• 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:
    A catalyst component comprising a titanium trichloride material and a saturated monocyclic monoterpenic ketone or a bicyclic monoterpenic ketone. A catalyst employing the component and an organoaluminum compound is used to polymerize alpha olefins, and particularly propylene. The monoterpenic ketone is effective in increasing the stereoregularity of the polymer.
    公开号:SU786863A3
    申请号:SU772455223
    申请日:1977-02-25
    公开日:1980-12-07
    发明作者:Дж. Арзоуманидис Грегори
    申请人:Стауффер Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) CATALYST COMPONENT FOR POLYMERIZATION The invention relates to components of the catalyst for the polymerization of propylene, which is part of catalytic systems including titanium halide and organo-aluminum compound. A known component of the catalyst for the polymerization of propylene, containing titanium trichloride l. A disadvantage of the catalytic system containing this component is the formation of a large amount of amorphous or hydrocarbon soluble polymer. The closest to the invention is a catalyst component for polymerization, including chlorine; -hydrous trivalent titanium and keto acetophenone, benzophenone, acetone 2 This component is prepared by grinding trichloride titanium in the presence of a ketone until the diffraction pattern characterizing the initial crystalline structure disappears. The resulting component is then extracted with an organic solvent. A disadvantage of the known component is the degree of stereoscopic regularity (up to 93.9%). Besides PROPYLENA, the photosensitivity of some ketones, for example, benzophenone and its derivatives, leads to a decrease in the stability of polymers. In order to increase the selectivity of the catalyst to form stereoregular polymers according to this invention, the catalyst component for propylene polymerization contains saturated monocyclic or bicyclic monoterpenic ketone as ketone in an amount of 3.1-13.3% by weight of chlorinated trivalent titanium. As the specified ketone, substances selected from the group are used; including camphor, fenchon-1, thujone, menton and Laura. Distinctive features of the invention are the use as a ketone of the above compounds, related to monocyclic or bicyclic monoterpene ketones, and the chosen ratio of the weight of the ketone to the weight of the chlorine derivative trivalent chitan. The catalyst component according to the invention is prepared by grinding a monoterpenic ketone powder with titanium chloride. Titanium trichloride can be obtained by various methods, including the reduction of titanium tetrachloride with a metal, such as aluminum or titanium, the recovered material being crushed or preferably not crushed; reduction of titanium tetrachloride with hydrogen; reduction of titanium tetrachloride with an organometallic compound, for example, aluminum alkyl; or grinding a mixture of titanium trichloride and a metal halide of Group III, such as aluminum halide.
    Monoterpenic ketone is taken in an amount of about 3.1-13.3% of the weight of titanium trichloride. When calculating the amount of monoterpene ketone, it is derived from the total nitrogen of chlorinated trivalent titanium, for example, if aluminum halide is used, reduced by aluminum, then it is derived from Z1 C1 A1C, and not from TiCl / alone.
    Grinding can be carried out in a ball mill or in another grinding device of suitable dimensions in the absence of diluents and in an inert gas atmosphere, such as nitrogen or argon, in the absence of oxygen, water and other catalyst grounds at a temperature and duration of grinding that is necessary for the conversion of the apparatus of the mixture in the pulverulent composition, which bonding with the organoalcium compounds forms an active catalyst, allowing the quadrivol to produce a stereoregular polymer.
    Usually, if conventional ball mills are used, the grinding process is carried out for 30-9-0 hours at 30-70 ° C. The best results are obtained at a temperature of 45-65 e and a grinding time of 40-80 hours. The grinding apparatus described in U.S. Patent 3,688,992 has a high grinding speed and reduces the grinding time to 3-12 hours.
    The use of catalytic systems comprising a component obtained according to this invention allows to obtain polypropylene with a degree of stereoregularity of up to 96.5%, compared to a maximum degree of stereoregularity of 93.9%, achieved using well-known catalytic systems 23.
    Example.
    A. Obtaining a catalyst. . Into a laboratory ball mill With an internal diameter of 11 and a length of 15 cm, 875 g of magnetized steel balls with a diameter of 1 cm are loaded, washed with acetone, dried in an oven at and placed in a glove
    nitrogen-filled box with absolute air and moisture mercury.
