• 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:
    A process for producing shaped articles of cellulose is disclosed, wherein the process includes steps of contacting a shaped solution of cellulose in DMSO and formaldehyde, containing at least 6% by weight of cellulose based on the volume of DMSO, and containing formaldehyde in a weight ratio of formaldehyde/cellulose of about 0.2 to about 0.6, with a coagulating solution of DMSO and water at a temperature no greater than 10 DEG C. The coagulant bath generally contains 30 to 50% by weight of DMSO, and the solutions are readily coagulated at coagulation speeds appropriate for commercial practice, and generally the coagulation occurs in less than 20 seconds.
    公开号:SU743586A3
    申请号:SU772503812
    申请日:1977-07-15
    公开日:1980-06-25
    发明作者:Родье Анри
    申请人:Рон-Пуленк-Текстиль (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to the chemical industry, in particular to the production of filaments, fiber films, cellulose-based membranes.
    A method of producing molded cellulose products is known, comprising preparing a 1-8% solution of cellulose in a mixture of dimethyl sulfoxide (DMSO) with paraform.aldehyde, then molding this solution into a methanol precipitation bath to form fiber products 1,
    However, in a known manner, fibers with low physicomechanical properties are obtained. In addition, the method cannot be implemented in industry, since it does not provide fast coagulation of the molded products.
    The aim of the invention is to improve the process technology and properties of molded products.
    This goal is achieved by using a 7-10% solution of cellulose with a degree of polymerization (SP) of 400-1500 In a mixture of da CO with paraformaldehyde at a ratio of paraformaldehyde to cellulose of 0.2-0.6, forming a wire 2
    d t at 2-80 Civ as a precipitation bath use a 30-50% aqueous solution of DMSO.
    The method is carried out as follows. The pre-dried cellulose is dissolved at elevated temperature. for example, at 90-130 C, in a mixture of DMSO and. paraformaldehyde in .so quantity so that the ratio
    10 paraformaldehyde: cellulose made 1-2. This ratio is then reduced to 0.2-0.6 by removing excess paraformaldehyde by any known method — anhydrous gas removal,
    ts by distillation, etc. If necessary, the amount of DMSO is brought to its original value, the resulting solution is molded into a precipitation bath.
    Precipitation bath temperature
    20 should be less, preferably cooling the solution for molding should be avoided. This is achieved either by thermal insulation of the die, or by heating the solution,
    25 or sharing these techniques.
    If necessary, the molded products can be washed before
    30 stretching Extraction is carried out one or more times in air or in a water bath, or sequentially in air and in a bath. Fibers with good physical and mechanical properties are obtained. Example. 90 g of sulphate pulp for viscose with SP 450 at 5.5% moisture content are dried, then added to 1000 cm of DMSO containing 106 g of 96% paraformaldehyde suspension (ratio of paraformaldehyde / cellulose 1.2). The temperature of the mixture is brought to h-a 1 hour with slow stirring, then the solution is kept at this temperature for 3 hours with stirring. In a polarizing microscope, complete dissolution is observed. Cellulose. A stream of dry nitrogen is bubbled into the resulting solution at 120 ° C to eliminate part of the formaldehyde and remove the formaldehyde / cellulose ratio to 0.27. Losses DMSO compensate. The solution is formed through a die with 200 holes with a diameter of 0.06 mm in a precipitation bath, which is a 30% aqueous solution of DMSO at 2 ° C. During molding, the temperature is maintained to avoid clogging of the spinneret. The threads pass 100 cm in the bath, and then they are removed from it with the aid of a mechanical means, on which the threads make several turns, and then they are rinsed in countercurrent in water at 2 ° C. The filaments are subjected to two successive stretches in the air, corresponding to 44% and 30%, with the circumferential speed of the last pair of cylinders being 25 m / min, then greased before winding on the reel and drying. The resulting yarns have the following characteristics: Number, dtex3 Specific strength in the conditioned state, g / tex 20.8 Elongation in the conditioned state,% 13 Specific strength in the wet state, g / tex12 Elongation in wet standing,% 14 Example 2. Dissolution was carried out as in Example 1, but 8 masses per 1000 cm of DMSO and 94 g of 9b% GO paraformaldehyde were taken (formaldehyde / cellulose ratio 1.19). Frequently, formaldehyde is removed by continuously passing through the evaporator thin with it in vacuum until the formaldehyde / cellulose reaches 0. The viscosity of the resulting solution is 600 pz at 2. Losses DMSO compensate. The solution at 75 ° C is formed through a die with 3000 holes with a diameter of 0.055 mm into a precipitation bath, which is a 40% aqueous solution of DMSO at 2 ° C. After leaving the precipitation bath, the filaments are washed with water containing 10 g / l of ammonia and countercurrently at the exit cylinders of the coagulation bath. The yarns are then stretched to 39% in air at room temperature, then 23% in water at 95 ° C. The stretched yarns are then washed in cold water, greased and dried. They have the following characteristics: Number, dtex3.1 Specific strength in the conditioned state, g / tex 19.5 Elongation in the conditioned state,% 13.5 Specific strength in the wet state, g / tex11 Elongation in the wet state,% 15 froze 80 g of bleached mass of C-SP 1050 at. 6% moisture is dried and injected in 1000 cm-DMSO containing 94 g of 96% paraformaldehyde (formaldehyde / cellulose ratio 1.20) and dissolved under the conditions given in example 1. A part of the formaldehyde is removed when the dry nitrogen at, to bring the ratio of formaldehyde / / cellulose to 0.30. The resulting solution has a viscosity of 2100 pz at 20 ° C. The solution is kept at and formed through a spinneret with 200 holes of 0.055 mm diameter into a precipitation bath at 2 ° C consisting of a 30% aqueous solution of DMSO. After extraction, the threads in the bath are washed with water at, then pulled out twice in air, first by 42%, then by 15%. They exit at a speed of 19 m / min, then they are washed with B water at 15 ° C, oiled and dried on a heating plate at 250 ° C. The threads have the following characteristics: Number, dtex. 2.6 Specific strength in conditioned condition, g / tex 23 Elongation in conditioned condition of scientific research institute,% 15
    Specific strength in the wet state, g / tex.14
    Wet elongation,% 17
    Example 4. A cellulose solution with a viscosity of NOi.pz at 2f) ° C, prepared as in example i, is poured onto a glass slab and leveled with a doctor blade.
