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    • 专利摘要:
    1490509 Solid catalytic complex for olefin polymerization SOLVAY & CIE 13 April 1976 [14 April 1975] 15054/76 Heading C3P Olefins are polymerized in the presence of a catalyst comprising (A) an organometallic compound and (B) a solid transition metal catalytic complex prepared by reacting, in any order, (1) a magnesium compound, (2) a titanium compound, (3) a zirconium compound and (4) an organo aluminium halide, compounds (1) to (3) being halogen- or organic oxygen-containing compounds, and the four compounds (1) to (4) being used in such proportions that the product (Zr/Ti).X/(Mg+Zr+Ti) is at least 3, where X is the halogen proportion, and Mg, Ti and Zr the corresponding metal proportions, in gram-atoms. Regulators such as hydrogen, zinc or cadmium diethyl, alcohols, carbon dioxide or Group IVa or Va alkoxides may also be added to the final catalyst. Typical examples refer to the polymerization of ethylene or ethylene/butene-1 in hexane in the presence of hydrogen and of catalysts (A) i-Bu 3 Al and (B) the reaction products of (1) Mg(OEt) 2 or MgCl 2 , (2) Ti(OnBu) 4 or TiCl 4 , (3) Zr(On.Bu) 4 or ZrCl 4 and (4) EtAlCl 2 .
    公开号:SU795488A3
    申请号:SU762350306
    申请日:1976-04-12
    公开日:1981-01-07
    发明作者:Берже Ожен；Бьенфэ Шарль
    申请人:Солвей Э Ко. (Фирма)；
    IPC主号:
    专利说明:

    (54) ETHYLENE POLYMERIZATION CATALYST
    This invention relates to polymer chemistry, in particular to an ethylene polymerization catalyst. A known catalyst for the polymerization of ethylene, consisting of a transition metal compound and an organometallic compound of metal 1 - i groups of the Periodic Table l. Closest to the proposed catalyst is a known catalyst for the polymerization of ethylene, consisting of magnesium alcoholate, titanium alkoxide or tetrachloride, zirconium tetrachloride or zirconium tetrachloride, and organochlorine aluminum 2. However, when this catheshiser is used to polymerize ethylene to produce a product with a wide range of weight distribution (MBR), the catalyst activity is low. The aim of the invention is to increase activity. This goal is achieved by the fact that the known catalyst for the polymerization of ethylene, consisting of alumina, alky, or tetrachloride of titanium, alcoholate or zirconium tetrachloride and organochlorine compound of aluminum, contains these components in the following ratio: Chtg) (1ms) where Zr, Ti, Md and C1 are gram equivalent of the corresponding compounds. Examples IK-5. The following reagents are used: 1) magnesium ethoxide 2) titanium tetrabutylate 3) zirconium tetrabutylate (this reagent contains about 14% by weight of free butyl alcohol and is in this condition as a viscous liquid), 4) ethylene aluminum dichloride 15.2 g of reagent 3 and 13.5 g of reagent 2 is added to 9 g of reagent 1. The resulting mixture is heated at 14 5 C for 150 minutes without removing the free alcohol present in reagent 3. This mixture is then dissolved in about 250 ml of hexane. In this mixture, the ratio of a Zr / Ti is about Of9 g-eq./g-eq. and the ratio b
    (Zr-f Ti) / Mg is about. 1.9 g-eq. / G-eq, ± 10% error due to impurities contained in the reagents. To the portions of the thus obtained solution (S), different amounts of reagent 4 are added. This reagent is added with stirring, in the form of a 50% solution in hexane, maintaining the bos environment temperature. The resulting suspension is then allowed to stand for about 1 hour at 65 ° C. The complex formed in the reaction medium is solid. It is separated, washed with warm hexane () and dried under vacuum for 3 hours (+ 60 ° C),
    Variable amounts of the catalytic complex and triisobutylaluminum were introduced into a 1.5 L autoclave containing 0.5 L of hexane. The temperature of the autoclave is then adjusted to about 85 s. Ethylene is introduced at a partial pressure of 10 kg / cm and hydrogen under varying pressures.
