• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    High strength, high modulus cellulose triacetate fibers are produced by spinning a 30-42% by weight solution of cellulose triacetate having an acetyl content of at least 42.5% and an inherent viscosity of at least 5 from a solvent mixture comprising trifluoroacetic acid and another solvent having a molecular weight of less than 160 in a mol ratio of 0.3-3.0 through an air gap into a coagulating bath. The fibers are optionally heat treated under tension or saponified to provide high strength high modulus regenerated cellulose fibers.
    公开号:SU1565350A3
    申请号:SU833638902
    申请日:1983-08-08
    公开日:1990-05-15
    发明作者:Филип Оъбрайен Джон
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    (21) 3638902 / 23-05
    (22) 08.08.83
    (31) 406533
    (32) 08/09/82
    (33) US
    15.05.90. Bul Number 18
    E.I. Dupont de Nemours and Company
    (46)
    (71) (us)
    (72) John Philip O'Brien (US)
    (53) 677.64.1 (088.8)
    (56) Patent of Germany No. 2705382,
    cl. D 01 F 2/24, ol. 1977.
    (54) METHOD OF OBTAINING TRIACETATOL CELLULAR FIBER
    (57) The invention relates to technology.
    chemical fibers, in particular, methods for producing high-strength, high-modulus fibers from cellulose acetate; The invention provides an increase in fiber strength by extruding a 30-40% solution of cellulose acetate with a characteristic viscosity of 5 and a content of bound acetic acid of 59.4-62.4% by weight in a mixture of water or methylene chloride, or of formic acid with trifluoroacetic acid in the ratio of 1: 0.5-2.5) or 1: (1-2.5), or 1: (0.3-1) through the air gap into methanol or water methanol precipitation bath. 5 tab., 3 Il.
    $
    This invention relates to chemical fiber technology, in particular to methods for producing high strength, high modulus fibers from cellulose acetate acetate.
    The purpose of the invention is to increase the strength of the fiber.
    Example. The original cellulose is first subjected to activation by the following method.
    To reduce unwanted chain breaks, cellulose activation is carried out under mild conditions, which allows subsequent acetylation at (-40) - (-28) ° C, using cellulose acetate acetate with a characteristic viscosity greater than 5.0 from cotton linter, combed
    cotton or wood pulp without lignin. Although cellulosic aquaculture is not necessary for high-temperature acetylation (40-80 ° C), it is necessary for successful reaction at low temperatures.
    With the simplest pre-activation process, 150 g of cellulosic material is boiled in 4 liters of distilled water under nitrogen for 1 hour. The mixture cools at room temperature. Cellulose is collected by suction filtration and wrung out using a rubber diaphragm ™ we. The mixture is resuspended in cold water for 15 minutes, separated again, and then immersed in 3 liters of glacial acetic acid for 2–3 minutes from U1.
    3) U1
    With ЈL

    S
    press as before. A second washing with glacial acetic acid is performed, then the mixture is drained and the raw cotton is immediately placed in a precooled acetylation medium.
    In tab. Figure 1 shows the conditions for performing the activation methods.
    Acetylation is carried out as follows.
    For the acetylation process, a man with a capacity of k l with resin, equipped with a beater-type stirrer for eggs and a thermocouple, is charged with 1 l of acetic anhydride, 690 ml of glacial acetic acid and 1020 ml of methylene chloride. The reagents are cooled externally to (-25) - (-30) ° C with a solid carbon dioxide-acetone bath and pre-activated cellulose (moistened with acetic acid) is added. The reagents are then cooled until during preparation for the addition of the catalyst.
    350 ml of acetic anhydride is cooled to (-20) - (-30) 4 in a 1-liter Erlenmeir flask containing a magnetic stirring rod, 10 ml of perchloric acid (60% aqueous solution) is added dropwise within 5-10 With vigorous stirring, the temperature is kept below -20 ° C. Due to the strong oxidizing ability of perchloric acid in the presence of organic matter, catalyst solutions should be prepared and used at low temperature.
    .
    Then a thick clear solution is precipitated in stages in a liter of cold methanol (at -20 ° C) using a high-speed mixer. The strongly swollen particles are filtered on two layers of (cheese) tissue by suction and pressing. The resulting layer is then broken up and placed in 3 liters of acetone for several minutes, after which it is squeezed to remove residual methylene chloride. After that, the white flakes are washed first in 4 liters of 5%
    Then the catalyst solution is poured with 4o sodium bicarbonate (once), then
    in k l of water (twice) and then in 3 l
    v 45 such 4J
    in the form of a steady stream into energetically stirred slurry at. Upon completion of the addition and thorough dispersion of the catalyst, the reactants are allowed to warm to (-20) - (-25) ° C with stirring. At temperatures, the reaction proceeds slowly and it is difficult to determine the exotherm. However, within 2-6 hours, the sludge consistency changes and the pulp begins to swell and decompose. After stirring for -6 hours, the reaction vessel is transferred to a cooler with a temperature of -15 ° C and left overnight. By morning, the reagents take on the appearance of a thick, transparent gel that, when mixed, behaves like a typical non-Newtonian fluid (rises through the shaft of the agitator). In that
    55
    acetone (twice).
