• 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:
    In a process for polymerizing ethylene in a two-zone autoclave reactor comprising a top reaction zone and a bottom reaction zone which process comprises polymerizing ethylene in said top reaction zone at 130 DEG to 200 DEG C and at a reaction pressure of 1,000 to 1,800 kg/cm2 using an initiator, sending the resulting reaction mixture from the top reaction zone to the bottom reaction zone, and further promoting the polymerization at 220 DEG to 280 DEG C using an initiator which is same as or different from the initiator in the top reaction zone, the improvement which comprises feeding 75% or more of the ethylene to the top reaction zone of the two-zone reactor, said two-zone reactor being constructed so that the volume ratio of top reaction zone to bottom reaction zone is 1.5 to 6 and being provided with two or more feed inlets for each of the ethylene and the initiator in the top reaction zone in the direction extending through the two reaction zones.
    公开号:SU1075978A3
    申请号:SU772498149
    申请日:1977-06-27
    公开日:1984-02-23
    发明作者:Накаи Сецуо；Кита Синичиро；Хики Фумихико；Симизу Масаюки
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

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    The invention relates to the plasticity of plastics, in particular to a method for producing polyethylene by the high pressure method.
    A known method of producing polyethylene by polymerizing ethylene by the method of high pressure in an autoclaved reactor, divided into zones. The turbidity of the polymerization product is 4.3-6.0% tl).
    The closest to the present invention is a method for producing polyethylene by polymerizing ethylene in the presence of a radical initiator at a pressure of 1000–1800 kg / cm in a multizone autoclave reactor, the reactor being divided into three zones with the following distribution of modes over zones: 175-210 3-200-280 with G2.
    However, the known process is complicated in technological design, the turbidity of the final product is not low enough.
    The aim of the invention is to simplify the process technology and improve the optical properties and processing ability of the final product.
     This goal is achieved by the fact that according to the method of producing polyethylene by polymerizing ethylene in the presence of a radical initiator at a pressure of 1000–1800 kg / cm in a multizone autoclave reactor, the polymerization is carried out sequentially in the first zone at 130–200 ° C and in the second zone at 220–280 seconds. The ratio of the first zone to the second is from 1.5 to 6.0, with 75-100 wt.% of ethylene being fed into the first zone.
    The method involves feeding ethylene and the initiator separately into at least two holes for each one located in the first zone.
    When carrying out the proposed method, an autoclave reactor is used, having a generally cylindrical shape or almost a cylindrical shape, the ratio of the length and diameter of the reactor a is from 2 to 20 (preferably from 5 to 15). Ethylene is polymerized in the upper (first) reaction zone and the lower (second) reaction zone at different temperatures using an initiator. This method can be carried out in a single autoclave reactor, which has two reaction zones, separated by a partition (separation plate) or other means. In addition, the proposed method can be carried out by connecting two automated reactors to conduct separate reactions in two reactors. For this, a pressure reducing valve can be installed on the line connecting the upper reactor to the lower reactor.
    When the volume ratio is less than 1.5, the average residence time in the upper reaction zone increases slightly, so that there is no significant increase in the efficiency of the initiator in the zone.
    In ethylene polymerization, polymerization heat (about 800 cal / d is generated and used to create a temperature difference between the reaction mixture leaving the reactor and cold ethylene leaving the reactor.
    The polymerization of ethylene takes place in accordance with an autothermal reaction, where the heat generated
    during polymerization, it is equal to the amount of heat required to raise the temperature of cold ethylene to the temperature of the reaction.
    Accordingly, when ethylene is fed at a certain rate, a too large volume ratio of the upper reaction zone and the lower reaction zone is unnecessary, since 5 the average residence time in the lower reaction zone becomes too short to generate enough polymerization heat to raise the temperature. of ethylene going to the nkzhuyu reaction zone (more precisely, the reaction mixture at a temperature of - 130 €, is obtained in the upper reaction zone to the unbroken reaction temperature in the lower reaction zone Accordingly, the required reaction temperature cannot be reached in the lower reaction zone.
    When the reatstor has a limited volume, then the volume ratio of the upper reaction zone and the lower reaction zone also becomes limited.
    The upper limit of the volume ratio cannot be determined because it depends mainly on the temperature of the lower reaction zone, the type of initiator, the volume of the reactor and the feed rate of ethylene. But, taking into account the feed rate of ethylene and the volume of the autoclave reactor, which are currently being produced in the production of polyethylene, the upper limit is 6. This also applies when two reactors are connected. The position of the inlets, through which the initiator and ethylene are fed into the upper reaction zone, may be different. To obtain polyzylene having high optical and technological properties for chemical-. The treatment, the position of the inlet orifices must be such that the distribution of the reaction temperature in the upper reaction zone is as even as possible.