    The polymerization is continued for 1 hour with stirring, maintaining the total constant pressure by continuously adding ethylene. After 1 h, the autoclave is degassed and the polyethylene (PE) thus obtained is collected.
    In tab. Table 1 lists the particular conditions for each example and the results obtained.
    The results shown in Table 1 indicate that the ratio between the melt flow rates characterizing the molecular weight distribution (higher ratios characteristic of broader molecular weight distributions) has the highest values when the product content is
    above 3. Comparative example 1, L shows that insufficiently high values of the product in do not allow obtaining examples characterized by a broad molecular weight distribution.
    PRI me R 6k. This example, given as a comparative one, is realized by repeating the experiment with: a known catalyst, which
    carried out in the presence of a solid catalytic complex obtained using the above reagents to obtain the following ratios:
    .g (Zr / Ti) SG / (Mgt-Zr + Ti) 2.8
    D C1 / (Mg4Zr-Hi) "2.1
    e / Zr / Tt 1, 33
    W (Ti + Zr), k.
    The polymer obtained has a MFR of 0.44 g / 10 min and MFR of 17.2 g / min. the ratio of MFR,. ftpTP, characterizing the molecules, and the equilibrium distribution, is only 39. Therefore, it is not enough that the ratios d, b and l, which determine the preparation of the catalytic complexes of P.O. of the invention,
    satisfactory if the ratio r is unsatisfactory.
    EXAMPLE 7-10. A series of catalytic complexes are prepared from the same reagents as in the examples, but a mixture of 2 and 3 is added to about 0.1 mol Mg (OCjiHj) (1) in varying ratios and amounts of T1 (0-H C H, ) (2) and Zr "C, Hj)
    Then the process is continued under the conditions of Examples 1-5. To the resulting solutions are added such amounts of Al () Cl5 (() g as the ratio qrc} / () 3paBHO 3.3 (examples 7-9) or 2.7 (example 10).
    The preparation of the catalytic complexes is completed as indicated in examples 1-5.
    The polymerization is carried out with the aid of the obtained catalytic complexes according to the conditions specified in these examples.
    In tab. .2 shows partial conditions for the preparation of catalytic 5 complexes, particular polymerization conditions and the results obtained. These ratios are given with an accuracy of ± 10% of the error due to impurities contained in the reagents.
    From tab. Figure 2 shows a significant expansion of the equilibrium molecules for the polymer using these catalytic systems.
    Example 11. A solid catalytic complex of the same reagents as in Examples 7-10 was prepared and used in such a way that the ratios of e, f, g and the product are the same as in Example 10. The process is carried out according to examples 7-10, with the exception that the butyl alcohol present in the reaction medium is removed by heating before adding reagent 4, Elemental analysis shows that the resulting solid 5 contains kafalit complex. per 1 Kf 69 g Id, 176 g Zr, 25 g Ti, 23 g / I And 565 g e 1, the polymerization was carried out with 8 of the same conditions as in examples 1-5, with 16 mg of the complex and 0 - triisobutylaluminum and when the pressure of hydrogen is 15 kg / cm, which makes it possible to obtain 93 g of PE with an MFR of 0.19 and 1 €, 9 g / 10 day. The OTPg / OTP 89 correlation. The catalytic performance is 2840 g PE / g complex.
