• 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 is disclosed for the discontinuous production of a polyamide having the generic formula: <IMAGE> and an inherent viscosity of at least 3, wherein 50 to 100% of the radicals R are p-phenylene radicals and 0 to 50% are n-butylene radicals. Terephthaloyl chloride, and optionally adipoyl chloride, are reacted in stoichiometric amounts with a solution of paraphenylenediamine and/or of 4,4'-diaminoadipanilide in a mixture of N-methylpyrrolidone-2 and calcium chloride which is homogeneous and substantially anhydrous, with a molar ratio of CaCl2/ unit: <IMAGE> of at least 0.7, and under conditions such that the final composition contains 5 to 16% by weight of polymer, relative to the N-methylpyrrolidone-2. The polymer obtained can be converted into films, fibers and high-performance yarns for reinforcing composite materials or articles made of rubber.
    公开号:SU929011A3
    申请号:SU782607003
    申请日:1978-04-26
    公开日:1982-05-15
    发明作者:Рошина Венсан；Сакко Жан
    申请人:Рон-Пуленк Текстиль (Фирма)；
    IPC主号:
    专利说明:

    () METHOD OF OBTAINING POLYAMIDE
    I
    The invention relates to the preparation of polyamides, in particular polyparaphenylene terephthalamide and its copolymers, with a high characteristic viscosity.
    A method is known for producing aromatic polyamides of the type poly-P-fe nylenterephthalamide tl} with a characteristic viscosity greater than 1, which can be liquid, in sulfuric acid and hydrofluoric acid, various amides and ureas: dimethylacetamide (DMAD), N-methylpyrrolidone-2 (NMP), hexamethylphosphorotriamide (HMPTA) and tetramethyl urea jj not (TMM). Salts such as lithium and calcium chlorides can be added to amides and ureas. Polyparaphenylene terephthalamide (PPD-T) is obtained in a HMPA / NMP mixture in a weight ratio of 1/2. However, HMPA is a carcinogenic product. It is also possible to obtain other aromatic polyamides in the solvent of the spinning compositions, for example poly-25.
    Rabenzamide, the production of which in TMM is completed in the presence of lithium chloride formed by neutralization with lithium carbonate of the formed HC1. However, low viscosity polymers are obtained. This is also the case for poly (p-chlorofeiyl terephthalamide) in a mixture of DMAA with 1% lithium chloride, but this is a polymer that is much more soluble than PPL-T.
    A known method for the production of PPL-T with a characteristic viscosity of at least 2.5 (measured in solution at a PPD-T concentration of 0.5 May. In 100 ml of 96% sulfuric acid) by reacting p-phenylenediamine with terephthalic acid chloride taken in stoichiometric amounts in mixtures of NMP and calcium chloride in a ratio of at least 5% relative to NMP, but preferably higher and reaching the limit of solubility to remain in suspension, and even with a total amount of at least a measure equal in weight to the resulting PPD-T if you want to get high values of characteristic viscosity T2. Such a process involving the use of large quantities of calcium chloride is costly and difficult to implement. In addition, calcium chloride is hygroscopic, it can cause significant difficulties during dehydration, handling, recovery and processing of streams. The aim of the invention is to intensify the process and reduce the cost of the product. This goal is achieved in that according to the method of producing polyamides by reacting terephthalic acid chloride or its mixture with chlorine anadride of adipic acid and p-fe. nylene diamine or its mixture with k, k-di. aminoadipanilide, taken stoichiometrically in the presence of N-methylpyrrolidone in the presence of calcium chloride, the latter is introduced in an amount that provides the ratio of the number of moles of calcium chloride to the degree of polycondensation equal to 0.72, 9. The diamine solution in the NMP + CaClp mixture is homogeneous and essentially anhydrous. The relative amounts of reagents and solvents are chosen so that at the end of the reaction the polymer content in the resulting composition is between 5 and 16 weight. counting on M-methylpyrrolidone-2. The content of calcium chloride is preferably 2-8 weight. in relation to the NWO. To obtain a polyparaphenylene terephthalamide / adipamide copolymer, it is possible to react terephthalic acid chlorides and adipic acid chlorides in a mixture or separately with paraphenylene diamine solution, or react terephthaloyl chloride with a solution, diamine adipanilide, alone or in a mixture with paraphenylene diamine, I will not apply. solution of a mixture of diamines. The addition of chloride or chlorides can be done in one or several steps in the intervals from a few seconds to several days of storage of