• 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:
    1. METHOD FOR OBTAINING A CATALYST FOR POLYMERIZATION OF ETHYLENE by reacting chromium trioxide with triethyl phosphate in an inert solvent and then applying an organochromophore product in an amount of 0.25-2.50%, calculated on the weight of chromium, onto a silica gel followed by heat treatment catalytic mass at 315-977 C and treatment with a reducing agent - triethidborane or triisobutylborane with an atomic ratio of boron and chromium. ma from 0.1: 1.0 to 20: 1, distinguished with I by the fact that, in order to obtain a catalyst with increased activity, an aluminum compound in the amount of 1-10 wt.% in terms of alcuminium is additionally applied to the carrier before heat treatment . 2. A method according to claim 1, distinguishing between i CO and y and the fact that a compound selected from the group comprising aluminum secondary butylate, diisobutyl aluminum ethylate, diethyl aluminum ethoxide, aluminum phenol t, triisobutyl aluminum is used as an aluminum compound.
    公开号:SU1145915A3
    申请号:SU762331205
    申请日:1976-03-12
    公开日:1985-03-15
    发明作者:Джозеф Рекерс Луис；Юлиус Кэтзен Стэнли；Герман Крекелер Джером
    申请人:Нэшнл Петро Кемикалз Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    Jib
    cl
    with
    ate
    The invention relates to methods for producing a catalyst for the polymerization of olefins, in particular ethylene.  A method is known for preparing a catalyst for the polymerization of olefins by reacting chromium trioxide and aluminum isopropylate, adding gallium or tin alkoxide, applying them to a solid inorganic carrier having surface hydroxyl groups, followed by heat treatment 1.  .  The closest to the proposed technical essence and the achieved effect is a method for preparing a catalyst for the polymerization of ethylene by reacting three I chromium oxides with triethyl phosphate in an inert solvent followed by the deposition of the chromophosphorus organic product, taken in an amount of 0.252.5% by weight of chromium, on a carrier-silica gel with subsequent thermal treatment of the catalytic mass at 315-977, with and treatment with a reducing agent — triethylborate or triisobutylborane with an atomic ratio of boron and chromium from 0.1: 1.0 to 20: 1 2. However, a catalyst with insufficiently high activity is obtained by known methods, as a result of which the polyethylene obtained in the presence of a catalyst prepared in a known manner differs by a relatively low melt index of 12.2.  The purpose of the invention is to obtain a catalyst with increased activity.  This goal is achieved by the fact that according to the preparation of a catalyst for the polymerization of ethyl by reacting chromium trioxide with triethyl phosphate in an inert solvent followed by application of an organophosphorus phosphorus product taken in an amount of 0.25-2.50% based on the mass of chromium on the support gel followed by heat treatment of the catalytic mass at 315 and treatment with a reducing agent triethyl borane or triisobutyl borane with an atomic ratio of boron and zhor from 0.1: 1.0 to 20: 1, on a carrier before the heat treatment, in addition Tel'nykh applied aluminum compound in an amount of 1-10 wt. % in terms of aluminiz.  As an aluminum compound, a compound selected from the group consisting of secondary butyl aluminum, ethylate diisobutylaluminum, ethylate DIETS1 aluminum, aluminum phenol, triisobutylaluminum is used.  The proposed method, in comparison with the known, allows to obtain a catalyst with increased activity.  Thus, the polyethylene obtained in the presence of a catalyst prepared by the proposed method has a high. melt index (67.5).  According to the invention, the catalyst is obtained by reacting chromium trioxide with triethyl phosphate in an inert solvent with the subsequent application of an chromophosphorus organic product, taken in an amount of 0.25-2.5%, based on the weight of chromium, and an aluminum compound selected from the group comprising the secondary aluminum butylate, diisobutylaluminum ethylate, diethylaluminium ethylate, aluminum phenol t, triisobutylaluminum, in an amount of 1-10 wt. % in terms of aluminum, on the carrier - silica gel with the subsequent. general heat treatment of the catalytic mass at 315-977 with and treatment with a reducing agent — triethyl borane or tri-isobutyl borane with an atomic ratio of boron and chromium from 0: 1, 1, O to 20.0: 1.0.  Polymerization of ethylene is carried out in an autoclave using isobutane as a diluent.  