• 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 direct dissolving process for the production of polysaccharide fibers containing as a fiber-forming substance α (1 → 3) -glucan, with sodium hydroxide solution as a solvent, and the fibers produced therefrom and their use.
    公开号:AT514474A1
    申请号:T490/2013
    申请日:2013-06-18
    公开日:2015-01-15
    发明作者:
    申请人:Lenzing Akiengesellschaft；
    IPC主号:
    专利说明:

    Lenzing AG, PL0559
    Polysaccharide fiber and process for its preparation
    The present invention relates to a process for the production of polysaccharide fibers containing as a fiber-forming substance a (1 ~ + 3) -glucan, with sodium hydroxide solution, and the fibers produced therefrom and their use.
    State of the art
    Polysaccharides play an increasingly important role as materials that can be obtained from renewable raw materials. One of the most abundant polysaccharides is cellulose. Cotton fibers, which consist almost exclusively of cellulose, are an example of the importance of polysaccharides. But also obtained from other cellulosic raw materials such. B. Cellulosic synthetic fibers are becoming increasingly important.
    The generic names "viscose fibers " and "modal fibers" were assigned by the BISFA (Bureau for the International Standardization of Man-Made Fibers) cellulose fibers, which are produced by chemical derivatization of cellulose using caustic soda and carbon disulfide (CS2).
    The term "modal fiber" is a generic term used in the definition of BISFA for a cellulose fiber with a defined high wet strength and also a defined high wet modulus (ie the force needed to stretch the fiber by 5% when wet). stands.
    However, to date, only a process for large-scale production of fibers of the genera Viscose and Modal has prevailed and that the viscose method and modifications thereof.
    How this method is carried out, the expert is known in principle for many years from many patents and other publications. A method for the production of modal fibers is known for example from AT 287.905 B.
    The big disadvantage of all viscose processes is the use of CS2, which has to be recovered with great effort.
    The generic name "lyocell fibers" was assigned by BISFA to cellulose fibers made from solutions in an organic solvent without formation of a derivative.
    To date, however, has only one method for large-scale production of fibers of the genus Lyocell prevailed and that the amine oxide process. In this process, the solvent used is a tertiary amine oxide, preferably N-methylmorpholine-N-oxide (NMMO).
    Tertiary amine oxides have long been known as alternative solvents for cellulose. For example, it is known from US Pat. No. 2,179,181 that tertiary amine oxides are able to dissolve pulp without derivatization and that from these solutions cellulosic shaped bodies such as e.g. Fibers can be made. US Pat. No. 3,447,939 describes cyclic amine oxides as solvents for cellulose.
    How this method is carried out, the expert is known in principle for many years from many patents and other publications. For example, EP 356 419 B1 describes the preparation of solutions and EP 584 318 B1 describes the spinning of such solutions of cellulose in hydrous tertiary amine oxides.
    From a ecological point of view, the lyocell process is much safer than the viscose process, but due to the economic necessity of almost complete cycle closure, it has procedural disadvantages, since substances can accumulate in the circuits.
    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 a
    Lenzing AG, PL0559 aqueous solution of sucrose with glucosyltransferase (GtfJ) isolated from Streptococcus salivarius (Simpson et al., Microbiology, vol 41, pp 1451-1460 (1995)). "Essentially" in this context means that within the polysaccharide chains occasionally flaws may occur at which other binding configurations occur. These polysaccharides are intended for the purposes of the present invention as "a (1-> 3) -glucan". be designated
    The US 7,000,000 first discloses possibilities for the enzymatic production of a (1- »3) -glucan from monosaccharides. Relatively short-chain polysaccharides can be produced on this catfish without loss of monomer units, since the polymer chains are built up from the monomer units. In contrast to the production of short-chain cellulose molecules, the shorter the polymer chains, the cheaper the production of a (1- * 3) -glucan, since then only a short residence time is necessary in the reactors.
    According to US Pat. No. 7,000,000, the a (1- »3) -glucan is intended 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.
