• 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 making poly-p-phenyleneterephthalamide having an inherent viscosity of at least 2.5 comprises reacting p-phenylene diamine with terephthaloyl chloride in a solvent which contains N-methyl pyrrolidone and at least 5% by weight of calcium chloride based on the weight of N-methyl pyrrolidone.
    公开号:SU822756A3
    申请号:SU762324504
    申请日:1976-02-20
    公开日:1981-04-15
    发明作者:Воллбрахт Лео；Йоханнес Веерман Теунис
    申请人:Акцо Н.В. (Фирма)；
    IPC主号:
    专利说明:

    greatly simplify the process of regeneration of the solvent and improve the quality of the target product. Introduction to the reaction medium 525 weight. % calcium chloride allows to obtain a polyp-phenylene terephthalamide with a viscosity of 2.5. or higher. Other combinations of organic solvents and salts result in low-viscosity poly-p-phenylene terephthalamide. The process according to the invention can be carried out in various ways. For example, N-methylpyrrolidone can be mixed with the required amount of calcium chloride, then you can add p-feni Lendiamine and add terephthaloyl chloride with vigorous stirring. The resulting polyp-phenylene terephthalamide together with the other, constituent parts of the reaction system form a gel-like mass. This mass is thoroughly mixed with a coil, such as water, the polymer is filtered and cleaned by washing. In addition, the constituents of the reaction system can be added in turn in different orders, for example, first add p-phenylenediamine to K-methyl pyrrolidone, and then Calcium Chloride. Reagents can be added to the reaction mixture at the same time, for example, a powdered mixture of p-phenylenediamine and terephthaloyl dichloride is added in the desired ratio to the N-methylpyrrolidone-calcium chloride system. Such a technique is preferred. Regardless of the chosen method of addition, the reaction between the diamine and the chloride. The acid must always proceed in N-methylpyrrolidone a medium containing at least 5 wt. % calcium chloride. The substances selected for the reaction should contain a minimum amount of impurities. In particular, the presence of water in an amount of more than 0.05 wt. % based on the total volume of the reaction mixture may result in an unacceptably low viscosity value. Therefore, N-methylpyrrolidone. and calcium chloride should be practically free of water. A dry calcium chloride can be carried out by drying a substance in the form of a pad (fine powder) in vacuum at 200 ° C. Besides the fact that the use of powdered calcium chloride accelerates the drying process, it also has the advantage that it can be more easily and effectively dispersed into N-methylpyrrolide. The amount of calcium chloride used in the process is at least 5 wt. % based on N-methylpyrrolidone and it depends on the concentrations of the obtained poly-p-phenylene terephthalamide and on its reduced viscosity. The best results, namely the highest value for the given viscosity, are obtained when using a mixture of N-methylpyrrolidone and 5-25% by weight of calcium chloride. At the reaction temperature, calcium chloride is only limited in N-methylpyrrolidone, approximately b weight. % at. In used in the process, calcium chloride is therefore partly in a soluble state, and partly in suspension. High viscosity viscosity values are obtained when part of the calcium chloride is in the solid phase at the beginning of the reaction. When reagents are added, calcium chloride will partially or completely pass from the dispersed to the soluble state. From the point of view of this transition, it is desirable that the calcium chloride be in a finely divided form when added to N-methylpyrrolidone. If you stick with the amount of calcium chloride in the area of 5-25 weight. %, in the reaction system, part of the calcium chloride will always be present in solid form. The concentration of poly-p-phenylene terephthalamide with which it is produced may vary within certain limits. From an economic point of view, it is undesirable to use low concentrations, which result in low values of reduced viscosity. On the other hand, very high Concentrations do not lead to sufficiently high values of reduced viscosity. It is desirable that the amounts of the two reagents be chosen so that at the end of the polyp-phenylene terephthalamide reaction, the amount of 7-20 wt. % based on L-methylpyrro. lidone. Particularly favorable results are obtained with a polymer concentration of 8-12 weight. % From the point of view of obtaining high values of viscosity, it is desirable that the weight amount of calcium chloride used in the reaction be at least equal to the amount (weight) of the resulting poly-p-phenylene terephthalamide. p-Phenylenediamine and terephthaloyl chloride are used in equivalent amounts or a slight excess of one is possible compared to the other. In addition, special agents and other conventional additives may be used to control the growth response of the polymer chain. In addition to N-methylpyrrolidone, small amounts can be present in the reaction system; 1e, for example, up to 10% of another solvent, such as dimethylacetamide. However, the use of such additional solids does not give any particular advantages. Adding acids, binding substances to the reaction mixture during low-temperature polymerization, for example: calcium oxide, pyridine, N-methylmorpholine, triethylamine, N-m tylaniline, usually results in poly-p-phenylene terephthalamide with a lower reduced viscosity compared to viscosity obtained when such substances are not added. However, it was found that the addition of N-dimethylaniline leads to a growth of viscosity and moreover causes an acceleration of the reaction. N, N-Dimr; tilaniline can be used in the amount of 5-25 wt. % based on N-methylpyrrolidone, but it is advisable to use it in amounts at least equivalent to the amount of hydrochloric acid formed in the reaction. When carrying out the process according to the invention, it is necessary that the reaction mixture is thoroughly mixed, especially at the stage of preparation in which p-phenylenediamine and terephthaloyl chloride react with each other. Insufficient mixing leads to such a high viscosity that it is impossible to carry out the process. Stirring should be carried out both in the process of feeding the reagents