. Water was then distilled off by lowering the pressure and heating the kneader.
  • the mixtures obtained were then formed into spheres and placed in water. It was then boiled in water for 6 hours to remove NMMO and the salt. In between the wash water was changed.
  • the moisture content of the test specimens obtained in% was determined as follows in these examples:
  • Moisture content in%> for once dried samples results from the formula (EW2 - AWl) / EW2 x 100.

Landscapes

  • 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)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention concerne un procédé de fabrication d'éponge de cellulose avec utilisation d'aminoxydes tertiaires, caractérisé en ce qu'on prépare un mélange de cellulose et d'autres ingrédients, tels que des agents porogènes (gaz, sels ou agents d'expansion) dans un aminoxyde tertiaire aqueux, ledit mélange renfermant de la cellulose non dissoute et/ou de la cellulose hautement gonflée, et en ce que ce mélange est ensuite mis en forme et coagulé.
EP02757951A 2001-07-25 2002-07-25 Eponge de cellulose et son procede de fabrication Withdrawn EP1427778A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0116101A AT410319B (de) 2001-07-25 2001-07-25 Celluloseschwamm und verfahren zu dessen herstellung
AT11612001 2001-07-25
PCT/AT2002/000221 WO2003010232A1 (fr) 2001-07-25 2002-07-25 Eponge de cellulose et son procede de fabrication

Publications (1)

Publication Number Publication Date
EP1427778A1 true EP1427778A1 (fr) 2004-06-16

Family

ID=3686378

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02757951A Withdrawn EP1427778A1 (fr) 2001-07-25 2002-07-25 Eponge de cellulose et son procede de fabrication

Country Status (5)

Country Link
US (1) US20040201121A1 (fr)
EP (1) EP1427778A1 (fr)
CN (1) CN1535293A (fr)
AT (1) AT410319B (fr)
WO (1) WO2003010232A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
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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AT502363B1 (de) * 2004-07-07 2007-07-15 Chemiefaser Lenzing Ag Verfahren zur herstellung eines celluloseschwammes
DE102009013515A1 (de) * 2009-03-19 2010-09-23 Carl Freudenberg Kg Verfahren zur kontinuierlichen Herstellung von Schwammkörpern aus regenerierter Cellulose und ein Schwammkörper
CN101942112B (zh) * 2010-09-09 2012-07-25 宁波尼可家用品有限公司 一种竹浆海绵制品及其制备方法
RU2650677C2 (ru) 2013-10-11 2018-04-17 КРЭЙТОН ПОЛИМЕРС Ю.Эс. ЭлЭлСи Олефин-ненасыщенный радиальный блок-сополимер стирола и усовершенствованный не содержащий вулканизатора латекс
CN108438529A (zh) * 2018-05-07 2018-08-24 中国农业科学院郑州果树研究所 一种空心李防震运输包装装置及包装材料

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102504327B (zh) * 2011-10-22 2013-05-01 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

Also Published As

Publication number Publication date
CN1535293A (zh) 2004-10-06
US20040201121A1 (en) 2004-10-14
WO2003010232A1 (fr) 2003-02-06
AT410319B (de) 2003-03-25
ATA11612001A (de) 2002-08-15

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