• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a modified Viscoseverfahren for the production of porous moldings containing as structure-forming substance a (1 3} · Giuean and the porous molded body produced therefrom.
    公开号:AT514473A1
    申请号:T4972013
    申请日:2013-06-19
    公开日:2015-01-15
    发明作者:
    申请人:Chemiefaser Lenzing Ag；
    IPC主号:
    专利说明:

    Lenzing AG, PL0557
    New environmentally friendly process for producing sponges and sponges from polysaccharides
    The present invention relates to a process for the preparation of spongy moldings prepared by a modified viscose process from a (1- + 3) glucan.
    State of the art
    The production of sponge structures by the viscose process has been known for decades. As starting material from renewable raw materials recoverable polysaccharides, especially cellulose, are used. Alternative polysaccharides, such as chitin (deacetylated) described in JP2007197649 (A), play only a very minor role.
    The production of cellulose regenerated sponges by the viscose process is carried out 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 in practice, the resulting pore structure and thus ultimately also the density of the resulting sponges being essentially determined by the particle 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 perceived as melting the sodium sulfate decahydrate and therefore often referred to as such. A corresponding process for producing artificial regenerated cellulose sponges similar in porosity to those of natural sponges using agglomerates of crushed sodium sulfate decahydrate with small amounts of anhydrous sodium sulfate as a pore-forming substance is described in DE1569226 (A1).
    In principle, in addition to salts, any other readily soluble or meltable substances, including water-soluble polymers (JP2007197649 (A) or gelatin-soluble particles (for example gelatin (JP2000186166 (A)), propellants, for example gas-blowing substances such as aluminum powder, are soluble at elevated temperatures (GB1005569 (A)), or replacing gases as pore formers, JP2001139718 (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 extrusion of the viscose, for example on perforated endless belts. Such processes are used for the production of sponge cloths. To regenerate the cellulose, the conveyor belts loaded with the extruded viscose mass are passed through tempered alkaline or acid baths, the salts used as pore formers being dissolved. Extruded viscose pastes can also be thermally, for example by heating by means of alternating current or by treatment with hot liquids, for. As hot water or sodium sulfate-containing solutions can be regenerated. GB1278586 (A) 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 on similar catfish as in the above-outlined continuous process, namely by chemical means, for. By acid treatment, or by microwave heating, as described in KR830001030 (A). For complete regeneration of the cellulose, 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.
    Lenzing AG, PL0557
    The addition of 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 cause an improvement in the mechanical properties of Regeneratcellulose8hwämmen. It is also possible to dye the viscose composition, for example by mixing in color pigments. DE10339113 (A1) describes, with the aid of reactive dyestuff, uniformly dyed sponge cloths which are distinguished by the same coloration of the regenerated cellulose and of 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. It is conceivable, inter alia, the incorporation of biozlder, fungicidal and / or antibacterial substances, but also the addition of components with ion-exchanging properties to viscose. The incorporation of chitosan can provide regenerated cellulose sponges with improved absorptive, antibacterial and deodorizing properties (KR20000033143 (A)).
    Despite its known drawbacks, the viscose process is still the only commercially used process for producing artificial cellulose sponges. Alternative methods such as the amine oxide method (CN101569757 (A), AT502363 (A1), US7189667 (B1), JPH11279323 (A)) or methods using ionic liquids as the direct solvent for cellulose (CN101792538 (A), WO2008087026 (A1)) have been found to be more intensive Research and development work to date, no large-scale implementation experienced.
    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 bonds. These polysaccharides 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)). "Substantially" in this context means that occasionally defects can occur within the polysaccharide chains at which other binding configurations occur. These polysaccharides are intended for the purposes of the present invention as "a (1-> 3) glucan". be designated.
    According to US Pat. No. 7,000,000, the a (1- »3) -glucan is to be derivatized, preferably acetylated. The solvent is preferably an organic acid, an organic halogenated compound, a fluorinated alcohol or a mixture of such components. These solvents are expensive and expensive to regenerate.
    However, studies have also shown that a (1-> 3) -glucans are soluble in dilute sodium hydroxide solution (about 4 to 5.5%).
    task
    The object was over this prior art is spongy, d. H. to provide porous shaped body consisting of a glucose-containing polysaccharide and an environmentally improved process for their preparation.
    The polysaccharide raw material should be inexpensive and the processing method should already be established on an industrial scale and be feasible economically and on existing facilities.
