• 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 system that is a combination of at least two com­ponents A and B, which components comprise: A : one or more titanium compounds and one or more vanadium com­pounds, mixed with one or more organoaluminium compounds in such an amount that the atomic ratio of aluminium to the sum of titanium and vanadium is at least 3, B : one or more organoaluminium compounds,one or both of components A and B containing a chloride, and which two components are fed, separately or in combination, direct to the reaction vessel in such an amount that the atomic ratio of the chlorine from components A and/or B to the sum of titanium and vanadium of component A is at least 6, is suitable for (co)polymeri­zation of ethylene and optionally minor amounts of 1-alkenes and/or dienes at high polymerization temperatures.
    公开号:SU1641193A3
    申请号:SU874028813
    申请日:1987-01-09
    公开日:1991-04-07
    发明作者:Бленкерс Йоханнес；Мария Констан Косеманс Люк
    申请人:Стамикарбон Б.В.(Лайсенсинг Сабсидиари Ов Дсм) (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the preparation of (co) polymerization catalysts and can be used to obtain polyethylene and ethyl copolymers with o-olefins by the method of high-temperature polymerization.
    The aim of the invention is to increase the activity of the catalyst.
    In the following table. 1-7 use the following abbreviations:
    C1 / Me is the molar ratio of chlorine in diethylaluminium chloride (DEAC) or sesquiethylaluminium chloride, (ethyl) 5) to the sum of Ti and V, g / mmol;
    v — catalyst activity in 10 min, g of polyethylene / imol Ti + V;
    M.I. - melt index, dg / min;
    SEAC - sesquiethyl aluminum chloride (ethyl {i5 A1C11 5);
    TBT - tetrabutoxytitanium;
    VB - vanadyl butoxide;
    TEA - triethyl aluminum;
    DEAHEH - diethylaluminium ethoxide;
    TPS - triphenylsilanol;
    DAD8 - diethylaluminum dimethylethyl ethylsiloxide;
    TEV - triethyl boron;
    EV - ethyl benzoate;
    IPA - isopropyl alcohol;
    PMHS - polymethylhydrosiloxane;
    BzCl is benzyl chloride;
    TVOT - tributoxy oleate;
    TIPT - tetraisopropoxytitanium;
    O5
    Ј MA
    s
    TIBAO - tetraisobutylalumoxane;
    AIOX - methyl alumoxane;
    TIBA - triisobutylaluminium;
    D1VAN - dizno-butyl aluminum hydride
    IPC1 - isopropyl chloride;
    Et is ethyl;
    BP benzophenone;
    EN - ethylenediamine;
    DRDMZ - diphenyldimethoxysilane;
    IPRA - isopropenyl aluminum;
    D1BVA - diisobutyl 1-buten-1-yl-aluminum.
    Example 1. Polymerization was carried out at 240 ° C in a 1 liter gas-liquid reactor with 500 ml of purified and dried pentamethylheptene (PMN) as the dispersion medium and ethylene (in an amount sufficient to create a 17 bar pressure in the reactor). ). The ingredients of the catalyst components are preliminarily mixed for 1 min at 25 ° C with PMN and then the catalyst components are separately pumped (if not specified) into the reactor.
    In tab. 1 indicates the sequence in which the components of the catalyst are mixed, as well as its concentration (in mmol / d) during the polymerization. The polymerization time is 10 minutes. If necessary, the polymer is stabilized, dried and weighed.
    Example 2. The components of the catalyst are mixed in the sequence specified in the table. 2. Catalyst preparation and polymerization are carried out analogously to Example 1, but at a pressure in the reactor of 8 bar.
    PRI me R 3 (comparative). Use the catalyst composition specified in the table. 3 "The polymerization was carried out analogously to example 2.
    PRI me R 4 (comparative). Coponent A is prepared by stirring 9 mmol of TiCl4 and 9 mmol of VB for 2 hours in 10 ml of PMN and glass container under nitrogen at 60 ° C. Then, 27 mmol of SEAC is added to the mixture at 20 ° C and stir it at this temperature for 3 hours. After decantation, the precipitate is washed 6 times with 40 ml of PMN.
    The prepared slurry is introduced into the reactor in such an amount that the total transition metal concentration is about 0.1 mmol / L. The polymerization is carried out analogously to example 2 at 200 and 240 ° C.
    The results are shown in Table. four.