    However, investigations have also shown that a (1- »3) -glucans are soluble in dilute sodium hydroxide solution.
    task
    The object of this prior art therefore was to provide an alternative direct dissolving process for the production of polysaccharide fibers, which manages without the CS2 necessary in the viscose process and without the complicated circuit closure of a lyocell process.
    Description of the invention
    The solution to the above-described problem is a new process for producing a polysaccharide fiber whose fiber-forming substance is a (1- »3) -glucan, the process being based on sodium hydroxide solution.
    The present invention therefore relates, on the one hand, to a process for producing a polysaccharide fiber whose fiber-forming substance is a (1-> 3) -glucan, the process being a dispersion dissolving process and the solvent being sodium hydroxide solution. Surprisingly, it has been found that standard spinning baths used in the viscose process (containing about 10Og / l H2S04 and about 250 g / l Na2SO4) give very poor results but two other very different spin bath compositions give significantly better results. 1. High-Acid Spinning: It has been found that increasing the sulfuric acid concentration in the spinning bath significantly improves the thread formation and stretchability of the regenerated thread. The investigated range with good spinning behavior ranges from 200 to 500 grams of sulfuric acid per liter of spinning bath. 2. Low-acid spinning: the second spinning area, which showed significantly better spinning safety, is at very low acid concentrations below 60 grams per liter spin bath, preferably 20-60 g / I. Good results were also achieved with a two-bath system in which the first Bad has very high salt contents and a very low acid concentration, whereby the filament is initially only coagulated and regenerated only in the second acid regeneration.
    In a preferred embodiment of the process according to the invention, therefore, the H2S04 concentration in the spinning bath is between 200 and 500 g / l.
    Lenzing AG, PL05S9
    In a second preferred embodiment of the method according to the invention, therefore, the H2S04 concentration in the spinning bath is between 20 and 60 g / l.
    In a preferred embodiment of the method according to the invention, the spun fiber is subsequently drawn in an acidic regeneration bath.
    According to the invention, the NaOH concentration in the spinning solution should be between 4.0 and 5.5% by weight, based on the total amount of the spinning solution. Outside this range, the solubility of glucan is insufficient. For the purposes of the present invention, the term "fiber" is intended to include both staple fibers of defined cut length and continuous filaments. All principles of the invention described below apply in principle both to staple fibers and to continuous filaments.
    The single fiber titer of the fibers according to the invention can be between 0.1 and 10 dtex. It is preferably between 0.5 and 6.5 dtex and more preferably between 0.9 and 6.0 dtex. In the case of staple fibers, the cut length is usually between 0.5 and 120 mm, preferably between 20 and 70 mm and particularly preferably between 35 and 60 mm. In the case of continuous filaments, the number of individual filaments in the filament yarn is between 50 and 10,000, preferably between 50 and 3,000.
    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)).
    In a preferred embodiment of the process of 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.
    The process for producing the fiber according to the invention consists of the following steps; 1. Preparation of a (1 - »3) -glucan solution in dilute sodium hydroxide solution 2. Spinning the a (1- * 3) -glucan-containing spinning solution through a nozzle into a sulfuric acid spinning bath, stretching the fibers in an acidic regeneration bath and aftertreatment
    The concentration of the fiber-forming substance In the spinning solution can be between 4 and 18 wt .-%, preferably 4.5 to 12 wt .-%.
    The degree of polymerization of the a (1-> 3) glucan used in the method of the present invention, expressed as weight average DP *, may be between 200 and 2000; preferred are values between 500 and 1000.
    In a preferred embodiment, the a (1- »3) -glucan of the polysaccharide fiber of the invention consists of at least 90% hexose units and at least 50% of the hexose units are linked by a (1- + 3) -glycosidic bonds.
    Likewise provided by the present invention is the above-described polysaccharide fiber whose fiber-forming substance is a (1- + 3) -glucan and which has been prepared by the direct dissolving process also described above in sodium hydroxide solution.
