• 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:
    High strength, high modulus cellulose triacetate fibers are produced by spinning a 30-50% 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 nitric acid and another solvent having a molecular weight of less than 160 in a mol ratio of 1-3 through an air gap into a coagulating bath.
    公开号:SU1618282A3
    申请号:SU864027006
    申请日:1986-02-18
    公开日:1990-12-30
    发明作者:Филип Оъбрайан Джон
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    1B
    This invention relates to methods for making cellulose acetate cellulose fibers from optically anisotropic cellulose cellulose acetate solutions.
    The purpose of the invention is to improve the strength properties of the fibers.
    The viscosity given is calculated by the formula
    etc
    In with MP -.-. With-g.
    where C is the concentration of the polymer, g polymer on the solvent. Relative viscosity (#) is determined by measuring the flow time, with using a standard viscometer, of a solution of 0.5 g of polymer in 100 ml of hexafluoroisopropanol at 30 ° C and dividing this value by the time elapsed, for a pure solvent.
    The dimension of the given viscosity is dl / g.
    The content of acetyl in cellulose acetate is determined by the method of ASTM-871-72.
    Fiber strength properties are determined using a stress and strain analyzer at 70 ° F (21.1 ° C) and 65% relative humidity. The excess length is 2.54 cm and the elongation rate is 10% / min. The measurement results are provided as T / E / M, where T is discontinuous: strength, dN / tex; E is the elongation at break, expressed as a percentage increase in the original length; M is the initial modulus of tensile strength, dN / tex. The average values of strength properties for fiber samples are given.
    thirty

    EO
    N5
    B
    W
    The individual fiber tex is calculated from the value of its own resonance frequency, determined by vibrating a 2.0-4.1 cm section of a variable frequency fiber. This fiber is then used for one tear.
    Measurement of apparent axial crystallite size (AACS).
    The AACS value is obtained from the meridional profile of the X-ray irradiation of the fiber. An automatic 20 diffractometer manufactured by Philips Electronics Instrument is used in combination with a monochromatic GJ.KV unit for single-crystal radiation. The generator operates at 40 kV and 40 mA. The diffractometer is equipped with slots for diverging and receiving the beam. at an angle of 1 °.
    About 2 m of fiber is wound on the sample holder so that all fibers are parallel to each other. The thickness of the layer thus obtained does not exceed 0.5 mm.
    The diffraction intensity is recorded as numbers between 14 and 20 29 with an interval of 0.025. The radiation intensity data is then corrected to take into account the Lorentz effects and polarization (the correction coefficient is equal to sin 20 (1 + cos2 20) and smoothed using a standard procedure using polynomials.
    The resulting fiber profile of the invention shows a peak in the range of 17.2-17.6 ° 20. The peak may be asymmetric due to radiation contributions outside the meridional direction.
    To decompose the smoothed profile into a baseline and either into a separate diffraction peak, if the experimental peak has a symmetrical shape, or at the main peak and background peak, if the experimental peak is asymmetrical, the machine sweep method is used.
    The theoretical peaks are calculated as a linear combination of Gaussian and Cauchy profiles. The position, the height of the recess at half the height of the peak (s) is chosen; they are chosen for the best combination with the experimental profile. The parts of the components according to Gauss and Cauchy are fixed and equal to 0.6 and 0.4, respectively, for the main peak in the range of 17.2-17.6 ° 2b and 0.4 and 0.6, respectively, for the background peak (if necessary ). Baseline initial
    -
    you j5
    20
    25 so
    , five
    five
    but is defined as a straight line connecting the intensity points in the region of 14.3 and 19.1 20. When refined, it is slightly shifted, but remains straight. The AACS value is obtained from the half-height width at (rad) of the main peak in the region of 17.2-17.6 ° 20, as specified during deployment:
    AACS (B2-Lg) / 2.
    This expression is the classical Scherrer equation with a form factor assumed equal to one. Other parameters in the equation are as follows: the x-ray wavelength fl 1.5418 AND; angle of diffraction 2 $ taken equal to 17.5 e .; instrumental expansion D, rad, is measured as the width (at half height) of the peak at 28.5 b 2c of standard silicon powder.
    Research on a differential scanning calorimeter (DSC).
    A Du Pont 1090 differential scanning calorimeter is used. A heat analyzer heated at a rate of 20 ° C / min from room temperature to 400 ° C. The sample mass is about 10 mg and the instrument is calibrated using a metal indium. Heat values are obtained directly from the instrument's computing device after selecting the appropriate baseline for the desired peak. The tufted fibers of the invention show a well-defined crystallization exotherm within the range of 190-250 C. After the heat treatment, the fibers show a flat line, the peak corresponding to a change in heat of more than 0.5 J / g is not detected.