    PRI me R 5 (comparative). Component A is prepared by treating 9 mmol TVT, 9 mmol VOClj and 27 mmol SEAC as in Example 4. When using 0.4 mmol DEAHEH as component VB and carrying out polymerization under the same conditions as in example 2, the catalyst does not active
    EXAMPLE 6 (comparative). Component A is obtained by treating 4.5 mmol of TiCl4., 4.5 mmol of VB and 54 mmol of SEAC as in Example 4. Catalyst (when used as component B of 0.4 mmol / l DEHAH and carrying out polymerization under the same conditions as in the case of example 2) does not possess activity.
    Example (comparative). Component A is obtained by treatment (2 mmol TVT + 3 mmol VB + 10 mmol BzCl) and 30 mmol SEAC as in Example 4. When using 0.4 mmol TEA as the VB component and carrying out the polymerization under the same conditions as in the case of Example 2, the catalyst activity is 341.
    Example 8 (comparative). Component A is prepared by adding dropwise to 12 mmol of SEAC at 25 ° C with a solution of 5 mmol of TBT + 5 mmol of VOClj and keeping (or aging) the mixture for 4 days. The resulting suspension is filtered into a solid, washed and dried. After that, 2.73 g of solid material is added to 1.58 g of TiCl in 10 ml of hexane. The precipitate that formed after keeping the mixture for -3 hours at 25 ° C was separated, washed, dried and resuspended.
    The polymerization is carried out analogously to example 2 using such an amount of said suspension that the total concentration of transition metals is about 0.1 mm / l. As a component B of the catalyst, 0.4 mmol / g TEA or 0.4 mmol / l DEHAH is used. Neither
    516
    otherwise, the catalyst is not active.
    PRI me R 9 (comparative). Component A is obtained by reacting titanium and vanadium compounds listed in Table 2. 5, in RMN. at room temperature, with DEAS. After stirring for 40 seconds at room temperature, the mixture is heated to 185 ° C for 1.5 minutes and fed to the reactor. Thereafter, TEA or DAD8 is introduced into the reactor as component B. The polymerization is carried out as in Example 2.
    Example 10. Component A is prepared by mixing the components at the temperatures indicated in Table. 6. PMN, in which the components are mixed, is preheated to the specified temperature. The rest of the process is carried out analogously to example 1. As component B, 0.4 mmol / l DAD5 is used.
    Example 11. The copolymerization of ethylene and octene is carried out analogously to example 1, using the catalysts indicated in Table. 7. Before feeding ethylene into the reactor, 1-octene is introduced.
    权利要求:
    Claims (3)
    [1]
    1. Catalyst for high-temperature polymerization of ethylene and copolymerization of ethylene with o-olefins, including diethyl- or sesquiethyl aluminum chloride, a compound of titanium selected from the group including
    five
    0
    0.3-1.0
    0.01-0.09
    0,012-0,075
    1936
    tributoxy oxyl titanate, tetrabutoxy titan, tetraisopropoxy titan and titanium tetrachloride, a vanadyl compound selected from the group including vanadyl butoxide, vanadium trichloride and vanadyl trichloride, and an aluminum orgumin compound, in a lt and a t a and a liquefied aluminum. , in order to increase the activity of the catalyst, it contains the components in the following ratio, mol.p.: Diethyl- or ses-viethylaluminium chloride Titanium compound Vanadium-compound Organum aluminum compound with atomic ratio of chloride and diethyl- or sesquietylaluminum Reed chloride to the total amount of titanium and vanadium 1,0-10,5 0,20-0,55
    [2]
    2. Catalyst according to claim 1, about tl in the form of additionally comprising benzyl chloride in an amount of 0.2 mol. or silicon tetrachloride in the amount of 0.2 mol.h.,
    0 or tin tetrachloride in an amount of 0.06-0.1 mol.h., or isopropyl chloride in an amount of 0.2 mol.h., or boron trichloride in an amount of 0.1-0.2 mol.h. 0.6 mol.ch. sesquiiethyl aluminum5 Klorida.
    [3]
    3. Catalyst according to claim 1, characterized in that it further comprises an electron-donating compound in an amount of 0.1-0.4 mol. on
    0 0.4 mol.h. organoaluminum compound.