and after that until those rtop until the final degree of polymerization of p-phenylene terephthalamide is achieved. Mixing can be carried out using a Waring BCendor type mixer at a speed of 10,000 rpm or more. Also, other mixers can be used to ensure a sufficient degree of mixing. The mixer used must, of course, correspond to the process volume and method. If the process according to the invention is carried out continuously, then mixing can also occur when the injection agents are sequentially or simultaneously injected into the turbulent flow of the reaction medium. According to the invention, the process is carried out at temperatures below 40 ° C .. —and after the reagents are in contact, a slight increase in temperature is observed, after which the subsequent increase in temperature occurs as a result of mechanical stirring. During polymerizations, the viscosity of the reaction mixture increases at a rate that depends on the initial reaction temperature. This initial temperature should be chosen such that the reagents can be mixed thoroughly before the mixture becomes too viscous. Preferably, the process is carried out at a reaction temperature of (-20) - (+ 40) s. This is achieved by cooling before, during and / or after the reaction. The polymerization reaction proceeds quickly and is completely completed within 15 minutes. Reagents should be added as quickly as possible, for example, during 10 seconds, followed by stirring until the viscosity reaches its final value. Stirring can be continued if required so that the reaction product, which is usually obtained in the form of a gel-like mass, can be formed into particles of such a ramer, which are suitable for coagulation. Next, poly-p-phenylene terephthalamide is isolated from the reaction mixture. This can be done, first, by thoroughly mixing the reaction mixture with water or aqueous alkali, for example, using a Warinq B endor mixer. From the resulting suspension. poly-p-phenyl terephthalamide is filtered off or separated by centrifugation, washed with water and dried. From the filtrate consisting of N-methylpyrrolidone, calcium chloride, water, and hydrochloric acid formed during the reaction, N-methylpyrrolidone and calcium chloride can be separated. In addition, for example, hydrochloric acid can be converted into calcium chloride with the help of calcium hydrate, oxides, and water can be distilled off. After separation, in whole or in part, the remaining mixture can be used again. The reduced viscosity of poly-p-phenylene terephthalamide is calculated by the formula and - refers. - the relation of time relates. the expiration of the polymer solution (0.5 g of poly-p-phenylene terephthalamide in 10.0 ml of 9b% 96% sulfuric acid) and pure solvent, measured in a capillary viscometer at 25 ° C. Poly-p-phenylene terephthalamide, obtained by the proposed method, is suitable for use as a similar substance in the production of openings, in particular, films, filaments of fibers having high strength (high values of the initial coefficient modules). The production of such substances can be carried out by conventional methods. Filaments and films can be obtained, for example, by drawing them from solutions / polymer in concentrated sulfuric acid. The yarns and fibers thus obtained are suitable for use as reinforcing agents for rubber, for example, in tires. In addition to the above-stated, all percentages in the examples by weight, amounts of calcium chloride and poly-p-phenylene terephthalamide are taken as ria N-methylpyrrolidone. PRI me R. 1. In a Waring BBendor mixer with a stirrer and a cooling bottom connected to a cryostat, 24 g of finely powdered and dried calcium chloride dispersed in 200 g of N-methylpyrrrlidone (12% by weight of calumium chloride) are introduced. Calcium chloride is partially in a solid state. With stirring, 7.3 g of p-phenylenediamine powder is added to this suspension. The resulting mixture is cooled to. Further, with constant mixing and cooling, 13.9 g of molten terephthaloyl dichloride are quickly added. Stirring is continued for another 30 minutes. The temperature rises to. A loose mass is formed. It contains 16 g of poly-p-phenylene terephthalamide (8 wt.%). Water is then added, and the mass is stirred vigorously until a suspension is formed. After filtration, washing and drying, poly-p-phenylene terephthalamide with a viscosity of 4.02 is obtained. EXAMPLE 2: The same procedure is used as described in Example 1. The reaction is carried out in a mixture of 200 ml. N-methylpyrrolidone and 36 g of calcium chloride (18 wt.%). 11.0 g (1.02 mol) of p-phenylenediamine and 20.7 g (1.02 mol) of terephthaloyl dichloride are used as reagents. 24 g of poly-P7-phenylene terephthalamide (12% by weight) with a viscosity of 4.05 are obtained. Example This example shows the effect of calcium chloride on the reduced viscosity of poly-p-phenylene terephthalamide obtained in the polymerization process. The same procedure is used as described in Example 1. The concentration of calcium chloride is changed, and the concentration of poly-p-phenylene terephthalamide at the end of the reaction is always the same and is 8 wt. % The results are shown in Table. one.
    Experience
    Calcium chloride content, wt. %
    about
    2
    four
    6
    eight
    ten
    12
    14
    sixteen
    20
    25
    Table 1
    one
    led
    0.30 0.55 1.40 3.05 3.15
    4.05
    4.05
    5.05
    4.25
    4.60
    3.80
    权利要求:
    Claims (1)
    [1]
    Claim
    A process for preparing poly-p-phenylene terephthalamide by reacting p-fenylendiamina with terephthaloyl chloride in a medium of an organic solvent N-methylpyrrolidone at (-20) (+40) ° C, 30 characterized in that, in order to simplify the process and povyieniya desired product quality, the process lead in the presence of calcium chloride, taken in an amount of 5-25% by weight of the reaction mixture.
    55 Sources of Information Taken into Examination 1. US Patent No. 3869429, cl. 260-78, published. 1971.
    VNIIIPI · Order 1908/85 Circulation 530 Subscription
    Branch of the PPP Patent, Uzhgorod, Project 4,
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NLAANVRAGE7502060,A|NL157327C|1975-02-21|1975-02-21|PROCESS FOR PREPARING POLY-P-PHENYLENE DEPHALAMIDE.|
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