    The reaction temperature is regulated, for example, by feeding the initiator by an automatic system so that the necessary positions in the autoclave reactor have the desired temperature.
    When the upper reaction zone has one inlet for the initiator and ethylene separately or has one inlet for the initiator and two inlets for ethylene, the resulting polyethylene is N7S. &Amp; in its optical and other qualities than the polyethylene of the invention, even if the positions of these holes are defined so that the distribution of the reaction temperature in the zone is equal to that.
    75% or more of ethylene is fed to the upper reaction zone, and the rest to the lower. When the amount supplied to the lower reaction zone exceeds 25%, the quality of polyethylene decreases.
    In Figures 1-3, a diagram is given of the preferred jN & Jx forms of the reactor used in the invention (in Figure 3, two autoclaves Indicators
    FIG. j 2 FIG. 4 I FIG. 5 I FIG. 6
    Volume ratio upper reaction zone
    lower reaction zone
    Ethyl Feed Rate
    kg / h;
    through line 7
    through line 8
    Average residence time, from upper reaction zone
    downstream reaction zone Chain transfer agent Concentration, mol%
    Reaction pressure kg / cm
    Reaction temperature: upper reaction zone
    upper reaction zone lower reaction zone
    Radical initiator, g / h:
    upper reaction zone through lines 9,10.
    reactor connections are connected through a system of pipes1; in FIG. 4-6 are diagrams of reactors for comparison (these are positions where reaction temperatures are measured.
    Reactor 1 (in Figs. 4.5-6 is divided into upper 3 and lower 4 reaction zones by a partition 5. Reac, torus has a mesh driven by a motor, and the agitator shaft b has blades and a partition.
    This syngon burns to the reaction pressure and is fed to the upper reaction zone via lines 7 and 8. The initiator is fed to the upper reaction zone via lines 9 and 10, thereby maintaining the required temperatures at the required positions.
     The initiator is fed to the lower zone of the reaction. Line 11, thereby, they confirm the temperature in the zone in the right places. The positions where the reaction temperature is regulated and these temperatures 1% 1 are shown in table 6.
    Schematic drawing of the reactor
    44 44
    44 44
    44
    44
    36/34
    59/14
    9/14 36/34 tan §tan
    Ethan ethan
    0.8 2.8 4.2 0.7
    1200
    1200
    1200
    200
    170 170
    170
    170 170 170 260 260
    2 € 0 260
    3,5,5-trimethylhex7 sanoyl peroxide 20
    Table continuation
    Table continuation
    Radical initiator, upper reaction zone through lines 9,10 and lower reaction zone through line 11 Polyethylene production rate, kg / h Density, g / s n Melting rate, g / 10 min Optical properties; pstsutnenie,%
    Polyethylene and unreacted ethylene are introduced into a conventional separator from the lower zone of the reactor through a reducation valve placed at the bottom. The polyethylene is separated and unreacted ethylene is compressed and. recycle to the reactor.
    All the physical properties of the poly ethylenomers obtained in this way were measured as follows: density measured {Iot according to A5TM D-1501, melting index according to A5TM D-1238, but-. Mutnenke according to ASTM D-100E, mass j. according to ASTM D-223 and D-2103.
    The smaller the degree of turbidity and the greater the mass, the higher the optical properties of the film.
    The quality required for fine: films show a minimum thickness of 50 P thioxide octanoyl Tert-butyl 14 peroxiben: zoate 2.0 1.8 11.3 15.5 0.926 0.92
    Noah film (/ U, which can be achieved when polyethylene is turned into a film with. The smaller the film thickness, the higher the quality.
    The results of examples 1-5 and comparative examples 1-5 are shown in the table. Comparative examples 1 - and 3 are a modification of the example. Comparative example 2 is a combination of example 2. Comparative example 4 is a modification of example 4. Comparative example 5 is an npiotep, illustrating the fact that the optical properties of polyethylene become worse with reactivity pressure 1800 kg / cm
    Thus, the proposed method allows to obtain a product with improved optical properties. 3,5,6-Trimethylhexanrylperrxide 17 3
    Phie.1
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    Ф14г.В
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING
    POLYETHYLENE by polymerization of ethylene in the presence of a radical initiator at a pressure of 1000-1800 kg / cm in a multi-zone autoclave reactor, characterized in that, in order to simplify the process technology and improve the optical properties and the ability to process the final product, polymerization is carried out sequentially in the first zone at 130-200 ° C and in the second zone at 220-280 ° C with a volumetric ratio of the first zone to the second from
    1.5 to 6.0, with 75-100 wt.% Ethylene being supplied to the first aeon.
