• 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:
    The continuous preparation of epoxy resins of low, moderate and high molecular weight is carried out from epichlorohydrin, 2,2-bis(4-hydroxyphenyl)propane, alkali metal hydroxide and water without further starting materials. The raw materials are mixed vigorously and continuously in a reactor at rates of from 15 to 50 ms<-1> in a very small space, where they are reacted in a maximum of 5 s at temperatures of from 60 to 180 DEG C. The reaction is optionally continued in a second reactor, in which case it is possible for only a proportion of the reaction participants to be reacted in the first reactor, while the remainder are added in the second reactor. The resultant resins and the effluent can be extracted in countercurrent with water or organic solvents in a pulsation unit.
    公开号:SU998470A1
    申请号:SU777770039
    申请日:1977-10-14
    公开日:1983-02-23
    发明作者:Фердинанд Албер；Волфганг Бем；Манфред Гайковзки；Кристиан Гюнтер；Херберт Хеккер；Вальтер Хернигклее；Лотар Кайзер；Хелмут Копп；Мартин Мюллер；Виеланд Шефер；Йюрген Шиллгалиес；Манфред Шолц；Гюнтер Зейдель；Эрна Ланге；Готтхолд Май
    申请人:Феб Леуна-Верке "Вальтер Ульбрихт" (Инопредприятие)；
    IPC主号:
    专利说明:

    (54) CONTINUOUS METHOD FOR OBTAINING EPOXY RESINS
    In order to improve the efficiency of batch processes, variants are described in which catalysts or dissolution agents are used. Such changes, however, only contribute to partial improvements and partially negative effects on the quality of the resin, or cause additional problems, such as the release of dissolution agents. Efficient improvement of batch processes is achieved by using high-speed agitators, as described in some patents (patent US376 618, DT-OS 2341303). On a technical scale, continuous methods for producing epoxy resins work much more efficiently than periodically. A method for the continuous production of low molecular weight epoxy resins is described, in which the resin is synthesized in several stages in a stirred cascade (US Pat. No. 2,840,541), a mixture of epichloro hydrin and 2,2-bis- (4-hydroxyphenyl propane reacts in two or three reaction zones with sodium liquor. If two zones are used, the reaction is supplied 40-75%, mainly 65%, the sodium liquor used in the first zone and the remainder in the second reaction zone. The capacity in the first zone is 1 mol dian per hour per 1 liter of reaction volume. The resultant and has a molecular weight of about 380-420, Also known by the use of dissolving agents, reducing the residence time in reactors (US Patent 2,848,435) .Aliphatic secondary alcohol is used as a dissolution agent. The reaction temperature is 70-80 ° C. The residence time is 2 hours, the productivity is 0.23 mol diana per hour per 1 liter of reaction volume, but the reaction time, however, is still too long by the known methods, so it is possible to achieve only minor yields in terms of volume and time. In the case of the use of cascades with an agitator, in addition, mixed products arise in each reaction channel, affecting negatively the quality of the resin. Stirred cascades are used to prevent these disadvantages.
    with a large number of reactors. 1 so, according to patent US 2 986 551 in a cascade with a stirrer work with six reactors. Acetone is used as a dissolving agent. The caustic liquor solution is gradually fed in amounts from 12.5 to 45%.
    The residence time is at 37.78-71, 3-15 minutes in each stage. The resulting resin has a molecular weight of 366 and a viscosity of 150 Pz at 25 ° C.
    According to patient US 3,069,434 also operate in a cascade with six reactors. B. Alcohol is used as a dissolving agent. The caustic liquor solution is fed to each stage. The temperature is 50-80 ° and a residence time of 10-20 minutes in each stage.
    Due to the large number of reactors and the associated gradual transformation of the reactants, the effect of displacement is reduced and very large production plants are required.
    Technically more advantageous are continuous processes for producing epoxy resins that do not require the use of reactors.
    All of the previously known continuous methods work either with auxiliary substances, such as dissolving agents or amines, and for these reasons have significant drawbacks, or have a long reaction time and realize only minor yields in terms of volume and time.
    Use of dissolution agents: Increases the cost of the process, makes it difficult to process the reaction mixture and usually requires expensive separation operations. In addition, increased costs are required for safety engineering. In catalytic processes, in addition to the cost of the catalysts (often using amines or quaternary ammonium bases), difficulties arise in isolating catalysts, so the resins are usually of poor quality.
