• 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 invention relates to the preparation of phosphorus-containing compounds, in particular linear polychlorophosphazenes containing a dichlorothiophosphoryl group, which can be used as additives to impart flame retardant properties to materials as coatings for seals, lubricants and biomedical materials. The invention improves the efficiency of the process by using for the synthesis of linear polychlorophosphazene by polycondensation at 180-290 s and a pressure of 100 mmHg. to atmospheric N-trichloro-N -dichloro-. thiophosphoron monophosphazene. SU) y O5 sd
    公开号:SU1426457A3
    申请号:SU843761601
    申请日:1984-07-05
    公开日:1988-09-23
    发明作者:Абу Шакра Таер；Де Жаежер Роже
    申请人:Сосьете Насьональ Елф Акитэн (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to chemistry, in particular to the preparation of phosphorus-containing compounds, namely, linear polychlorophosphazenes containing a dichlorophosphoryl group. Linear prichlorophosphazenes are of considerable interest in being able to be used as additives before imparting flame retardant properties to materials, as coatings for seals, lubricants and biomedical materials.
    The purpose of the invention is to increase the efficiency of the process.
    Example 1 but. Synthesis of P NSClj
    To perform this synthesis, Pj is first obtained by reacting PClyCNH Cl in POClj, after which the resulting compound PJ is reacted with PrC.
    The reaction is carried out in a reactor equipped with a paddle mixer and two refrigerators that are protected from atmospheric moisture by two columns of c.
    282 g (1.35 mol 29.2 (0.54 mol) NH C1 and 180 ml (1.95 mol) POCl are introduced into the reactor. The contents of the reactor are kept under agitation in an inert atmosphere. The temperature is raised to then This temperature is maintained for 6 hours. An intense precipitation of HC1 is observed for a period of time.The reaction mixture is then allowed to cool to room temperature, after which 78.5 g (0.35 mol) of P-Sj is added to it and the resulting reaction mixture is maintained. 2 hours at 80 C.
    The resulting reaction mixture is then filtered and, after the solvent is removed from the filtrate in vacuo, a liquid is obtained which solidifies at room temperature and atmospheric pressure. After distillation of the liquid at 75-80 0 and reduced pressure (about 13 Pa), 45.75 g of product is obtained, which consists almost entirely of P NSClj-, which is confirmed by a study of this. IR Product Spectroscopy
    and NMR on r.
    b. Polycondensation P; NSClj.
    The reaction is carried out in a reactor equipped with a magnetic stirrer and a WIGRO column (VIGREVX), which
    five
    pa - connected to a dropping funnel with fission by means of a refrigerator. All equipment is generally protected from exposure to atmospheric moisture through P-Oj- speakers.
    48.5 g (0.170 mol) of Pj NSCl are introduced into the reactor; - obtained according to example 1a. The temperature of the supported reactor, which is under moderate stirring, is adjusted to a value in the range of 220-240 seconds, after which it is held. at this temperature for 6 hours. During heating 5. PSC1 is observed to be distributed, initially slow, but accelerating after removing about half of the theoretical amount, which can be obtained from the amount used by P NSClj.
    After heating for 8 hours, the amount of the collected RBS1c is 28.3 g (0.167 mol), which practically corresponds to the theoretical amount of PSC1 that can be formed during the reaction. After this time has elapsed, heating is continued under the same conditions for an additional 0-2 hours.
    The resulting crude product (20 g) is completely soluble in benzene, indicating the absence of branched polychlorophosphazenes.
    Calculated,%: C1 61.21, N 12.07; 26.72.
    Found,%: C161.3, N11.7; 0 P 26.8. ,
    The said crude product is treated at 40-60 ° C with petroleum ether, which is a precipitant for high polymers, a solvent for cyclic phosphazenes and phosphazenes of the type
    . ciH-s) .-- C1,
    G1
    where has a small value (2 or 3). The fraction solubilized in this way constitutes approximately 3% by weight of the total amount of the processed product.
    The control of the composition of the insoluble fraction in petroleum ether by chromatography using thin-layer chromatography on silica using hexane as a solvent) confirms the absence of
    0
    five
    1426D57 PjNSCls and cycvia in it of residual lytic phosphates.