    Cellulose is precipitated using a coagulation bath, which is a 30% aqueous solution of DMSO at 8 ° C,
    A clear film is obtained, which is washed in cold water to remove the solvent, then immersed in a 2% aqueous solution of glycerin for 15 minutes and dried on a plate at 50 ° C.
    A film with a thickness of 0.090 mm is obtained which is transparent, light, colorless, having a form and characteristics close to the appearance and characteristics of cellophane.
    Try it on. 240 g of sulphate mass for viscose, dried at 12 hours, is added to 2472 g of DMSO and to 288 g of paraformaldehyde (the ratio of paraformaldehyde / cellulose is 1.2). The temperature of the mixture is brought to 130 ° C for 1 hour with slow stirring, and then the temperature is maintained at 130 ° C for 3 hours.
    The resulting solution is sparged with a stream of dry nitrogen at 120 ° C. Hem to restore the formaldehyde / cellulose ratio to 0.31. The resulting solution has a viscosity of 1,300 pz at 20 ° C, and the number of undissolved particles is about 150.
    Then the solution is filtered through a nickel mesh with a cell size of 50 microns at a pressure of 2 kg / cm, and then maintained at 75 ° C. The solution is then passed through a funnel (the distance between the edges of the discharge is 14/100 mm) into a precipitation bath with a temperature of 2 ° C containing 30/70 daso / water mixture.
    After distillation of 13.5 civf in this bath (contact time 4 s), the mechanical gel is washed in water at room temperature. Dry it with a smooth surface.
    Get a clear film with a thickness of 18 microns. The appearance of this film and its properties are similar to those of cellophane.
    The loss in width and swelling of the gel is less than in the case of viscose production.
    Example b. 70 g of cellulose linter with a degree of polymerization, 1500 and a moisture content of 6% are added to 100Q.CM
    dimethyl sulfoxide with 100 cm of water and left overnight at room temperature. Distill a portion of the dimethyl sulfoxide to remove water from it and restore the volume. Reduce the temperature to 130 ° C, then add 94 g of 96% paraforcealdehyde (formaldehyde / cellulose ratio 1.37) with stirring. Dry nitrogen is bubbled into this solution at 120 ° C to remove some formaldehyde and
    0 to reduce the ratio of formaldehyde to cellulose to 0.57. Maintain the temperature for 3 hours 30 minutes with stirring. The resulting solution has a viscosity of 3300 pz at 20 s, the number of insoluble particles 100 and the clogging index 83.
    The solution was poured onto a glass plate, as in Example 4, but at the temperature of the precipitation bath.
    0 and get a clear transparent and colorless film.
    Example 7, 240 g of sulphate pulp with a degree of polymerization of 450, dried at 110 ° C for
    5–12 hours are added to 2472 g of dimethyl sulfoxide, which corresponds to a concentration of 10%, and 288 g of paraformaldehyde (the ratio of paraformaldehyde ... guide / cellulose 1.2).
    The smsi temperature is adjusted to 130 ° C.
    0 for 1 h with slow stirring, then maintain the temperature at 130 ° C for 3 h.
    Dry nitrogen was bubbled into this solution at 120 ° C,
    5 to remove part of formaldehyde and reduce the ratio of formaldehyde to cellulose to 0.57,
    Cellulose dissolution is observed in a polarized microscope. Number
    0 undissolved particles 150, Solution viscosity 1200 pz at 20 ° C.
    The solution was poured onto a glass plate, as in Example 4, into a precipitation bath with a DMSO content of 50%.
    5 and a temperature of 2C and get a clean, transparent and colorless film.