    The relatively insignificant passage speeds contribute to the disproportionately large sizing of production plants or a multitude of reactors.
    The aim of the invention is to economically produce low, medium and high molecular weight epoxy resins of good quality and high molecular weight. The invention is based on the task of developing a continuous process for the preparation of epoxy resins, which allows large yields in volume and time and in which, apart from the starting products, epichlorohydrin, 2,2-bis- (4-hydroxyphenyl) propane,
    alkali metal hydroxide and water - no other starting materials are required.
    This problem is solved in that the starting materials — 2,2-bis- (4-hydroxyphenyl) -propane, epichlorohydrin and aqueous solutions of alkali metal hydroxide — are continuously fed into the reactor, here in the closest volume they intensively mix with each other at a rate of 15 -50 msec and react.
    The reaction temperature is 60-180 ° C, the residence time is a maximum of 5 seconds. The reaction may be terminated in a series reactor. The design and residence time correspond to the first reactor.
    This task is also solved by the fact that part of the reaction components reacts in the reactor, goes to the second reactor and here reacts with another part of the reaction components,.
    Due to the high energy concentration of movement in the cramped volume, the separation surfaces of the heterogeneous reaction mixtures are extremely increased. The reaction in the reactor proceeds with a high yield in volume and time very evenly, and as a result of the conversion of the energy of the movement into thermal energy and the heat of reaction of chemical transformation, the reaction system inside the reactor is maintained at the required temperature.
    Both a solution of 2,2-bis (4-hydroxyphenyl) -propane in an aqueous solution of an alkali metal hydroxide and epichlorohydrin, and a solution of 2,2-bis (4-hydroxyphenyl) -propane in epichlorohydrin, as well as an aqueous solution of alkali metald hydroxide, and the synthesis of the resin proceeds in the reactor.
    This can occur as follows:
    A) The starting materials, 2,2-bis (4-hydroxyphenyl) propane, epichlorohydrin and sodium liquor, in the reactor are mixed at a speed of 1550 M: preferably 20-25 m / s, continuously and react. If necessary, the product is then continuously fed to the second reactor, in which the reaction proceeds further.
    The reaction product is then processed in a known manner.
    c) Part of the starting materials — epichlorohydrin, 2,2-bis- (4-hydroxyphenyl) propane, and aqueous sodium liquor — continuously enter the reactor, here it reacts and is directed to the second reactor. To this, the second part of the starting materials is added in a continuous manner and reacts here. The finished reaction product is processed in a known manner. The reaction can be continued in the second reactor, which, if necessary, is heated, since only a small amount of heat is released during the sequential reaction. Since the reactive mixture during a continuous reaction very quickly reaches a relatively high viscosity, a diluent is required to maintain the flow of the substance in the ca. water or an aqueous solution of an alkali metal hydroxide is used. The method according to the invention surpasses all the known until now periodic. And continuous methods. It has all the advantages that continuous methods have in comparison with the periodic ones. In addition to starting materials 2, 2-bis- (hydroxyphenyl) -propane, epichlorohydrin and an aqueous solution of alkali metal hydroxide, it requires neither additional catalysts nor dissolution agents in the form of organic diluents. The reaction rate is much faster than with all known methods. Due to the use of the heat of reaction and the heat of friction, a very favorable energy balance is achieved. Example 1. Mixture A, consisting of 55% by weight of 2,2-bis- (4-hydroxy-phenyl) -propane and 45% by weight of epichlorohydrin, is heated to 8f) ° C and -. direct in a continuous manner into the reactor. At the same time, a mixture of B, consisting of 50 wt.% Hydroxide on ry and 50 wt.% Of water, is added to the reactor in a continuous manner, also heated to 80 C. The mixture is added to the reactor in a ratio of A and B equal to 2.58: one. The reaction mixture flows through the reactor and is processed at a shear rate of 25, the temperature being set at 95 ° C. The mixture coming from the reactor is collected in a vessel and then treated in the usual way. The epoxy resin obtained has the following properties: Epoxy equivalent198 Viscosity (20s) cPs45 200 Washed chlorine,% 0.11 Volatile constituents,% 0.23 This resin is suitable as a cast resin in electrical engineering, since it has good dielectric properties. properties. Example 2. A mixture consisting of 23.2 wt.