• 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:
    N-substituted oligo-imides of the formula: <IMAGE> [I] in which D represents a divalent radical selected from the group comprising: <IMAGE> in which m is 0 or 1, Y is hydrogen, chlorine or methyl, n is a positive integer of 5 or less, and R is an organic radical of valency n, containing up to 50 carbon atoms, are prepared by reacting an anhydride of the formula: <IMAGE> [II] with an amine of the formula: R--NH2)n [III] in which formulae D, R and n are as above defined, said reaction being carried out in the presence of a catalyst system comprising a mixture of a compound (1) and a compound (2), (1) being a strong inorganic or organic oxygen-containing acid and (2) being an ammonium salt of such acid, said ammonium salt being di-, tri- or, preferably, tetra-substituted on the nitrogen atom by organic radicals.
    公开号:SU969157A3
    申请号:SU782652602
    申请日:1978-08-08
    公开日:1982-10-23
    发明作者:Бодуэн Мишель；Абблар Жан
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    50 ml of ethylbenzene at 120 ° C, filtered hot, then cooled to. The resulting crystals are filtered, washed 3 times with 5 cm of ethylbenzene, and after drying, 4.52 g of product is obtained containing 95.4% bis-4,4-maleimidiphenylmethane.
    Example 3. A flask with a capacity of 250 cm equipped with a stirrer and a distillation column was charged with 0.4875 g of benzenesulfonic acid (3.09 mmol); 5.666 g of tetraoctylammonium benzene sulfonate (9.09 mmol 15.012 g of maleic anhydride (153.1 mmol); 60 cm of ethyl benzene.
    With constant stirring, a solution heated to containing 70 cm of ethylbenzene and 7.54 g of 4,4-diaminodiphenylmethane (38.1 mmol) was gradually added over 6 minutes.
    Then, gradually over 34 minutes, the mixture is heated to 133 ° C and distilled over 88 minutes. The distillation and treatment of the reaction medium is carried out according to the method of example 1.
    . 13.0635 g of product are obtained, containing (according to polarography) 93.6% bis-4,4-maleimidodiphenylmethane. The mother water after filtration contains 3.07 mmol of bis-4,4-maleimidodiphenylmethane.
    Example 4. In the apparatus described in example 1, download 0,616 g of benzenesulfonate. (0.0039 mol); 8.243 g-dimethyloctadecylammonium benzene sulfonate, purity 98.2% (0.01114 mol); 30.036 g of maleic anhydride (0.3065 mol); 85 cm-chlorobenzene.
    This mixture is stirred. A solution maintained at 100 ° C and containing 19.86 g of 4,4-diaminodiphenylmethane (0.1003 mol) and 86 cm of chlorobenzene is continuously added to it for 13 minutes.
    After mixing, the temperature of the wound. The reaction mass is heated and distilled off as in Example 1. The distillation is carried out for 2 hours and 8 times. The temperature of the reaction mass rises from 127 ° C to. At the end of the distillation, the mixture is a homogeneous liquid. Then it is cooled to. The resulting crystalline precipitate is filtered and trimaf pramav.akt-every time. 25 cm of chlorobenzene, then dried at room temperature () under reduced pressure of 1 mm Hg. (absolute pressure).
    Thus, it is obtained from 29.503 g of a product with a melting point of 159.5 C containing 99.5% bis-4,4-maleimidodiphenylmethane (according to the gender of JbHH).
    0,018 mol of bis-4,4-maleimidodiphenylmethane is found in the mother waters of filtration with the aid of a polygraphy.
    5 Example 5. The apparatus described in Example 1 was charged with 2.210 g (0.0230 mol) of methanesulfonic acid; 15 g (0.066 mol) of tetraethylammonium methanesulfonate; 33.4 g
    Q (0.840i mol) of maleic anhydride; 75 cm 1,2-dichloroethane.
    This mixture is heated to boiling and stirred. A solution of 22.556 g (0.1139 mol) of 4,4-diaminodiffeylmethane and 130 cm of 1,2-dichloroethane was continuously added to it for 22 minutes.