    Likewise provided by the present invention is the use of the fibers according to the invention for the production of textile products such as yarns, fabrics. Knitted or knitted fabrics and also of a wide variety of dry and wet laid papers, nonwovens, hygiene articles such as tampons, panty liners and diapers and other nonwovens, in particular absorbent nonwovens products.
    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 / LiCl. In the following, the weight average of the degree of polymerization (DP ") is always indicated.
    Example 1:
    An aqueous glucan solution containing 9% a (1- »3) -glucan with a DPW of 800 and 4.5 wt% NaOH was cooled to 3 ° C, filtered and vented. The solution was spun by means of a spinneret into a 35 ° C. splashing bath containing 300 g / l of sulfuric acid and 50 g / l of sodium sulfate. The spinneret had 53 holes of 50pm diameter. To achieve a corresponding fiber strength, stretching was carried out in the regeneration bath (97 ° C., 25 g / l of H 2 SO 4). The take-off speed was 30 m / mln.
    The properties of the resulting fibers are given in Table 1:
    Example 2:
    An aqueous glucan solution containing 9% a (1- + 3) glucan with a DPW of 1000 and 4.8% by weight NaOH was cooled to 0 ° C, filtered and vented. The solution was spun by means of a spinneret into a spinning bath containing 20 eC containing 35 g / l of sulfuric acid, 280 g / l of sodium sulfate and 45 g / l of zinc sulfate. The spinneret had 53 holes of 40 pm diameter. To obtain a corresponding fiber strength, stretching was carried out in the regeneration bath (92X, 55 g / l H2SO4). The take-off speed was 25 m / min. The properties of the resulting fibers are given in Table 1:
    Lenzing AG, PL0559
    Table 1
    FFk fiber strength conditioned FDk fiber elongation conditioned
    权利要求:
    Claims (13)
    [1]
    1. A process for producing a polysaccharide fiber whose fiber-forming substance is a (1- »3) -glucan, characterized in that the process is a direct dissolving process and the solvent is sodium hydroxide solution.
    [2]
    2. The method of claim 1, wherein the NaOH concentration in the spinning solution is between 4.0 and 5.5 wt .-%, based on the total amount of the spinning solution.
    [3]
    3. The method of claim 1, wherein the H2S04 concentration in the spin bath is between 200 and 500 g / l.
    [4]
    4. The method of claim 1, wherein the H2S04 concentration in the spin bath is between 20 and 60 g / l.
    [5]
    5. The method of claim 1, wherein the spun fiber is subsequently drawn in an acid regeneration bath.
    [6]
    6. The method of claim 1, 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.
    [7]
    A method according to the preceding claims, wherein the fiber is a staple fiber or an endless filament.
    [8]
    8. polysaccharide fiber whose fiber-forming substance is <x (1-> 3) -glucan, characterized in that it was prepared by a direct dissolution method in sodium hydroxide solution.
    [9]
    A fiber according to claim 7, 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.
    [10]
    A fiber according to any one of the preceding claims, wherein the fiber is a staple fiber or a continuous filament.
    [11]
    11. Use of the fiber according to claim 7 for the production of textile products such as yarns, fabrics, knitted or knitted fabrics.
    [12]
    12. Use of the fiber according to claim 7 for the production of nonwovens.
    [13]
    Use according to the preceding claims, wherein the fiber is a staple fiber or an endless filament.
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    法律状态:
    2022-02-15| MM01| Lapse because of not paying annual fees|Effective date: 20210618 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA490/2013A|AT514474B1|2013-06-18|2013-06-18|Polysaccharide fiber and process for its preparation|ATA490/2013A| AT514474B1|2013-06-18|2013-06-18|Polysaccharide fiber and process for its preparation|
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    PCT/AT2014/000122| WO2014201481A1|2013-06-18|2014-06-13|Saccharide fibres and method for producing same|
    US16/038,471| US11001941B2|2013-06-18|2018-07-18|Polysaccharide fibers and method for producing same|
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