    Example 1. Activation of cellulosic material.
    To reduce undesired chain-separation, cellulose activation. It is conducted under mild conditions, which contributes to acetylation at low temperatures, ensures the production of triacetylcellulose with a true content of over 5,0 from cotton fluff or cotton mint.
    During the pre-activation process, a 4 l plastic container is filled with 3 l of distilled water and 10.0 g of cotton fluff. A reflux condenser is added and the mixture is heated to boiling under a nitrogen atmosphere. Heat is removed from the vessel after
    5 16
    5 hours after boiling. The vessel is cooled for 30 minutes, after which the cotton fluff is removed by vacuum filtration on gauze. Excess water is squeezed under vacuum using a rubber diaphragm. The cotton fluff is placed in a stainless steel beaker equipped with a stirrer to beat the eggs, and then filled with methanol. After stirring at room temperature for 30 minutes. cotton fluff is filtered and squeezed. The soaking is repeated with methanol followed by two identical treatments with methylene chloride. Cotton fluff (moistened with methylene chloride), thus activated, is used directly or stored in a tightly insulated container for later use. The activation of materials B, C, D, E, which are used for the preparation of cellulose triacetate, is presented in the table.
    Acetylation of activated cellulosic material.
    For the acetylation process, a 4 l plastic vessel is combined with a stirrer and a thermocouple and loaded with acetic anhydride (1 l), glacial acetic acid (690 ml) and methylene chloride (1020 ml). The reactants are cooled externally to a temperature of (-25) - (30) ° C using a solid carbon dioxide / acetone bath and pre-activated cellulose is added. The reactants are then cooled to a temperature of -40 ° C to be added during the catalyst preparation process.
    Acetic anhydride (450 ml), cooled to (-20) - (-30) ° C in a 1 l Erlenmeyer flask equipped with a magnetic stirring rod. Perchloric acid (60% aqueous solution, 10 ml) is added dropwise over 5 minutes with vigorous stirring, maintaining the temperature below -20ffC.
    The catalyst solution in the form of a constant stream is poured into a vigorously stirred suspension at a temperature of -40 ° C. After the addition is complete and the catalyst is thoroughly dispersed, the reactants are heated to (-20) - (-25) ° C with stirring until the state of consistency is 26
    The suspension Qi begins to change, and the slurry swells and dissolves. After that, the reaction vessel is placed in. the freezer is at and left there overnight. By morning, the reagents take on the appearance of a thick, pure gel, which, when mixed, as a typical non-Newtonian fluid, is wound
    on the agitator shaft. At the same time, a small sample is precipitated by pouring it into methanol (at -20 ° C), using a high-speed electric mixer with a nitrogen purge, and then
    collected by vacuum filtration. A small portion is filtered through paper to remove excess methanol and checked for solubility in methylene chloride or
    1002% trifluoroacetic acid. The absence of gel particles in the solution after 5-10 minutes indicates that the reaction is complete and the weight of the polymer is ready for finishing. In addition, part of the reaction mixture is examined microscopically between cross-polarizers for the possible presence of unreacted fibers, which manifests itself in the form of discrete (isolated) regions
    birefringence. If the reaction is not complete, then the reagents are further stirred at a temperature of (-15) - (-20) ° C and checked through. every hour for solubility until clean solutions are obtained. The thick, clear solution is then precipitated in portions in cold methanol (6 L, -20 ° C) using a high-temperature mixer. Highly swollen particles are filtered on
    two layers of gauze using vacuum and squeeze. The resulting mat is destroyed and immersed in acetone (3 l) for a few minutes, and then squeezed
    to remove all residual methylene chloride. The white flakes are sequentially washed with the following substances: 4 liters of 5% sodium bicarbonate, once; 4 liters of water, twice; 3 liters of acetone, twice.
    The product is then placed in a shallow pan and air dried overnight. Output 160 g
    Properties of the obtained triacetate cellulose are given in table.1.
    Preparation of anisotropic spinning pastes.
    Spinning solutions with a high concentration of solid particles from triacetate cellulose in an aqueous solution of nitric acid are prepared at a temperature below room temperature in a mixer. The technique involves cooling the acid (contained in a plastic vessel) to
    -10 ° C and the slow addition of freshly dried cellulose triacetate flakes. The dissolution takes place exothermically, while maintaining the contents of the plastic vessel at a temperature below room temperature during the entire period of addition. After adding two-thirds of the flakes and thoroughly mixing the moistened polymer with a stainless steel spatula, the high-viscous mass is transferred to an electric mixer. The mixing tank is cooled to 0 ° C using an external cooling unit, and mixing is started. Regulating the temperature in the mixing tank, the remaining polymer flakes are slowly added, preventing any large formations from the dry polymer. Stir for 3 hours after the addition of the polymer flakes. Then, using a microscopic examination, it is confirmed that the dissolution is completed, and the paste is transferred to a stainless steel spin cell.
