• 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:
    METHOD FOR OBTAINING POLYESTERMS by homogenizing the reaction mixture consisting of polyamide. gt content of its terminal carboxyl groups, 0, Q-dioxy (polytetrachdrafurana), diamine of polytetrahydrofuran or ethylene oxide diamine, or polyamide containing terminal amino groups, and polytetrahydrofuran with end carboxyl groups, when using under pressure, followed by subject; 100 mbar, characterized in that, in order to increase the purity of the product, the homogenization of the reaction mixture is carried out with stirring under a pressure of water vapor of 2-25 bar.
    公开号:SU1155160A3
    申请号:SU802954177
    申请日:1980-08-04
    公开日:1985-05-07
    发明作者:Мумку Сали；Иоахим Панох Ханс
    申请人:Хемише Верке Хюльс Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the production of thermoplastics, in particular to a process for the preparation of polyetheramides. The purpose of the invention is to increase the purity of the product. PRI m i r 1. A mixture containing 280 kg of laurinelactam, 13 kg of adipic acid and 12.6 kg of water is heated to 270 ° C in an autoclave with a 1 m stirrer with no air access, and an internal pressure of 18 bar is established. After holding for 7 hours, 107 kg o (, CJ -dioxy (polytetrahydrofuran) with a molecular weight of 1200 are fed to the reactor under pressure, and the mixture is stirred for 2 hours at a pressure of 20 bar and a temperature of 230-270 0. Then the pressure in the reactor is reduced to atmospheric within 2 hours. Polycondensation is carried out at normal pressure with passing nitrogen over 1 hour over a reaction mass of 5 hours. Samples of the reaction mixture are taken at 6-hour intervals and the relative viscosity in m-cresol is determined at 25 ° C. The following values relate to Polycondensation Time. The results: 1.51 6 12.1.65 181.90 The target product has a melting point of 168 ° C (according to the differential thermal calorimetry). The amount of the extract after treatment with hot ethanol is 2.3% by weight,%. Example 2, Mixture containing 16 kg of laurinelactam, 0.7 kg of dodecane dicarboxylic acid, and 750 ml of water are heated to a 50-liter autoclave with a stirrer without access to the spirit, and an internal pressure of 19 bar is established. After 7 hours, 3 are added, 3 kg of a polytetra of hydrofuran-diamide with a molecular weight of 1100, obtained by 1a-ethylation and hydrogenation of l, (o- Ioxy (by lithetrahydrofuran) and under a pressure of 22 bar is stirred for 2 hours at 230-270. Then the pressure in the reactor is reduced to atmospheric for 2 hours. Poly condensation is carried out at normal pressure, passing over a reaction mass of 200 liters of nitrogen per 1 4-hour. At intervals, samples of the reaction mass are taken and the bone-relative product in m-cresol is determined at 25 s. At the same time, a value of only 2 is attributed to the polycondensation time, h 4 8 12 1.53 1.85 2.05. The target product has a melting point of 174 ° C (according to differential thermal calorimetry). The amount of the extract after processing the product with hot ethanol is 1.6 wt.%. Example 3. A mixture containing 260 kg of laurinelactam, 26 kg of dodecanedicarboxylic acid and 11.7 kg of water is heated to 270 seconds in an autoclave with a stirrer with a capacity of 1 m without air, and an internal pressure of 18 bar is established. After a b-hour vvderzhki add a mixture containing 114 kg (X, co-dioxy (polytetrahydrofuran) with a molecular weight of 1000 and 0.3 kg of tetraisopropyl orthotitanate and stirred the reaction mixture at 230-260 seconds for 2 hours. Then the pressure in the reactor is reduced to atmospheric for 2 hours, with the temperature being twisted to 270 C. Then a vacuum of 20 mbar is set for 3 hours and maintained for 10 hours. The resulting product has a temperature of 90. Melting point (according to differential thermal calorimetry). The amount of extract after treatment of the product is hot m ethanol 2.2 wt.%. Example 4. A mixture containing 280 kg of laurinelactam, 25 kg of dodecanedicarboxylic acid and 12.6 kg of water is heated to 270 ° C for 4 hours in an autoclave with a stirrer with a capacity of 1 m, and an internal pressure of 18 bar. After 7 hours of exposure, 95 kg of it are added, and α-dioxy (polytetrapedrofuran) with a molecular weight of 1000 and stirred at a temperature of 230-260s at a pressure of 20 bar for 2 hours. Then the pressure is reduced to atmospheric in those 2 hours. and increase the temperature to 27 C. In this case, the Schju polycondensation is carried out at a constant pressure with passing over the reaction mass of nitrogen. After 24 hours, a product is obtained with a viscosity of H d 1.92. The amount of the extract after processing the product with hot ethanol is 1.6 wt.