    [2]
    2. The method according to claim 1 ', characterized in that ethylene and initiator are served separately in at least two openings for each located in the first zone.
    / '8X65X01
    Ftz. 1 *>
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    同族专利:
    公开号 | 公开日
    JPS532585A|1978-01-11|
    HU179321B|1982-09-28|
    NL7707167A|1978-01-02|
    BR7704172A|1978-03-28|
    CA1065544A|1979-10-30|
    JPS5415904B2|1979-06-18|
    FR2356677A1|1978-01-27|
    FR2356677B1|1981-03-06|
    DE2729103A1|1978-01-12|
    GB1538633A|1979-01-24|
    US4085266A|1978-04-18|
    MX4569E|1982-06-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2564023C2|2009-11-10|2015-09-27|Базелль Полиолефине Гмбх|Ldpe for use in medicine|CA676159A|1963-12-17|R. Saunders William|Ethylene resins|
    US2964515A|1957-07-01|1960-12-13|Nat Distillers Chem Corp|Ethylene polymerization process|
    US3178404A|1959-12-23|1965-04-13|Eastman Kodak Co|Preparation of polyethylene in a two zone reactor employing caprylyl peroxide in the first zone as the catalyst|
    US3756996A|1964-10-02|1973-09-04|Nat Distillers Chem Corp|Process for the production of ethylene polymers|
    US3536693A|1968-01-31|1970-10-27|Eastman Kodak Co|Process for preparing polyethylene having improved properties|
    GB1208120A|1968-02-01|1970-10-07|Ici Ltd|Ethylene polymerisation|
    NL160292C|1969-09-19|1979-10-15|Stamicarbon|METHOD AND REACTOR FOR CONTINUOUS POLYMERIZATION OF ETHENE.|
    DE2322554A1|1973-05-04|1974-11-21|Sumitomo Chemical Co|METHOD AND DEVICE FOR THE PRODUCTION OF AETHYLENE POLYMERIZES|
    US3923767A|1974-08-22|1975-12-02|Gulf Research Development Co|Ethylene polymerization process in the presence of quinone alkides|
    US3963690A|1974-10-07|1976-06-15|The Dow Chemical Company|Polymerization of ethylene in stirred autoclave with cooled inner wall|
    IN145649B|1974-12-16|1985-01-05|Standard Oil Co|JPS5415905B2|1976-08-13|1979-06-18|
    US4282339A|1978-10-02|1981-08-04|National Distillers And Chemical Corp.|Dual reactor process and apparatus for polymerizing ethylene|
    US4252924A|1979-04-05|1981-02-24|E. I. Du Pont De Nemours And Company|Continuous process for the preparation of nonrandom ethylene/acid copolymer|
    US4607086A|1979-04-05|1986-08-19|E. I. Du Pont De Nemours And Company|Continuous process for the manufacture of low-density polyethylene in stirred autoclaves|
    JPS5819284U|1981-07-30|1983-02-05|
    US4979987A|1988-07-19|1990-12-25|First Miss Gold, Inc.|Precious metals recovery from refractory carbonate ores|
    NO178790C|1993-12-13|1996-06-05|Borealis Holding As|Process for preparing olefin polymers in an autoclave reactor|
    US5648438A|1994-04-01|1997-07-15|Exxon Chemical Patents, Inc.|Process for producing polymers with multimodal molecular weight distributions|
    US6407191B1|1998-01-12|2002-06-18|The Dow Chemical Company|Medium density ethylene polymers, a process to prepare these polymers and use of carbonyl group containing chain transfer agents in this process|
    EP0928797B3|1998-01-12|2012-01-11|Dow Global Technologies LLC|Medium density ethylene polymers, a process to prepare these polymers and use of carbonyl group containing chain transfer agents in this process|
    JP2005097483A|2003-09-26|2005-04-14|Sumitomo Chemical Co Ltd|High pressure radical polymerization process polyethylene|
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    US20110172354A1|2010-01-04|2011-07-14|Dow Global Technologies Inc.|Ethylene-based polymer compositions for use in fiber applications|
    US8653207B1|2012-11-30|2014-02-18|Westlake Longview Corporation|Process and apparatus for polymerizing ethylene under ultra-high pressure|
    EP3168239A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|High pressure free radical polymerizations|
    EP3168237A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|High pressure, free radical polymerizations to produce ethylene-based polymers|
    EP3168238A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|Ethylene-based polymers formed by high pressure free radical polymerizations|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP7730076A|JPS5415904B2|1976-06-29|1976-06-29|
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