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    • 专利摘要:
    A process for polymerizing ethylene under the high temperature and high pressure conditions by using a battery of two or more autoclave reactors connected in series by means of piping provided with a heat exchanger, each of said reactors having an upper reaction zone and a lower reaction zone. According to this process, the reaction yield of polyethylene is higher than that attainable from the conventional two-zone polymerization methods, and the obtained polyethylene is improved in optical properties and processability.
    公开号:SU738514A3
    申请号:SU772512754
    申请日:1977-08-12
    公开日:1980-05-30
    发明作者:Кита Синитиро；Хики Фумихико；Симизу Масаюки；Кондоу Акира
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING POLYETHYLENE
    The invention relates to the technology of producing low density polyethylene and can be used in petrochemical industry. A known method for producing polyethylene by polymerizing ethylene at 1000–2800 kg / cm in the presence of radical initiators in two successively connected autoclave reactors when fresh ethylene is fed into both reactors and cooled the reaction mixture transferred from the first reactor to the second {1. The process is carried out in odious reactors and the temperature in the first reactor does not exceed 140-200 °, therefore the amount of heat required for removal using a heat exchanger located between the reactors is small, since the temperature of the reaction mixture supplied to the second reactor cannot be lower 120 ° C. As a consequence, the increase in the yield of polyethylene reactants is extremely small, i.e. for the production of low pressure polyethylene, the yield of the reaction increases in proportion to the difference in heat content and heat from the water. At the same time, polyethylene used according to a well-known method has relatively low characteristics in terms of optical properties and reproducibility. The core of the invention is to increase the polymer yield, improve its processability and optical properties. This goal is achieved by the fact that in a known method of producing polyethylene by polymerizing ethylene at 1000-2800 kg / cm in the presence of radical initiators in two successively connected autoclave reactors when fresh ethylene is fed into both reactors and the reaction mixture is cooled from the first reactor to the second. carried out in reactors with upper and lower reaction zones at 130–200 ° C in the upper zones and 220–280 ° C in the lower zones, with 60–95 wt.% of fresh ethylene being fed to the upper zone of the first reactor and the reaction mixture from first reactor to the lower or upper reaction zone of the second reactor. The essence of the present invention concludes with the polymerization of ethylene under high conditions.
    This temperature and high pressure when using a battery of two autogas reactors, connected in series with Tpy6oiip o-water and equipped with a heat exchanger, and the reaction mixture withdrawn from the first reactor is cooled, and the cooled one. The cyokna mixture is fed to the second reactor. At the same time, a significant proportion of iodine ethnlen is directed to the upper reaction zone of the first reactor, which has upper and lower reaction zones, the remaining fraction of ethylene to be prepared is directed to the BcpxisMio zone of the second reactor, which has an upper and lower reaction zone, polymerized ehi-10 in the upper reactor in the zone of the first reactor, under the DKVTKM, 1000–2800 kg / slg and at 13 () in the presence of an iplator, polymerized. The mixture obtained in peaKsosoHHjno is introduced in this way into the lower reactioncon zone of the first relaxor and the mixture is tulimerized in it at 220-280 ° C in the presence of a polymerization initiator, the reaction mixture that is removed from the whole portion of the reactor coolant is cooled to higher than low than the reaction type in the quadra reaction; and; the onion zone of the first reactor 20 ° C or large iron with the help of a heat exchanger, preconfigured between the reactors; then the cooled reaction 1 g / i mixture into the second reactor and polymerized in it said mixture under dazlenkem 1000-2800 kg / cm in the presence of a polymerization initiator,
    Thus, the temperature of the reactor in the reaction zone of the first reactor can be reduced to a higher value than the reaction temperature in the first reactor used in the dual-zone Tiponecce polymer back according to a known method, as a result, inevitably increases The difference is the terature, it is recoverable by cooling the reactive mixture with Pomokhtge. heat exchanger, and thereby increases the heat removal from the outside and increases the yield of the reaction polygltgen.
    When realizing; the invention does not use autoclave-type reactors, which have a substantially substantially linear cylindrical shape with a relative length — I am iiopHiiKa 2–20, preferably 5–15.
    Each of the autoclave reactors is divided into two zones (upper reaction zone and lower reaction zone) by means of a partition (separation plate) or other separation means. The polymerization of ethylene in these two zones is carried out at different reaction temperatures.
    Volumetric oTiiomemie between the upper and lower reaction zones, from i to 6. This is the ratio of the first and second reactors. The weight is different.