    Description of the invention
    The solution to the above-described object is to provide a novel process for producing a porous shaped body whose structure-forming substance contains a (1-> 3) -glucan, which consists of the following steps: a. Preparation of an alkaline, a (1- »3) -glucan-containing polysaccharide solution;
    Lenzing AG, PL0557 b. Addition and mixing of CS2 c. Addition of pore-forming agents, dyes and optionally other additives (e.g., biocides or reinforcing fibers) d. Shaping the mass (e.g., by extrusion on perforated endless belts or filling molds) e. Coagulation and regeneration of the mass
    The process according to the invention is a modified viscose process. The devices and general process conditions suitable for carrying out these steps are generally known to the person skilled in the art from the viscose method.
    Thus, a porous shaped body having a sponge structure can be produced, whereby a (1- + 3) -glucan-containing sodium hydroxide solution is mixed only with small amounts of carbon disulfide (CS2). Surprisingly, it has been found that in step b. to be added CS2 amount in the process according to the invention may be significantly lower than In the viscose process of the prior art. The process thus differs significantly from existing processes for the production of viscose sponges.
    In the following, for moldings having a porous structure, the term "sponge" can also be used. be used. Such a porous structure can therefore also be described as "sponge-like". be designated.
    For the purposes of this invention, "structurally structurable substance" is to be understood as meaning the homogeneous solid material of the shaped body surrounding the pores. While in certain embodiments of the invention this homogeneous solid material may contain reinforcing materials such as fibers or fabrics, for the purposes of this invention these reinforcing materials should not be included in the structure-forming substance.
    The a (1-> 3) glanic can be prepared by contacting an aqueous solution of sucrose with glucosyltransferase (GtfJ) isolated from Streptococcus salivarlus {Simpson et al. Microbiology, vol 41, pp 1451-1460 (1995)).
    In a preferred embodiment of the process according to the invention, 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.
    In the process according to the invention, the structure-forming substance contains between 20 and 100% by weight of a (1 - * 3) -glucan. In addition to the a (1-> 3) -glucan, the step a. solution also contain cellulose. Pulp is preferably used as cellulosic raw material. But in principle, any other cellulosic raw material suitable for viscose processes is suitable for this purpose, for example cotton wool, recycled old textiles, waste paper or the like.
    In a preferred embodiment of the process according to the invention, 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 degree of polymerization of the a (1- »3) glucan used in the process according to the invention, expressed as weight average DPW, can be between 200 and 2000; values between 800 and 1500 are preferred.
    If necessary, after step b. a short Nachreife, filtration and / or venting of the polysaccharide solution.
    As pore-forming agents, 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. B. gas-forming substances such as aluminum powder or gases are used. The resulting pore structure, and thus ultimately the density of the resulting Schwömme 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. This reinforcing material may consist, for example, of fibers, preferably short-fiber fibers, which are added to the polysaccharide solution in the process according to the invention. In this case, a shaped body is obtained, in which the reinforcing fibers are distributed throughout the structure-forming material.
    A further embodiment according to the invention comprises applying the polysaccharide solution to a planar reinforcing material, preferably to a textile fabric, so that this reinforcing material surrounds the porous shaped body according to the invention essentially on its outer side. A variant of this embodiment is to apply the polysaccharide solution so that the sheet-like reinforcing material is located inside the porous shaped body.
    The textile fabric can be, for example, a dry or wet-laid paper or another nonwoven, but also a woven, knitted or knitted fabric. In principle, films or thicker, rigid plates made of almost any materials are of course possible as a flat reinforcing material.
    Combinations of several of the above-mentioned reinforcing materials in the same shaped body are possible and are included in the invention.
    The subject matter of the invention is also a porous shaped body which contains a (1-> 3) -glucan as structure-forming substance. This shaped body can also be referred to as a sponge.
    Lenzing AG, PL0557
    The structure-forming substance contains between 20 and 100% by weight, preferably 100% by weight of a (1-> 3) -glucan.
    In a preferred embodiment, 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.
    In a preferred embodiment, the shaped body contains cellulose as further structure-forming substance.
    In a preferred embodiment, the molding according to the invention contains a reinforcing material, as already described above.
    The moldings of the invention can be used as sponges or sponge cloths of all kinds.
    In the following the invention will be described by way of examples. However, the invention is expressly not limited to these examples, but includes all other embodiments based on the same inventive concept.
    Examples
    The degree of polymerization of the a (1- * 3) -glucans was determined by GPC in DMAc / LlCl. In the following, the weight average of the degree of polymerization (DPW) is always stated.
    Example 1;
    An aqueous glucan solution containing 9% by weight of a (1-> 3) -glucan having a DPW of 1000 and 4.7% by weight of NaOH was reacted with 15% by weight of CS2 (by weight based on glucan content). The viscose thus prepared contained 8.9% by weight structure-forming material, 4.6% by weight NaOH and 1.1% by weight sulfur. 900% by weight Glauber's salt, based on glucan content, was added to this viscose solution and mixed in. In addition, as a reinforcing fiber, the solution still contained 25% by weight.
