Catalyst components for the polmerization of olefins

• US 6,395,670 B1
• Filed: 05/06/1999
• Issued: 05/28/2002
• Est. Priority Date: 05/06/1998
• Status: Expired due to Term

• Current Assignee: Basell Technology Company BV
• Original Assignee: Basell Technology Company BV
• Inventors: Vitale, Gianni, Morini, Giampiero, Balbontin, Giulio
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): PASTERCZYK, JAMES W
• Application Number:
  US09/306,532
• Time in Patent Office: 1,118 Days
• Field of Search: 502/126,127 526/124.3,125.3,125.6
• US Class Current: 502/104
• 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 4/6494 containing oxygen
• CPC Class Codes: C08F 4/651 Pretreating with non-metals or metal-free compounds
• CPC Class Codes: C08F 4/6543 halides of magnesium

Abstract

The present invention relates to catalyst components for the polymerization of olefins having Mg, Ti, halogen and at least two internal electron donor compounds, said catalyst components characterized by the fact that at least one of the electron donor compounds is selected from ethers containing two or more ether groups which are further characterized by the formation of complexes with anhydrous magnesium dichloride in an amount less than 60 mmoles per 100 g of MgCl₂ and by the failure of entering into substitution reactions with TiCl₄ or by reacting in that way for less than 50% by moles, and at least another electron donor compound selected from esters of mono or polycarboxylic acids. Said catalyst components are able to produce propylene polymers which, for high values of xylene insolubility, show a broad range of isotacticity.

Claims

1. In a catalyst component for the polymerization of olefins CH₂═

CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, comprising Mg, Ti, and halogen, the improvement comprising;

in the catalyst component, the presence of at least two internal electron donor compounds, a first internal electron donor compound selected from the group consisting of ethers containing two or more ether groups, wherein said ethers are further characterized by the formation of complexes with anhydrous magnesium dichloride in an amount less than 60 mmoles per 100 g of MgCl₂ and by the failure of entering into substitution reactions with TiCl₄ or by reacting in that way for less than 50% by moles, and a second internal electron donor compound selected from the group consisting of esters of mono and polycarboxylic acids.

2. A catalyst component according to claim 1 in which the first internal electron donor compound is an ether selected from the group consisting of 1,3-diethers.

3. A catalyst component according to claim 2 in which the 1,3-diethers are of formula (I)

where R^I and R^II are the same or different and are hydrogen or linear or branched C₁-C₁₈ hydrocarbon groups which can also form one or more cyclic structures; R^III groups, equal or different from each other, are hydrogen or C₁-C₁₈ hydrocarbon groups;

R^IV groups, equal or different from each other, have the same meaning of R^III except that they cannot be hydrogen;

each of R^I to R^IV groups can contain heteroatoms selected from the group consisting of halogens, N, O, S and Si.

4. A catalyst component according to claim 3 in which the 1,3-diethers are of formula (II)

where the radicals R^IV have the same meaning explained in claim 3 above, and the radicals R^III and R^V radicals, equal or different, are selected from the group consisting of hydrogen, halogens, C₁-C₂₀ alkyl radicals, linear or branched;

C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, C₇-C₂₀ alkaryl and C₇-C₂₀ aralkyl radicals, and two or more of the R^V radicals can be bonded to each other to form condensed cyclic structures, saturated or unsaturated, optionally substituted with R^VI radicals selected from the group consisting of halogens, C₁-C₂₀ alkyl radicals, linear or branched;

C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, C₇-C₂₀ alkaryl and C₇-C₂₀ aralkyl radicals;

said radicals R^V and R^VI optionally containing one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both.

5. A catalyst component according to claim 3 in which the R^III radicals are hydrogen, and all the R^IV radicals are methyl.

6. A catalyst component according to claim 4 in which two or more of the R^V radicals are bonded to each other to form one or more condensed cyclic structures.