    A fraction that is insoluble in petroleum ether, which consists of what would be cleared during the reaction
    ten
    15
    20
    The polymer is dissolved in anhydrous benzene and CFj CHzONa is processed to replace the chlorine atoms in the polymer with CP3CH2O groups that have lower reactivity, which makes it possible to obtain a polymer with which it is easier to perform various operations and for which it is convenient to determine the molecular weight.
    The obtained trifluoroethoxylated polymer has a weight average molecular weight (M) equal to 440000, a number average molecular weight (Mz) equal to 265000, and a polydispersity index equal to 1.66. The polymer corresponding to the end of the polycondensation P NSClj has a number average molecular weight of 126600, which corresponds to the average number n of repeating fragments -fNPClj in
    This formula is approximately 1090.
    An X-ray fluorescence study of the polymer obtained as a result of polycondensation shows that it does not contain elemental sulfur. The IR spectra and NMR spectra of P obtained for the indicated polymer are in full accordance with the linear dichlorothiophosphoryl polychlorophosphase a formula for the indicated polymmer. This formula can be written in the following expanded form:
    thirty
    the result of the distillation of a small quality P NSCly.
    The crude product (8.2 g), resulting from the polycondensation, is completely soluble in benzene, which confirms the absence of branched polychlorophosphases. .
    Calculated,%: C1 61.21; N 12.0 P 26.72.
    NPClz
    Found,%: C1 61.4} N 12.2; P 26.5.
    Said crude product is treated with petroleum ether at 40-60 ° C and a fraction of 4% by weight of the total processed product is solubilized.
    The control of the composition of the insoluble petroleum ether fraction by the chromatographic method (thin layer chromatography on silica using hexane as solvent) confirms the absence of residual and cyclic phosphazenes in it.
    The fraction insoluble in petroleum ether, which consists of a pure polymer, is dissolved in anhydrous benzene and treated with CF according to example 1.
    The obtained trifluoroethoxylated polymer has a number average m 40 therapeutic mass of 25,000. C is the corresponding polymer obtained by the end of the polycondensation I NSClj. has a number average molecular
    35
    S C1
    II g 1t
    1 L 1 J
    C1
    C1
    has in this case an average value of about 1090.
    PRI me R 2-. The reactions were carried out in a reactor of the same type as in Example 1. 20.5 g (0.072 mol) of P NSClff prepared in Example 1 a was introduced into the reactor. The temperature of the contents of the reactor, held with moderate agitation, is adjusted to about. then kept at this temperature for 6 hours,
    After a specified period of time, polycondensation is stopped. The amount of PSC1 collected. at the same time, 12.20 g. This amount slightly exceeds the theoretical amount (12.17 g) of PSClj, which could occur during the reaction in
    the result of the distillation of a small amount of P NSCly.
    The crude product (8.2 g) resulting from the polycondensation is completely soluble in benzene, which confirms the absence of branched polychlorophosphase-α. new .
    Calculated,%: C1 61.21; N 12.07; R 26.72.
    NPClz
    Found,%: C1 61.4} N 12.2; P 26.5.
    The crude product is treated with petroleum ether at 40-60 ° C and a fraction of 4% by weight of the total amount of the treated product is solubilized in this way.
    Control of the composition of the fraction insoluble in petroleum ether by the chromatographic method (thin layer chromatography on silica using hexane as a solvent) confirms the absence of residual in it, and cyclic phosphazenes.
    The fraction insoluble in petroleum ether, which consists of the purified polymer, is dissolved in anhydrous benzene and treated with CF according to Example 1.
    The obtained trifluoroethoxylated polymer has a number average molecular weight of 25,000. The corresponding polymer obtained at the end of the polycondensation I NSClj has a number average molecular weight
    the mass is equal to 11900, which corresponds to the average value of n in the formula indicated, equal to 101.
    An X-ray fluorescence study of the polymer obtained as a result of polycondensation shows that it does not contain elemental sulfur. The IR spectra and NMR spectra of P obtained for the indicated polymer are in FULL correspondence with the general formula of linear dichlorothiophosphoric chloride of chlorophosphazene of the type indicated by the formula with an average n value of 101.
