• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    1503134 Purifying 2,5-dioxo-1-oxa-2-phospholanes HOECHST AG 14 July 1976 [17 July 1975] 29330/76 Heading C2P A process for the distillative purification of a 2,5-dioxo-1-oxa-2-phospholane of the formula in which R<SP>1</SP> stands for an alkyl radical having 1, 2, 3 or 4 carbon atoms, or a phenyl radical, and R<SP>2</SP> and R<SP>3</SP> each stand for hydrogen or CH 3 , comprises: preheating the respective crude compound to 120‹ to 160‹ C. and feeding it to the head of a distilling column provided with a plurality of individually heatable trays maintained at temperatures increasing (as herein defined) from the uppermost tray to the lowermost, the uppermost tray in the column being maintained at 120‹ to 160‹ C., and the lowermost tray being maintained at 160‹ to 200‹ C., the pressure at the head of the column being 20 to 200 mm. Hg, introducing an inert gas preheated to 160‹ to 200‹ C. countercurrently at the base of the column; withdrawing overhead those impurities having a boiling point lower than that of the respective 2,5-dioxo-1- oxa-2-phospholane, together with the inert gas; withdrawing the 2,5-dioxo-1-oxa-2-phospholane thus freed from low-boiling impurities from the base of the distilling column and passing it to a film evaporator; and distilling off the 2,5-dioxo- 1-oxa-2-phospholane from higher-boiling impurities in the film evaporator under a pressure of 0À1 to 5 mm. Hg. Specified inert gases are nitrogen and air and the increase in temperature from the top tray to the bottom tray is intended to mean that temperature increments occur between successive trays or successive groups, e.g. pairs, of trays. Suitable apparatus is described with reference to a drawing (not shown) and examples are given for the purification of the 2-methyl- and 2-phenyl compounds. The products are useful for condensation with polyester-forming reactants to give products which may be formed into filaments, fibres, sheets or articles having flame-retardant properties.
    公开号:SU847925A3
    申请号:SU762379609
    申请日:1976-07-13
    公开日:1981-07-15
    发明作者:Германн Клаус；Охородник Александер；Ломар Эльмар；Рихманн Вернфрид
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR CLEANING 2,5-DIOXO-1-OXA -2 PHOSPHANANES
    one
    The invention relates to a method for the distillation purification of 2,5-dioxo-l-OKca-2-phospholanes of the general formula
    B - (JHj
    Oh oh
    where R is alkyl or Lenil, which, as you know, when introduced into the polyester material. impart to the fibers, films and moldings obtained from it, non-flammable or self-extinguishing properties.
    A known method for producing, for example, 2-methyl-2,5-dioxo-1-oxa-2-fbsfolan by reacting the acid chloride G | L- (chloroformyl) ethyl methylphosphonic acid with acetic anhydride 2.
    However, 2,5-dioxo-1-oxa-2-phospholanes are suitable as a component for introduction into the polyester molecules only as compounds,. possess a high degree of purity ..,
    2,5-dioxo-1-oxa-2-phospholanes, due to their high boiling point and reactivity of this type of compounds, cannot be dried
    5 us in the usual way. Thus, thermal decomposition of 2-methyl-2,5-dioxo-1-oxa-2-phospholane, which has the lowest boiling point in the range of these, begins in the region.
     phospholanes (at 0.5 mm Hg) and the decomposition proceeds the faster, the lower the purity of the product. Increase a few mm Hg. leads to increasing point
    15 boiling to temperatures above 2000s, T.ei exceeding the limits of decomposition.
    The purpose of the invention is to measure the purity of 2,5-dioxo-1-oxa-220-phospholanes.