    The reaction mixture (83C) was distilled off according to the method of Example 1, continuously removing the reaction water. Stripping 0 is carried out for 10 hours.
    154.45 g of this reaction mass is treated 5 times with water 30 cm each, the organic phase is dried over anhydrous magnesium sulfate, filtered, evaporated to dryness, the residue is washed with ethyl ether, drained, dried. Thus, a light yellow product with a melting point, containing 99% (according to polarography) of bis-4,4-maleimidodiphenylmethane, is obtained. The yield with respect to the converted diaminodiphenylmethane is 99%.
    Example 6.In the equipment
    5 described in example 1, load 1,473 g (0,0153 mol) of methanesulfonic acid; 10.0 g (0.0444 mol) of tetraethylammonium 1 tetanesulfonate; 22.3 g (0.227 mol) of maleic anhydride;
    0 80. cm 1,1,2,2-tetrachloroethane. The mixture is heated to boiling (147,) and mechanically stirred. Then for 6 min. add a solution containing 15.013 g
    . (0.0758 mol) 4,4-diaminodiphenylmethane and 30 cm 1,1,2,2-tetrachloroethane.
    The mixture is then distilled according to the procedure of Example 1 for an additional 9 minutes. The resulting reaction mass is cooled to 20 ° C and washed successively 3 times with 25 cm of water. The resulting organic phase of cyiaaT is over anhydrous magnesium sulphate and is concentrated in vacuo. The resulting liquid oily product was poured into 100 cm of ether, resulting in a yellow crystalline product. This product is squeezed, sieved with ether and dried. 27.35 g of solid product are obtained, containing 95.4% bis-4,4-maleimodifenylmethane, melted at 159 s.
    Example 7. In the apparatus described in example 1, load
    5 0.146 g (0.00152 mol} of methanesulfonic acid; 0.857 g (0.0088 mol) of tetraethylammonium methanesulfonate; 22.3 (0.227 mol) of maleic anhydride; 45 cm of 1,1,2,2-tetrachloroethane. The mixture is heated to boiling and fur. The solution containing 15.062 g (0.0760 mol) of 4,4-diaminodiphenylmethane and 50 cm of tetrachloroethane is continuously spilled for 13 minutes. Then the solvent is distilled off according to the procedure of Example 1 for 1 hour and 51. The reaction mass is treated with the method of example 5 and get a solid yellow product in the amount of 26.95 g, containing according to the field of p p graphical analysis and 93.9% bis-4.4,4 maleimidodiphenylmethane Example. 8. A 250 cm reactor equipped with a stirrer and a column distillation was charged with 19.032 g of dichloromaleic anhydride (114 mmol); 0.548 g of Paratoluene sulphonic acid, .HjO (2.88 mmol); 6.024 g of para-toluenesulfonate dimethyl dialkylammonium (the alkyl units of this salt are linear kidney chains containing from 16 to 18 carbon atoms), mol. Mass is 724 g (8.32 mmol); 90 cm of toluene. Within 5 minutes, a solution containing 8.025 g of para-toluidine (75 mmol) was gradually and continuously introduced; 40 cm of toluene. The temperature E) of the reaction medium exceeds 35 ° C during the introduction of this solution. Gradually bring the temperature of this mixture to, i.e. to boiling point. Then the mixture is distilled for 1 hour and 25 minutes; the distillate is condensed and then decanted, the aqueous layer is removed, and toluene is fed up the columns. The reaction mixture is cooled. The crystalline precipitate is filtered, washed in hexane, then dried at ambient temperature () under reduced pressure. Thus, 14.39 g of product are obtained, containing 90% N-tolyl dichloromelaimide. This compound is recrystallized in toluene with heating, filtered, washed with hexane and dried under reduced pressure. The melting point of this compound. Another 9.696 mmol of N-tolyl dichloromalemide (a polarographic definition) is recovered from the mother liquor obtained from filtration. The yield with respect to the loaded para-toluidine is 80%. ,, Example 9. A flask of 250 cm equipped with a stirrer and a distillation column was charged with 22.344 g of maleic anhydride (228 