RU2001131727A - ORGANOMETALLIC COMPOUND SUITABLE AS A CO-CATALYST FOR POLYMERIZATION OF OLEFINS - Google Patents

Claims (19)

1. The organometallic compound obtained by contacting a) a compound having the following formula (I):

where R ^a , R ^b , R ^c and R ^d , identical or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl , C ₇ -C ₂₀ arylalkyl and C ₇ -C ₂₀ alkylaryl groups optionally containing O, S, N, P, Si or halogen atoms, or two or more adjacent substituents R ^a , R ^b , R ^c and R ^d form one or several C ₄ -C ₇ rings optionally containing O, S, N, P or Si atoms which may be substituted; with b) Lewis acid of the formula (II) MtR ¹ ₃ (II) where Mt is a metal belonging to group 13 of the Periodic Table of the Elements (IUPAC); R ¹ , identical or different from each other, is selected from the group consisting of halogen, halogenated C ₆ -C ₂₀ aryl and halogenated C ₇ -C ₂₀ alkylaryl groups; two groups of R ¹ can also form a single condensed ring with the metal. 2. The organometallic compound of claim 1, wherein Mt is B or A1; R ¹ substituents are selected from the group consisting of fluoro, C ₆ F ₅ , C ₆ F ₄ H, C ₆ F ₃ H ₂ , C ₆ H ₃ (CF ₃ ) ₂ , perfluorobiphenyl, heptafluoronaphthyl, hexafluoronaphthyl and pentafluoronaphthyl. 3. The organometallic compound according to claim 1 or 2, having the formula (III)

where Mt is a metal belonging to group 13 of the Periodic Table of the Elements (IUPAC); R ¹ , identical or different from each other, is selected from the group consisting of halogen, halogenated C ₆ -C ₂₀ aryl and halogenated C ₇ -C ₂₀ -alkylaryl groups; two groups R ¹ can also form one condensed ring with the metal Mt; the substituents R ⁵ , R ⁴ , R ³ and R ² , identical or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated, C ₁ -C ₁₀ -alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ arylalkyl and C ₇ -C ₂₀ alkylaryl groups optionally containing O, S, N, P, Si or halogen atoms, or two or more adjacent R ² -R ⁵ substituents form one or several C ₄ -C ₇ rings optionally containing O, S, N, P or Si; with the proviso that at least one of R ⁵ , R ⁴ , R ³ and R ² is different from hydrogen. 4. The organometallic compound of claim 3, wherein Mt is B or A1; R ¹ substituents, identical or different from each other, are selected from the group consisting of fluorine, C ₆ F ₅ , C ₆ F ₄ H, C ₆ F ₃ H ₂ , C ₆ H ₃ (CF ₃ ) ₂ , perfluorobiphenyl, heptafluoronaphthyl , hexafluoronaphthyl and pentafluoronaphthyl; at least one of the substituents R ⁵ and R ⁴ is a C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ arylalkyl and C ₇ -C ₂₀ alkylaryl group optionally containing O, S, N atoms, P, Si or halogen, or together they can form an aromatic C ₅ -C ₇ ring, optionally containing O, S, N, P or Si atoms, which may be substituted. 5. The organometallic compound according to claim 3 or 4, having the formula (V)

where B is a boron atom; the substituents R ¹ , R ³ and R ² have the meanings given in claim 3 or 4; R ⁶ substituents, identical or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ arylalkyl and C ₇ -C ₂₀ alkylaryl groups optionally containing O, S, N, P, Si or halogen atoms, or two or more adjacent R ⁶ substituents form one or more C ₄ -C ₇ rings, optionally containing O, S atoms , N, P or Si, which may carry substituents. 6. The organometallic compound according to claim 3 or 4, having the formula (VI)

where the substituents R ¹ and R ⁶ have the meanings defined in paragraph 5. 7. The organometallic compound according to claim 1 or 2, having the following formula (IV):

