• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    1501574 Polymethylene polyphenyl polyamines and polyisocyanates UPJOHN CO 7 July 1976 [24 July 1975] 28264/76 Heading C2C [Also in Division C3] A mixture of di(aminophenyl)methanes and oligomeric polymethylene polyphenyl polyamines wherein the diamine content is within the range of about 40 to 60% by wt., is obtained by a process which comprises the steps of (a) reacting aniline and HCHO in a proportion within the range of 4-10 moles of aniline per mole of HCHO at a temperature of 20‹ to 60‹ C., in the absence of a catalyst to form a mixture of aminals; (b) separating water therefrom; (c) contacting the remaining aminals with at least 1% by wt. of a solid catalyst selected from diatomaceous earths, clays and zeolites at a temperature of about 20‹ to 60‹ C. until from 80-100% by wt. of the aminals has been converted to benzylamines; (d) subjecting the remaining benzylamines to distillation under reduced pressure at a temperature not more than 150‹ C. to remove aniline until the aniline content of the undistilled fraction is within the range of about 3 to 22% by wt.; and (e) contacting said undistilled fraction with at least 1% by wt. of a solid catalyst selected from diatomaceous earth, clays, and zeolites at a temperature of 100 to 190‹ C. until conversion to the required mixture is complete. The process may be carried out continuously or in a batchwise manner. Mixtures of polymethylene polyphenyl polyisocyanates may be obtained by phosgenation of the mixtures of polymethylene polyphenyl polyamines obtained above.
    公开号:SU1036246A3
    申请号:SU762387956
    申请日:1976-07-23
    公开日:1983-08-15
    发明作者:Фрэнсис Фрула Флоро；Абдул Рида Саигх Эднан；Ульрич Хенри；Джон Витман Питер
    申请人:Дзе Апджон Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of di- (aminophenyl) methanes and polymethylene polyphenyl polyamines by the condensation of aniline and formaldehyde. Such methods are widely used in industry for the production of these polyamines, which are intermediates in the synthesis of the corresponding isocyanates used for the production of a wide variety of polyurethanes and other polymers as cellular. never h, eistyh. A known method for producing mixtures of polyphenylpolyamines with polymethylene bridges containing diaminodiphenylmethanes by condensation of aniline with formaldehyde in the presence of an aqueous inorganic acid as a catalyst for Cl, which leads to the occurrence of corrosive effects. . The closest to the proposed method is to obtain a mixture of di- (aminophenyl) -methanes and oligomeric polymethylene polyphenyl polyamines with a diamine content of 40-60 wt.% By condensation of aniline and formaldehyde in the presence of an aluminosilicate catalyst at 125-300 ° C. 2. The disadvantages of this method are l The high content of 2, -isomer in the target diamine and a significant amount of higher oligomers in the rest of the mixture. The purpose of the invention is to improve the quality of the target product. This goal is achieved by the fact that according to the method for producing a mixture of di- (aminophenyl) -methanes and oligomeric polymethylene polyphenylpl-amines, including the condensation of aniline with formaldehyde, using an acid catalyst, the condensation stage is carried out in a molar ratio of 2121 to formaldehyde equal to 4-10 : 1, respectively, at. 20-60 to form a mixture of amines, separate water from this mixture and subject it to contact with a catalyst — diatomaceous earth, clay or zeolite in an amount of 1–10% of the weight of the reactants; the benzylamines obtained are distilled under reduced pressure at Sl- To achieve an aniline content in the roast of 3-22%, the resulting residue is heated at 100-190 ° C in the presence of a catalyst — diatomaceous earth, clay, or zeolite. Moreover, clay attapulgite is used as a catalyst. The preferred molar ratio of aniline and formaldehyde is 5-7: 1. Thus, the proposed method for the condensation of aniline and formaldehyde is carried out under heterogeneous catalysis conditions. The first stage of the process is carried out without a catalyst. The above molar ratio of reagents at this stage is necessary to obtain the target product, which does not contain byproducts. The proposed method provides a mixture of polyamines in which the main component is di- (aminophenyl) methane, in comparison with the known one-step method, while the remaining mass of the mixture consists of only two components, namely, triamine and tetraamine, while In the process, the remainder of the mixture is a complex mixture of. oligomeric polymethylene polyphenyl polyamines. The importance of the difference in the compositions of the target products becomes apparent when the resulting mixture of polyamines is converted by phosgenation into the corresponding mixture of polyisocyanates, which are characterized by a lower equivalent weight, have a much lighter color than the previously known corresponding products, and have a lower viscosity. The useful and new properties of polyisocyanates derived from polyamines according to the proposed method are entirely correlated with the new composition of polyamines. Of the total amount of diamine present in the reaction mixture, 75% is the share of 4,4 -isomer. Measurement 1. (a) 2.976 g (32 M) aninil is placed in a 5-liter flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer. The system is cooled down with the aid of an ice bath and at this temperature 422.6 g (5.2 M) of a 37% aqueous solution of formaldehyde are introduced in 30 minutes. The mixture is stirred for 1 hour at and then 5 hours at room temperature (about 20 ° C). The resulting product was separated and the lower aqueous layer was distilled off. The resulting amines are dried at 40-50 ° under a pressure of 0.1 mm Hg. Art. within 1 hour. {Get 2999 g of a dry mixture of amines (water content: 0.1%). b) a part (1406 g) of the obtained mixture of aminals is brought into contact with 140.2 g (10% by weight) of clay attapulgite with stirring, the mixture is heated to 5.5 hours. At the end of the indicated period, using the PMR spectrum, determine that the conversion of amines to benzylamines is 99%. The resulting product is filtered, the catalyst is washed on the filter with 200 ml of methylene chloride. The combined filtrates are evaporated under reduced pressure to distill off methylene chloride.