Chromium and aluminum compounds are added together with isobutane with stirring.  The contents of the stirred autoclave are heated to the polymerization temperature, t. e.  to 88-108 ° C.  Hydrogen is added, if used, and then ethylene, to give 10 mol. % at which time the total pressure should be about 425-455 psi. inch (29.88-32 kg / cm).  Polymerization begins almost immediately when ethylene is supplied from the feed system to the reactor.  Approximately after T h of polymerization, the reaction is terminated by discharging the -containing reactor into the low pressure system.  Melt Indices (MI) and Melt Index under High Load () of the polymers produced are determined in accordance with ASTM D-1238-65T (conditions F and F, respectively).  The catalysts used in polymerization experiments which correspond to the data given in Table.  1-5 were prepared according to the indicated catalyst preparation procedure.  A. The prepared microspherical silica gel, having a pore volume of approximately 2.5 cm / g, is introduced into a 2000 ml three-neck flask with a round bottom, equipped with a stirrer and having an inlet for nitrogen supply and a Y-shaped tube with a water condenser.  During the deposition operation, the flask is maintained under a nitrogen atmosphere.  Then, dichloromethane is added to the flask containing silica gel and the stirrer is started, with the aid of which a uniformly moistened silica gel is obtained.  Prepare a solution in d chloromethane of the reaction product CgO and triethyl phosphate, then add to the flask in an amount sufficient to obtain a catalyst in a dry state (contains about 1% by weight of chromium).  The supernatant is removed by filtration, the gel coated forces are dried in a rotary evaporator at a vacuum of 29 inches Hg. Art.  (736.6 mm Hg. Art. ) B.  In a similar (A) flask entering dichloroethane, with a nitrogen atmosphere, start the stirrer.  Chromium composition is added to the flask on a carrier, prepared in Step A.  In a dropping funnel, a solution is prepared in dichloromethane sec. butylated aluminum, the funnel is connected to a stirred flask. The solution is gradually added from a dropping funnel to the flask at a rate of 10 g of the solution for 1 minute.  lata lata aluminum.  After the entire solution has been introduced into the flask, the pulp in the flask is stirred for approximately 1 hour.  The supernatant is separated by filtration, the silica-coated gel is dried in a rotary evaporator at a temperature of approximately 60 ° C and at a vacuum of 736.6 mm Hg. Art.  The amount of added aluminum compound is determined by the percentage of aluminum required to produce olefin polymers with certain properties required for a particular application.  B. In order to thermally activate the catalytic composition prepared in step B, the supported catalyst is placed in a cylindrical vessel and fluidized with air, linear. a feed rate of which is 0.20 feet per minute 134 (6 cm / min) is heated to and held at this temperature for 6 hours.  The activated catalyst on the support is recovered in B1 of the powder.  In tab.  Figure 1 shows the data illustrating polymerization with additional amounts of the aluminum compound used in the preparation of the catalyst.  The catal from ltora was prepared in accordance with the indicated method for the preparation of catalysts.  With the exception of specially specified cases, the polymerization is carried out at 93.5 ° C and a hydrogen pressure of 30 pounds per square meter. an inch (2.1 kg / cm) with the addition of triethylborane (atomic ratio of boron to: chromium 2.7).  In tab.  2 Illustrates the strong sensitivity of the catalytic systems of the invention to an increase in the concentration of hydrogen.  The catalysts prepared in accordance with the specified method.  For comparison, data on the use of catalysts that do not contain the aluminum compound from Step B in the polymerization are included.  The polymerization is carried out at a temperature of -v 90 s and the addition of triethyl boron to the polymerization reactor based on the boron to chromium atomic ratio of 2.9.  In tab.  Figure 3 illustrates the improved hydrogen sensitivity of the proposed catalytic systems, which appears in the specific melt indices compared to catalysts without aluminum and / or triethyl boron.  The catalysts are prepared in accordance with the 5 t method, with the exception of Toroi that, in those cases where this is indicated, the aluminum compound is omitted from stage B, the polymerization is carried out at - 90 ° C, hydrogen is added to the reactor at a pressure of t20 pounds per sq. inch- (8.44 kg / cm) except as otherwise indicated.  