the intermediate mixture of diamine I and the prepolymer thus obtained. In the following text, dichloride means both terephthaloyl chloride and its mixture with adipoyl chloride, and the diamine as para phenylenediamine as well as k, α-diamine adipanilide, or their mixture with each other or in some cases with the prepolymer formed. For the implementation of the method, it is important to observe the stoichiometry between the dichloride and the diamine in order to obtain a high viscosity. Thus, it is necessary to study the preliminary reaction using simple experiments in order to adjust the ratio between dichloride and diamine well, depending on their respective purity and on the moisture content of the solvent. The reaction between the dichloride and the diamine is very fast, ranging from a few seconds to a few minutes depending on the temperature, very effective stirring of the reaction mixture should be carried out. A solution of a diamine in a mixture of NMP + CaClp should be very homogeneous, i.e., in particular, it should not contain at the time of use of calcium chloride itself or complex calcium chloride in suspension, which increases its cost. For this, the weight concentration of calcium chloride in the NMP should not exceed about 6-8, the solubility limit varies depending on the water content and on the temperature of the diamine solution, the nature and amount of the diamine, the dissolution process (in particular, time and temperature) as well as no calcium chloride (powder, flakes or crystals). A solution of diamine in a mixture of NMP + CaClO should be anhydrous, i.e. its water content should not exceed 1500 ppm, but it is preferable that it does not exceed 1000, and even more preferably 500 and even 200 ppm by weight. The temperature of the diamine solution should be lower or equal, and preferably O - to get high viscosities, although it is also possible in some cases to use slightly higher temperatures than 30 ° C, but nevertheless temperatures lower than 0 ° C, while the diamine solution does not crystallize. . Terephthaloyl chloride is preferably introduced in the form of a powder so that the reaction mixture does not overheat, although its melt can also be used. Adipoyl chloride, which is liquid at ambient temperature and before, is usually introduced into the reaction medium in this state. The viscosity of the polymers obtained by the proposed method is much higher when working very close to the actual stoichiometry, i.e. the purity of the reagents and solvent is taken into account, and it is determined by preliminary experiments at several molar ratios, both lower and higher than 1. In addition, the temperature of the diamine solution should be the lower, the higher the polymer concentration in the final composition. However, it should be lower, the lower the calcium chloride concentration. It is preferable to use a diamine solution at a temperature below 20 ° C so that the concentration of the polymer is above 10. It is preferable to use a temperature lower when the content of calcium chloride with respect to the NMP is below i wt.%. The method makes it possible to obtain highly regular PPD-T or its copolymers with adipic acid with a characteristic viscosity (measured as described above) of at least p; avna 3, usually above k and easily reaching 5 or even 6. These results were obtained with calcium chloride concentrations that do not exceed its limiting solubility in the NMP – diamine solution, and often below 5 wt.% with respect to the UTI, and by a known method, higher values of PPD-T characteristic viscosity are obtained, when a lot of calcium chloride is in the solid phase at the beginning of the reaction and, in particular, when the weight amount of calcium chloride is at least equal to the amount of polymer, which corresponds to the molar ratio of C mole CaCli / fragment –NH- {O) b NR-ClO-I - 0-higher 2. This method, as compared to the known (HMFTA), does not pose any toxicological hazard and there is no need for special precautions, which lead to the appreciation and complication of the process technology. In addition, NMP is more stable than HMPT with respect to hydrolysis and thermolysis reactions, its losses are greatly reduced during recovery. In addition, in comparison with the known method, low concentrations of CaCl are used, which greatly facilitates the operations of dehydration, manipulation, recovery and treatment of streams. The polyamides obtained in accordance with the invention are suitable for use in the manufacture of products such as films, filaments and high-quality fibers, for example, by dissolving the precipitated polymer in a sulfuric acid solvent and drawing the film or fibers in a known