    Example 12: A solid catalytic complex was prepared from the same reagents and according to the same process as in Examples 1-5, but used reagents 1-4 so as to obtain the following relationships:
    g (Zr. / Ti) - Cl / CMg + Zr Ti) 31.3
    d Cl / (Mg + Zr4-Ti), 5
    e Zr / Ti 12.5
    5 g () / Mg "3 Elemental analysis shows that the solid catalytic complex obtained contains 1 kg of 66 g of Mg, 229 g of Zr, 13 g of Ti, 4.1 g of Al, and 574 g of C1. Polymerization is carried out under the same conditions as in Examples 1-5, with 24 mg of complex, 200 mg of triisobutylaluminum and at a partial pressure of hydrogen of 15 kg / cm 2, which allows to obtain 86 g of PE with MFR of 0.26 and PTRa is 17.7 g / 10 min. The ratio PT L1TP is 68. The catalytic capacity is 3580 g PE / g complex. Example 13. A solid catalytic complex was prepared from the same reagents and according to the same method as in Examples 1-5, but reagents 1-4 were used so as to obtain the following ratios: g (Zr / Ti) (C1 / () 5 D (Mg-t-Zr-Ti) e Zr / Ti 0.5 {{Ti-vZr) Mg 2 The resulting catalytically solid complex contains per 1 kg 6.3 g MD, 99 g Zr 174 g Ti, 26 g A1 and 573 g C 1. The copolymerization is carried out under the same conditions as in Examples 1-5 with 14 mg of complex, 200 mg of triisobutylaluminum and at a partial pressure of hydrogen of 5 kg / cm, which allows to obtain 43 g of PE with MFR 0.50 and MFR 25.1 g / 10 min. The ratio PTRD / PTR 50. Catechesite productivity is 3750 g PE / g complex. POR and mep 14. A catalyst complex is prepared in the same way as in example 9, but not isolated from the suspension obtained after adding 8 ml of reagent 4. This suspension is introduced into the autoclave for polymerization by polymerization under conditions of examples 1-5 with 400 mg of triisobutylaluminum with a partial pressure of hydrogen of 15 kg / cm H 90 g of PE with MFR 0.38 and PTR2 31 g / 10 l & n are obtained. The ratio PTRg / MFR 82. PRI me R 15. Prepare a catalytic complex of the same reagents as in examples 7-10 using reagents 1,2 and 3 so that the ratios of e and g are the same as in example 10. After removal of the free butyl alcohol, as indicated in example 11, the mixture obtained from these reagents is dissolved in hexane and added in four successive locks to a 50% solution in hexane reagent 4 temperature medium support about 65C, the ratio of d is equal to 3.6 and the value of the product in about 14.4. The treatment of the resulting suspension and the catalytic complex, which is then issued; 1 is eluted from it, as described in examples 1-5. Elemental analysis of the solid catalytic complex shows that it contains per 1 kg of 51 g Nd 195 g of Zr, 26 g of Ti, 32 g of Al, 544 g of C1, the polymerization is carried out with 18 g of this complex under the conditions of examples 1-5, but at hydrogen partial pressure of 15 kg / cm 2, which allows to obtain 98 g of PE with MFR of 0.06 and MFR of 4.59 g / 10 min. The ratio of PTR2 / PTR 77. The catalyst productivity is 5450 g of PE / g complex. Example 16. A catalytic complex was prepared using the same reagents 2,3 and 4 as in examples 1-g5, but using MgCl2 for analysis containing 24 g per 1 kg as reagent 1. Reagents are used under the conditions of examples 1-5 , but in such a way as to obtain the following ratios g (Zr / Ti) - Cl / (Zr- -Ti4-Mg) 6 d Cl / (Zr4-T - Mg) 3 e Zr / Ti 2 g () / Mg 2 The preparation is carried out as indicated in examples 1-5. The resulting catalytic complex contains per kg 60 g MD, 178 g Zr, 48 g Ti 23 g A1, 600 g C1. The polymerization is carried out under the same conditions as in Examples 1-5, with 21 mg of complex, 200 mg of triisobutylaluminum and with a partial pressure of hydrogen of 10 kg / cmg. 104 g of PE with MWT of 0.17 and MFR are obtained; -13.9 g / 10 min. Ratio 82. Catalyst productivity 4950 g PE / g complex. Example 17: Prepare a catalytic complex of the same reagents as in Examples 1-5, except that the reagent 2 is TiCl4. Pigmentation is carried out as indicated in Examples 1-5, except that reagent. 2 add to suspension after adding reagent 4. After keeping this mixture for 1 hour at 65 ° C, the solid catalytic complex is washed and dried as indicated in examples 1-5, but so as to obtain the following ratios: g (Zr + Ti) (Zr- -Tii-Mg) "I, 2 d Cl / (Zr4Ti-Mg), 1 e Zr / Ti 2 and (Zr -" - Ti) / Mg- 3 The resulting catalytic complex contains 1 kg 53 g MD, 172g Zr, 81 g Ti 17 g A1 and 527 g C1. The polymerization is carried out under the same conditions as in Examples 1-5, with 20 mg of the complex, 200 mg of triisobutylaluminium and under partial hydrogen loading of 15 kg / cm S, which allows to obtain 78 g of PE with MW 0.18 and PTR2 17 34 g / 10 min. The ratio PTR1 / PTR2. 96. Catalyst productivity 3900 g PE / g complex.