    The proposed method allows one to obtain quickly and economically cellulose molded products with similar viscose properties.
    权利要求:
    Claims (1)
    [1]
    Formula izobre.teni.
    The method of obtaining molded products by molding cellulose raster in a mixture of dimethyl sulfoxide and paraformaldehyde into a precipitation bath followed by a stretch; with respect to paraformaldegi17435868
    yes, to pulp 0,2-0,6, in quality sources of information,
    30% aqueous solution of dimethylsulfu-1 is taken into account during the examination of the precipitation bath. 1. Johnson D., Nicholson M.,
    oxide, and the formation in the bath wire-Haigh F. JPS, Technical Paper, 1975,
    dt at. 5 (prototype).
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    同族专利:
    公开号 | 公开日
    BR7704613A|1978-06-06|
    FR2358477A1|1978-02-10|
    NO147675C|1983-05-25|
    FI772205A|1978-01-17|
    ATA518077A|1979-07-15|
    AT355181B|1980-02-25|
    SE420612B|1981-10-19|
    DE2732152B2|1981-04-23|
    NO772532L|1978-01-17|
    JPS6028847B2|1985-07-06|
    IT1082133B|1985-05-21|
    GB1540044A|1979-02-07|
    FR2358477B1|1978-12-22|
    US4129640A|1978-12-12|
    PT66815A|1977-08-01|
    ES460788A1|1978-05-01|
    FI63971C|1983-09-12|
    CA1078569A|1980-06-03|
    JPS5327648A|1978-03-15|
    DE2732152C3|1982-03-04|
    MX148612A|1983-05-18|
    NO147675B|1983-02-14|
    BE856876A|1978-01-16|
    NL7707933A|1978-01-18|
    DE2732152A1|1978-01-26|
    CH624152A5|1981-07-15|
    SE7708258L|1978-01-17|
    DD131384A5|1978-06-21|
    NL178174B|1985-09-02|
    OA06111A|1981-06-30|
    PT66815B|1978-12-21|
    NL178174C|1986-02-03|
    FI63971B|1983-05-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3236669A|1963-04-19|1966-02-22|Du Pont|Cellulose solutions in dimethyl sulfoxide and nitrogen dioxide|
    US3706526A|1971-12-06|1972-12-19|Cotton Inc|Process for treating cellulosic material with formaldehyde and sulfur dioxide|
    US4022631A|1975-05-19|1977-05-10|International Telephone And Telegraph Corporation|Process for producing regenerated cellulosic articles|
    US4044090A|1975-07-09|1977-08-23|International Telephone And Telegraph Corporation|Process for producing regenerated cellulosic product|
    US4028132A|1975-11-25|1977-06-07|International Playtex, Inc.|Cellulose solutions and products prepared therefrom|AT344867B|1977-04-05|1978-08-10|Chemiefaser Lenzing Ag|PROCESS FOR THE MANUFACTURING OF FIRES OR FILMS FROM REGENERATED CELLULOSE|
    IT7821922D0|1978-04-03|1978-04-03|Ind Applic Viscosa Snia Viscos|PROCEDURE FOR THE DISSOLUTION OF CELLULOSE IN ORGANIC SOLVENTS, SOLUTIONS OBTAINED WITH THIS PROCEDURE, AND PROCEDURE FOR THE REGENERATION OF CELLULOSE FROM THE SAID SOLUTIONS WITH PRODUCTION OF FORMED BODIES.|
    IT7826174D0|1978-07-27|1978-07-27|Snia Viscosa|PROCEDURE FOR THE PREPARATION OF BODIES FORMED OF REGENERATED CELLULOSE FROM SOLUTIONS OF CELLULOSE DERIVATIVES IN DIMETHYLSULPHOXIDE.|
    IT7826175D0|1978-07-27|1978-07-27|Snia Viscosa|PROCEDURE FOR THE PREPARATION OF BODIES FORMED OF REGENERATED CELLULOSE FROM SOLUTIONS OF CELLULOSE DERIVATIVES IN ORGANIC SOLVENTS.|
    FR2478116B1|1980-03-14|1985-06-14|Rhone Poulenc Textile|CONFORMABLE SOLUTIONS FROM CELLULOSE AND POLYAMIDE-IMIDE MIXTURES AND FORMAL ARTICLES OBTAINED|
    FR2483966B1|1980-06-10|1984-02-17|Rhone Poulenc Textile|
    DE4134190A1|1991-10-16|1993-04-22|Tomka Ivan|METHOD FOR IMPROVING THE MECHANICAL PROPERTIES OF ONE-OR MULTILAYER FOILS|
    DE19613990A1|1996-04-09|1997-10-16|Wolff Walsrode Ag|Thermoplastic material consisting of aliphatic carbamic acid derivatives of polysaccharides and low molecular weight urea derivatives and a process for the production and use thereof|
    US5962005A|1997-04-17|1999-10-05|Rengo Co., Ltd|Transparent cellulose hydrogel and production process thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7622031A|FR2358477B1|1976-07-16|1976-07-16|
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