manner. The products thus obtained can be used, for example, as a filler of composite structures or of rubber products such as tires, belts, tapes, and the like. In the examples, intrinsic viscosity is calculated from the following expression: RELEASED in which C is the concentration by weight per volume, expressed in grams per LLP ml; relative viscosity is measured for a solution at 25 ° C in sulfuric acid and at a polymer concentration of 0.5 g per 100 ml of solvent. The water content of solvents and solutions is measured by coulometry. chesky way. Examples 1-25. To the reactor; with a capacity of 45 l load NMP with a water content of 200 parts per million and calcium chloride, dried at 140 ° C at atmospheric pressure and containing another 0.2 weight. water in various proportions. The mixture is heated to. Cool and add paraphenylenediamine at 60 ° C and continue cooling to selected temperatures. Then, with vigorous stirring, terephthaloyl chloride powder is added in exactly the stoichiometric amount relative to the amount of p-phenylenediamine, taking into account the purity of the reagents and the solvent. Continue stirring for 1 hour. The amounts of the starting materials correspond to the preparation of 6 mol of polymer. . The working conditions and the results are shown in Table 1. Example 26. In the reactor, as in the previous examples, k, 8 mol of terephthaloyl chloride are introduced as a powder into a solution of a mol of para-phenlendiamine and 1.2 mol of diamine adipanilide in a mixture of NMP + SaSTg at 5 ° C. CaClrj was 6.76 wt.% With respect to the NMP and that the molar ratio of CaCl1 / middle fragment of the copolymer was 1.50. A composition is obtained containing the copolymer of E with characteristic viscosity. Examples 27 and 28. In the same reactor as in the previous examples, 1052.85 T of terephthaloyl chloride were introduced as a powder into a solution of "67 2 g of pa-phenylenediamine and 27.2 g of k, k -d mini-unipanilide 8 NMP + mixture CaCTQ p 30 ° C, containing 235 ppm of water. Operating conditions and results obtained, respectively, for example 27 and 28 are given below. Copolymer / NML, 5.7 5.5,% 6, 2.59 -CaCll. 2.39 1.0 middle nozzle fragment. Characteristic viscosity 6.10 5.37 Example 29. In a 2 liter reactor, 93.25 g of terephthaloyl chloride are introduced as a powder into a solution, 3 g of para-phenylenediamine and 2.23, V-diamino adipanilide in a mixture of NMP + CaCl (with containing 235 ppm of water, the working conditions and the result obtained are as follows: Copolymer / NIP,% 15.7 V 1, 5.5 CM 0.75. Intrinsic viscosity, 11 Example 30. In a 5 L reactor ready t solution containing 25 g of para-phenylenediamine in a mixture of NMP + CaCl (2 from 150 ppm of water, which is cooled to. Add first 526.2 g of terephthaloyl chloride, then after 3 min. 15 , 5 g finally, via adipoyl chloride, and 3 min, another 526.2 g of aloyl chloride reflux. The operating conditions and the result obtained are as follows: Copolymer / NMP,% CaClQ / NMP,% Characteristic viscosity, 5.2 Examples. Work according to the method of example 30, but adipoyl chloride was added first, and then all of terephthaloyl chloride at one time after 3 minutes in examples 31-33, and after 12 minutes in example, 3. The operating conditions and the results are shown in Table 2. Example 38. In a 2 liter reactor, a solution is prepared containing 57.1 g of para-phenylenediamine in a mixture of NMP + CaClrj with a water content of 35 hours; per million, which is cooled to. First, 13.69 g of adioyl chloride are added, then after 1 h 93.25 g of terephthaloyl chloride. The operating conditions and the result are as follows: Copolymer / NMP, 15.3 CaClO / NMP,% Characteristic viscosity3.6 Examples 39 and iO. They work according to the method of Example 30, but with different amounts and methods of introducing both chlorides (cMiol.3)
    table 2
    权利要求:
    Claims (2)
    [1]
    Invention Formula
    Method for producing polyamides by reaction of terephthalic acid chloride or its mixture with acid chloride
    adipic acid and p-phenylenediamine or its mixture with 4, diamine-adipanilide, taken in a stoichiometric ratio in the medium of N-methylpyrrolidone in the presence of calcium chloride) l 929011l
    chi, distinguished so as Sources of information, MTS- with the aim of intensifying the process-taken into account in examinations; and reducing the cost of the product, 1. French Patent If 2010753 calcium chloride is introduced in the amount of, cl. From 08 g, pub. 19b9. its providing the ratio of number 5
    [2]
    2. French patent If 23015ч8, moles of calcium chloride to degree C 08 G 69/02, published 1976 (propane condensation, equal to 0.7-2.9. Type).