    PREMIERS 18-22. The same reagents 1,2 and 4 are used as in Examples 1-5, but zirconium tetrachloride c is used. as reagent 3.
    114 g of reagent 1 is added to 136 g of reagent 2. The mixture is heated at 140 ° C for 4 hours with stirring and it is determined that almost complete dissolution of reagent 4 occurs. In the mixture, the Ti / Mg atomic ratio is 0.6 G eq / g -eq + 10% error due to impurities contained in the reagents.
    The resulting mixture was adjusted to 1 L by adding hexane and heated under reflux for 1 hour. To 100 ml of the thus obtained solution, a varying amount of powdered ZrCl was added. in the form of a suspension in hexane. The resulting boiling suspension with reflux for 1 h, finally, variable amounts of reagent 4 are slowly added with stirring to maintain the medium temperature at about 50-55 ° C. Reagent 4 is added as a 50% solution in hexane. Contact with reagent 4 is continued for about 15 minutes after it has been added.
    The catalytic complex formed in the reaction medium is solid. It is separated, washed with heated hexane (t 60 ° C) and dried under vacuum () until constant weight.
    Product, 8
    Elemental analysis of the catalytic used. complex mg / g: MD
    Ti Zr
    Al27
    Cl512
    Amount of catalytic complex used, mg
    Amount of triisobutylaluminum, - mg
    Hydrogen partial pressure, kg / cm
    The polymerization is carried out under the conditions of examples 1-5.
    The characteristics of the preparation of catalytic complexes, particular conditions of polymerization and the results obtained are presented in Table 3.
    Example 23: Copolymerization of ethylene with butene is carried out with the benefit of a solid catalytic complex prepared as indicated in Example 9. The general conditions for the polymerization are the same as in Examples 1-5.
    The following are the conditions and results obtained:
    The amount of catalytic complex introduced into the autoclave is 20 mg,
    The partial pressure of hydrogen is 15 kg / cm.
    The number of input of the co monomer: 0 0.1 mol n-butene-1, dried over alumina. about
    The amount and nature of the activator: 200 ml of triisobutylamini The amount of copolymer obtained is 81 g.
    Catalyst productivity: 4050 g copolymer / g catalytic complex.
     copolymer 0.5 g / 10 min,
    PTR2 copolymer 40.6 g / 10 min.
    The ratio is 81.