The data table.  4 illustrates the effect of increasing the temperature of the polymerization reaction on the melt index of the polymers obtained using the proposed catalysis systems.  The catalysts are prepared in accordance with the indicated catalyst preparation method.  For comparison, the data obtained using catalysts that are 51 prepared without an aluminum compound from stage B are included.  Hydrogen is fed to the reactor at a pressure of 120 psig. inch (8.44 kgAsm) and triethylborane are given in table.  5, the data illustrate the possibility of using aluminum compounds, other than sec, in catalytic systems according to the proposed method. aluminum butyl.  The catalysts are prepared in accordance with the above procedure for the preparation of the catalyst, using as the aluminum compound in step B the compounds indicated in Table 5.  The polymerization is carried out at a temperature of 90 ° C and at a hydrogen pressure of 120 psig. inch (8.44 kg / cm) and the supply of triethylborane at the rate of achieving the atomic ratio of boron to chromium 2.9.  Are given in table.  6 data illustrate the use in catalytic systems in Figs. Other media and other compounds containing chromium.  In experiments 1 and 2, catalysts were prepared in accordance with the procedure for the preparation of catalysts by stage 4 using MS 952 silica gel from U. TO. Grace with a pore volume of about 1.6.  In experiments 3 and 4, an analogous catalyst on silica gel MS 952 was used with the addition of an aluminum compound from stage B. Used in experiments 1-4, the catalyst is activated by heating according to the method of stage B at a temperature of 840 C instead of 900 C.  In experiments 5 and 6, a catalyst was used, which was prepared by depositing CrOj on a chicagel having a pore volume of about 2.5 cm / g and activated by heating at a temperature of 900 s for 6 hours.  B, experiments 7 and 8 use the same w; :,. Thu9 and in experiments 5 and 6, chromic acid catalyst. c, by removing a compound of omeane according to step 5 of the catalyst preparation procedure.  The chromium content of the catalysts used in Experiments 5-8 is 0.69%.  In experiments 1-8, polymerization was carried out at a temperature of 99 ° C with the use of triethylborane | J (with an atomic ratio of boron / chromium 2.9) and with or without the addition of hydrogen, as indicated in Table.  6 , Example 1.  125 ml of dichlrmet is placed in a 500m vial with three goltkami, equipped with inlet 56.  a nitrogen supply port for reproduction, a gas outlet tube, a magnetic stirrer, and a 100 ml stem dropping funnel.  Under the nitrogen coating, 1.14 g of CgOz (0.0144 M), 2.07 g of triethyl phosphate (0.114 M) dissolved in 75 ml of dichloromethane are added to a shaken vial containing a dichloromethane solvent, added over a period of 20 min. .  Within 5 minutes from the start of the addition of triethyl phosphate, the solution in the vial becomes dark.  By the end of 1 hour of stirring, all of the CrO3 disappears and the solution takes on a reddish brown shade.  Found that the solution weighs 265.2 g.  In order to place the compound on a carrier material, 240 g.  The polypore silica gel is placed in a 2000 ml round bottom bottle equipped with a stirrer and in which a nitrogen protective layer is provided.  1200 ml of dichloromethane are then added to the bottle containing the gel and mixed to ensure that the gel is uniformly moistened.  Then, 265.2 g of a dark reddish-brown color of the filtered solution prepared as above is added to the vial containing the gel and the dichloromethane solvent.  After stirring for about 15 minutes, the agitator is turned off and the gel is allowed to settle.  At this time, the gel is brown and the dichloromethane solvent is completely colorless.  It.  indicates that the catalyzing compound was very strongly and preferably absorbed by the gel.  Floating  on the surface, the liquid is removed by filtration, and the gel is dried with an iBQ rotary evaporator with a vacuum of 736.6 mm (29 inches) Hg. Art.  Then 240 g of dried to catalyst-coated gel containing 0.25 weight. % chromium and 0.15 carried. % phosphorus added to 2000 ml vial.  three bowls and a round bottom equipped with a mixing device, a nitrogen inlet and a Y-shaped tube with a water condenser.  During the coating operation, the nitrogen atmosphere is retained.  Then 1200 ml of dou was added to the vial containing the catalyst. lormethane and stirred to ensure uniform catalyst moistening.  