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    • 专利摘要:
    1458265 Preparing monomer/polymer syrup MITSUBISHI RAYON CO Ltd 7 Jan 1974 [18 Jan 1973] 00604/74 Heading C3P A methyl methacrylate monomer/polymer mixture is produced by partial polymerization followed by cooling effected at least partially by reducing the pressure continuously or intermittently to below the vapour pressure of the monomer-polymer mixture causing it to boil while controlling the bubbles formed by the boiling. This control is effected by cooling the walls of the vapour space of the reactor and by refluxing the evaporated monomer. Further cooling of the product can be effected by mixing with cooler monomer-polymer mixture and/or by circulating through a heat exchanger. An apparatus is shown having separate heating or cooling jackets for the polymerization mixture and vapour spaces.
    公开号:SU738512A3
    申请号:SU741993907
    申请日:1974-01-17
    公开日:1980-05-30
    发明作者:Като Тецудзи
    申请人:Мицубиси Рэйон Ко, Лтд (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING A MONOMERICINE-POLYMER MIXTURE
    one
    This invention relates to the field of producing a low temperature monomer-polymer mixture.
    The monomer-polymer blend (syrup) can be cast or further limited in order to obtain solids.
    A known method for the preparation of a methacrylate monomer-polymer syrup periodically, methyl methacrylate, together with one or more vinyl compounds, copolymerisation-C-methyl methacrylate, is loaded into a polymerization boiler, and the heating agent is fed into a shirt or coil 15 for heating, 15 Heater, and a heating coil 15 is heated for heating, and the heating agent is fed into the polymerization boiler, and the heating agent is fed into the jacket or coil 15 for heating, and the heating agent is fed into the polymerization boiler and heating agent 15 “The temperature is higher. At the same time, to initiate the polymerization reaction, a ONE polymerization catalyst selected from free radical initiates is added. 20 dies, such as azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide and lauryl peroxide. The polymerization stops until completion, using a chain breaker and / or cooling 25, and a syrup is obtained. As a drive for vinyl compounds copolymerised with methyl methacrylate, it is syruped. vinyl acetate. These vinyl compounds can be used 30
    i
    in an amount of 20% or less of the total weight of the vinyl compound and methyl methacrylate A,
    At the end of the polymerization, the MS of acyllate acrylic polymer syrup has a temperature of 50 to 150 ° C. Therefore, the syrup should be cooled to a lower temperature, preferably to room temperature, to prevent subsequent polymerization during storage and to provide preferred viscosity for supply to subsequent manufacturing processes, such as casting into plates or sheets 11.
    However, obtaining a syrup in a periodic manner is associated with two major inconveniences. One of them is that polymers stick in the form of solid deposits to the inner walls of the polymerization apparatus and its parts, for example, a shaft, a mixer, and therefore the polymerization boiler must often be disassembled for cleaning (polymerization waste)
    Another disadvantage is that the production cycle is long and the production efficiency is low. A typical batch syrup preparation process includes the steps of loading the monomers, raising -TeiMnepaTypu, adding initiating ps-limerization, maintaining the reaction mixture at the polymerization temperature and cooling the resulting syrup. At the cooling stage, it is not possible to achieve a high cooling rate, if it is carried out only with the help of an external cooling jacket, this is the main reason for the slowdown in the entire production process. Typically, to reduce the cooling time, a coil is immersed in the syrup, through which a cooling agent and an outer cooling jacket are passed, is used in the boiler. However, in the case of such a coil, rop usually stagnates in certain spaces of the boiler and inevitably solidified waste is generated here. Although with such a coil, the production cycle can be shortened, but the boiler must be disassembled during accumulation: some such waste and the frequency of operations of the pile increases. Another disadvantage of the periodic method of syrup production is related to viscosity. To obtain a syrup with a relatively low viscosity and conversion to polymer is maintained moderate or partial, polymerization at high temperature continues as far as possible and, stopping it, requires quick cooling. If the conversion increases the viscosity of the syrup it becomes more difficult to achieve rapid cooling of the outer jacket, Coy and internal serpentine. The purpose of this invention is to prevent deposition; polymer waste on the internal walls of the s: apparatus and process technology simplification This goal is achieved by carrying out polymerization up to T0 50% of its monomer conversion at oTHOLdeBKH volume of free space above the reaction mixture to a reaction volume of 0.5: 1 - 5: 1, - and after reaching the monomer conversion, the pressure in the system; the polymerization is kept below the vapor pressure of the monomer-polymer mixture and is cooled by one coolant to the polymerization system with a temperature of less than 4 ° C. A cooling cooling method or a circulation cooling method can be used to increase the cooling effect pressure reduction method. The term “cooling method” is understood to mean the method, by mixing which V is a sub syrup that is kept at temperature C, is mixed with Vj a syrup that maintains at t C and the temperature of the syrup mixture can be expressed as follows: tj, (t, | V-f-,) . {V ,, - + V.). According to this method, the temperature is reduced by adding a low-temperature syrup to the syrup. oh temperature. The term "method of circulation cooling" is understood to mean a method which allows the cooling to take place by means of forced circulation of iropa through an external heat exchanger using wear. This method includes cooling by passing an ox-giving agent through the outer grip and through the coil inside the boiler. Usually, by cooling with a reduction in the blood pressure, the syrup is cooled to a temperature below 80 ° C, it is advisable to close to room temperature. However, when circulating cooling and cooling by cooling are applied together with cooling by reducing pressure, it is preferable to perform cooling by reducing pressure at the beginning of the cooling stage, and then circulation cooling and / or cooling by mixing. For example, the syrup can be cooled from 30 to 50 ° C by reducing the pressure and then to room temperature by circulation cooling and / or mixing. EXAMPLE 1 In a polymerization boiler, syrup is obtained under the following conditions: the volume of the polymerization boiler is 140 liters; quantity of methyl methacrylate loaded 50 kg; the amount of polymerization initiator (azobisvaleronitrile) .250 ppm; the time during which the syrup is maintained at a boiling point of 20 minutes; the temperature at which the blender is added; the temperature of the cooling agent (water) supplied through the taps is 5 ° C; heating agent-steam 3 kg / cm. The syrup thus obtained, maintained at the boiling point, is then cooled by discharging gas through the pipe at a speed of 0.35 l / s. During the cooling of the building, a cooling agent with a temperature of 5 ° C is passed through the jacket. The conditions for cooling are as follows: the heat transfer area of the upper shirt is 0.3 the heat transfer area of the lower shirt is 0.7 m; gas discharge rate of 0.30 l / s; the temperature at which the cooling is over is 60 ° C. During cooling, a part of the bubbles was continuously cooled and disappeared upon contact with the walls of the polymerization boiler; the bubbles occupied a larger half of the space in the upper part of the boiler. The inner walls — incessantly — were liquefied with a liquefied monomer and the formation of solidified waste was not observed. Under the conditions of this example, the formation and growth of bubbles was controlled, and the syrup was cooled to 60 ° C without splashing on the inner walls of the polymerization boiler. The physical properties of the syrup obtained under the specified conditions are as follows: the polymer concentration in the syrup is 15%; polymer E characteristic viscosity E syrup 0.13; viscosity of syrup at 2 ° C 3200 SP. In the case of cooling the syrup to BS without applying the 0x7 method described above, by reducing the pressure, it took about one hour, while using this method it was reduced to 8 minutes. Example 2. This example illustrates an embodiment in which, after cooling by a decrease in pressure, mixing chilling and circulation chilling were applied. The syrup is cooled. The polymerization is carried out in a boiler according to Example 1. Under the conditions described in Example 1, 800 kg of syrup is obtained with a temperature of 100 ° C and a viscosity of 1200 cP (at 20 ° C) and cooled in a polymerization boiler to 71 ° C by the method of pressure reduction. The cooling conditions are the same as in example 1, except that the cooling water temperature is 7 ° C, 800 kg of the cooled syrup from the polymerization boiler is then transferred to an intermediate tank for mixing with 2000 kg of syrup temperature. As a result, the temperature of the mixture decreases to 31 ° C. The syrup is cooled before circulation through an external heat exchanger having a heat exchange surface of 9.1 m. The circulation rate through the pump is 400 kg / min and the cooling temperature of the water entering the heat exchanger. Time for the cooling process is as follows: min: Cooling by reducing pressure (100-71 ° C) Cooling by mixing (71 ° C 31 ° C) 10 Circulating cooling (31 -) eO Total81 minutes For the purpose of comparing syrup with the same physical properties, it is cooled in a polymerization boiler only outer jacket, not applying the method of cooling by pressure reduction. For cooling the syrup from 100 to it took the following amount of time, min: 100 71C50 71 8l ° C140 31 15C110 Determining the physical properties of the resulting syrups gave the following results: Method EXPERT Multi-stage lapping method okhtolko jacket jacket Syrup viscosity, 980 2100 Conversion POLY-measure syrup,% 16.1 16.2 Characteristic viscosity of the polymer in syrup When comparing both methods based on these results, it can be seen that the multi-stage cooling according to the invention has advantages against the conventional method of cooling external air azhdayuschey shirt. Under conditions similar to those used in Example 2, mixtures of monomer and methyl methacrylate polymer are prepared. The volume of the reactor in which the polymerization was carried out is 2000 liters. The amounts of monomer-polymer blends are indicated. In this: blitz 1. The results are shown below.
