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    • 专利摘要:
    1507932 Polymerisation catalyst STANDARD OIL CO 30 April 1975 [9 May 1974 31 March 1975] 18015/75 Heading B1E [Also in Division C3] A brown solid olefin polymerization catalyst component comprising beta-TiCl 3 and up to 10 mol % of an electron donor which is an ether, thioether, thiol, ketone, ester, amide, amine, phosphine, or stilbine, and having a surface area of above 50 m<SP>2</SP>/g and a pore volume of above 0.10 cc/g, is obtained by (i) reacting TiCl 4 and a trihydrocarbyl aluminium or a dihydrocarbylaluminium halide in an inert liquid at below 0‹C, (ii) heating the product to below 100‹C, (iii) treating the product with a solution of the electron donor in an inert solvent at ambient to 80‹C, (iv) treating the product with an electron acceptor selected from a titanium tetrahalide or tetraalkoxyhalide, AlBr 3 , GeCl 4 , and SiCl 4 , at ambient to 100‹C, the acceptor also being dissolved in an inert liquid, and (v) isolating the required particulate catalyst component. The electron donor is preferably an ether e.g. isopentyl ether.
    公开号:SU917683A3
    申请号:SU752133352
    申请日:1975-05-08
    公开日:1982-03-30
    发明作者:Мариос Караяннис Николас；Грамс Гарольд
    申请人:Стандарт Оил Компани (Фирма)；
    IPC主号:
    专利说明:

    stirring, followed by heating the catalyst mass to cooling it to room temperature, separating the resulting precipitate, adding to it with stirring ether at a molar ratio of 0.89-1.22, selected from diisopentyl groups or its mixture with di-butyl at molar with respect to 2.5, respectively, dioctyl, benzyl isopentyl, isobutylvinyl, an sol, keeping the suspension obtained for 1 h with, separating the precipitate and treating it with four titanium chloride at a molar ratio of 0.58-1.16 with b2-b5 C for 1.5-2.0 hours followed by washing of the obtained brown solid with a specific surface of 89.0-.147.0 and a pore volume of 0.188 0.197 cMVr and the addition of diethyl aluminum chloride to it at a molar ratio of 2.8-3.0 :one. . During the polymerization of propylene on the catalyst prepared by the proposed method, the reaction rate increases and, depending on the conditions, is 106-2320 g / g / h. For example, when using 0.0875 brown matter with diethylaluminum chloride in hexane at a molar ratio of 3: 1, a pressure of 0 psi and 70 ° C, the rate is 253 g / g / h. At the same time, when using the known AATiCC-i catalyst (0.2 g) under similar conditions, the polymerization rate is only 65 g / g / h. With an increase in polymerization temperature to 89 ° C and a pressure of up to 250 psi on the catalyst (0.1-0, t g) according to the invention, the polymerization rate increases to 1,222,220 g / g / h, while at the same time known to the talizator (0.4 g) it does not exceed 401-623 g / g / h. The polypropylene obtained by using the catalyst obtained by the proposed method consists of opaque particles of the polymer during block polymerization of propylene and during polymerization in suspension. All the solvents and polymerization media used in the inventive method are treated to remove water and polar impurities. The disaggregations of the substances are removed in the glass tubes with 9 ;, 4 diffractometer powers. The porosity of the samples was measured with a high-pressure porosimeter (BOOOO psi manufactured by American Instrument Co., Silver Springs, Md. The specific surface was measured by BET using a mixture of: nitrogen 10, helium 90. The sample was pretreated at room temperature 1 hour in a weak stream of this mixture of gases, then cooled to a temperature