    The specific weight of the copolymer: 0,952 kg / dm
    Thus, the proposed catalyst flatters a lot of activity; 5 contributes to the efficiency of the process of polymerization of ethylene. Table
    4.6 5.2
    29 22
    25 22 618 588 596 562
    11 18 10 14
    200 100 100 200
    15 15 15
    Melt flow index (IlTPi), measured according to ASTM-D 123857 T (load: 2.1b kg), g / 10 min
    Melt flow rate (PTRz.), Measured according to ASTM-D 1238-57 T (load: 21, b kg), g / 10 min
    The ratio of PTR2 / PTR
    k) For this experience, ethylene is introduced under partial
    pressure of 5 kg / cm
    and 3 added to reagent 1, g: reagent 3
    Reagent 2 Ratio a Ratio g
    The amount of reagent used 4 ml
    Product in
    Elemental anashie solid catalytic complex, mg / g:
    Md
    Ti Zr
    Al C1
    Used amount of catalytic complex, mg
    Continued tabl, 1
    0.33 0.17 0.26 0.26 0.35
    8.52 37
    35.1
    34 50 142
    131,100
    table 2
    22.8 20.929.7
    6.7 5.47
    3 3.54
    2 1.82
    250 250250
    9.9 11,610,8
    15 26
    15
    20
    The number of triyeobutylaluminum, mg
    Hydrogen partial pressure, kg / cm 2 Amount of PE obtained, g
    Activity, g PE / g complex
    PTR, g / 10 min PTR, g / 10 min Ototnosti PTRd / PTR
    ) Excluding the amount of free butyl alcohol present. lek Continued tab. 2
    200 200 200
    15 15
    15 66 60 93
    69004000 35804400
    0.190.11 0.240.43
    14.3710.01 21.933.38
    7691 9178
    T a b l and c a 3
    3442 372470
    815 B1215
    134140 11085111
    39403380 197035401590
    0.170.3 0.220.130.26
    12.97.24.48 15.59.3613.84
    7698 707253
    权利要求:
    Claims (2)
    [1]
    1. US patent number 3113115, cl. 252-429, pub. 1963.
    .Q
    [2]
    2.Patent of Belgium 791676,
    cl. From 08 f, pub. 1972 (prototype).
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    同族专利:
    公开号 | 公开日
    AT347677B|1979-01-10|
    DE2615390A1|1976-10-21|
    DK149864C|1987-06-29|
    NL7603907A|1976-10-18|
    DK168976A|1976-10-15|
    FI61494C|1982-08-10|
    NO146991B|1982-10-04|
    TR19292A|1978-11-21|
    PT64985A|1976-05-01|
    DE2615390C3|1981-10-08|
    ES446816A1|1978-02-01|
    NL164569B|1980-08-15|
    CA1080208A|1980-06-24|
    AR207281A1|1976-09-22|
    JPS558083B2|1980-03-01|
    BR7602156A|1976-10-05|
    ATA265676A|1978-05-15|
    SE7604279L|1976-10-15|
    PT64985B|1977-09-07|
    MX3477E|1980-12-11|
    LU72278A1|1977-02-03|
    JPS5529597A|1980-03-01|
    BE840378A|1976-10-05|
    JPS5846204B2|1983-10-14|
    GB1490509A|1977-11-02|
    DD126387A5|1977-07-13|
    US4109071A|1978-08-22|
    IN143034B|1977-09-24|
    FI761019A|1976-10-15|
    NL164569C|1981-01-15|
    JPS51138785A|1976-11-30|
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    SE430253B|1983-10-31|
    ZA762076B|1977-04-27|
    FI61494B|1982-04-30|
    CH617212A5|1980-05-14|
    AU1287276A|1977-10-20|
    IT1059283B|1982-05-31|
    NO761239L|1976-10-15|
    FR2307824A1|1976-11-12|
    DK149864B|1986-10-13|
    NO146991C|1983-01-12|
    GR58454B|1977-10-10|
    FR2307824B1|1979-04-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL213149A|1955-12-22|
    US3678025A|1970-05-22|1972-07-18|Dow Chemical Co|Preparation of linear alpha olefin polymers having broad molecular weight distributions|
    FR2093306A6|1970-06-09|1972-01-28|Solvay|ADVANCED CATALYSTS AND PROCESS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF OLEFINS|
    DE2128760A1|1970-06-12|1971-12-16|Shell Int Research|Process for the polymerization of olefins|
    BE791676A|1971-12-08|1973-05-21|Solvay|Process for the polymerization of olefins|