jPacTBOp 220 g of dichloromethane and 219.5 dry aluminum butylate are prepared in a pressure-balancing droplet thief, ke, which is attached to the agitated vial.  A solution of dry butyl aluminum is gradually added to the vial at a rate of 10 g of solution per minute.  After adding the entire solution, the liquid solution in the vial is stirred for approximately 1 hour.  Then, the coated gel is dried in a rotating evaporator at a temperature of about 60 s and a vacuum of 736.6 mm (29 inches) of mercury. Art.  The amount of added aluminum compound gives a catalyst of 10% alumina additive.  In order to activate the warmer composition of the catalyst prepared by the method described above, the catalyst is placed in a cylindrical container and converted into liquid-dried air having a surface linear velocity of 6.096 cm / s (0.20 pounds per second), and also heated to a temperature of 976.5 ° C (1790P) and hold at this temperature for 6 hours.  The activated catalyst is obtained as a powder.  The catalyst thus activated is used in the polymerization as follows.  0.9 kg of isobutane and ethylene are added to the agitated autoclave to a pressure of 3.566 kg / cm (132 pounds per square meter). in) to get 10 mol in the liquid phase, 0.1 g of hydrogen per kilogram of solvent, 1.6 g of catalyst and 67 mg of 1.1 weight. % solution of boron triztilate in hexane (0.1 cm) to obtain a boron to chromium atomic ratio of 0.1: 1.  Shaken, the autoclave with the specified contents is heated to 93.3 € 200).  At this time, the total pressure reaches 15.412 kg / cm (412 psi.  inch).  Polymerization began almost immediately after ethylene was supplied from the feed system of the desired ethylene to the reactor.  After 1 hour of polymerization, the reaction is terminated by merging the contained reactor into a pressure relief system.  A total of 259 grams of polyethylene is opened, having a melting index (Ml) of 4.8 and a high melting index of (HLM1) 398 (ASTM D-1238). Calculated on a 1.6 g catalyst amount, the yield is 162 g of polyethylene per gram of catalyst. at one o'clock.  Example 2  250 ml of dichloromethane is placed in a 500-ml vial with three necklets, equipped with a nitrogen inlet to reproduce the output gas tube, magnetic. a mixing device and a 100 ml addition funnel.  Under a nitrogen coating, 11.4 g of CgO (0.114 M) was added to a shaken vial containing a dichloromethane solvent.  20.7 g of triethyl phosphate dissolved in 75 ml of dichloromethane are added from the dropping funnel over 20 minutes.  Within 5 minutes from the start of the addition of triethyl phosphate, the solution in the vial became dark, reddish-brown in color.  By the end of 1 hour of stirring, the entire CrOj disappears and the stretcher takes on a reddish brown shade.  Found that the solution weighs 457 g.  In order to place the compound on a carrier material, 240 g of polypore silica gel is placed in a 2000 ml round bottom bottle equipped with a mixing device and in which a nitrogen protective layer is provided.  1200 ml of dichloromethane are then added to the vial containing the gel and stirred to ensure uniform wetting of the gel.  Then 457 g of a dark reddish-brown color of the filtered solution, prepared as indicated above, is added to the vial containing the gel and dichloromethane solvent.  After stirring for about 15 minutes, the agitator is turned off and the rejBo is allowed to settle.  At this time, it was observed that the gel was brown and the dichloromethane solvent was almost completely colorless.  This indicates that the catalytic compound was very strong and preferably absorbed by the gel.  The liquid floating on the surface is removed by filtration, and the gel is dried in a rotary evaporator with a vacuum of 5,736.6 mm (29 inches) RT. Art.  Then 265 g of dried and catalyst-coated gel containing 2.5 wt. % chromium and 1.5 wt. % phosphorus added in. 2000-CH4-FLILL FLAN 11 Kon with three necks and round bottom, equipped with a mixing device, a nitrogen inlet and a Y-shaped tube with a water condenser.  . During the operation.  The coatings retain a nitrogen atmosphere.  Then, 1400 ml of dichloromethane is added to the vial containing the catalyst and stirred to ensure uniform catalyst moistening.  A solution of 50 g of dichloromethane and.  2.4 g of dry aluminum butyl is prepared in a pressure equalizing addition funnel, and the funnel is attached to an agitated vial.  A solution of dry aluminum butylate is gradually added to the vial at a rate of 10 g of solution per minute.  