of liquid nitrogen for 45 minutes to absorb nitrogen and heated to room temperature, and the composition of the desorbed gas is determined using a thermal conductivity detector. Analytical analyzes are performed by dissolving a sample of the catalyst sample in methanol or water acidified with sulfuric acid. Portions of these solutions are taken to determine titanium and aluminum using atomic absorption, and chlorine is determined by Folgar titration. Ether is determined by neutralizing the methanol solution or extracting an aqueous solution with hexane and gas chromatography in a gas chromatography column calibrated with standard solutions containing the corresponding ester. The brown catalyst described above forms a purple solution upon decomposition by dissolving in dilute sulfuric acid and a blue (blue) solution upon decomposition by dissolving in MeOH-HjSOi ,. The degree of suspension (degree of suspension) is grams of crystalline polymer (total amount of polymer minus soluble) per gram of brown solid (in terms of TiCt, after 1 hour of polymerization). The degree or rate of polymerization is non-dispersive grams of the total polymer per gram of solid (in terms of TiCtx per 1 h of polymerization). When calculating the amount (mol) of a brown solid, negligible organic content is usually neglected. Example 1. 2.6 ml of dry hexane and 12.5 ml of titanium tetrachloride (0.11 mol) were introduced into a 300 ml round-bottom flask. The flask and its contents are protected in the process. operation atmosphere dry nitrogen. The solution is stirred with a magnetic stirrer and cooled in an ice bath maintained at. To the titanium tetrachloride solution for 3 hours, 7.8 ml (o, 112 mol) of diethylaluminum chloride solution (0.98 mol / 1.0) are poured in drops. Ti) in hexane (2, weight L diethyl aluminum chloride, solution density 0.739 g / ml). At the end of the tide, the suspension is stirred for 15 minutes while the flask is connected to a condenser (a tank). The mixture is heated for 1 hour to BSC. The suspension is stirred for 1 hour at 6 ° C. washing is carried out at. The brown solid is decanted, Hi ml of dry hexane and 21.3 ml (0.105 mol) of diisopentyl ether are added. The mole ratio is 0.92 / 1.0 Ti) and the suspension is stirred for 1 hour at 35 ° C. The solid is washed 5 times 2 ml of dry hexane with decantation. To the solid residue remaining after decantation, 70.8 ml (0.131 mol) of 20.3% by volume of a solution of titanium tetrachloride (molar ratio 1.15 / 1.0 Ti) in hexane, 3 ml of titanium tetrachloride plus I8l, 8 ml of hexane). The suspension is stirred for 2 hours at 62-65 ° C and cooled to room temperature. The solid is washed five times with dry hexane (42 ml portions) with decantation, the last washing is carried out at. Decanted and poured 50 ml of dry hexane, 1 ml of the final suspension contains 0,295 g of solid brown substance. The pattern of dry brown substance (powder) detects peaks corresponding to: 5.8 (cl); 5. + (Forces); 2.98 (ate); 2, 77 (forces differential.); 2.15 (wednesday); 1396 (eaten); 1.78 (sr., -Sil.dif,), 1, U8 (sl.och.shir) 1, 1 i (primary service). Dry brown product has a specific surface of 106 m / g. Analysis of solid brown color,%: titanium 2A, 2) aluminum 0.7, chlorine 64.3, isopentyl ether 10.8. Example 2. A 500 ml round bottom flask was introduced with 2 ml of dry hexane and 25 ml of 4 ml of titanium chloride (0.228 mol). The contents of the flask in the process of the whole opera3 are contained in a dry nitrogen atmosphere. The solution is slowly stirred with a magnetic stirrer, cooling at an ice bath while maintaining the temperature at -1 ° C. For 3 hours, 6 ml (0, mol) of diethyl aluminum chloride (0.99 / 1.0 Ti molar ratio) are added dropwise in hexane (2k, i wt.