    3i
    Example 5. In a 50-liter autoclave with a stirrer, a mixture containing 8 kg of G-aminoundecanoic acid and 1.2 kg of hexahydrotereLtalic acid is heated to 0.5 bar under nitrogen overpressure. After 3 hours, a mixture of 600 ml of water and 11.2 kg of diamine polyethylene oxide with a molecular weight of 1620, obtained by cyanostillation and hydrogenation of polyethylene glycol oxide, is added. Then it is stirred for 1 hour at a temperature of 230-260 ° C and pressure: 17 bar, after which the pressure is reduced: to atmospheric within 2 hours. the reaction mixture is subjected to polycondensation at normal pressure for 8 h with passing nitrogen over it. The viscosity of the resulting product is 1.8 (in m-cresol at 25 ° C). The amount of the extract after treatment with hot ethanol is 1.3 wt.%. .
    Example 6. In a 50-liter autoclave with a stirrer, a mixture containing 7.46 kg of dodecanedicarboxylic acid and 4.65 kg of dodecanmethylenediamine is heated to 260 ° C in the presence of a mixture containing 700 ml of water and 12 g of 85% aqueous phosphoric acid, and internal pressure, 17 bar. After stirring for 3 hours, the pressure is reduced to 10 bar. Then, 8.2 kg s are added (, (0-dioxy (polytetrahydrofuran) with a molecular weight of 860 and stirred for 2 hours at 230-260 ° C and pressure 12 bar. Then the pressure is reduced to atmospheric for 1 h in the reactor Then, nitrogen is passed over the reaction mass for 3 hours, a vacuum of 20 m bar is established for 2 hours and polycondensation is carried out for 7 hours. The viscosity of the resulting target product is 2.05 (in m-cresol at): The amount of extract after treatment hot ethanol 1.7 wt.%.
    Examples 7-27 illustrate the effect of time and water vapor pressure in the mixing (homogenization) stage on the polycondensation rate and product purity.
    Examples 7-27. A mixture of 1.27 kg dodecanedicarboxylic acid and 670 mp of water containing t4 kg of laurinelactam is heated to, in a 50-liter autoclave with an agitator without air, and is set internally
    The maximum pressure is 20 bar. After a 7-hour exposure, 4.9 kgC, oo-dioxy (polytetrahydrofuran) with a molecular weight of 860 pr of pressure indicated in the table are fed to the reactor and the reaction mixture is stirred at 230-270 ° C for the time specified in the table. In all examples, after the end of the mixing process, the pressure in the reactor is reduced to atmospheric within 90 minutes. Then the reaction mass is subjected to polycondensation at normal pressure with passing nitrogen over it. The table indicates the relative viscosities of the target products in m-cresol at 25 ° C and the amount of the extract after the product has been treated with hot methanol.
    Example 28. In a 1 m autoclave with a mixer with a capacity of 1 m, a mixture containing 280 kg of laurinelactam, 23.8 kg of dodecanethylene diamine and 12.6 kg of water is heated to 270 ° C without access of air for 4.5 hours, and an internal pressure of 18 bar is established . After an 8-hour lump in locate 1 (ice under pressure, the reactor serves 100 kg of polytetrahydrofuran with carboxyl end groups (molecular weight 810) and stirred for 90 minutes at a pressure of 20 bar and a temperature of 230-270 ° C. Then the pressure in the reactor is reduced to atmospheric for 2 hours, after which polycondensation is first carried out for 5 hours and nitrogen is passed over the reaction mass. After that, the pressure is reduced to 20 Mbar for 2 hours and the polycondensation is continued for another 4 hours. The resulting product has a viscosity of 172C(according to differential thermal calorimetry.) The amount of the extract after treatment with hot ethanol T, 5 wt.%.
    Example 29. In an autoclave, a mixture containing 171 kg of dodecanedicarboxylic acid, 149 kg of dodecanmethylenediamine and 13.9 kg of isophorone diamine is heated to 280 ° C for 5 hours in the presence of 80 kg of water without air, and the internal pressure is maintained at a continuous pressure release at the level 18-20 bar. Then the pressure is reduced to 10 bar.n for 2 h, then in the pressurized
    I115
    the reactor is fed with 69 kg of polytetrahydroluran with terminal carboxyl groups (molecular weight 810) and the reaction mixture is stirred at a pressure of 12 bar and a temperature of 230270 s for 2 hours. Then the pressure is reduced to atmospheric for 2 hours. Polycondensation is carried out with passage over 5 m of nitrogen. After 13 hours, a viscosity product, .1, 95, is obtained. The pressure point is 176 ° C according to differential thermal calorimetry). The amount of the extract after treatment with a hot standard is 1.9 wt.%.