    Lyocell fibers, based on glucan content, added with a cut length of 2-3 mm.
    The sponge raw material was extruded onto a fine-meshed grid, coagulated with hot water (97 ° C.) and then regenerated with a sulfuric acid bath. During coagulation and regeneration, the Glauber's salt is partially melted and washed out. Thereafter, the porous structure was washed and dried.
    Example 2:
    An aqueous glucan solution containing 9.5% a (1-> 3) -glucan having a DPW of 1000 and 4.7% by weight of NaOH was reacted with 18% by weight of CS2 (percent by weight based on glucan content). The viscose thus prepared contained 9.3% by weight of structuring material and 4.8% by weight.
    NaOH and 1.4% by weight of sulfur. To this viscose solution, 1500% by weight of Glauber's salt, based on glucan content, was added and mixed.
    In addition, 25% by weight of lyocell fibers, based on glucan content, were added to the solution as reinforcing fibers with a cutting length of 2-3 mm.
    The sponge stock was extruded onto a fine mesh screen with an acidic sodium sulfate solution (400 g / l Na 2 SO 4) and at a temperature of > 95 eC coagulated and regenerated. During coagulation and regeneration, the Glauber's salt is partially melted and washed out. Thereafter, the porous structure was washed and dried.
    权利要求:
    Claims (14)
    [1]
    Lenzing AG, PL0557 Claims 1. A process for the preparation of a porous shaped body, the structure-forming substance of which contains a (1- + 3) -glucan, comprising the steps of: a. Preparation of an alkaline, a (1- »3) -6lucan-containing polysaccharide solution, b. Addition and mixing of CS2, c. Addition of pore-forming agents, dyes and optionally further additives, d. Shaping the mass, e. Coagulation and regeneration of the mass.
    [2]
    2. The method of claim 1, wherein the structure-forming substance contains between 20 and 100 wt .-%, preferably 100 wt .-% a (1-> 3) glucan.
    [3]
    The method of claim 1, wherein the method is a modified viscose method.
    [4]
    4. The method of claim 1, wherein the a (1-v3) -glucan consists of at least 90% hexose units and at least 50% of the hexose units are linked by a (1- * 3) glycosidic bonds.
    [5]
    5. The method of claim 1, wherein the pore-forming agent is Glauber's salt
    [6]
    6. The method of claim 1, wherein the shaped body contains as further structure-forming substance cellulose.
    [7]
    7. The method of claim 1, wherein the viscose solution reinforcing material in the form of fibers, preferably Kurzschnlttfasem added.
    [8]
    8. The method according to claim 1, wherein the viscose solution is applied to a sheet-like reinforcing material, preferably to a textile fabric.
    [9]
    9. porous shaped body, characterized in that it contains as Strukturblldende substance a (1 ~ * 3) -glucan.
    [10]
    10. A porous shaped body according to claim 9, wherein the structure-forming substance contains between 20 and 100 wt .-%, preferably 100 wt .-% a (1- »3) -glucan.
    [11]
    A porous shaped body according to claim 9, wherein the a (1-> 3) -glucan consists of at least 90% hexose units and at least 50% of the hexose units are linked by a (1- * 3) -glycosidic bonds .
    [12]
    12. Porous shaped body according to claim 9, wherein the shaped body contains as further structure-forming substance cellulose.
    [13]
    13. Porous shaped article according to claim 9, wherein the shaped body contains a reinforcing material.
    [14]
    14. Porous shaped body according to claim 13, wherein the reinforcing material consists of fibers, preferably short cut fibers, and / or a textile fabric.
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    同族专利:
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    引用文献:
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    EP3374400A1|2015-11-13|2018-09-19|E. I. du Pont de Nemours and Company|Glucan fiber compositions for use in laundry care and fabric care|
    EP3374488B1|2015-11-13|2020-10-14|DuPont Industrial Biosciences USA, LLC|Glucan fiber compositions for use in laundry care and fabric care|
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    法律状态:
    2021-02-15| MM01| Lapse because of not paying annual fees|Effective date: 20200619 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA497/2013A|AT514473B1|2013-06-19|2013-06-19|New environmentally friendly process for producing sponges and sponges from polysaccharides|ATA497/2013A| AT514473B1|2013-06-19|2013-06-19|New environmentally friendly process for producing sponges and sponges from polysaccharides|
    PCT/AT2014/000120| WO2014201479A1|2013-06-19|2014-06-13|New environmentally friendly method for producing sponges and sponge cloths from polysaccharides|
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