    LU65587A1|1972-06-22|1973-12-27|
    IT1020055B|1973-09-08|1977-12-20|Solvay|LOW PRESSURE POLYMERIZATION OF OLEFINS|
    JPS5239714B2|1974-10-18|1977-10-06|
    US3939137A|1974-11-22|1976-02-17|Phillips Petroleum Company|Silane adjuvant for chromium oxide catalyst|LU77489A1|1977-06-06|1979-01-19|
    JPS5757042B2|1978-02-02|1982-12-02|Sumitomo Chemical Co|
    US4258167A|1978-02-13|1981-03-24|Nissan Chemical Industries, Ltd.|Process for producing powdery isotactic polyolefin|
    US4226964A|1978-02-23|1980-10-07|Mitsubishi Chemical Industries Ltd.|Process for polymerizing olefin|
    US4260723A|1978-06-27|1981-04-07|Chisso Corporation|Method for producing olefin polymers|
    US4210559A|1978-10-30|1980-07-01|Standard Oil Company |Catalyst for the preparation of polyalpha-olefins having broad molecular weight distributions|
    JPS5919567B2|1978-11-27|1984-05-07|Showa Denko Kk|
    US4233182A|1978-12-26|1980-11-11|Standard Oil Company |High activity catalyst for the polymerization of alpha-olefins|
    WO1980001485A1|1979-01-18|1980-07-24|Mitsubishi Chem Ind|Process for producing olefin polymer|
    US4384087A|1980-03-24|1983-05-17|Phillips Petroleum Company|Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst|
    US4363746A|1979-05-29|1982-12-14|Phillips Petroleum Company|Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst|
    JPS6352643B2|1979-06-01|1988-10-19|Chisso Corp|
    US4366298A|1979-07-05|1982-12-28|Wacker-Chemie Gmbh|Process and heavy metal catalyst for the polymerization of α-olefins, particularly polyethylene|
    JPS6024805B2|1979-09-05|1985-06-14|Nippon Oil Co Ltd|
    US4269733A|1979-09-28|1981-05-26|The Dow Chemical Company|Ultra high efficiency catalyst for polymerizing olefins|
    US4363902A|1980-03-17|1982-12-14|Wacker-Chemie Gmbh|Process and heavy metal catalyst for the polymerization of α-olefins, particularly polyethylene|
    EP0043473B1|1980-06-25|1985-08-07|Idemitsu Kosan Company Limited|Process for the production of polyethylene|
    JPS6312083B2|1980-06-27|1988-03-17|Idemitsu Kosan Co|
    DE3025760A1|1980-07-08|1982-02-04|Wacker-Chemie GmbH, 8000 München|METHOD FOR THE POLYMERSATION OF-OLEFINES|
    US4326988A|1980-08-12|1982-04-27|Phillips Petroleum Company|Catalyst, method of producing the catalyst, and polymerization process employing the catalyst|
    US4325837A|1980-08-12|1982-04-20|Phillips Petroleum Company|Catalyst, method of producing the catalyst, and polymerization process employing the catalyst|
    US4356111A|1980-10-20|1982-10-26|The Dow Chemical Company|High efficiency catalyst containing titanium and zirconium for polymerizing olefins|
    US4310648A|1980-10-20|1982-01-12|The Dow Chemical Company|Polymerization of olefins in the presence of a catalyst containing titanium and zirconium|
    US4399053A|1980-12-24|1983-08-16|The Dow Chemical Company|High efficiency catalyst containing titanium, zirconium and zinc for polymerizing olefins|
    US4525554A|1981-03-04|1985-06-25|Mitsubishi Chemical Industries Ltd.|Process for polymerizing olefin|
    US4394291A|1981-03-04|1983-07-19|Phillips Petroleum Company|Polyolefin polymerization process and catalyst|
    US4472523A|1981-05-22|1984-09-18|Phillips Petroleum Company|Zirconium-titanium catalyzed olefin polymerization|
    US4396747A|1981-05-22|1983-08-02|Phillips Petroleum Company|Zirconium-titanium catalyzed olefin polymerization|
    US4376065A|1981-06-01|1983-03-08|The Dow Chemical Company|Organo zirconium-chromium compound, catalyst prepared therefrom and polymerization of olefins therewith|