% diethylaluminium chloride, the specific gravity of the solution is 0.739 g / mol). At the end of the tide, the suspension is slowly stirred for 15 minutes at a time, the flask is connected to a condenser and heated to 1 hour. The suspension is slowly stirred for 1 hour at. After cooling to room temperature, the solid brown substance is washed five times with portions of dry hexane (8 ml each time) to decant each time, and the last washing is carried out at 5 ° C. The brown solid is decanted, 288 ml of hexane and 42.6 ml are poured diisopentyl ether (0.210 mol), (molar ratio 0.92 / 1.0 T1), the suspension is slowly stirred at 35 ° C for 1 hour. Then the solid is washed five times with dry hexane (8 ml each time) and the resulting the slurry is divided into four equal parts. One part, containing 0.057 mol of titanium, is decanted and 5.5 ml (0, mol) of a 13% v / v solution of titanium tetrachloride (molar ratio 1, 1.0 TI) in hexane is poured to the solid. The slurry is slowly stirred at 65 ° C for 2 hours and cooled to room temperature. The solid is washed five times with portions of dry hexane (25 ml each) decant, the last wash is carried out at. Decant off, add 50 ml of hexane to the solid. 1 ml of the final suspension contains 0 g of a brown solid. The pattern of dry brown powdery substance detects the corresponding peaks: 5.8 (ate); 5.3 (power.); 2.75 (power dio.); 2, (n); 2, o6 (sred. Force); 1.9b (el.); 1.77 1.49 (full-time); (sil. diff); 1.52 (el.); 1.13 (full-time) Analysis of a brown solid, titanium 28, aluminum 0.7, chlorine 61.3, isopentyl ether 10.0. P-p and me R 3. The operation was repeated as in Example 2, however, after separation of the slurry into four equal parts, one part containing 0.057 mol of titanium is decanted and 35.4 ml (0.065 mol) is poured into the brown solid 20 3 vol.th solution of titanium tetrachloride (molar ratio 1.15 / 1.0 T |) in hexane. The slurry is slowly stirred while cooling for 105 minutes to room temperature. The solid is washed five times with portions of dry hexane (25 ml each) decant, the last wash is carried out at. Decanted, 50 ml of hexane are added to the residue. 1 ml of the final suspension contains 0.158 g of brown solid; The pattern of powdered brown substance shows peaks corresponding to: 5.9 (very good), 5.4 (strong), 2.9 (cl); 2.75 (broad force); 1.95 (cl. 1.77 (cl.); 1.48 (cl.). Analysis of brown matter,%: titanium 28.31 aluminum 0.8, chlorine 64.1 isopentyl ether 6.8. Example 4. The operation is repeated as in Example 1, but after five times washing with portions of dry hexane (42 ml each time) with decantation, 35.4 ml (0.0 6 mol) of 20.3 ml is poured into the brown solid containing 0.14 mol of titanium. of a solution of titanium tetrachloride (molar ratio 0.58 / 1.0 Ti) in hexane. The suspension is slowly stirred for 105 min at 65 ° C and cooled to room temperature. The solid is washed five times with dry hexane (2 5 ml of decantra, the last wash is carried out at 5 ° C. The 50 ml of hexane is decanted, poured into the solid, 1 ml of the final suspension contains 0.158 of the brown solid. Example 5-Repeat the operation as in Example C, but processing the isopentyl ether-titanium complex 0% v / v solution of tetrachloride germanium (0.12 mol), (mole ratio 1.09 / 1.0 Ti) in hexane is carried out. Example 6. Polymerization of propylene is carried out in an autoclave at kQ psi. inch and for 2 using the amount of brown catalytic component are given in table. 