    0
    Example 30. Example 3 is repeated with the difference that the polycondensation is carried out at a pressure of 100 mbar for 10 hours. A product with a relative viscosity of 1.76 is obtained. The amount of the extract after processing the product with hot ethanol is 2.1 wt.%.
    Example 31. Example 8 is repeated with the difference that the polycondensation is carried out at a pressure of 1 mbar for 10 hours. A product with a relative viscosity of 1.99 is obtained. The amount of the extract after processing the product with hot ethanol is 2.3 wt.% .
    权利要求:
    Claims (2)
    [1]
    METHOD FOR PRODUCING POLYETHYRAMIDES by homogenizing a reaction mixture consisting of polyamide containing terminal carboxyl groups, οί, 4) -dioxide (polytetrazztrafuran), diamine polytetrahydrofuran or diamine of ethylene oxide, or polyamide containing terminal amine groups of carboxyne acid and polytetrate under pressure followed by polycondensation at atmospheric or reduced pressure
    1-100 mbar, characterized in that, in order to increase the purity of the product, the homogenization of the reaction mixture is carried out with stirring under pressure of water vapor
    [2]
    2-25 bar.
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    同族专利:
    公开号 | 公开日
    US4429081A|1984-01-31|
    DE2932234C2|1982-01-28|
    EP0023956A1|1981-02-18|
    DE2932234A1|1981-02-19|
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    JPS5665026A|1981-06-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1570392A1|1965-10-12|1970-01-29|Huels Chemische Werke Ag|Process for the production of polyamide powders of increased viscosity|
    DE1921738A1|1969-04-29|1970-11-12|Bayer Ag|Polyester amide elastomers with polyether segments|
    US3839245A|1972-03-30|1974-10-01|Emery Industries Inc|Poly antistatic compositions derived from dimr acids|
    GB1449315A|1973-02-06|1976-09-15|Toyo Boseki|Block copolymer of polyamide and polyether and its preparationand use|
    FR2273021B1|1974-05-31|1977-03-11|Ato Chimie|
    FR2307834B1|1975-04-15|1977-11-25|Ato Chimie|
    FR2318185B1|1975-07-17|1977-12-09|Ato Chimie|
    US4143025A|1975-10-09|1979-03-06|Chemische Werke Huls Ag|Method for producing polylaurolactam powder compositions for the coating of metals at high temperatures|
    FR2378058B1|1977-01-24|1979-05-11|Ato Chimie|
    DE2707589C3|1977-02-22|1980-02-21|Siemens Ag, 1000 Berlin Und 8000 Muenchen|Continuous current switch for short-circuiting a superconducting magnet|
    DE2712987C2|1977-03-24|1981-09-24|Chemische Werke Hüls AG, 4370 Marl|Process for the production of thermoplastic polyetheresteramides with units of the starting components randomly distributed in the polymer chain|
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    DE2855920C3|1978-12-23|1982-01-07|Chemische Werke Hüls AG, 4370 Marl|Process for the production of powder-form coating compositions for coating metallic objects by the melt-coating process on the basis of polylaurolactam powder|
    CH642982A5|1979-02-26|1984-05-15|Inventa Ag|POLYAETHER POLYAMIDE.|DE2936977C2|1979-09-13|1986-06-12|Hüls AG, 4370 Marl|Process for the production of polyetheramides|
    FR2497518B1|1981-01-05|1983-12-30|Ato Chimie|
    CH658062A5|1983-08-04|1986-10-15|Inventa Ag|Method for producing blockpolyetheresteramiden.|
    CH658063A5|1983-08-05|1986-10-15|Inventa Ag|METHOD FOR PRODUCING hydrolysis BLOCKPOLYETHERESTERAMIDEN.|
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    US5130382A|1990-03-30|1992-07-14|Texaco Chemical Company|Hydroxy terminated polyoxypropylene polyamides|
    FR2672053B1|1991-01-30|1993-04-23|Atochem|POLYETHER BLOCK AMIDES, THEIR SYNTHESIS PROCESS.|
    FR2709129B1|1993-08-20|1995-09-22|Atochem Elf Sa|Polymers comprising polyether sequences and polyamide sequences.|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19792932234|DE2932234C2|1979-08-09|1979-08-09|Process for the production of polyetheramides|
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