    Then camphor (about 2.7 g) is loaded into the mill and the mill is shaken to evenly distribute camphor. Then, 50 g of titanium trichloride, obtained by reduction of titanium tetrachloride with metallic aluminum, is added to the mill. It is a product of co-crystallization, corresponding to the formula ЗТ i С lij-А1 С 1, (TiClixA of the company Stauffer Chemical Co., Spec, Cham.DiV.Vestport, Connecticut). The mill was shaken again to mix the contents evenly, then sealed and rotated at 110 rpm for 45 hours at 50 seconds. The temperature is maintained by means of a system consisting of a thermocouple installed in a deaf channel inside the mill, a temperature controller and a recorder. Heat from the outside is brought in to infrared radiation. By the end of the 45-hour period, the components of the catalytic system, consisting of finely divided, mostly non-sticky particles, are transferred in a vessel to a glove box, where they are tested for activity and stereoregularity, as described in paragraph B.
    B, Polymer preparation.
    The example describes the test procedure, which consisted in determining the activity of the catalyst and the stereoregularity of the product obtained using the catalyst components described in paragraph A. -.
    In an autoclave with a shirt with a capacity of 3.76 liters, equipped with a stirrer, with a speed of 600 rpm, load 1 liter of dry heptane. About 0.3 g of the product obtained in A is suspended in heptane under a nitrogen atmosphere, then another 500 ml of heptane and 8 ml of a 20% (by weight) solution of diethyl aluminum chloride in heptane are added. In the autoclave load another 0.5 l of dry heptane and close. The temperature is maintained at 70 ° C, and since the nitrogen pressure in the autoclave rises, gas is released from the autoclave to maintain a constant pressure in the autoclave. Then hydrogen gas is introduced up to partial pressures of 0.2 kgf / cm and propylene to a total pressure of 9.8 kgf / cm. During the polymerization process, additional propylene is introduced to maintain the specified pressure. Propylene is purified by passing it through a column of copper catalyst to remove traces of oxygen and through a molecular sieve (Linde type 4A to remove traces of water. Experimental polymerization lasts for 3 hours. At the end of this period, the catalyst is decomposed by adding isopanol / methanol, then the polymerization product is filtered off, washed with an isopropane / water mixture, dried overnight, and then weighed.About 10 g of the dry polymer is extracted with heptane for 3 hours in a Soxhlet extruder. The non-extracted portions of the polymer (in percentages) are designated C-ji. i. From the aliquot part of the combined filtrates and washings, the amount of soluble polymer contained in the filtrate is determined by distilling off the solvents: resulting from the reaction) in grams per gram of the catalyst containing T i C Irjj obtained in A; the average activity for the two series of experiments is 99 Stereoregularity index (PS), indicating quantities the obtained insoluble polymer is determined by the following formula: CJ 1) C Weight of solid polymer Weight of the total polymer obtained The total amount of polymer obtained includes the above insoluble material (stereoregular) as well as a polymer soluble in boiling heptane and soluble in the combined filtrate and wash waters. For the polymer obtained in two series of experiments using the catalyst obtained in paragraph A, the average PS was 98.3. Comparative example 1. To demonstrate the effectiveness of camphor, one trichloride titanium material TiCln-A (50 g) is loaded into the mill and crushed for 48 hours at 50 C. After the polymerization reaction is performed under conditions similar to those described in Example 1, for two series of experiments, the average activity is 796 and the average PS is 89.6. A second batch of crushed A is prepared, for two test runs using this material, an average activity of 828 and an average PS of 89.6 are obtained. These results prove that, without the use of terpenic ketone, a lower catalyst activity and lower PS are achieved. EXAMPLE 2 The procedure described in Example 1 was repeated, with the exception that about 2.8 g camphor was taken, and about 0.058 g sodium bromide was mixed in the camphor before loading and grinding continued at 43 hours. When carrying out the polymerization according to the procedure described in example 1 but using 5 ml of a 20% (ps5 by weight) solution of diethyl aluminum chloride in heptane, an activity of 1350 and PS 34.4 are obtained. Example 3. Another part of the catalyst prepared in Example 2 was used to prepare the polymer according to the procedure described in Example 1; receive activity 1386 and PS 92.3. Example 4. Once again, a portion of the catalyst prepared in Example 2 was used to prepare the polymer according to the procedure described in Example 1, with the exception that about 0.627 g of the catalyst component was taken for polymerization; an activity of 1188 and PS 94.6 is obtained. Examples 5 and 6. In these two examples, the