% Wt.% 2,2-bis- (4-hydroxyphenyl) propane; 5.7% by weight of sodium hydroxide and 71.1% by weight of water are heated before being sent to the reactor in a continuous manner. At the same time, epichlorohydrin is metered in a continuous manner into the reactor, so that a weight ratio of 2.2bis- (4-hydroxyphenyl) propane and epichlorohydrin is achieved,. equal to 1.75: 1. The reaction temperature is that the product is processed in a shear reactor 20. The reaction product coming from the reaction is processed in a known manner. The epoxy resin is characterized by the following assay data. Epoxy equivalent 350 Viscosity at, cPs750 Washed chlorine,% 0.21 Volatile constituents,% 0.32 Example 3. A mixture consisting of 20% by weight of 2,2-bis- (4-hydroxyphenyl) - propane, 75.4% by weight of water and 4.6% by weight of sodium hydroxide are continuously fed to the reactor. At the same time, epichlorohydrin is sent in a continuous manner to the reactor so as to maintain a weight ratio of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin, equal to 1.88: 1. In the reactor, the mixture is processed at a shear rate of 20 ms. The reaction proceeds in the reactor at. The reaction product then enters the second reactor, in which the product is heated up to improve the reaction. After passing through the second reactor, the product is processed 1)) t in the usual way. The reaction product has the following properties: Epoxy equivalent495 Viscosity at 100 ° C, cPs2 100 Washed chlorine,% 0.15 Volatile constituents,% 0.23 Example 4. Solution, state of 51% by weight of water, 12.7% weight. % sodium hydroxide and 36.3 wt.% 2,2-bis (4-hydroxyphenyl) propane, is fed to the reactor. At the same time, epichlor is continuously fed into the reactor.
    权利要求:
    Claims (4)
    [1]
    Claim
    1. A continuous method for producing epoxy resins of low, medium and high molecular weight by the interaction of 2,2-bis- (4-hydroxyphenyl) propane, epichlorohydrin and alkali metal hydroxide in an aqueous medium, characterized in that the components are continuously mixed in the reactor at a speed from 15 to 50 ms'4 at 60-180 ^ 3 flow 'for a maximum of 5 s, while, if necessary, the process is completed in the second reactor of the same design and with the same residence time or part of the components react in the first reactor, the reaction product nap ulation second reactor where the second part is introduced starting materials.
    [2]
    2. The method of pop. 1, characterized in that a solution of 2,2-bis- (4-hydroxyphenyl) propane in an aqueous solution of alkali metal hydroxide and epichlorohydrin are mixed.
    [3]
    3. The method of pop. 1, characterized in that a solution of 2,2-bis- (4-hydroxyphenyl) propane in epichlorohydrin and an aqueous solution of alkali metal hydroxide are mixed.
    [4]
    4. The method according to PP. 1-3, characterized in that continuously adding water and an aqueous solution of alkali metal hydroxide as a diluent.
    Recognized as an invention based on the results of an examination carried out by the Office for Inventions and Patents of the German Democratic Republic.
    VNIIIPI Order 1068/43
    Circulation 492 Subscription
    Branch of PPP Patent, Uzhhorod, Project 4,
    类似技术:
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    同族专利:
    公开号 | 公开日
    BG30542A1|1981-07-15|
    CH636867A5|1983-06-30|
    DE2745150A1|1978-06-08|
    CS199099B1|1980-07-31|
    BG30681A2|1981-08-14|
    GB1551204A|1979-08-22|
    PL202600A1|1978-07-17|
    NL7713352A|1978-06-06|
    HU178813B|1982-06-28|
    RO77284A|1981-08-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EA012957B1|2003-11-20|2010-02-26|Солвей |Method for producing dichloropropanol, epichlorohydrin and epoxy resins|
    US4306054A|1979-11-05|1981-12-15|Veb Leuna-Werke "Walter Ulbricht" Leuna|Process for the production of epoxide resins|
    US4447598A|1983-04-07|1984-05-08|The Dow Chemical Company|Method of preparing epoxy resins having low hydrolyzable chloride contents|
    US5245057A|1990-07-20|1993-09-14|The Dow Chemical Company|Horizontal continuous reactor and processes|
    US5372790A|1991-01-18|1994-12-13|The Dow Chemical Company|Vertical continuous reactor|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DD19612476A|DD138017A3|1976-12-04|1976-12-04|METHOD FOR CONTINUOUS CLEANING OF EPOXY RESIN SOLUTIONS AND WASTEWASHERS|
    DD19612376A|DD137805A3|1976-12-04|1976-12-04|CONTINUOUS PREPARATION OF EPOXY RESINS|
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