    Example 3. Reactions are carried out in a reactor of the same type as in the reactor.
    51
    measure 1. 48.5 g (0.170 mol) obtained in example 1a are introduced into the reactor. The temperature of the contents of the reactor, maintained with moderate stirring, is raised to a value of about 230 ° C, after which it is maintained at this temperature for 6 hours.
    After a specified period of time, polycondensation is stopped. The number of collected PSClj is equal to 26.3 g.
    The crude product (22 g resulting from polycondensation, is completely soluble in benzene, which confirms the absence of branched polychlorophosphazenes
    Calculated,%: C1 6J, N 12.07;
    R 26.72.
    Wpcl
    Found,%: C1 61.2; .N 12.3; R 26.6,
    The indicated crude product is treated with petroleum ether at 40-60 ° C and a fraction of less than 5% by weight of the total amount of the treated product is solubilized in this way.
    The control of the composition of the fraction insoluble in petroleum ether by the chromatographic method, carried out according to Example 1, indicates the absence of residual P NSCly and cyclic phosphazenes.
    The fraction insoluble in petroleum ether, consisting of a purified polymer, is dissolved in anhydrous benzene and treated with C FjCH ONa according to Example 1.
    The resulting trifluoroxy-ethylated noniiMep of the Schlevt has a mean numerical molecular weight of 3300. The polymer corresponding to the end of the polycondensation, PO NSCl, has a number average molecular weight of Lu, equal to 1600, which corresponds to an average value of 12 in this formula.
    The IR spectra and NMR spectra of P obtained for the indicated polymer are obtained; as a result of polycondensation, they are in agreement with the linear dichlorothiophosphoryl-polychlorophosphazene formula, and in this example n has an average value of 12.
    In addition, the specified pol1-1mer does not contain elemental sulfur, about which
    26457-6
    The data of radiation of the product by X-ray fluorescence analysis.
    PRI me R 4. Operate in a reactor equipped for operating at reduced pressure and equipped with a mechanical stirrer, a heating system and a system for cleaning the inside of the reactor with an inert gas.
    Heated 4805 g of PgNSClj-in the specified reactor at 80 ° C and at a pressure of 100 mm Hg. Art. (about 13)
    15
    20
    25
    thirty
    35
    40
    45
    50
    55
    xlO Pa) for 8 h, and this heating is carried out in a nitrogen atmosphere with moderate stirring of the reaction medium.
     At the end of this term, the amount of PSClj collected is 27.9 g, which corresponds to the theoretical quantity that can be obtained / received. After this period, the heating is still continued for J h.
    The resulting crude product (19.6 g) is completely soluble in benzene, which proves the absence of branched polychlorophosphazenes. Calculated,%: C1 61.2 G, N 12.07,
      - (NPC1, L
    Found%: C1 61; N 11.6, P 27.1.
    The crude product is treated with petroleum ether. Thus, a fraction of about 4% of the treated product is dissolved.
    Chromatographic analysis of the fractionally-1CHI insoluble in petroleum ether, carried out according to Example 1, shows the absence of residual PjNSClj and cyclic phosphazenes.
    The petroleum ether-insoluble fraction as an och. One polymer is dissolved in anhydrous benzene and treated with CP CH2RIA as described in example 1.
    The obtained trifluoroethoxylated polymer has a number average molecular weight of 102,000. The corresponding polymer obtained by polycondensation of p NSClyi has a numerical molecular weight of 64,000, which corresponds to the number average value of n in this formula, equal to 550.
    In addition, the analysis of the polymer, carried out in x-rays.
    confirms the absence of elemental sulfur.
    Example 5. Operate in a reactor equipped according to example 1.
    60 g of P, NSClf prepared in Example 1a are introduced into the reactor. The contents of the reactor with moderate stirring are brought to a temperature of 290 ° C and then maintained at this temperature and at a pressure equal to the atmospheric pressure for 20 hours. After this time, the polycondensation is stopped and the amount of collected PSCIj is 35 g.