catalyst prepared in example 2 is tested according to the polymerization procedure described in example 1, with the exception that 5 ml of a 20% (by weight) solution of diethyl aluminum chloride in heptane is used, and, in addition, 5 sub- keep the polymerization temperature of 65 ° C, and in example 6 - bO. In example 5, activity 1217 and PS 93.4 are obtained, and in example 6, ak. tivnost 1147 and PS 94.0. Example 7. To demonstrate the effectiveness of camphor as an electron donor substance in various types of grinding devices, 6.525 g of TiClj-A and 367 g of camphor are ground for 11 hours at 48-50 ° C in the apparatus described in US Pat. No. 3,688,992. The device contains 90 , 7 kg balls of magnetized stainless steel with a diameter of 0.5 12.7 mm. The energy input was 7., 5 A, the rotation speed of 285 rpm. The ground mixture of TiC1j A-camphor is sieved to remove all particles with a diameter greater than 2.69 mm. Two experimental polymerizations were carried out using the described TiC 1j A-camphor sifter according to the general procedure described in Example 1, item B. The polymerization was carried out for 4 hours at 70 ° C. A mean activity of 1438 and PS 92.8 was obtained. EXAMPLE 8 The experiment was repeated according to the procedure described in Example 7, with the exception that 6.20.0 g T i C was taken. The average activity for the two test polymerizations is 1270, and the average PS is 90.8. Due to the fact that the properties of this catalyst are worse than the properties of the catalyst obtained in Example 7, it has been suggested that the catalyst component was contaminated during grinding. Example 9. The procedure described in Example 7 was repeated one more time, but using 5.860 g of TiCln-A and 330 g of camphor. The average activity for the two test polymerizations is 1222, and cpe, r; Hfl PS 93.4.
    Comparative example. 2. Approximately the same amount of TiCUA as in example 7 is ground without camphor in the same manner as described in example 7. The average activity for the two test polymerizations is 1150, and PS 90.1.
    P ROME ery 10-17. The catalyst was prepared from TiCI.A, camphor and sodium bromide mainly according to the procedure described in Example 7. Table. Table 1 lists the quantities of ingredients, catalyst preparation conditions, as well as the catalyst activity and the PS of the polymer obtained. If more than one test polymerization was carried out, the activity and PS carried out are average for all the experiments performed.
    Examples 18 and 19. In order to demonstrate the effectiveness of the invention at a reduced grinding rate, the equipment described in example 7 is used, but it is loaded with 68 kg of steel balls. The energy input is 6A, the rotation speed is 285 rpm. The conditions described in example 1 were accepted, unless there are special reservations.
    In example 18, 8100 g, - A, 455 camphor and 9.1 g of sodium bromide are ground at 24–400 ° C for 2 hours, then at 48–52 ° C for 11 hours, the average activity is 1173 and the average is obtained at 48–52 ° C for 11 hours. PS 95.2. Example 19 is basically a repetition of Example 18, except that 8165 g A is taken and the components are ground first at 40 for 1.5 h and then at 48-52 s for 11.5 h. For two test polymerizations, an average activity of 1107 and of PS 95.3.
    Comparative Example 3. 8625 g of TiC 1 A are ground without camphor and without sodium bromide according to the procedure described in examples 18-19. Grinding is carried out at 24-400 s in those; 3 hours and then, at 48-520 ° C for 11 hours For two experimental polymerizations of 6tina, an average activity of 1164 and an average PS.89.8 were obtained.
    Examples 20-34. These examples show the use of various other terpene ketones, except camphor, both in the absence and in the presence of the third component. The methods and equipment described in Example 1 are used. The ingredients, conditions and results are shown in Table. 2. In all examples, 8 ml of a solution of diethyl aluminum chloride are used in the polymerization and the polymerization is carried out at 70 seconds. A comparative example can be used for comparison with a three-hour experimental polymerization. Comparative Example 4 (C-4 in Table 2) is a repetition of Example 1 with the exception that the polymerization is carried out for 4
    P r and m p S 35-51. To show the effectiveness of adding terpenic ketones in situ, a series of experiments is carried out, in which trichloride titanium material is first introduced into the autoclave, then camphor, then 8 ml of a 20% (by weight) solution of diethyl aluminum chloride in heptane. In Example 51, 12 ml of a solution of diethyl aluminum chloride is added. Titanium trichloride in the form of TiCli / 1, 1, which corresponds to T i C 1, A, was used in the previous experiments, crushed at 50 for 48 hours and sifted to remove large lumps and small particles. The equipment and methods described in Example 1 are used. Item B. In the example, diethyl aluminum chloride is added first, then camphor, and then TiCli1.1. In tab. 3 given the results.