mmol); 0.548 g paratoluenesulphonic acid, lHj.O (2.88 mmol); 6.024 g paratoluenesulphonate dimethyldialkylammonium (linear alkyl), mol. Mass 724 g (8.32 mmol); 60 cm of toluene. For 23 minutes, a solution containing 70 cm of toluene, 16.09 g of para-toluidine (150 mmol) was continuously and gradually introduced into this mixture. During this process, the temperature of the reaction mixture gradually rises from 30 to. Then the mixture is gradually heated to i. temperature at which boiling begins. The mixture was distilled for 1 hour and 50 minutes, the distillate obtained was condensed, then decanted, after which the aqueous layer was removed and the toluene was sent to the top of the column. The reaction mixture is cooled. The bright yellow crystalline precipitate is separated, washed in hexane, then dried at ambient temperature (23 ° C) under reduced pressure. Thus, 23.592 g of pure N-tolylmaleimide having a melting point of .147 ° C are obtained. Another 22.34 mmol of N-tblylmaleimide was detected from the mother liquor obtained after filtration (polarographic determination). The yield relative to the loaded para-toluidine is 98.9%. Example 10. A flask per 250 cm equipped with a stirrer and a distillation column was charged with 22.345 g of maleic anhydride (228 mmol) -, 0.546 g of para-toluenesulfonic acid, 1H o (2.88 mmol), 6.025 g of para-toluenesulfonate dimethyl dialkyl 1 mon (alkyl, 7 linear); . weight. 724 g (8.32 mmol)} 60 cm of chlorobenzene. A suspension containing 15.19 g of 4, 4-diaglyniphenyl ether (75 ;, 87); 70 cm of chlorobenzene is gradually added over 5 minutes. After adding the suspension, the temperature of the reaction medium gradually increases from 30 to. Then the temperature of this mixture is gradually adjusted to, i.e. to boiling point. The mixture is distilled for 1 hour 30 minutes. The distillate obtained is condensed (water + + chlorobenzene), the aqueous layer is removed, and chlorobenzene is directed to the top of the column. The reaction mixture is cooled to 18 ° C. The yellow precipitate is filtered off, washed with hexane, then dried at ambient temperature () under reduced pressure. Thus, 27.992 g of compound are obtained, melting point 170c, containing 86.4% bis-4,4-maleimidiphenyl ether. In the mother liquor obtained after filtration, it is found that
    6.47 mmol bis-4,4-maleimidiphenylester ether (polarographic definition). The yield with respect to the charged 4,4-diamine diphenyl ether is 97%.
    EXAMPLE 11 To a flask of 250 cm equipped with a stirrer and a distillation column, 22.346 g of maleic anhydride (228 mmol), 0.547 g of para-toluenesulfonic acid (2.88 mmol), 6.024 g of para-toluenesulfonate dimethyl dialkylammonium (alkyl), linear are charged; . weight 724 g (8.32 mmol); 60 cm of chlorobenzene.
    Within 20 minutes, a solution, at a temperature of 20.211 g of bis1, 1- (4-aminophenyl) -cyclohexane (75.87 mmol), and 70 cm of chlorobenzene, is gradually and continuously introduced into the mixture in the indicated mixture. The temperature of the reaction medium as a result of this addition will gradually rise from 30 to. Then, the temperature of this mixture is gradually brought to i. : boiling point. The mixture is distilled for 3 hours. The distillate obtained is condensed (water: + + chlorobenzene) ....
    The reaction mixture is cooled to. The precipitated crystalline precipitate is filtered off, washed in hexane, then dried at ambient temperature () under reduced pressure. Thus, ps uchitot 32.3715 g of a compound containing 91.6% bis-: 4,4-maleimido-1,1-da1phenylcyclohexane. This United | 1e is recrystallized in toluene with heating, filtered, washed in hexane, dried under reduced pressure. Melting point of the obtained compound.
    In the mother liquor obtained after filtration, another 3.07 mmol of bis-4,4-maleimido-1,1 diphenylcyclohexane is detected (polarographic determination). The yield with respect to the loaded bis-1,1- (4-aminophenyl) -cyclohexane is 95.7%.