After the solution is added, the completely Ashd solution in the vial is stirred for approximately 1 hour.  Then, the coated gel is dried from a rotary evaporator at a vacuum of about 736.6 mm (29 inches) of mercury. Art.  The amount of Added Aluminum Compound gives a catalyst with a 0.1% aluminum additive.  In order to activate the thermal catalyst composition prepared in this way, the catalyst is placed in a cylindrical container and converted into liquid by dried air having a linear linear velocity of 6.096 cm / s (0.20 feet per second), and is also heated to a temperature of 315 ° С ( 600). and hold. at this temperature for. 6 hours  The active catalyst is obtained as a powder.  Thus activated catalyst is used in the polymerization as follows. .  To a stirred autoclave, 0.9 kg of isobutane and ethylene are added to a pressure of 3.878 kg / cm (140 psig.  inch) to get 10 mol. %, in the liquid phase, 0-1 g of hydrogen per kilogram of solvent, 0.6 g of catalyst and 4.1 g of 15 wt. % solution of triethyl boron in hexane (5.8 cm) to obtain an atomic ratio of boron to chromium of 21.7: 1.  Agitated aktoklav with the specified content is heated to 98.9 ° C (210 ° F).  At this time, the total pressure reaches 12.465 kg / cm (450 psi.  inch).  Polymerization began almost immediately after ethylene was supplied from the feed system of the desired ethylene to the reactor.  After 1 hour of polymerization, the reaction is terminated by draining the contents of the reactor into a pressure relief system.  In general, 151 g of polyethylene having a melting index (Ml) of 0.05 and a high melting index are discovered. (HBM1) 12.2 (ASTM D-1238).  The calculated yield of catalyst in 0.6 g yield is 252 g of Polyethylene per gram of catalyst per hour.  Example 3  The catalyst was prepared analogously to example 1, but using Triisobutylborane as the reducing agent.  Triisobutyl gives results similar to those obtained using three: ethylborane at a hydrogen pressure of 30. pSi (2.109 kg / cm) for productivity, melt flow rates and densities of the polymer powder obtained.  The densities of the polymer powder without the use of hydrogen in the reactor are significantly lower than the densities of the polymer powder in those cases when c. hydrogen is present in the reactor.  The results are presented in Table.  7  The proposed method, in comparison with the known, allows to obtain catalysate with permeable activity, which results in polyethylene with a high melt index.  Table 1
    717,780
    926 886 616 Note.
    eleven.
    67.5
    116.5
    340
    390/1 / Gram1 aluminum per 100 g of silicon oxide, use; as a carrier, / 2 / Polymerization temperature, atomic ratio of boron to chromium 2.9, Table 2
    No no
    btor. aluminum butyl 3.7
    0,69
    524
    22,6
    Tall
    .., „..
    Etilate diieobutylaluminium
    Etilate Diethylapuminium
    Phenol t aluminum
    Trieee about butyl aluminum
    1.52
    20.8
    16.8
    1093 417 4.3
    1980
    24.2
    660
    Not
    669 No 3.7
    701 3.7
    639 No
    1097
    832 No 3.7
    704 3.7
    683
    Table 6
    9.6
    0.05
    0.125
    17.9
    0.62
    85.6
    3.3
    497
    0.15
    18.1
    0.86
    62
    19.6
    1823
    114.2
    Tall
    Table 7 Note. .
    Continued table. 7 Reaction conditions: catalyst - zinsat explosive, temperature. (98,), the diluent is isobutane ethylene 10 mol.%
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING A CATALYST FOR POLYMERIZATION OF ETHYLENE by reacting chromium trioxide “with triethyl phosphate * in an inert solvent followed by applying chromophosphorus organic product taken in an amount of 0.25-2.50%, based on the mass of chromium, on silica gel carrier with subsequent heat treatment of the catalytic mass at 315–977 ° C and treatment with a reducing agent — triethizborane or triisobutylborane with an atomic ratio of boron to chromium. from 0.1: 1.0 to 20: 1, characterized in that, in order to obtain a catalyst with increased activity, an aluminum compound in an amount of 1-10 wt.% in terms of aluminum is additionally applied to the carrier before heat treatment.
    [2]
    2. The method of pop. 1, distinguished by the fact that as an aluminum compound, a compound selected from the group consisting of secondary aluminum butylate, diisobutylaluminate, diethylaluminate, aluminum phenolate, triisobutylaluminium is used.
    SU <H . 1,145,915 A
    1145915 2
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/558,504|US3984351A|1975-03-14|1975-03-14|Olefin polymerization catalyst|
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