1, 1 ml of 2, wt.% Diethyl aluminum chloride (DZACH) and 200 ml of hexane as a polymerization medium (molar ratio 3.0 DEAC / 1.0 Ti). 9 . 8 Example 7. The polymerization is carried out at 160 F for 1 hour in a 1 gallon reactor at a pressure of 250 psig of propylene and a small partial elasticity of hydrogen in 1200 ml of hexane as the polymerization medium. The catalyst was diethylaluminium chloride, brown titanium trichloride, BTS and a molar ratio of 2.8 / 1, 0 / 0.01t / 0.027 (Table 2). Example 8. The polymerization in the liquid phase of propylene (non-dispersive) was carried out in a liter reactor for 2 hours at 160 ° F under a pressure of psig of propylene and a small amount of hydrogen. In each experiment, O, 3 ml of a 2% by weight solution of diethylaluminium chloride in hexane was used. The molar ratio is 3.0 DEAH / 1, O Ti (table. Example 9. In a flask with a capacity of 500 ml, a solution of the brown catalyst component is prepared from 80 ml of hexane and 40 ml of titanium tetrachloride (0, mol) cooled to OC. 3 h of dropwise poured into the resulting solution ml (0.369 mol) of a 24.4 wt.% Solution of diethyl aluminum chloride (molar ratio 1.01 / 1.0 T1), (0.739 g / ml). The resulting suspension is heated to room temperature, then for 1 hour to 65 ° C, wash and determine the concentration of the suspension. In a 200 ml flask make 25 ml of the last suspension (about 6 tons of solid a brown substance containing 0.033 mol of titanium) is decanted and 40 ml of hexane is poured in. 8.8 ml (o, 0298 mol) of dioctyl ether (0.9 / 1, 0 Ti molar ratio) are added and the suspension is heated for 1 h. the solid is then washed with hexane. The brown solid is decanted and 12 ml of hexane and 4 ml of tetrachloride of titanium C) (0365 mol, molar ratio 1.11 / 1.0 Ti) are poured. The mixture is heated for 2 hours at which the solid brown product formed is washed with hexane and portions of the suspension are used in the polymerization. Example 10. A solution of a brown catalytic component is prepared, analogously to Example 9, except that: (|) 24.6 ml of 991 hexane and 12.5 ml of titanium tetrachloride (0.11 i mol) are cooled to 0 ° G and poured 7 , 8 ml (0.112 mol) of diethyl aluminum chloride (molar ratio 0.98 / 1.0 Ti) (2). The washed brown solid from (1) is powdered with tk ml of hexane and 20.1 ml of benzyl isopentyl ether. Smolny ratio 0.89 / 1.0 Ti), (0.102 mol) (3). To the solid substance from (2), 60, ml of 0.0b5b mol) of 11.9 vol.% Solution of tetrachloride titanium (molar ratio 0.58 / 1, 0 T) is poured. Example 11. Example 10 is repeated with the exception of that 79.5 ml (0.0656 mol) of a 9.0 + obD solution of titanium tetrachloride (molar ratio 0.58 / 1.0 T) in hexane are used. PR and measure 12. A solution of a brown catalytic component is prepared as in Example 9, with the exception that (1) 196.8 ml of hexane and 100 ml of titanium tetrachloride (0.913 mol) are cooled to 0 ° C and 59.8 ml are poured (0.911 mol) 25-solution of diethylaluminum chloride (molar ratio of 0.99 / 1, -O Ti). After decanting, washed to the solid, 00 ml of hexane is poured in. (2) 181 ml of hexane, 1.2 ml (O, 07 mol) of diisopentyl ether and 5.9 are poured into a 50 ml suspension containing O, 11 mol Ti of (1) ml (0.03 mol) of di-n. butyl ether (molar ratio of 0.89 total ether / 1.0 T1). (3) To the washed brown solid from (3), 5b ml of hexane and 1 +, 2 ml (0.132 mol) of four titanium chloride are poured (molar ratio 1, 16/1, 0 Ti), Example 13. A solution of brown is prepared. the catalytic component is