    ) 44
    In order to obtain Iolithi., Having more than BbjCOKjic optical characteristics and processability, it is preferable that two or more be provided for the length of the reactor
    (lugshe 2-10) of the input, for feeding with ethylene and polymerization in the upper reaction zone in the first and / or second reactor. The polymerization initiator may be supplied from the same inputs as ethylene, Inc. from others.
    - „
    are possible; raz.chichkye komoy15adii
    PV.ODZ of supplied ethylene and polymerization initiator; 1BP .1} the upper reaction zone.
    The reaction rate and the solution of ethylene is 5bng; 01s3; ti; 1zone is 000-2800 KI / CM; , „Predictedly i 100-2500 kg / cm.
    After the pressure has been subtracted, the pressure loss arising roughly: opt -: -; yes / to the second reactor, from the pressure. ro; ;.: - iti in perBOi; the reactor turns out to be a macop: - g ;;:; Noah Peldg, the pressure in the second m of the syrg, so that the pressure of the reaction can be controlled by the need to adjust the pressure valve first reactor. , Gedredyucht sang; Ny interval: about: - p-: pa, tour reactive 130--200 ° C, credtsotpelg) g: o A-U-190 C tp upper pea) ashon zone ;, j: 220-280 ° C, preferably 230- 2704 for:, cxc; c;: -: rzakanokkoy zon soot; t1 about k; ys:;:;; Levom, TUK to for the second reactors.
    The temperature of the reaction in the upper zone of the reactor zone should be different in the first and second reactors.
    The grate / temperature from {4cj i re., Atc. 3O} ibi of the first reactor ea cop mixture is cooled to 120 ° C, but with an eolaic diesel, KM reaction temperature in the first reaction zone of the first reactor at 20 ° C, klk is greater than , with the help of heat exchanger, uetans, j leshugo meyschu 5eaktorov. The coolant mixture is fed to the upper or lower 1-E reaction zone of the second reactor. 1-sp1; the initiator of the polymerization in the upper reaction reactors of the reactor is an initiator, which disintegrates at 40-60 ° C with a half-life of 10 hours, examples; similar probes are: di: 13oprop) 1-peroxidylcarbonate, dp-2-ethylhexyl peroxide-S, Sarbokat, - / rech-buripsrox divalate, 3,5,5-trIlMet} shhexanoyl. octazhla peroxide, peroxide) | eka; 1oyl, laurocla peroxide, propionyl peroxide, ursg-bujlperoxy-2- these L1-e to sanoat, tert-buty perper with iz o butyrate, and so on. The amount of initiator in the upper reactive zones of both reactors is 50-1000 parts by weight. per 1,000,000 weight.h. ethylene. As used in the lower reaction zones in the two reactors should desirably initiator polimerizaschsh refer to disintegrating at 70-140 ° C with a half-life of 10 hours. Examples of such initiators are butllperoksi Treg-2-ethylhexanoate, Treg-butilperoksiizobut rat, tert-butilperoksilaurat, Treg-Buti peroxy isopropyl carbonate, treg-butylperoxyacetate, treg-butylperoxybenzoate, dicumyl peroxide, treg-butyl hydroperoxide, di-greg-butyl peroxide, and the like. The amount of initiator in the lower reaction zones of both reactors is 5-500 parts by weight. per 1,000,000 weight.h. ethylene. Polymerization initiators may be used alone or in combination in an amount that is used in both the upper and lower reaction zones of the reactors. The ethylene used as the starting material may contain a chain transfer agent, usually in an amount of 0.1-10 mol%, based on the amount of ethylene fed. Examples of chain transfer agents. paraffinic hydrocarbons, such as ethane, propane, butane, pentane, hexane and heptane; a-olefins such as propylene, 1-butene, 1-hexene, and 3-methyl ifpsreHt-1; aldehydes such as formaldehyde, acetaldehyde and propionaldehyde; ketones, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene and xylene. Chain transfer agents may be used alone or in combination. FIG. 1, 2 and 3 are a block diagram of preferred reactor variants used to implement the method according to the described invention; in FIG. 4 is a block scheme of a conventional reactor system, given for comparison. In these figures, similar positions are used 1 to designate similar nodes or lines. The process is conducted according to the flowchart of FIG. 1., in two autoclave reactors 1 and 2, separated by non-campuses 3 and 4 into upper reaction zones 5 and 6 and lower reaction zones 7 and 8. The volume ratio between the upper and lower reaction zones} in reactors 1 and 2 was 1 Each reactor is equipped with a stirrer for stirring the reaction mixture and the partition is mounted on a stirrer, PRI me R 1. 88 kg / h of ethylene feed containing 1.5 mol.% Of ethane and under pressure of 1300 kg / cm filed through the pipeline 9 and loaded into the upper reaction zone 5 of the reactor 1 through the pipes 10 and 11 with the costs 22 u 44 kg / h, respectively. 