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    同族专利:
    公开号 | 公开日
    IT1094734B|1985-08-02|
    AT379157B|1985-11-25|
    DK181078A|1978-10-28|
    JPS5415996A|1979-02-06|
    SE7804808L|1978-10-28|
    US4297478A|1981-10-27|
    IE46740B1|1983-09-07|
    SE443984B|1986-03-17|
    DE2818669A1|1978-11-02|
    ATA304278A|1985-04-15|
    FR2388844B1|1980-11-28|
    NL7804478A|1978-10-31|
    LU79532A1|1978-11-28|
    IE780825L|1978-10-27|
    BE866408A|1978-10-26|
    ES469214A1|1978-11-16|
    IT7822760D0|1978-04-27|
    GB1602916A|1981-11-18|
    CA1096543A|1981-02-24|
    BR7802624A|1978-11-28|
    FR2388844A1|1978-11-24|
    CH630654A5|1982-06-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3671542A|1966-06-13|1972-06-20|Du Pont|Optically anisotropic aromatic polyamide dopes|
    JPS5344957B2|1973-12-28|1978-12-02|
    DE2556883C2|1974-12-27|1981-11-26|Teijin Ltd., Osaka|Aromatic copolyamides and their use for the production of fibers, threads, films and foils|
    NL157327C|1975-02-21|1984-05-16|Akzo Nv|PROCESS FOR PREPARING POLY-P-PHENYLENE DEPHALAMIDE.|
    JPS53294A|1976-06-23|1978-01-05|Teijin Ltd|Preparation of aromatic polyamide with high degree of polymerization|US4309528A|1980-01-16|1982-01-05|Standard Oil Company |Injection moldable amide-imide copolymers|
    JPS60201401A|1984-03-26|1985-10-11|Yokogawa Hokushin Electric Corp|Process controlling method|
    KR860001141B1|1984-06-29|1986-08-16|한국과학기술원|Manufacturing process of high polymer a mixture textile|
    US5202184A|1989-06-05|1993-04-13|E. I. Du Pont De Nemours And Company|Method and apparatus for producing para-aramid pulp and pulp produced thereby|
    DE4010941A1|1990-04-05|1991-10-10|Hoechst Ag|METHOD FOR PRODUCING AROMATIC POPYAMIDES WITH HIGH HYDROLYSIS RESISTANCE|
    KR970003083B1|1992-12-04|1997-03-14|주식회사 코오롱|Aromatic polyamide and method thereof|
    US5432254A|1993-04-26|1995-07-11|Zimmer Aktiengesellschaft|Discontinuous catalytic process for the production of polyamide-6,6|
    US5306804A|1993-04-26|1994-04-26|Zimmer Aktiengesellschaft|Discontinuous process for the production of a polyamide-6,6|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7713620A|FR2388844B1|1977-04-27|1977-04-27|
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