    The product is then placed in small bowls and allowed to dry overnight. The output is 230-250 g.
    The properties of the triacetate polymer are shown in Table 1. 2
    FIG. Figure 1-3 shows the zone in which there are optically anisotropic solutions with solvent mixtures of specific compositions that give good stability from solutions with high solids content to produce high strength, high modulus fibers. Charts are drawn from quantitative observations to determine solubility. Areas limited by BCFG points are anisotropic zones of complete solubility.
    , ten
    15
    20
    25
    thirty
    35
    A small sample is deposited by adding methanol (at -20-20 ° C) using a high-speed electric mixer with a nitrogen purge and subsequent collection using suction filtration. A small part is absorbed to remove excess methanol and check the solubility in methyl chloride or 100% trifluoroacetic acid. The absence of gel particles in the solution after minutes shows that the reaction is complete and the block polymerisation polymer is ready for processing. In addition, a portion of the reaction mixture is examined with a microscope between crossed polarizers to identify the possible presence of unreacted fibers, which appear as discrete double-focus domains. If the reaction is not complete, the reagents are stirred at (-15) - (-20) 6C and checked every hour for solubility until clear solutions are obtained.
    Then a thick clear solution is precipitated in stages in a liter of cold methanol (at -20 ° C) using a high-speed mixer. The strongly swollen particles are filtered on two layers of (cheese) tissue by suction and pressing. The resulting layer is then broken up and placed in 3 liters of acetone for several minutes, after which it is squeezed to remove residual methylene chloride. After that, the white flakes are washed first in 4 liters of 5%
    4 ° sodium bicarbonate (once), then

    acetone (twice).
    The product is then placed in small bowls and allowed to dry overnight. The output is 230-250 g.
    The properties of the triacetate polymer are shown in the Table. 2
    FIG. Figure 1-3 shows the zone in which there are optically anisotropic solutions with solvent mixtures of specific compositions that give good stability from solutions with high solids content to produce high strength, high modulus fibers. Charts are drawn from quantitative observations to determine solubility. The zones bounded by the BCFG points are anisotropic zones of complete solubility.
    51
    The axes are graduated in molar fractions so that at any point in the diagram you can determine the molar ratio.
    In the cellulose triacetate / trifluoroacetic acid / water (TAC / TFA /) system, the maximum solubility of the polymer is achieved at a molar ratio of TFA / Hg.0 equal to 2. This corresponds to the molar fraction of TAC / TFA / H O 0.17 / 0.55 / 0,28 or 40 may. TAC by units of cellulose triacetate.
    In practice, the optimal prestrate and the necessary properties of the fibers were obtained using 30–40% TAC solutions at molar ratios of TPA / HeO 1.5–2.5. The molar ratio of 1.5 is shown by the BF line (molar fraction of TPA of 0.6), and the ratio of 2.5 is indicated by the CF line (molar fraction of TPA of 0 ,.
    You can use the system TAC / TF / CHj.Cl.fc, obtained using the above method. As in the TAC / TFA / H O system, the solubility increases significantly, since the stoichiometry unit of cellulose triacetate solvent converges at a molar ratio of 0.17 / 0.83. Optimal straightness and high strength properties are obtained with a 35-40% solids content in solutions, in which the molar ratio of TPA / CHaC1 / g is 1.0-2.5, which corresponds to a mole fraction of TPA of 0.50 - 0.71.






    /
    35 Fiber with good properties is obtained at the temperature of the forming bath in the range (-1) - (-33) ° С and the coefficients of forming the stretching in the range of 2.0 - 7.6. You can also use the system obtained by the method described above. As in the preceding example, the solubility of the polymerization of cellulose acetate triacetate obtained is greatly increased when the walls of the polymers A, B, C, and E are tabulated. 1. chiometry polymer - solvent converges on a molar ratio of 0.15 / 0.85. A mixture of TPA in combination with formic acid (98-100 wt.%) And 100% formic acid were used.
    Polymer F, which (Prepared from cellulose activated in 1% NaOH, has somewhat worse properties, but 45 is still superior to the known cellulose triacetate fiber. More low-grade polyacid is not a sufficient quality fiber can be explained
    exactly a good solvent for the use of non-optimal conditions
    the polymer polymer is triacetate cellulose-forming. On the used equipment for the purpose of obtaining anisotropic processing (the maximum pressure of the pastors with a high solids content is 56.3 kg / cmi)
    particles, however, a mixture of TPA and formovinoy amounted to 4.57-15.2 m / min. In the case of molar ratios in 0.3-but increase the speed of the jet
    1.0 are excellent solvents due to localized heating in zo (molar fraction of TPA is 0.23-0.50). Opti-55 non-multi-channel mouthpiece (up to
    minimum straightness and strength characteristics are obtained at the indicated molar ratios with a solids content of 30-40 wt.%.
    kQ0C). Liquid crystalline solutions can go into an isotropic state when heated above certain critical temperatures and are optimal.
