• 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:
    A process for the preparation of white nylon 4,6 polyamide of high molecular weight from a tetramethylenediamine adipic acid prepolymer, formed under controlled conditions of temperature and water vapor pressure and wherein the plurality of cyclical end-groups in the prepolymer does not exceed 0.20 mg. equivalent per gram of prepolymer.
    公开号:SU1205774A3
    申请号:SU813372848
    申请日:1981-03-25
    公开日:1986-01-15
    发明作者:Яп Гейманс Рейноуд；Хендрик Йозеф Пит Боур Эдмонд
    申请人:Стамикарбон Б.В. (Фирма)；
    IPC主号:
    专利说明:

    t
    This invention relates to the synthesis of dashed molecules of ryn polymers that can be used to make fibers.
    The aim of the invention is to reduce the yellowing of the final product due to chemical and / or thermal degradation.
    Example 1: A solid product consisting of 1,4-diaminobutane and adipic acid is prepared by dissolving 1 part by weight of diamine in 8 parts by weight. methanol and enter this solution into the reactor, equipped with a stirrer and reflux condenser. Then, with stirring, solid adipic acid is injected medically until the equivalent point is reached. After cooling, the precipitated salt is filtered off, washed with cold methanol and dried. An excess of 1, 4-diaminobutane (2.1 mol.%) Is then added.
    1700 g of the obtained salt and 170 g of water are introduced into a 5-liter autoclave. After purging with a stream of nitrogen, the reaction mass is heated for 80 minutes before and this temperature is maintained for. 100 min During the process, the pressure is increased to 8 bar and maintained during the reaction. Then the pressure is released to 1 bar. And the reaction mass is cooled. A solid, pre-synthesized white polymer is extracted from the reactor, the relative viscosity si is 1.33 (1 g of poly-iepa per 100 g of 96% sulfuric acid, at 20 ° C), the content of cyclic terminal groups (py)
    0.032 mEq. on 1 g of polymer. I
    The pre-synthesized polymer is ground to a particle size of about 0.1-0.2 mm and introduced into a rotating reactor to carry out the reactions. After purging with nitrogen, a mixture free of oxygen containing 30% by volume of water vapor and 70% by volume is passed through a rotating reactor. % nitrogen heated to 260 s at a pressure of 1 bar. The pre-synthesized polymer is thus subjected to additional condensation for 6 hours at 260 C.
    The result is a white colored polytetra of methylenadipamide with a relative viscosity (
    057742
    and the content of cyclic terminal groups (g) is 0.005 mEq. for 1 year
    PRI mme R 2. As described in Example 1, a preliminarily synthesized polymer was prepared, containing diaminobutane (8 mol.%), By heating for 55 minutes at 75-155 ° C and then for 160 min at 55- 10 200 C. The maximum pressure is 19 bar.
    The pre-synthesized white polymer has, 23, corresponding to the th M (i3500
    (Mh is the number average molecular t ;; mass) (rug) 0.028.
    one
    As a result of the additional condensation of a pre-synthesized polymer (according to Example 1 for 6 hours at 260 seconds), a high molecular weight white polyamide can be obtained with 7TG. EO corresponding to M 34700.
    Example 3. A mixture of 1.3 weight.h. water and 100 weight.h. salts of 1,4-diaminobutane and adipic acid,. obtained in example 1 and containing an excess of diamine (3.4 mol.% 7, heated for 75 minutes at 75-. 175 C, and then for 100 minutes to 207 ° C. Pressure is limited by blowing to 10 bar. Pre-synthesized Polymer HMeeT e 1, 20 () and (rug) 0.122 As a result of additional condensation for 6 hours at 260 ° C (as in Example 1), the previously synthesized polymer is converted into white polyamide, 37, corresponding to M (27400.