    The crude product obtained by polycondensation (24 g) is completely soluble in the besole, which proves the absence of branched polychlorophosphazenes.
    Calculated,%: C1 61.62; N 12.07;
      (
    Found,%: C1 61.5; N P, 8; R 26.8.
    This crude product is treated at 40-60 ° C with petroleum ether. Thus, a fraction representing about 3.5% of the treated product is dissolved.
    Chromatographic analysis of the insoluble petroleum ether fraction.
    conducted according to example 1, indicates the absence of residual Pj NSCl5 and cyclic phosphazenes.
    The petroleum-insoluble fraction in the form of a purified polymer is dissolved in anhydrous benzene and treated with CFj according to Example I.
    0 Received trifluoroethoxylated-. The polymer has a number average molecular weight of 320,000. Corresponding. the polymer obtained by polycondensation P NSCly, has a numeric
    5, the molecular weight is 204,000, which corresponds to the number average value n in the indicated formula of approximately 1760.
    Q CRO1 Moreover, the analysis of the polymer, carried out in x-rays x, proves that this polymer does not contain elemental sulfur.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining linear polychlorophosphazene by polycondensation of monochlorophosphazene at 180-290 ° C and at a pressure of 100 mm Hg. Art. to atmospheric, characterized in that, in order to increase the efficiency of the process, S-trichloro-K-dichlorothiophosphoryl monophosphazene is used as monochlorophosphazene.
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    同族专利:
    公开号 | 公开日
    BE900090A|1984-11-05|
    US4554113A|1985-11-19|
    IT8421773D0|1984-07-06|
    CA1251011A|1989-03-14|
    FR2548652A1|1985-01-11|
    EP0132188B1|1987-12-09|
    JPS6071504A|1985-04-23|
    IT1180203B|1987-09-23|
    EP0132188A1|1985-01-23|
    DE3468009D1|1988-01-21|
    FR2548652B1|1985-11-22|
    JPH0465004B2|1992-10-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3193343A|1962-07-11|1965-07-06|Olin Mathieson|Composition having the formula p2nscl5 and process for preparing same|
    US3348927A|1962-11-29|1967-10-24|Olin Mathieson|Composition and process|
    DE2234373A1|1972-07-13|1974-03-28|Basf Ag|Phosphinimino-thiophosphonyl cpds prepn - from phosphorus trichloride, chlorine, ammonia and sulphur |
    FR2466435B1|1979-09-27|1983-01-07|Inst Mondial Phosphate|FR2571710B1|1984-10-17|1986-12-26|Elf Aquitaine|PROCESS FOR THE PREPARATION OF LINEAR POLYCHLOROPHOSPHAZENES HAVING A PXCL2 TERMINAL GROUPING, X DESIGNATING O OR S, BY POLYCONDENSATION IN SOLUTION OF P2NXCL5 MONOMERS|
    FR2629442B1|1988-03-29|1990-11-23|Atochem|PROCESS FOR THE PREPARATION OF POLYDICHLOROPHOSPHAZENES COMPOSITIONS WITH A CONTROLLED RATE OF CYCLIC OLIGOMERS AND THE COMPOSITIONS RESULTING FROM THE IMPLEMENTATION OF THIS PROCESS|
    FR2647100A1|1989-05-19|1990-11-23|Atochem|METHOD FOR MASS POLYCONDENSATION OF N-DICHLOROPHOSPHORYL- OR N-DICHLOROTHIOPHOSPHORYL-P-TRICHLOROPHOSPHAZENE|
    FR2653423A1|1989-10-20|1991-04-26|Atochem|METHOD FOR CONTROLLING MOLECULAR MASSES OF POLYDICHLOROPHOSPHAZENES.|
    US5620499A|1992-12-14|1997-04-15|Farley; James J.|Chemical dispensing device and method|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8311264A|FR2548652B1|1983-07-06|1983-07-06|LINEAR POLYCHLOROPHOSPHAZENES HAVING A DICHLOROTHIOPHOSPHORYL TERMINAL GROUP, PROCESS FOR PREPARING THESE COMPOUNDS, AND THEIR USE|
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