    800
    400 1500
    The preparation of the monomer polymer mixture was repeated 150 ra in the same solution, however; no noticeable waste deposition
    Similar to experience 1
    权利要求:
    Claims (1)
    [1]
    After five times the preparation of the MOnomer-polymer mixture, the amount of deposition of polymer waste on the upper part of the inner walls of the reactor and on the mixer reached such a value that further work on the reactor is impossible without prior purification. It was established that when the amount of monomer-polymer mixture was less than 330 kg, the mixture was sprayed stirrer on the inner walls of the reactor. In this case, the amount of deposits of polymer wastes was significant. When applying the ratio of the volume of free space to the volume of the monomerpolymer mixture exceeding about 5: 1, it is not possible to realize the advantages of the invention due to an increase in the deposits of polymer waste and also a decrease in productivity. In the case where the ratio of the volume of free space and the monomer-polymer mixture is less than about 0.5: 1, the amount of waste polymers increases. Thus, in accordance with the cooling method of reducing the pressure of the present invention, the formation of solidified waste is almost completely prevented by flushing the internal walls and internal devices of the boiler with a monomer supported by oxygenation of the boiler and devices. The bubbles formed and melted on the free surface of the syrup are not scattered on the walls and devices of the boiler and the formation and growth of bubbles is expediently controlled by the monomer flowing along the walls of the polymerization boiler. The cooling by pressure reduction of mycJeCeT is carried out in a continuous or {Periodic manner. The invention method of obtaining a monomer-polymer mixture by partial polymerization of methyl methacrylate or its mixture with vinyl compounds in the reactor and subsequent cooling of the monomer-polymer mixture, characterized in that in order to prevent the deposition of polymer waste on the inner walls of the apparatus and simplify the process technology, the polymerization is carried out up to 10-50% conversion of monomers with a ratio of the volume of free space above the reaction mixture to the volume of the reaction mixture, equal to 0.5: 1-5: 1, and after The monomer conversion pressure in the polymerization system is maintained below the vapor pressure of the monomer-polymer mixture, and at the same time, the polymerization system is cooled with a refrigerant with a temperature below 40 ° C. Sources of information taken into account in the examination 1. US patent No. 2122805, cl. 260-89.1, 1958 (prototype).
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    同族专利:
    公开号 | 公开日
    FR2214707B1|1978-03-31|
    GB1458265A|1976-12-15|
    BR7400386D0|1974-08-22|
    DE2402064A1|1974-08-08|
    DE2402064C2|1983-03-03|
    CA1021895A|1977-11-29|
    NL7400569A|1974-07-22|
    IT1003417B|1976-06-10|
    FR2214707A1|1974-08-19|
    JPS4999186A|1974-09-19|
    NL150807B|1976-09-15|
    JPS5339918B2|1978-10-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE634278C|1930-10-03|1936-08-22|Ig Farbenindustrie Ag|Process for the production of polymerisation products suitable as synthetic materials from styrene, indene, vinyl esters and similar polymerisable organic compounds|
    US3153022A|1958-10-03|1964-10-13|Du Pont|Monomer-polymer acrylic sirups|JPS58158716U|1982-04-19|1983-10-22|
    CA2167247A1|1995-01-24|1996-07-25|Chi-Wai Hui|Method for controlling reaction temperature|
    DE102005001768A1|2005-01-13|2006-07-20|Vinnolit Gmbh & Co.Kg Profit-Center Vintec|Process for the polymerization of vinyl-containing monomers|
    JP5804324B2|2010-03-17|2015-11-04|三菱レイヨン株式会社|Surface light source device, light guide used therefor, and manufacturing method thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP816373A|JPS5339918B2|1973-01-18|1973-01-18|
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