    PRI me R 4. A mixture of 15 weight.h. water and 100 weight.h. salts from 1,4-diaminobutane and adipic acid obtained in Example 1 and containing an excess of diamine (8 mol%) are heated for 240 minutes at 20-210 C. The pressure is increased to 19 bar. As a result of additional condensation (within 6 hours) at 260 ° C, as a preliminary synthesized nolmer, it can be converted into a white polyamide with MH 24,800.
    EXAMPLE 5 A salt of 1, 4-diaminobutane and adipic acid is obtained by introducing a solution of dicarboxylic acid in methanol until an equivalent point is reached. The reaction mixture is cooled and salt.
    0
    five
    0
    five
    0
    five
    is removed by filtration, then it is washed with methanol and dried. 1.3 wt.% Of the diamine is added to the dried salt, based on the total weight of the salt. This salt is introduced into the autoclave. After purging with gas, the autoclave is heated. Within 220 minutes, the temperature is reached during heating at an average speed of 0.8 degrees / min (during the experiment, the heating rate is 0.15-2.3 degrees / min). The pressure is increased from 1 to 14.6 bar. Then the pressure is dropped to 1 bar (by blowing) and the reaction mass is cooled. Thus, get a white pre-synthesized polymer, Mh 3500.
    Example 6. Carried out the process according to example 5, get a salt with an excess amount of 1,4-diaminobutane 1.3 wt.%.
    The prepolymerization process is carried out by heating the salt in an autoclave to 233 ° C for 245 minutes with an average heating rate of 0.8 degrees / min. During the process, the pressure is increased to 18.7 bar. The prepolymerization process is terminated by depressurizing to 1 bar and cooling the reaction mass. Get white pre-synthesized polymer, H 4100.
    Example 7. A mixture of 1700 g of a salt from adipic acid and 1,4-diamino butane containing an excess amount of diaminobutane (2.4 mol.%) And 170 g of water is heated to 180 ° C for 60 minutes and then for 50 minutes from 180 to. In the temperature range 200-260 ° C, the pressure is limited (by blowing) to 13 bar and in the temperature range 260-295 ° C the pressure is gradually reduced, so that at 295 ° C it reaches a value of 1 bar. The melted pre-synthesized polymer is removed from the reactor, cooled and ground. The resulting white pre-synthesized polymer has 1.66 and (arg) 0.064 mEq./g. As a result of the additional condensation in the solid phase (for 4 hours at 260 ° C), the preliminary synthesized polymer is converted into polyamide 2.65.
    205774
    EXAMPLE 8 The process of Example 7 is carried out using the same starting composition, with the difference that the temperature is raised in
    5 for 60 minutes to 180 seconds, maintain this temperature for another 60 minutes at a pressure of 8 bar, after which the reaction mass is heated to 295 ° C for 40 minutes. Pre-synthesized polymer has a Tff of 1.66 and (rug) of 0.053 Ml-eq./g and can be converted into a polyamide with 1 2.75. PRI me R 9. The mixture according to example 15 RU 7 is heated for 75 minutes to 220 ° C, maintained at this temperature for 20 minutes with increasing pressure to 18.5 bar, then the reaction
    mass is heated to for
    20 30 min with a slow rise
    pressures starting at 260 ° C. The pre-synthesized polymer has 1.63 and (arg) 0.078 mg-eq./g. After condensation (for 4 h at 260 ° C) of the previously synthesized polymer, polyamide is obtained with 7he 2.65.
    Example 10. The process is carried out as described in example 9, with the difference that the reaction mass is maintained at 220 ° C for 120 minutes while increasing the pressure to 22.5 bar. The pre-synthesized polymer has it and (rug) 0.192 mg eq./g. As a result of the additional condensation of the pre-synthesized polymer, polyamide 1.81 is obtained. This result shows that it is undesirable to maintain the temperature above 200 ° C for too long, as this leads to a decrease (Rug) and to a decrease in the molecular weight of the final product.