where Mt and R ¹ are as defined in claim 1 or 2; the substituents R ^{2 '} , R ^3' , R ^{4 '} and R ^5' , identical or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C ₁ -C ₁₀ -alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ arylalkyl and C ₇ -C ₂₀ alkylaryl groups optionally containing O, S, N, P, Si or halogen atoms, or two or more adjacent substituents R ^{2 '} , R ^{3 '} , R ^4' and R ^{5 '} form one or more C ₄ -C ₇ rings optionally containing O, S, N, P or Si atoms which may be substituted; said rings may be aliphatic or may optionally contain double bonds, provided that said rings are not aromatic. 8. The organometallic compound according to claim 7, in which the substituents R ^{2 '} , R ^3' , R ^{4 '} and R ^5' , identical or different from each other, are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C ₁ -C ₁₀ alkyl optionally containing O, S, N, P or Si atoms, or two or more adjacent substituents R ² , R ³ , R ⁴ and R ⁵ form one or more C ₄ -C ₇ rings, optionally containing O, S, N, P or Si atoms which substituents may carry; said rings may be aliphatic or may optionally contain double bonds, provided that said rings are not aromatic. 9. The organometallic compound according to claim 7 or 8, having the formula (VII)

where the substituents R ¹ have the meanings given in claim 1 or 2; substituents R ^{2 ′} and R ^{5 ′} , identical or different from each other, are C ₁ -C ₂₀ alkyl. 10. A catalytic system for the polymerization of olefins, comprising a product obtained by contacting: (A) at least one organometallic transition metal compound, with the exception of pyrrolidyl bis (η-cyclopentadienyl) methylzirconium and (B) organometallic compound obtained by bringing in contact (a) of the Lewis base having the following formula (I):

where R ^a , R ^b , R ^c and R ^d , identical or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C ₁ -C ₁₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₇ -C ₂₀ arylalkyl and C ₇ -C ₂₀ alkylaryl groups optionally containing O, S, N, P, Si or halogen atoms, or two or more adjacent substituents R ^a , R ^b , R ^c and R ^d form one or more C ₄ -C ₇ cycles, optionally containing O, S, N, P or Si atoms, which may be substituted; with b) Lewis acid of the formula (II) MtR ¹ ₃ (II) where Mt is a metal belonging to group 13 of the Periodic Table of the Elements (IUPAC); R ¹ , identical or different from each other, is selected from the group consisting of halogen, halogenated C ₆ -C ₂₀ aryl and halogenated C ₇ -C ₂₀ alkylaryl groups; two groups R ¹ can also form one condensed ring with a metal atom Mt; and (c) optionally an alkylating agent. 11. The catalytic system of claim 10, in which the organometallic compound (B) has the formula (III)

where Mt, R ¹ , R ⁵ , R ⁴ , R ³ and R ^{2 are} defined as in claim 3. 12. The catalytic system according to claim 10, in which the organometallic compound (B) has the formula (IV)

where Mt, R ^{1 '} , R ^2' , R ^{3 '} , R ^4' and R ^{5 'are} defined as in claim 7. 13. The catalytic system according to each of paragraphs.10-12, in which the catalytic organometallic transition metal compound has the following formula (VIII) (Cp) (ZR ⁷ _m ) _n (A) _r ML _p (VIII) where (ZR ⁷ _m ) _n is a divalent group connecting Cp and A with a bridging bond; Z is C, Si, Ge, N or P and R ⁷ groups, identical or different from each other, are hydrogen or linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl and C ₇ -C ₂₀ arylalkyl groups or two R ⁷ can form an aliphatic or aromatic C ₄ -C ₇ ring; Cp is a substituted or unsubstituted cyclopentadienyl group, optionally fused to one or more substituted or unsubstituted, saturated, unsaturated, or aromatic rings containing from 4 to 6 carbon atoms, optionally containing one or more heteroatoms; A is O, S, NR ⁸ , PR ⁸ , in which R ⁸ is hydrogen, linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₇ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ arylalkyl, or A has the same meaning as Cp; M is a transition metal belonging to 3, 4, 5, 6 or lanthanoid or actinoid groups of the Periodic system of elements (IUPAC version); substituents L, identical or different from each other, are monoanionic sigma ligands selected from the group consisting of hydrogen, halogen, R ⁹ , OR ⁹ , OCOR ⁹ , SR ⁹ , NR ⁹ and PR ⁹ ₂ in which R ⁹ is linear or a branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ arylalkyl group, optionally containing one or several Si or Ge atoms; preferably, the substituents L are the same; m = 1 or 2 and, in particular, equal to 1 if Z is N or P, and equal to 2 if Z is C, Si or Ge; n is 0 to 4; r is 0, 1 or 2; n = 0 if r = 0; p is an integer equal to the oxidation state of the metal M minus r + 1. 14. The catalytic system according to any one of claims 10 to 12, in which the catalytic organometallic transition metal compound has the following formulas (IX) or (X) L ^a M ^a X ^a p ^a (IX) L ^a M ^a A ^a (X) where M ^a is a metal belonging to 8, 9, 10 or 11 groups of the Periodic table of elements (new IUPAC record form); L ^a is a bidentate or tridentate ligand of the formula (XI)