    The delivered chain is achieved according to the method of distillation purification of 2,5-dioxo-1-oxa-2-phospholate 25, the crude product is preheated from 120-160 ° C and injected into the upper part of the distillation column with a separate heating wake up
    30 top to bottom, with the top ta,
    The temperature is set at 120-1600 s, at the bottom - 1bO-200c, and in the upper part of the distillation column a pressure of 20,200 mm Hg is set, the inert gas, preheated to 160-200 ° C, is introduced below the distillation column. boiling lower than 2,5-dioKco-1-OKca-2-phospholane to be purified, distilled out together with an inert gas, freed from low-boiling 2,5-dioxo-1-OKca-2-phospholane from high boiling contamination in a thin film evaporation apparatus at 0.1–5 mm Hg.
    It is desirable to inject 0.1-1 nm of inertial gas per cadd of liter of 2,5-dioxo-1-oxa-2-phospholane, heat the bottom plate of the distillation column to a boiling point of 2, 5-dioxo-1-oxa-2 Phospholane, the raw product is heated to the temperature of the upper plate, and the inert gas supplied is not lower than the temperature of the lower plate of the distillation column.
    The drawing shows a device that implements the proposed method.
    The 2,5-dioxo-l-oxy-2-phospholane to be purified is supplied in liquid form through a heated conduit 1 and a heater 2, where the product is heated to 120-160 0 and sent to a distillation column 3. The column 3 is equipped with separately heated segments shirts, as well as separately heated screen plates 4-13 in such a way that an increasing temperature level is set down from the top of the column. In addition, superheated water vapor or a heat transfer fluid is used for indirect heat supply. The heat is supplied in such a way that the temperature on the upper plate 4 is set at 120-1 bO and on the bottom plate 13 is 160-200C Between them there are 5 to 12 Simultaneously with the supply of phospholane to the upper part of the column, to the lower part of the column 3, countercurrent heater 15 is introduced with a pre-heated inert gas. The temperature of the incoming inert gas corresponds to the temperature of the liquid product effluent on the bottom plate 13. Thus, the light-boiling contaminants contained in the phospholane are quantitatively removed with the flow of inert gas.
    The phospholane carried with the inert gas condenses in the reflux condenser 16 above the head of the column and returns to the column 3. The light boiling stream of vapor-inert gas is sucked away by a vacuum pump 17 so that a pressure of 20-200 gm.Hg is established at the top of the column.
    The phospholane released from low-boiling contaminants flows from the bottom plate 13 to the discharge of column 3, from where it is fed up via thin-walled pipe 18 upwards of thin-film evaporator 19. Here under vacuum, about 1 mm Hg. Distillation of phospholane occurs. The heat required to evaporate the phospholane is supplied through a heater. 20 shirts. The pure product is liquefied in the internal condenser 21 and is discharged through conduit 22, while high-boiling residues are removed from the evaporator 19 through the effluent stream and through conduit 23. The 2.5-dioxide produced by the proposed method 1-oxa-2-phospholanes are odorless liquids and
    colors that, when cooled, solidify into white crystalline masses. By gas chromatographic studies, products with a purity degree of over 99.9 wt.% are obtained.
    suitable for the production of polyester materials.
    Example 1. Purification of 2-methyl-2, 5-dioxo-1-oxa-2-phospholane.
    6.2 kg / h of raw 2-methyl-2.5-dioxo-1-oxa-2-phospholane to be cleaned is preheated with heater 2 and fed to the uppermost sieve tray 4. The plates 4 and 5 are heated
    at 130C, 6 and 7 - at, 8 and 9 at 155 ° C, 10 and 11 - at, and 12 and 13 - at 170 ° C. A vacuum of 50-100 mm is maintained at the top of the column with the help of a vacuum pump 17
    Hg, while the pipeline 14 and the heater 15 are simultaneously injected with 1.5 nm of nitrogen preheated to 170 ° C. At the top of column 3
    the reflux condenser 16 is set to the temperature OO-s. The crude phospholane freed from the light boilers is collected from the bottom of the column 3, from where it is metered into the thin-film evaporator through line 18. The distillation of 2-methyl-2.5-dioxo-1-oxa-2-phospholane is performed at 0.5 mmHg. At the same time through the pipeline 22 receive 5.8 kg / h of pure phospholane, which corresponds to
    yield 97%, based on the content of phospholan in the raw product. Melting points of various batches of purified 2-methyl-2, 5-dioxo-1-oxa-2-phospholane
    lies around, the amount of impurities determined by gas chromatography is about 100 ppm. Table 1 shows the yield data for purity and melting point.
    phospholane produced
    Similarly, five parallel experiments were carried out with a different temperature distribution on the plates of the distillation columns.