analogous to example 12, however, instead of diisopentyl and di-n-butyl ethers, 15, t ml (0.139 mol) of isobutylvinyl ether (molar ratio 1.22 / 1.0 Ti) are used. Example H. A solution of a brown catalytic component is prepared analogously to example 12, however, instead of diisopentyl and iso-n-butyl ethers, 11.8 ml (o, 109 mol) of anisole (molar ratio 0.9b / 1.0 Ti) are taken. Example 15. Suspension polymerization was carried out at 70 ° C. Pressure of pp q.p. of propylene during 7683 2 hours 182 BTS 5 3.0 (that pen 10 I drank drill and 1 3,0 5 CC 16, and 0 3.0 20 (this is when the re-55 .10 is in an autoclave, using 80 mg of the brown substance from Example 9. mg diethyl chloride, 9.5 mg and 3.7 mg CoEt. DEAC / 1.0 molar ratio, 03 BTS / 0.06 SoP bl.) Example 16. Suspension polymerization is carried out similarly to Example 15, with the exception that VT5 or Coft is not charged, but 0.08 g of the catalytic component is used per ml of 25% diethyl aluminum chloride solution. The molar ratio DEAH / 1.0 Ti (ta l. 5). Example 17: polymerization in Penzov lead prmmeru analogously but using 0.008 mlVTZ, 00 ml Co ft. The molar ratio of DEAC / .1,0 Ti / 0,03 BTS / 0,06 Cott bl.6). Example 18. Brown catalytic component is obtained similarly to measure 1, taking into the following amounts of genes, ml: (1) Hexane 19b, 8 Titanium tetrachloride (0.913 mol) 100 Diethylaluminium chloride (0.911 mol), (molar ratio 0.99 /, 0 Ti) 598, Hexane at each washing336 (2) Hexane 1,152 Di-isopentyl ether (0.839 mol) (molar ratio. 0.92 / 1.0 Ti) 170 Hexane at each washing336 (3) Hexane separately from 113.6 ml titanium tetrachloride (1, OA mol), (molar ratio 1, l, OTi) 8 Hexane with each wash 336
    1191768312
    The resulting brown product has an analysis of the level of the product,%; titanium specific surface l m / g and a specificity of 28; chlorine 6A, 2; aluminum O ,, izone pore volume 0,197.
    Analysis of brown product,%: titanium 28.5, chlorine b ,, aluminum O ,, 5 cue component get similar
    isopentyl ether.
    Debagram detects spikes. relevant: 5.9 (cf.); 5, (forces); by sodium. In the resulting brown substance 2, 75 (Och. Force); wide 2,13 (ate); wa specific surface 89 and 1.98 (cf.); 1.9 (e); 1.77 (sr. Wide) CHO specific pore volume of 0.188 cMVr. 1.72 (cl), 1, (cf. sh), 1.23 (cl.) Example 21. Polymerization 1.13 (slr). propylene is carried out similarly
    Example 19 Brown catalytic example 6 (Table 7). cue component is obtained similarly
    Example 18. The resulting brown 15 Example 22. The polymerisation of the product has a specific surface area of 101 m / g of propylene as in Example 8. The specific pore volume is 0.193 cMVr. (tab. 8).
    g 7 --.-, - - f y.- pentyl ether 6.7.
    Example 20. Brown catalytic
    Example 18, but before consumption, the eopentyl ether is distilled over
    Table 1
    x) With this polymerization, 0.008 ml of bis-tributyl tin sulphide (BTS) and 0.05 ml of 2.41.6-collidine (Coft) are added, the molar ratio is 3.0 DEAC / 1.0 Ti / 0.03 BTS / 0, 06 Co) xx) In these experiments, instead of brown titanium trichloride, the addition was AATiCE ,, of Stauffer Chemical Co.
    :Table 2
    x) AATiCt of the firm Stauffer Kemi1 al Ko.
    xx) Experience using diethyl aluminum chloride, titanium trichloride, VTB and Cott in a molar ratio of 2.8 / 1.0 / 0.028 /
    / O .. XXX) Experience in the continuation of h.
    u) AATICt from Stauffer Chemical Co. xx) 0.0025 ml of BTS and 0.00125 ml of Coh are used. molar
    the ratio of 3.0 DEAH / 1.0 T5 / 0.03 BTS / 0.6 Cott. xxx) 0.32 ml 2 weight. solution of diethylaluminium hexane.