     PRI me R II. The process is carried out as described in Example 9, but the temperature is raised to 250 ° C over 80 minutes, maintained for 250 seconds over 20 minutes, while
    50 increases the pressure to 27 bar and then increases the temperature to within 20 minutes. The pre-synthesized polyamide has 1.49 and (rug) 0.173 mEq./g. AT
    55 As a result of additional condensation, polyamide 1.90 is obtained.
    Example 12. The process is carried out as described in example 9,
    thirty
    but the molten pre-synthesized polymer is held at 295 ° C and a pressure of 1 bar (water vapor) for 60 minutes. The resulting pre-synthesized polymer has e i, 73 and (rug) 0.072 meq / g. As a result of additional condensation, a yellowed polyamide is formed (7, 2.38),
    Example 13: The process is carried out as described in Example 12, but using a mixture of 1000 g of salt and 300 g of water. A pre-synthesized polymer gwe (yf} 0.074, which can be converted (as a result of additional condensation for 4 hours at 260 s)) into a polyamide having 71 2.50 is obtained.
    PRI me R 14. A mixture of 1000 g of salt from butanediamine and adipic acid (an excess of diamine 2, 4 mol.%) And 700 g of water is heated to 60 minutes, maintained at 180 ° C for another 60 minutes at The maximum pressure is 6 bar, then the reaction tviaccy is heated to 295 ° C for 35 minutes at a maximum pressure of i 3 bar and the pressure is slowly lowered, starting at a temperature. The resulting synthesized polymer has 7 i and (rg) 0.068 equivalents / g. As a result of additional co-denction (for 4 h at 260 s), polyamide is obtained having
    P., g 2.47. . .
    Example 15. A process was carried out to prepare nylon 6.65 using as the starting material a mixture of 1000 g of salt from diaminobutane and adipic acid (2.4 mol% excess diamine) and 700 g of water. This mixture is heated to 215 C for 60 minutes and then the temperature is raised from 215 to 120 for a maximum of 120 minutes while maintaining a maximum pressure of 18 bar. Then the reaction mass is heated to 295 ° C for 15 minutes while slowly lowering the pressure. Thus, pre-synthesized white color is obtained, having 1; nd 7 gf 1.36 and (more) 0.263 mg-eq. / G. As a result of additional condensation (for 4 hours at), poly05 746 is obtained.
    amide, having Zt.e 1.71. This procedure cannot be used to make nylon 4.6.
    Example 16. Processes, as described in Example 15, are carried out with the difference that the temperature is raised from 215 to for 30 minutes. The pre-synthesized polymer has 7 e 1, 50 and
    fO (rug) 0.143. As a result of the additional condensation, the teE of the product is increased to 1.88.
    Example 7. A mixture of 100 weight.h. salts of diaminobutane and adipic
    15 acids (an excess of diamine 2.0 mol.%), 10 weight.h, caprolactam and 10 weight.h. the water is heated to 180 ° C for 60 minutes and maintained at 80 ° C for 180 minutes, while maintaining
    20 maximum pressure V bar. A pre-synthesized polymer is obtained as in Example 1. The pre-synthesized polymer has 1 ep 1.18 and (arg) 0.046 mg5 eq / g. As a result of the additional condensation (for 4 hours at 260 ° C), a nylon 6.46 copolymer having 3.25 is obtained.
    PRI me R 18. Carry out
    0 process, as in example 17, but using 10 weight.h. 1-aminoundecano-, howl acid. The pre-synthesized polymer has i-hc 1, 20 and (rug) 0.030 meq / g. As a result of additional condensation (for 4 h at 260 C), nylon i 1 5 46 is obtained, having 2, 51.
    In carrying out the process in the same way, but using 20 weight.h. 11-aminoundecanoic acid, the previously obtained synthesized polymer has a p of 1.18 and (Rug) 0.035 meq./g, and as a result of g of additional condensation (during 6 hours at 250 ° C), a copolyamide having 2.42 is obtained. .