    Table 1
    five
    1641193
    8 Continuation of table 1
    13
    1641193
    14 Continuation of table 2
    VOC13)
    20.1 DEAC / 0.04 T1C14 + 0.06 VOC13)
    30.1 DEAC / (0.075 TVT + 0.025 VOC13)
    40.2 DEAC / (0.075 TVT + 0.025 VOC13)
    50.1 DEAC / (0.04 TVT + 0.06 VOC1.)
    6- 0.2 SEAC / 0.04
    TBT / 0.06 VB / 0.2 BzCl
    TEA2,25200185 TIBA .2,25200130 TEA / ROH2, 25200160
    TIBA2,25240 50
    TEA / ROH2,25240: 50
    Table3
    one
    0.28 TEA
    0.28 TEA 347 0.72
    0.28 TEA T 50 2 0.28 TEA 152 0.28 TEA 50
    one
    0.4 TEA 50
    Table 4
    15
    .1641193
    Experience
    Component A
    10.1 DEAC / (0.075
    T1C14 + 0.025 VOC13)
    20.1 DEAC / (0.04
    TiCl + 0.06 VOC13)
    30.1 DEAC / (0.04
    TiCl4 + 0.06 VOC13)
    40.1 DEAC / (0.075
    TBT + 0.025 VOC13)
    50.1 DEAC / (0.075 TVT +
    + -0.025 VOC13)
    60.1 DEAC / (0.075 TVT +
    + 0.025 VB),
    70.1 DEAC / (0.075 TVT +
    + 0.025 VB)
    80.6 SEAC / (0.04 TiCl4 + 0.06 VOCla)
    90.6 SEAC / 0, 04 TiCl4 +
    + 0.06 VOC13)
    100.6 SEAC / (0.04 TiCl4 +
    + 0.06 VOC13)
    Experience Component A
    10.6 SEAC / 0; 04 TBT /
    0.06 VB9
    20.6 SEAC / 0.04 TBT /
    0.06 VB9
    30.6 SEAC / 0.04 TBT /
    0.06 VB9
    40.6 SEAC / 0.04 TBT /
    0.06 VB9
    50.6 SEAC / 0.04 TBT /
    0.06 VB9
    torture
    Quantity okten.mp
    30 35 30 30 75 30 50 30
    Component A
    0.7 SEAC / 0.04 TBT / 0.06
    0.4 TEA
    10.5 10.5 10.5
    VB / 0,2 BzCl
    0.7 SEAC / 0.04 TUT / 0.06
    VB / 0,2 BzCl0.4 DEAHEUH 10.5
    0.7 SEAC / 0.04 TBT / 0.06
    VB / 0.2 SiClq
    0.7 SEAC / 0.04 TBT / 0.06
    VB / 0.2 SiCl.)
    0.7 SEAC / 0.04 TBT / 0.06
    VB / 0,2 BzCl0,4 DADZ
    0.7 SEAC / 0.025 TBT /
    0.075 VB / 0.2 BzCl
    0.7 SEAC / 0.04 TBT / 0.06
    VB / 0,2 BzCl
    0.7 SEAC / 0.04 TBT / 0.06
    VB / 0,2 S1C14
    0.4 TEA 0.4 DEUHUH, 5 10.5
    0.4 DAD510.5
    10.5 DADZ 10.5
    1051-941.2
    1189 935.8
    1152 938.5
    1239
    1142
    1249
    1212
    935.2 925.0 931.6 924.0
    5.7 5.0 5.6 6.8 6.8 7.9 8.2
    10.5 TEA / 0.2 EB 10.5 1319 934.4 6.9
    16 Table 5
    C1 Component B
    Me j
    About ML.
    0.28 TEA450 0.45
    0.28 TEA448 0.60
    0.28 DAD8239 0, 28
    0.28 DAD8 50
    0.28 TEAOO
    0.28 DADZ L5Q 0, 2 TEA255 0.8
    0.4 TEA352 0.5
    0.3 DAD8466 0.5
    a b l and ca 6
    Temperature
    Era- about, ° C |
    1284
    1100
    844
    838
    735
    T a b l and c a
    TEA
    10.5 10.5 10.5
    DEUJUH 10.5
    DADZ
    TEA DEAHUH, 5 10.5
    DAD510,5
    DADZ 10.5
    1051-941.2
    1189 935.8
    1152 938.5
    1239
    1142
    1249
    1212
    935.2 925.0 931.6 924.0
    5.7 5.0 5.6 6.8 6.8 7.9 8.2
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    引用文献:
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    US5492876A|1990-05-02|1996-02-20|Novacor ChemicalsS.A.|Solution process for the preparation of polymers of α-olefins|
    US5519098A|1991-10-03|1996-05-21|Novacor ChemicalsSa|Activation of catalyst in ethylene polymerization at high temperatures|
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    US7144964B2|2004-08-19|2006-12-05|Equistar Chemicals, L.P.|Solution polymerization process utilizing preassembled bimetallic Ziegler-Natta catalyst|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NL8600045A|NL8600045A|1986-01-11|1986-01-11|CATALYST SYSTEM FOR HIGH TEMPERATUREPOLYMERIZATION OF ETHENE.|
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