    Table3 ((““ “... In Example 9 -“ “x) as a control, catalytically brown at a rate of 178 g / Example 1 Note“ .-. - - 12 13 I - “in - Note.“ BB “BBV v, v, v. "" "" M "tK" ", N, V Speed g / g / h Soluble,% -" - eeee.eteeB e-eweeeeee,. ", IW" M .. "" WWMV-. Is an isopentyl ether containing the component i, obtained in Examples 1 g / h and 1.3 soluble. Speed, g / g / h Soluble,%. As a control is the isopentyl ether containing the brown catalytic component obtained similar to that described in examples I. -. soluble 6.1. xx) Control. The rate of 157 g / g / h, soluble 5.8. xxx) Control. The speed of 170 g / g / h, soluble 5 ,. Speed, g / g / h Soluble,% - ", - - - - - - - - - - -. - - - - - - - - --- - --- - - - - - - - 56 7.2 Control dl 12-1 - brown catalytic components containing isopentyl ether, obtained analogously to examples 1-, with speeds 178.16 and 15 g / g / h respectively and a percentage of soluble 1.1.2 and 1.2, respectively. Table C 613.2. ;:: Table 5. 68.520.3 51.721.5 161if, 2 5 &amp; 17.2 6515.5 x) Control. Speed 165 g / g / h, table 6 1591.2 5511.6
    17
    0.08 0.08 0.08 0.08 0.08 0.08
    x) The molar ratio of 3.0 DEAH / 1.0 Ti. xx) This is 0.008 ml BTS and 0.004 ml.
    The molar ratio of 3.0 DEAH / 1.0 Ti / 0.03 VT5 / 0, About CoU.
    x) Experience within 2 hours. xx) Experience within 4 hours.
    xxx) Titanium / diethylaluminium chloride / BTS / CoEE in a molar ratio of 1.0 / 3.0 / 0.03 / 0.06.
    权利要求:
    Claims (2)
    [1]
    The invention method for producing a catalyst for the polymerization of propylene by reacting diethyl aluminum chloride with titanium tetrachloride at a molar ratio of 0.98-1.01: 1 in an inert solvent at -10-0 C with stirring, followed by heating the catalyst mass to 65-90 ° C, cooling it to room temperature and separating the resulting precipitate, about tl and h and y and the fact that, in order to obtain a catalyst with increased activity, to the precipitate obtained by reacting diethylaluminium chloride with four loristam titanium dobav18
    917683 Table 7
    5.0 3.9 5.7 5.2 6.A 1,
    Table 8
    with stirring, the ether has a molar ratio of 0.89-1.22, selected from the group: diisopentyl or its mixture with di-n-butyl at a molar ratio of 2.5: 1.0, respectively, dioctyl, isobutylvinyl, anisole, and kept the obtained suspension for 1 h at, then the precipitate is separated and treated with titanium tetrachloride at a molar ratio of 0.58-1.16 at 62-65 0 for 1, 0 h, followed by washing the obtained brown solid with a specific surface 89-147 m / g and a pore volume of 0.188-0.197 and the addition of diethylaluminium to it Reed at a molar ratio of 2.8-3.0: 1
    9 917683.20
    Priority Featured Sources of Information
    09.05.7. Titanium tetrachloride taken into account in the examination
    di-isopenol ether. U.S. Patent No. 3,76233, Cl. 2b93 .7, published. 1973.
    31.03-75. Mixture of di-n.butyl and
    [2]
    2. US patent H 3058970,
    di-isopentyl ether.kl, 260-93.6, published. 1965.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US46846374A| true| 1974-05-09|1974-05-09|
    US05/563,679|US3984350A|1974-05-09|1975-03-31|Catalyst component comprising brown titanium trichloride|
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