7 6 and the remaining 22 kg / h of ethylene feed was sent to the upper reaction zone 5 of another reactor 2 through a pipeline} 12. In addition, 33.4 g / h octanoyl peroxide was fed to the upper reaction zone 5 via datubes 13 and 14 a polymerization initiator, and ethylene polymerization under a pressure of 1300 KG / CM and at 170 ° C. The reaction mixture from the upper reaction zone 5 was introduced into the lower reaction zone 7, in which 2.1 g / h of treg-butyl peroxide, a polymerization agent, was also fed through the nozzle 15, and the mixture was then polymerized at 260 ° C. In this way, the polymerized reaction mixture was removed from the bottom of the autoclave reactor 1 through the pressure regulating valve 16 into the heat exchanger 17, as a result, the reaction mixture was cooled to 140 ° C and then introduced into the lower reaction zone 8 of the autoclave reactor 2. In the upper reaction zone of the reactor 2 e with ethylene fed there was introduced 6.8 g / h of octanoyl peroxide from nozzle 18 and carried out with a polyluxidation at 1200 kg / cm and 170 ° С, after which the reaction mixture was fed into the lower reaction zone 8 and replaced with the reaction mixture coming from the reactor I and enter into the reaction zone 8 of reactor 2 through heat mixer 17. 4.6 g / h of D i-2pcT-butnl peroxide, polymers of polymerization was loaded into the mixture from nipple 19, and then the mixture was subjected to polymerization at 260 ° С. The pressure of the reaction mixture discharged from 1; the reactance zone 8 zones were dumped to the level of the usual pressure gauge used: pressure separation valve 20, and the mixture flowed into ethyl acetate and unreacted; lgn After compression, unreacted ethylene rztsirkul 1 was fed into the reaction system. The amount of polyethylene thus obtained was 19.4 kg / h with a yield of polyethylene of 22.1%. The product density, measured according to ASTM D-1505, was 0.922 g / cm, the melt index, measured in accordance with ASTM D-1238, was 2 g / 10 min. Characteristics of turbidity and glossiness of polyethylene film, measured in accordance with the standards ASTMD-003 and ASTIViD-523 and D-2103, respectively 2.8 n 130%. The processing capacity of polyethylene into thin films was expressed by the minimum thickness of the flax that can be achieved at
    7 7385148
    processing of polyethylene into film at a temp. From the table, the positive effect of the resin invented at 160 ° C was 13 microns. The shadow is visible in high reaction yields from
    Examples 2-13 carried out similarly polyethylene, as well as improved optical
    Example 1. The results obtained show the film properties (low
    in the table. The turbidity given in the table for comparative-j and high glossiness) and
    权利要求:
    Claims (1)
    [1]
    ki examples 1 and 2 are compared examples of fine processing 4.ku. 13 The claims of the method for producing polyethylene by polymerizing ethylene at 1000-2800 kg / cm in the presence of radical initiators in two series-connected autoclave reactors when fresh ethylene is fed into both reactors and cooling the reaction mixture transferred from the first reactor to the second, characterized in that the goal of increasing polymer output, improving its reproducibility and optical properties, the process
    -P
    G9
    13
    -wl
    n
    7J
    13
    14 d t in reactors with upper and lower reaction zones at 130–200 ° C in the upper zones and 220–280 ° C of the lower zones, with 60–95 wt.% Of fresh ethylene being fed to the upper zone of the first reactor and the reaction mixture from the first reactor is introduced into the lower or upper reaction zone of the second reactor. Sources of information taken into account during the examination 1. US Patent No. 3875128, cl. 260-86.7, publ. 04/01/75.
    17
    , /
    (put. 2
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    引用文献:
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    RU2564023C2|2009-11-10|2015-09-27|Базелль Полиолефине Гмбх|Ldpe for use in medicine|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|
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    DE2322554A1|1973-05-04|1974-11-21|Sumitomo Chemical Co|METHOD AND DEVICE FOR THE PRODUCTION OF AETHYLENE POLYMERIZES|
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    US4282339A|1978-10-02|1981-08-04|National Distillers And Chemical Corp.|Dual reactor process and apparatus for polymerizing ethylene|
    US4229416A|1978-10-02|1980-10-21|National Distillers And Chemical Corporation|Dual reactor apparatus for polymerizing ethylene|
    JPS5938961B2|1978-12-26|1984-09-20|Sumitomo Chemical Co|
    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|
    JPS643883B2|1982-11-25|1989-01-24|Showa Denko Kk|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP9716276A|JPS5415905B2|1976-08-13|1976-08-13|
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