    Get 1395 g of a mixture of benzylamin and aniline residue.
    c) a portion (200 g) of the mixture of benzylamines and aniline obtained in step (b), is distilled under reduced pressure 1.5-1.7. mm Hg Art. for 1 h, initially at and then at 100 ° C, as long as the content
    aniline in distillate will not be equal to 131.2 g. The residue (68.4 g) according to gel chromatography data contains 12.0 wt.% aniline.
    d) 60.3 g of benzylamines obtained in step (c) and 3 g (5% by weight) of clay attapulgite are heated at
    | 180 ° C; With stirring for 40 minutes to complete the conversion of methylene polyphenyl polyamines. The resulting product is filtered, the catcher is 50 ml of methylene chloride. The combined filtrates are washed and dried to obtain 59.9 g of colored liquid j containing 95% of triamines and tetrami. Di- (aminophenyl) methane contains .75.6 wt.% 4,4-isomer, 21.2 wt.% 2,4 isomer and 3.2% 2,2-isomer. The mixture of polyamines contains 49.9% by weight of di (aminophenyl) methane and 50.1% by weight of higher oligomers.
    Example 2. A second portion (200.0 g) of a mixture of benzylamines containing aniline prepared analogously to Example 1, stage (b) is distilled under reduced pressure, stage (c). Distillation was completed when 135.2 g of aniline was distilled off. The non-distilled fraction (71.4 g) contains 7.3% by weight of aniline. This residue is heated with 3 g of clay attapulgite at 180 ° C with stirring, stage
    (d) The complete conversion of benzylamines to methylene polyphenyl polyamines is completed after 40 minutes. The mixture is filtered, the catalyst is pressed with methylene chloride (50 ml). The combined filtrates are washed and dried, and 59.9 g of colored liquid is obtained, which contains 13.9% by weight of aniline, the rest is methylene polyphenyl polyols, 44% of which are di-. O (aminophenyl) methane and 56% higher oligomers containing 95% triamines and tetramines. Di- (aminophenyl) methane contains 75.6% by weight of the 4,4-isomer, 21.2% by weight of 2,4-iscera, and 3.2% by weight of 5 2,2-isomer.
    Example 3. The third portion (200.0 g) of a mixture of benzylamines and aniline, obtained analogously to example 1, 0 | stage (b), is subjected to distillation with tipH reduced pressure, stage (s}. Distillation; yu finish when 129.6 g of aniline was distilled.The non-distilled fraction (70.3 g) contains 12.2% by weight of aniline. This residue is heated with 3 g of clay attapulgite at 180 ° C with stirring as in Example 1, step (d). The mixture obtained filtered, the catalyst is washed with methylene chloride (50 ml). The combined filtrates are washed, dried, and 69.8 g of colored liquid are obtained, which contains It contains 20.5% aniline, the rest is methylene polyphenyl polyamines: 49.9% di- (aminophenyl) methane and 50.1% higher oligomers (95% tri- and tetramines). Di- (aminophenyl) methane contains 73.2 wt. % 4,4 -isomer, 24, 6 wt.% 2,4-isomer and 2.2 2.2. Isomer.
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING A MIXTURE OF DI- (AMINOPHENYL) METHANES AND OLIGOMERIC POLYMETHYLENE POLYPHENYL POLYAMINES, in which the content of diamine is in the range between 40 and 60 wt.%, The interaction of aniline and formaldehyde using acid catalysts, which is characterized in that quality of the target product, aniline is subjected to interaction with formaldehyde in a molar ratio of 4-10: 1 at 20-60 ° C with the formation of a mixture of amines, water separation and contacting of the amines with a catalyst diatomaceous earth, clay or zeolite in an amount In the range of 1–10% of the weight of the reacting substances, the obtained benzylamines are distilled under reduced pressure at 51–150 ° С until the content of aniline in the residue of 3–22% is reached; the obtained residue is heated at 100–190 ° (in the presence of a catalyst - diatomaceous earth, clay or zeolite. §
    [2]
    2. The method of pop. 1, distinguished by the fact that. clay attapulgite is used as a catalyst.
    [3]
    3. The method according to p. 1, characterized in that the molar ratio of aniline and formaldehyde is 5-7: 1.
    SU „1036246
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    同族专利:
    公开号 | 公开日
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    DD126295A5|1977-07-06|
    BR7604755A|1977-08-02|
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    引用文献:
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    法律状态:
    优先权:
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