    0
    Anisotropic solutions with a high solids content of triacetate cellulose are molded through an air gap in cold methanol. The piston, driven by a hydraulic press and interacting with the piston stroke indicator, is located above the surface of the spinning solution, excess air is removed from the upper part of the chamber, and the chamber is sealed. The lower part of the molding chamber is provided with screens for filtering the spinning dope. The spinning solution is passed through a multichannel mouthpiece containing the following additional sieves: 1X 100 mesh, 2X mesh, 2X 100 mesh, and the last sieve of 325 mesh. Spinning solutions are extruded through a variable-speed air gap into a static bath using a Zenith metering pump to apply hydraulic pressure to the piston. Partially coagulated fiber is passed around the first pin, dragged through a bath, passed under the second pin, and wound. The fiber is continuously washed on a bobbin reel, water, and extracted with water overnight to remove residual TFA, followed by air drying.

    The molding parameters are given in Table 2.
    5 Fiber with good properties is obtained at the temperature of the forming bath in the range (-1) - (-33) ° C and the stretch forming coefficients in the range of 2.0 - 7.6 using a cellulose acetate acetate made from polymers A, B, C and E table. one.
    For the production of cellulose triacetate obtained from polymers A, B, C, and E of the table. one.
    Polymer F, which (obtained from cellulose activated in 1% NaOH, has somewhat worse properties, but still surpasses the known cellulose triacetate fiber. Lower than a multi-channel mouthpiece (to
    kQ0C). Liquid crystalline solutions can go into an isotropic state when heated above certain critical temperatures and are optimal.
    the strength and strength properties of the fiber are obtained only below this temperature.
    The strength properties of the fiber for freshly formed cellulose triacetate are given in table. 3
    In the examples, the molding is carried out in a water-methanol (50:50) precipitation bath.
    In tab. Figure 4 shows the conditions suitable for heat treatment of cellulose yarn triacetate and cellulose hydrate.
    The cellulose yarn acetate is formulated as shown in Table 2. 2, but in some examples, the treated yarn is obtained from the various shape reels indicated in Table 2. 2. Strand is treated under tension. Tension can give 1-10% tensile yarn. Mere tempering in the form of a bundle does not ensure high-strength yarn, i.e. fibers with a tensile strength of more than 10., 6 dyn / T. The heat treatment apparatus includes a conventional steam pipe that can create a saturated steam pressure of up to 7 kg / cm 12 between the feed and draw rollers. The steam in the processing chamber is maintained at a pressure of 4.22-6.33 kg / cm (5, -7.22 MO Pa). For heat treatment, superheated steam rather than saturated steam is fed to the modified steam pipe.
    Saponification of cellulose triacetate to cellulose.
    The triacetate fibers are converted to hydrated cellulose by saponification into
    A. Cotton linter Boiling in water
    for 1 h
    B. Cotton linter Boiling in water
    for 2 h
    C. Wood creeping in water
    for 2 hours
    (Floranier F) Do Cotton Linter Boiling in water
    for 1 h
    -
    5 0 5
    0
    five
    sealed container at room temperature, the container is blown. nitrogen before sealing. Scouring medium contains 0.05 molar sodium methoxide in methanol. The yarn is processed at room temperature (CT) or at the temperature shown in Table. 5, within a few hours. The cellulose triacetate fibers are well washed under tension (6.6 g / t). The coils of triacetate fiber are suspended with loads of lead shot in a saponification medium. No buoyancy correction is made.
    The properties of the initial cellulose triacetate fibers and cellulose hydrate fibers are shown in Table. five.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing cellulose triacetate fiber by extruding a polymer solution in a mixture of trifluoroacetic acid with another solvent through a heartless interlayer into a methanol or water-methanol precipitation bath, characterized in that, to increase the strength of the fiber, water, methylene chloride, or formic acid are used to increase the strength of the fiber. acid in relation to trifluoroacetic acid 1: 1.5-2.5; 1: 1-2.5 or 1: 0.3-1, respectively, and extrusion is carried out from a 30-40% aqueous solution of cellulose acetate with a characteristic viscosity of 5.35-7.7 and a content of bound acetic acid 59 , 4-62.4 wt.%.
    Table 1
    62.7 59.4 62.0
    61.4
    Combed Cotton
    Cotton linter
    Cotton linter
    Extraction of ethanol, boiling for 12 h in 1% NaOH. Washing, neutralizing with 1% acetic acid
    Boiling for 1 h in 1% NaOH
    Soaking for 3 days in 2.65 l of water containing 750 g of urea and 18.2 g
    1565350
    10 Long Cause 1
    (-32Н-6)
    (-15Ы-5)
    62.9 60.7
    eleven
    156535012
    Continued table. 2
    Strength characteristics of cellulose hydrate obtained from anisotropic triacetate starting material
    Table 4
    Continuation of taOl
    Table 5
    fs
    s
    GACO
    I / O .90.80.70.60.50.40.30.20U.IOC 0
    Oh ne
    Tfk
    U.IOC
    Oh ne
    fig.Z
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    引用文献:
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    法律状态:
    优先权:
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