    US4361685A|1981-06-01|1982-11-30|The Dow Chemical Company|Polymerization of olefins in the presence of catalyst prepared from organo zirconium-chromium mixtures|
    US4518751A|1981-06-05|1985-05-21|Idemitsu Kosan Company Limited|Process for the production of polyethylene|
    US4409126A|1981-10-22|1983-10-11|The Dow Chemical Company|Ultra high efficiency catalyst for polymerizing olefins|
    US4381253A|1981-10-22|1983-04-26|The Dow Chemical Company|Ultra high efficiency catalyst for polymerizing olefins|
    US4380508A|1981-10-22|1983-04-19|The Dow Chemical Company|Ultra high efficiency catalyst for polymerizing olefins|
    US4379760A|1981-11-12|1983-04-12|The Dow Chemical Company|High efficiency catalyst for polymerizing olefins|
    EP0083671A1|1982-01-07|1983-07-20|The Dow Chemical Company|High efficiency catalyst containing titanium and zirconium and process for polymerizing olefins|
    US4497906A|1982-02-16|1985-02-05|Sumitomo Chemical Company, Limited|Solid catalyst component for olefin polymerization|
    US4550094A|1982-02-16|1985-10-29|Sumitomo Chemical Company, Limited|Solid catalyst component for olefin polymerization|
    US4675368A|1982-10-04|1987-06-23|Solvay & Cie.|Process for inhibiting crust formation in reactors during alpha-olefin prepolymerization modification of Ziegler catalyst|
    US4587727A|1983-07-05|1986-05-13|International Business Machines Corporation|System for generating circuit boards using electroeroded sheet layers|
    JPH0345725B2|1983-08-16|1991-07-12|Sumitomo Chemical Co|
    IT1212779B|1983-10-14|1989-11-30|Enichimica Secondaria|PROCEDURE FOR THE POLYMERIZATION OF ETHYLENE AND FOR THE COPOLYMERIZATION OF ETHYLENE WITH ALPHA-OLEPHINS AND RELATED CATALYST.|
    US4496661A|1983-10-24|1985-01-29|The Dow Chemical Company|High efficiency catalyst for polymerizing olefins|
    US4618660A|1984-06-29|1986-10-21|Exxon Research & Engineering Co.|Polymerization catalyst|
    US5064797A|1987-04-03|1991-11-12|Phillips Petroleum Company|Process for producing polyolefins and polyolefin catalysts|
    US4939217A|1987-04-03|1990-07-03|Phillips Petroleum Company|Process for producing polyolefins and polyolefin catalysts|
    JPH0725827B2|1987-06-02|1995-03-22|出光石油化学株式会社|Method for producing ethylene polymer|
    EP0522424B1|1991-07-03|1996-12-18|Tosoh Corporation|Method for producing a polyolefin|
    US5332707A|1992-07-31|1994-07-26|Amoco Corporation|Olefin polymerization and copolymerization catalyst|
    US5374597A|1993-02-12|1994-12-20|Quantum Chemical Corporation|Vanadium based olefin polymerization catalyst|
    US5399540A|1993-02-12|1995-03-21|Quantum Chemical Corporation|ZR/V multi-site olefin polymerization catalyst|
    US5405817A|1993-02-12|1995-04-11|Quantum Chemical Corporation|V/TI multi-site olefin polymerization catalyst|
    BE1009308A3|1995-04-28|1997-02-04|Solvay|Ethylene polymer and methods for obtaining.|
    JP2003503589A|1999-06-30|2003-01-28|ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・テクノロジー・コーポレイション|Magnesium-zirconium alkoxide complexes and polymerization catalysts produced therefrom|
    WO2001000685A2|1999-06-30|2001-01-04|Union Carbide Chemicals & Plastics Technology Corporation|Mixed metal alkoxide complexes and polymerization catalysts made therefrom|
    US20090048402A1|2007-08-17|2009-02-19|Lynch Michael W|Preparing multimodal polyethylene having controlled long chain branching distribution|
    US8809220B2|2010-04-13|2014-08-19|Union Carbide Chemicals & Plastics Technology Llc|Method of making Ziegler-Natta type catalysts|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    LU72278A|LU72278A1|1975-04-14|1975-04-14|
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