      Example 12. A flask with a capacity of 400 cm, equipped with a stirrer and a distillation column, was charged with 33.34 g of maleic anhydride (228 mmol), 6.35 g of 85% orthophosphoric acid (3 mmol); O, 39 g dihydrogen phosphate tetrabutylammonium ((C4Hpi4 1% purity (9 mmol); 80 cm of toluene.
    Then, within 10 minutes, a solution having a temperature of 60 ° C containing 15.04 g of 4,4-diamine diphenylmethane (75.95 mmol) and 10 cm of toluene was introduced into the Henppi JBHo flask with vigorous stirring.
    The reaction mixture is then heated while stirring the temperature, i.e. temperature at which boiling begins. The mixture was distilled for 2 hours. The distillate formed was condensed, after which the decant was decanted, the aqueous layer was removed and the toluene was returned to the top of the column.
    After distillation, the reaction mass is treated with 150 cm of warm chlorobenzene. The filtration is carried out at elevated temperature, after which the filtrate is cooled to. The precipitated product is then separated from the filtrate, dried at ambient temperature and reduced pressure.
    13 g of 4,4-bis-maleinoimide diphenylmethane are obtained, m.p. which
    The yield pj with respect to the loaded 4,4-diaminodiphenylmethane is 47.8%.
    权利要求:
    Claims (2)
    [1]
    1. The method of obtaining oligoimides by the interaction of dicarboxylic anhydride with the amine in the medium of an organic solvent, which is also used in order to simplify the process, an anhydride of the general formula
    Gox „
    where D is a residue of the formula
    -i
    where Y is H, d, CHj,
    and as an amine, a compound of the general formula
    RCNH) ,,
    where h is 1 or 2, with n | 1 R is unsubstituted or lower alkyl
    scrap
    with
    . P 2 R represents -boy
    // // V J / - V
    and the process is carried out at 80-140 ° C in a hydrocarbon medium in the presence of a catalytic system comprising an acid selected from the group of alkylsulfonic acid, arylsulfonic acid, alkarylsulfonic acid, phosphoric acid, and quaternary ammonium salt of the formula1
    Yad-ME-X,
    U
    l is the residue of the indicated. above acids;
    R,, 1 have the same or different values and represent each C of C, and the sum of carbon atoms is 6–42.
    [2]
    2. Method pop.1, otlichayuts and with the fact that the process is carried out at a molar ratio of acid to ammonium salt, equal to 0.1-10, the ratio, the sum of moles of acid and ammonium salt to the number of NHj-rpynn in the amine, 5 equal to 0 , 1-1, and anhydride to the number NH, j -rpynn in the amine 1.01-1.5.
    Sources of information taken into account in the examination
    1. US patent 3627780, 0 CL.260-326.3 ,. publication 1971 (prototype).
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    同族专利:
    公开号 | 公开日
    NL189668B|1993-01-18|
    NL7808296A|1979-02-13|
    US4225498A|1980-09-30|
    SE7808485L|1979-02-10|
    ATA578578A|1981-11-15|
    DE2834919C2|1986-08-21|
    LU80084A1|1979-09-07|
    CH634049A5|1983-01-14|
    FR2400014A1|1979-03-09|
    IT7826631D0|1978-08-09|
    SE429860B|1983-10-03|
    IT1098370B|1985-09-07|
    IE781591L|1979-02-09|
    DK156433C|1990-01-22|
    BE869612A|1979-02-08|
    NL189668C|1993-06-16|
    FR2400014B1|1980-02-01|
    IE47288B1|1984-02-08|
    GB2002378B|1982-03-10|
    IL55314D0|1978-10-31|
    DK156433B|1989-08-21|
    AT367438B|1982-07-12|
    DE2834919A1|1979-02-22|
    GB2002378A|1979-02-21|
    DK349478A|1979-02-10|
    JPS5430155A|1979-03-06|
    BR7805080A|1979-04-10|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7725215A|FR2400014B1|1977-08-09|1977-08-09|
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