Components and catalysts for the polymerization of olefins

• US 4,472,524 A
• Filed: 02/10/1983
• Issued: 09/18/1984
• Est. Priority Date: 02/12/1982
• Status: Expired due to Term

• Current Assignee: Montedison SPA Milano 31 FORO Buonaparte
• Original Assignee: Montedison S.p.A. (Government of France)
• Inventors: Albizzati, Enrico
• Primary Examiner(s): Garvin, Patrick
• Application Number:
  US06/465,593
• Time in Patent Office: 586 Days
• Field of Search: 502/113, 502/118, 502/119, 502/124, 502/125, 502/123, 502/132, 502/129
• US Class Current: 502/113
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 4/606 Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by groups C08F4/60 C08F4/60003 - C08F4/60196 take precedence
• CPC Class Codes: C08F 4/6065 containing silicium
• CPC Class Codes: C08F 4/6141 and metals of C08F4/60 or compounds thereof
• CPC Class Codes: C08F 4/6583 and magnesium or compounds thereof
• CPC Class Codes: Y10S 526/903 Monomer polymerized in presence of transition metal containing catalyst and hydrocarbon additive affecting polymer properties of catalyst activity

Abstract

Catalysts for the polymerization of alpha-olefins, comprising the product of the reaction between:

(a) a metalorganic Al compound;

(b) an electron-donor compound reactive towards MgCl₂ but which results not to be completely complexed with Al-triethyl at the equivalent point of the potentiometric titration under standard conditions;

(c) a solid comprising a halogenated Ti compound supported on an anhydrous Mg halide and at least one of the following activators:

(1) an Al, Fe, Mn, Sb or Zn compound containing at least one metal-halogen bond;

(2) a complex between an electron-donor compound and a Lewis acid chosen among the halides of the metals of Groups II-VIII of the Periodic System other than Ti;

(3) a compound or composition, inert towards the Mg halide, having a dielectric constant at 20° C. higher than 2;

compounds (1), (2) and (3) being extractable from the solid for at least 30% by mols by treatment with toluene at 80° C. for 2 hours, and the surface area of the solid after extraction being higher than 20 m² /g.

Claims

1. Catalysts for the polymerization of alpha-olefins CH₂ ═

CHR, wherein R is an alkyl radical with 1-4 C atoms or an aryl radical, comprising the product of the reaction between at least the following components;

(a) an Al-alkyl compound;

(b) an electron-donor compound (or Lewis base) which, under the standard conditions of measurement, reacts with MgCl₂, but results not to be completely complexed with Al-triethyl at the equivalent point of a potentiometric titration;

(c) a solid comprising a Ti compound containing at least a Ti-halogen bond, said Ti compound being supported on an anhydrous Mg halide, and at least one of the following activators in an amount not lower than 5% by mols with respect to the Mg halide;

(1) an Al, Fe, Mn, Sb or Zn-compound containing at least a metal-halogen bond;

(2) a complex between an electron-donor compound and a Lewis acid selected from the halides of metals of Groups II to VIII of the Periodic System other than Ti;

(3) a compound or composition inert towards the Mg halide, having a dielectric constant at 20°

C. higher than 2;

compounds (1), (2) and (3) being extractable from the solid for at least 30% by mols by treatment with toluene at 80°

C. for 2 hours, and the surface area of the solid after extraction being higher than 20 m² /g.

2. Catalysts according to claim 1, in which the activator is selected from the group consisting of Al compounds containing Al-halogen bonds, complexes of AlCl₃ or SbCl₃ with esters of aromatic monocarboxylic acids or with ethers and π

-bonds forming compounds containing polyalkyl substituted aromatic rings.

3. Catalysts according to claim 1, in which the activator selected from the compounds (c)-(1) and (c)-(2) is formed "in situ".

4. Catalysts according to claim 1, in which in the preparation of component (c) an electron-donor compound is employed.

5. Catalysts according to claim 1, in which the catalyst component (c) comprises a π

-bonds forming compound containing at least one polyalkyl substituted aromatic ring and an electron-donor selected from the group consisting of esters or ortho-dicarboxylic acids, esters of monocarboxylic acids containing at least one branched radical linked to the carboxyl group, esters of unsaturated dicarboxylic acids and esters of carbonic acid.

6. Catalysts according to claim 5, in which the catalyst component is prepared by co-grinding its components.

7. Catalysts according to claim 1, in which the activator dissolved in an aromatic or halogenated hydrocarbon is contacted with a pre-activated Mg halide.

8. Catalysts according to claim 1, in which compound (b) is selected from the Si compounds containing at least one Si-OR, Si-OCOR or Si-NR₂ bond, wherein R is an alkyl, alkenyl, aryl, arylalkyl or cycloalkyl radical with 1-20 C atoms.

9. The catalysts according to claim 1, in which the catalyst component (c) has been subjected to treatments with aromatic or halogenated hydrocarbon solvents at a temperature and for a time insuring at least partial solubilization of the activator contained in it, and the resulting suspension is employed as such as a catalyst component without previous substantial separation of the hydrocarbon solvent.

10. The catalyst components of the catalysts according to claim 5.

11. The catalyst components of the catalysts according to claim 9.

12. The catalysts according to claim 1, in which the Mg halide is MgCl₂.

13. The catalysts according to claim 1, in which the Mg halide is MgBr₂.