where B is a C ₁ -C ₅₀ bridging group connecting E ¹ and E ² , optionally containing one or more atoms belonging to 13-17 groups of the Periodic Table; E ¹ and E ² , identical or different from each other, are elements belonging to the 15th or 16th group of the Periodic table and are associated with the indicated metal M ^a ; substituents R ^a1 , identical or different from each other, are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl and C ₇ -C ₂₀ arylalkyl radicals optionally containing one or more atoms belonging to 13-17 groups of the Periodic Table of Elements (such as B, Al, Si, Ge, N, P, O atoms , S, F, and Cl); or two R ^a1 substituents attached to one atom of E ¹ or E ² form a saturated, unsaturated or aromatic C ₄ -C ₇ ring having from 4 to 20 carbon atoms; m ^a and n ^a are independently 0, 1 or 2, depending on the valency of E ¹ and E ² , so as to satisfy the valency of E ¹ and E ² ; q ³ is the charge of the bidentate or tridentate ligand so that it satisfies the oxidation state of M ^a X ^a _p ^a or M ^a A ^a , and the compounds (IX) or (X) are generally neutral; X ^a , identical or different from each other, are monoanionic sigma ligands selected from the group consisting of hydrogen, halogen, R ^a , OR ^a , OSO ₂ CF ₃ , OCOR ^a , SR ^a , -NR ^a ₂ and PR ^a ₂ groups where R ^a substituents are linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ -alkylaryl or C ₇ -C ₂₀ -arilalkilnymi radicals, optionally containing one or more atoms belonging to groups 13-17 of the Periodic table of the elements (new IUPAC form of records) such ka In, N, P, Al, Si, Ge, O, S and F atoms; or two groups X ^a form a metalcyclic ring containing from 3 to 20 carbon atoms; X ^a substituents are preferably the same; p ^a = 0 - 3, so that the final compound (IX) or (X) is generally neutral; And ^a is a π-allyl or π-benzyl group. 15. A method of obtaining an organometallic compound according to each of claims 2 to 9, comprising a reaction step, in approximately stoichiometric amounts, of a compound having the formula (I)

where R ^a , R ^b , R ^c and R ^{d are} defined in claim 1; with Lewis acid of the formula (II) MtR ¹ ₃ (II) where Mt and R ^{1 are} defined in claim 1. 16. A method of polymerizing one or more olefins, comprising contacting one or more olefins under polymerization conditions in the presence of a catalyst system according to any one of claims 10-14. 17. The method according to clause 16, in which ethylene is homopolymerized or copolymerized with a comonomer of the formula CH ₂ = CHR ', where R' is a linear, branched or cyclic C ₁ -C ₂₀ -alkyl radical or cycloolefins. 18. The method according to 17, in which propylene is homopolymerized. 19. The method according to 17 for producing elastomeric copolymers of ethylene with α-olefins of the formula CH ₂ = CHR ″, where R ″ represents a C ₁ -C ₁₀ alkyl radical, optionally containing a small proportion of units derived from polyenes.