    EXAMPLE 19 Pre-polymers are prepared using a salt of I, 4-diaminobutane and adipic acid with excess of diaminobutane 1.1 mol.% And varying the amount of water. The mixture is heated for 2 hours each time to the reaction temperature, this temperature is maintained for 5 minutes, after which the reaction mass is discharged from reactor II and cooled with pressure relief.
    The relative viscosity and the cyclic end group content of each prepolymer are determined. The prepolymers are then subjected to additional condensation for 4 h at 260 ° C as in Example 1.
    The table shows the water content in the initial mixture, the maximum temperature and pressure, the physical properties of the prepolymer and the final polyamide.
    Determination of pyrrolidinose terminal groups in nylon 4.6.
    A glass tube containing 0.25 g of dry polyamide and 0.5 ml of 6 N hydrochloric acid is rinsed with nitrogen, sealed, and heated to 130 ° C in an oil bath. This temperature is maintained until the polyamide is diluted, and for the next 4 hours. The tube is then cooled, which is accompanied by the formation of crystals.
     The pressure is maintained up to this value with water vapor.
    Compiled by L.Platonov Editor I.Rybchenko Tehred I.Astalosh Corrector I.Erdeyi
    Order 8550/62 Circulation 471 Subscription
    VNII1Sh State Committee of the USSR
    on inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Branch PPP Patent, Uzhgorod, st. Project, 4
    12057748
    and open up. A sample is obtained for gas chromatographic anapine by dissolving 0.20 ml of the supernatant liquid in 0.70 ml of 2 N alcohol sodium hydroxide. The analysis is performed on placing a 1 ml sample in a pre-prepared Chromosorb (RTM) 130 1.5 x x1 / 4 column, which is heated for 1 minute. to 150 ° C and then to 220 ° C at a heating rate of 13 degrees / min.
    The determination is carried out in a flame ionizer. The pyrrolide peak 15 is determined after 4.5 minutes, and
    1,4-diaminobutane peak - after 8 min. The content of diaminobutane in nylon 4.6 is 0.005 ml / g. The pyrrolidone content is calculated based on the ratio between the diaminobutane peak area and the pyrrolidone peak area using the formula (RU) 5000 (peak ratio, mmol pyrrolidone / g of polymer).
    权利要求:
    Claims (3)
    [1]
    1. A METHOD FOR PRODUCING PETETETETHYLENE DIPAMIDE by heating a salt of 1,4-diaminobutane and adipic acid in a nitrogen atmosphere in the presence of water with the formation of a prepolymer and subsequent additional polycondensation at 200-275 ° С, characterized in that, in order to reduce the yellowing of the final product due to chemical and / or thermal degradation, heating the salt of 1,4-diaminobutane and adipic acid to form the prepolymer is carried out up to 150290 ° C at a heating rate of 0.3-
    3.3 dg / min with a total reaction time of 1.5-4 h the formation of the prepolymer, the 'reaction time at 150-220 ° C is from 25 minutes to 2.73 hours while heating at 220-290 C e - to 2h and the partial pressure of water vapor is 5-27 bar, and the prepolymer formation reaction is interrupted before the number of cyclic groups reaches 0.2 mEq. per 1 g of prepolymer.
    [2]
    2. The method of pop. 1, characterized in that the heating of the salt of 1,4-diaminobutane and adipic acid is carried out at 180 220 ° C.
    [3]
    3. The method according to PP. 1 and 2, about aphids. - characterized in that in the reaction mixture additionally enter water in an amount of 9-10% by weight of 1,4 diaminobutane, adipic acid and water.
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    同族专利:
    公开号 | 公开日
    EP0039524B1|1984-06-27|
    US4408036A|1983-10-04|
    BR8101824A|1981-09-29|
    ES8202040A1|1982-01-01|
    IN154656B|1984-12-01|
    EP0039524A1|1981-11-11|
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    NL8001763A|1981-10-16|
    EP0039524B2|1989-04-26|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NL8001763A|NL8001763A|1980-03-26|1980-03-26|PREPARATION OF POLYTETRAMETHYLENE ADIPAMIDE.|
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