7. A catalyst component according to claim 6 in which the 1,3-diethers are selected from the compounds of formula (III):

where the R^VI radicals, equal or different, are hydrogen;

halogens;

C₁-C₂₀ alkyl radicals, linear or branched;

C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, C₇-C₂₀ alkylaryl and C₇-C₂₀ aralkyl radicals, optionally containing one or more heteroatoms selected from the group consisting of N, O, S, P, Si and halogens, as substitutes for carbon or hydrogen atoms, or both, and the radicals R^III and R^IV are as defined in claim 4 above for formula (II).

8. A catalyst component according to claim 1 in which the second internal electron donor compound is an ester of aliphatic dicarboxylic acids.

9. A catalyst component according to claim 8 in which the second internal electron donor is an ester of malonic acids of formula (IV):

where R₁ is H or a C₁-C₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, R₂ is a C₁-C₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, R₃ and R₄, equal to or different from each other, are C₁-C₂₀ linear or branched alkyl groups or C₃-C₂₀ cycloalkyl groups.

10. A catalyst component according to claim 1 in which the second internal electron donor compound is an ester of an aromatic carboxylic acid.

11. A catalyst component according to claim 10 in which the ester of the aromatic carboxylic acid is C₁-C₂₀ alkyl or aryl esters of benzoic or phthalic acid, optionally substituted.

12. A catalyst component according to claim 1 in which the second internal electron donor compound is a C₁-C₆ linear or branched alkyl ester.

13. A catalyst component according to claim 1 in which the molar ratio between the first internal electron donor compound and the second internal electron donor compound is in the range of from 0.02 to 50.

14. A catalyst component according to claim 1 in which the molar ratio between the first internal electron donor compound and the second internal electron donor compound is from 0.1 to 30.

15. A catalyst component according to claim 14 comprising a titanium compound having at least a Ti-halogen bond and the at least two internal electron donor compounds supported on a Mg halide in active form.

16. A catalyst component according to claim 15 in which the titanium compound is TiCl₄ or TiCl₃.

17. A catalyst component according to claim 1 having a spherical form, a surface area (by B.E.T. method) between 20 and 500 m²/g, and a total porosity (by B.E.T. method) higher than 0.2 cm³/g.

18. A catalyst for the polymerization of olefins CH₂═

CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, comprising the product of the reaction between;

(i) the catalyst component according to claim 1 and

(ii) an alkylaluminum compound.

19. A catalyst according to claim 18 further comprising an external electron donor compound.

20. A catalyst according to claim 19 in which the external electron donor compound is selected from the group consisting of ethers, esters, amines, heterocyclic compounds, 2,2,6,6-tetramethyl piperidine, ketones and 1,3-diethers of the general formula (V):

wherein R^I, R^II, R^III, R^IV, R^V and R^VI, equal to or different from each other, are hydrogen or hydrocarbon radicals having from 1 to 18 carbon atoms, and R^VII and R^VIII, equal to or different from each other, have the same meaning of R^I-R^VI except that they cannot be hydrogen, wherein one or more of the R^I-R^VIII groups can be linked to form a cycle.

21. A catalyst according to claim 19 in which the external electron donor compound is selected from silicon compounds of formula R_a⁵R_b⁶Si(OR⁷)_c, where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4;

R⁵, R⁶ and R⁷ are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.

22. A catalyst according to claim 21 in which a is 1, b is 1, and c is 2.

23. Catalyst according to claim 22 in which R⁵ or R⁶, or both, are branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionally containing heteroatoms, and R⁷ is a C₁-C₁₀ alkyl group.

24. A catalyst according to claim 21 in which a is 0, c is 3, R⁶ is a branched alkyl or cycloalkyl group, and R⁷ is methyl.

25. A catalyst according to claim 22 in which the silicon compound is selected from the group consisting of methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)hexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, and methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane.

26. Process for the (co)polymerization of olefins CH₂═

CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, carried out in the presence of a catalyst comprising the product of the reaction between;

(i) the solid catalyst component according to claim 1;

(ii) an alkylaluminum compound and,

(iii) optionally an external donor compound.