    The temperature distribution is presented in table 2.
    Example 2. Purification of 2-phenyl-2, 5-dioxo-1-oxa-2-phospholia.
    In the apparatus analogous to example 1 in heater 2, 8.15 kg / h of 2-phenyl-2.5-DIOXO-1ox-2-phospholane to be cleaned is preheated to and through heating, pipe 1 is fed to the uppermost sieve tray 4 of column 3. The temperatures on the plates 4 and 5 are 135 ° C, b and 7 are 1500 s, 8 and 9 are 165, 10 and 11 are 170 C
    Physico-chemical characteristics
    Phospholan yield (from theoretically calculated value),%
    Impurities, ppm
    and 12 and 13 - 175 ° C. With a vacuum of 50-80 mm Hg. in the upper part of the column 3 and the cooling temperature of 90 ° C in the reflux condenser 16 through the pipe 14 and the heater 15 in-. d t 1,5 them preheated to 175 C nitrogen. Distillation of 2-phenyl-2, 5-dioxo-1-oxa-2-fosflana was carried out in a thin-film evaporator apparatus 19 with a dosage of 0.3 mm Hg. Wherein
    receive. 7.8 kg / h of pure product, which corresponds to a yield of 97%, based on the content of phospholane in the raw product. Melting point of the resulting 2-phenyl-2,5-dioxo-1-ox-5-phospholane. The sum of all impurities in the pure product ranges between 100 and 300 ppm. Table 1
    Pressure, mm Hg
    76 D 38 D 23 D 68 D 144
    97
    98
    96
    96
    100 500
    50
    300
    Melting point, 0s
    权利要求:
    Claims (4)
    [1]
    Claims 1. Purification method of 2,5-dioxo-1-oxa-2-phospholanes with formula of formula F
    0, - F1. ,
    106 103
    106
    104
    where R is C. - Cj, alkyl or phenyl, which is distinguished by the fact that the crude product is tentatively heated to 120-160 ° C and introduced into the upper part of the distillation column with separately heated plates, the temperature of which rises from top to bottom
    65 plate set temperature.
    120-1600С, at the bottom - 160-200 оС, and in the upper part of the distillation column, a pressure of 20200 mmHg is established, preheated up to 160-200 inert gas is introduced below the distillation column below, than 2,5dioxo-1-oxa-2-phospholane to be purified is distilled off with an inert gas; The 2,5-dioxo-1-oxa-2-phosphonane, which is free from niecoclipol contaminations, is distilled from the high-boiling contaminants in a thin-film evaporator at a pressure of 0.1-5 mm Hg.
    [2]
    2. A method according to claim 1, characterized in that 0.11 nm of inert gas is injected for each liter of liquid 2,5-dioxo-1-oxa-2-phospholane.
    [3]
    3. Method according to claims 1 and 2, characterized in that the bottom plate of the distillation column is heated to the boiling point
    2,5-dioxo-1-oxa-2-phospholane.
    [4]
    4. A method according to Claims 1 to 3, characterized in that the crude product is preheated to the temperature of the upper plate, and the inert gas supplied is not lower than the temperature of the lower plate of the distillation column.
    Sources of information taken into account in the examination
    1. For the FRG 2346787,
    cl. C 08 G 63/68, published 1975.
    five
    2. Khairullin V.K. and others. About the reaction of methyldizlsorfina. with acrylic acid. -) HOH, 1967, t. 37,
    with. 710-714.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19752531920|DE2531920C2|1975-07-17|Process for the preparation of 2,5-dioxo-1-oxa-2-phospholanes|
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