    Preparation of a cellulose triacetate dope
    The drawing shows the region in which optically anisotropic solutions with dissolved mixtures of certain compounds are obtained. In addition, the drawing shows areas within an anisotropic region where fibers are obtained with high strength and modulus.
    The diagram is constructed using qualitative observations to determine solubility. Homogeneous solutions are considered anisotropic if the samples placed between the microscope slide and the sliding lid have birefringence when observed between transverse polarizers. All observations are carried out at room temperature.
    after mixing the solutions and you | hold them for 24 hours. A sample is classified as a boundary line: if more than 80-90% of the polymer is hoc
    0 5 0
    50
    $
    five
    l
    five
    is in solution, but a microscopic examination reveals some amount of incompletely dissolved particles. Surfaces bounded by ABCDEFGH dots are areas with complete anisotropic solubility. BCFG points cover surfaces in which the composition of the solution is suitable for use with the invention. The axes are graded directly in mole mole, so that any point on the chart can be determined. molar ratios. The moles of cellulose triacetate are calculated as repeating units of triacetyl glucose (CTA) (unit weight 288.25).
    As follows from the drawing, there is a well defined compositional region in which anisotropic solutions are prepared. The maximum solubility of the polymer is achieved at a molar ratio of about 2: 1.
    .
    Pr.
    Highly homogeneous anisotropic solutions of cellulose triacetate are spun in an air gap in mixtures of water and methanol using a special device. A piston driven by a hydraulic press and connected to the piston movement indicator is positioned above the paste surface, the excess air is blown out through the top of the cell and the cell is sealed. A spin cell at the bottom is connected to the following sieves for filtering the paste: 2 X 20 mesh, 1 Dyna lloy (X5), 2,100 mesh, and mesh. Then the filtered paste passes through a spinning block containing the following set of sieves: U100 mesh, 2 325 325 mesh, mesh, and finally, a 325 mesh sieve, installed in the spinning mechanism itself. The pastes are forced through the air gap at a controlled speed into the fixed bath using a measuring pump to apply the hydraulic pressure to the piston. The partially coagulated yarn is passed around a roller (finger) with a diameter of 1.42 cm, pulled through a bath, passed under a second roller L.: mother; We continuously wash the coil with water, extract it in water overnight to remove residual HNO, and then cy-1: shat in air. The parameters of the spinning process are listed in Table 2.
    权利要求:
    Claims (1)
    [1]
    The fiber with enhanced strength properties was obtained at temperatures in a spinning bath in the range (-P). (50) ° C using triacetylcellulose obtained from polymers A, B, C, and D (Table 1). The elongation ratio for fiber spinning is 2.9-6.0, which is confirmed by the data in Table 3. Invention Formula
    The method of obtaining cellulose triacetate fibers by forming a solution of cellulose triacetate in a water-organic j coagulation bath, cast cotton fluff
    In Cotton Fluff
    M cotton
    Boiling for 2 hours in water
    Boiling for 2 hours in water
    Extraction with ethanol, boiling for 12 h in 1% NaOH, washing, neutralizing with acetic acid
    one
    Heterogeneous acetylation, toluene is present in the acetylating medium. Short term;}
    Scale the percentage of water.
    in order to improve the strength properties of the fibers, cellulose triacetate with an acetyl number of 42.7-44.2 and a reduced viscosity of 5.1-8.0 is used, the molding is carried out from a 30-40% optically anisotropic solution cellulose triacetate in a mixture of nitric acid - water with a molar ratio of 1 mixture components equal to (1.15-2.6): respectively, through an air gap into a water-methanol coagulation bath with a water-methanol volume ratio of (60- 75): (25-40), and the bath temperature (-11) - (-50 ° C).
    : T a b l and c a
    - (-5) 6.4
    - (-17) 8.0
    Ґ - (+ 12) 5.1.
    44.2
    42.7
    44.2
    eleven
    Forward I Polymer AACS
    Note. Maximum fiber strength
    obtained in a known manner (T), equal to 3.2 dN / Tex.
    1.0 0.9 0.6 0.7 0.8 0.5 0.4 0.3 0.2 B K Ј O
    1618282
    . Table 3
    ------------.
    AS-przh, T / E / M
    M HNOs / HzO 0.6
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    引用文献:
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    法律状态:
    优先权:
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