    Example 52. According to the method described in example 1, 50.0 g of TiGlj-H are crushed with 5.6% camphor based on the weight of TiClx-H for 48 h at. TicTjH is obtained by hydrogen reduction of tetrachloride titanium and is manufactured by Stauffer Chemical, Westport, Connecticut. Two parts of the ground component of the catalyst, one weighing 571.1 mg and the other weighing 605.7 mg, are used for the polymerization according to the procedure described in Example 1. An average activity of 584 and an average PS of 85.5 were obtained.
    Comparative Example 6. Repeat Example 52, except that camphor was not added and grinding was carried out for 48 hours at. D two experimental polymerization using in one case 556, .6 mg and in the second case 532.1 mg received an average activity of 367 and an average PS of 37.6.
    Table
    The following ingredients were loaded (g): 5500 TiClj.-A, 1000 crushed mixture of TIC1} A-camphor prepared in example 13, 350 fresh camphor and 7 NaBr.
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    Table3
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    权利要求:
    Claims (2)
    [1]
    Claim
    1. A component of a catalyst for the polymerization of propylene, including a 50 chloro derivative of trivalent titanium and a ketone, characterized in that, in order to increase the selectivity of the catalyst for the formation of streamer polymers, it contains 55 saturated monocyclic or bicyclic monoterpene ketones in the amount of 3.113.3% by weight of the chlorine derivative of trivalent titanium.
    [2]
    2. The catalyst component π π. 1, characterized in that as the specified ketone contains a substance selected from the group comprising camphor, fenkhon-1, thujone, menton and lauron.
    类似技术:
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    ES456358A1|1978-01-16|
    GB1575238A|1980-09-17|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3129256A|1959-12-01|1964-04-14|Gulf Research Development Co|Alkylation of benzene with propylene in the presence of a catalyst containing titanium tetrachloride, alkyl aluminum sesquichloride, and oxygen|
    US3210332A|1963-05-03|1965-10-05|Phillips Petroleum Co|Production of solid olefin polymers|
    GB1257221A|1968-02-28|1971-12-15|
    US3843619A|1968-10-12|1974-10-22|Sir Soc Italiana Resine Spa|Process for polymerizing olefins|
    US3530107A|1968-11-06|1970-09-22|Mitsui Toatsu Chemicals|Modified catalyst system and process for production of polymers of 1-olefins|
    US3701763A|1969-10-20|1972-10-31|Mitsui Petrochemical Ind|Process for polymerization of olefins and catalysts therefor|
    US3850899A|1970-06-15|1974-11-26|Mitsui Petrochemical Ind|Process for polymerizing olefins and catalyst therefor|US4415714A|1979-01-02|1983-11-15|Conoco Inc.|Catalyst and method for preparation of drag reducing substances|
    US4493904A|1981-06-29|1985-01-15|Conoco Inc.|Catalyst and method for preparation of drag reducing substances|
    US4493903A|1981-05-12|1985-01-15|Conoco Inc.|Polymerization process for drag reducing substances|
    US4433123A|1979-01-29|1984-02-21|Conoco Inc.|Polymerization process for drag reducing substances|
    US4701505A|1984-09-26|1987-10-20|Mitsubishi Petrochemical Company Limited|Process for production of olefin polymers|
    US5259986A|1991-12-31|1993-11-09|Phillips Petroleum Company|Coppercarboxylate-containing olefin complexing reagents|
    US5841627A|1997-06-03|1998-11-24|Univ Chicago|Pseudo-capacitor device for aqueous electrolytes|
    US6306983B1|1999-05-14|2001-10-23|3M Innovative Properties Company|Ziegler-Natta polymerization of alpha-olefins in the presence of non-polymerizing olefins|
    US8796589B2|2001-07-15|2014-08-05|Applied Materials, Inc.|Processing system with the dual end-effector handling|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/731,267|US4124530A|1976-10-12|1976-10-12|Olefin polymerization catalyst comprising a monoterpenic ketone and process employing same|
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