RU2004114267A

RU2004114267A - COMPOSITIONS OF METAL COMPLEXES AND THEIR APPLICATION AS CATALYSTS IN THE PRODUCTION OF POLYDIENES

Info

Publication number: RU2004114267A
Application number: RU2004114267/04A
Authority: RU
Inventors: Свен К-Х. ТИЛЕ (DE); Свен К-Х. ТИЛЕ; Виктор М. МОНРОЙ (US); Виктор М. МОНРОЙ; Дэвид Р. УИЛСОН (US); Дэвид Р. УИЛСОН; Хартмут ШТОЙЕ (DE); Хартмут ШТОЙЕ
Original assignee: Дау Глобал Текнолоджиз Инк. (Us); Дау Глобал Текнолоджиз Инк.
Priority date: 2001-10-12
Filing date: 2002-10-07
Publication date: 2005-09-10

Claims

1. Compositions of metal complex catalysts containing

a) at least one metal complex in accordance with formula I) or formula II);

b) at least one activator compound;

c) optionally a halide compound of a transition metal;

d) optionally a catalyst modifier;

e) optionally one (or several) inorganic (s) or polymer (s) carrier material (s),

in which formulas I) and II) of compounds a) are

where M is a lanthanide or vanadium;

Z, Z ₁ and Z ₂ are divalent bridge groups connecting two groups, each of which contains P or N atoms, where Z, Z ₁ and Z ₂ , selected independently from each other, are (CR ¹¹ ₂ ) _j , or (SiR ¹² ₂ ) _k , or (CR ²⁹ ₂ ) _l O (CR ³⁰ ₂ ) _m , or (SiR ³¹ ₂ ) _n O (SiR ³¹ ₂ ) _o , or a 1,2-disubstituted aromatic ring system, where the substituents R ¹¹ , R ¹² , R ²⁹ , R ³⁰ , R ³¹ and R ³² , selected independently from each other, are hydrogen or represent a group containing from 1 to 80 non-hydrogen atoms, which is hydrocarbyl, halogen substituted hydrocarbyl or hydrocarbylsilyl,

R ', R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , selected independently from each other, all represent groups R and represent hydrogen, or represent a group containing from 1 to 80 non-hydrogen atoms, which is hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbyl stannyl;

[ER " _p ] is a compound having a bond with a neutral Lewis base,

E represents an atom of oxygen, sulfur, nitrogen or phosphorus;

R "represents a hydrogen atom or represents a group containing from 1 to 80 non-hydrogen atoms, which is hydrocarbyl, halogenated hydrocarbyl or hydrocarbylsilyl;

p is 2, if E represents an oxygen or sulfur atom; and p is 3 if E is a nitrogen or phosphorus atom;

q is a number from zero to six;

X represents halogen (fluorine, chlorine, bromine or iodine);

M 'represents a metal from group 1 or 2;

N, P, O, S are elements from the Periodic table of elements;

b, c are zero, 1, 2, 3, 4, 5, or 6;

a, d, e, f are zero, 1 or 2;

g, h, i, r, s, t, u, v are zero, 1, 2, or 3;

j, k, l, m, n, o are 1 or 2;

w, y, z are numbers from 1 to 1000;

the sum of a + b + c + d + e + f + g + h + i + r + s + t + u + v is less than or equal to 6, and the sum of a + b + c + d + e + g + h + i + r + s + t + u + v is 3, 4 or 5;

where the oxidation state of the metal atom M is from 0 to +6, and

a metal complex may contain no more than one type of ligand selected from the following group: R ', (OR ⁵ ) and X, and may not contain an allyl, benzyl or carboxylate ligand, and

at least one activator compound b) is selected from the group consisting of 1) fluorinated or perfluorinated tri (aryl) boron or aluminum compound selected from tris (pentafluorophenyl) boron, tris (pentafluorophenyl) aluminum, tris (o-nonafluorobiphenyl) boron , tris (o-nonafluorobiphenyl) aluminum, tris [3,5-bis (trifluoromethyl) phenyl)] boron and tris [3,5-bis (trifluoromethyl) phenyl] aluminum; 2) polymer aluminoxanes; 3) oligomeric aluminoxanes; 4) non-polymeric, compatible, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions).

2. The metal complex catalyst compositions of claim 1, wherein the at least one activator compound comprises a non-polymer, compatible, non-coordinating, ion forming compound that is an ammonium, phosphonium, oxonium, carbonium, silylium, sulfonium or ferrocenic salt of a compatible non-coordinating anion .

3. The metal complex catalyst compositions of claim 1, wherein the activator compound b) comprises a non-polymer, compatible, non-coordinating, ion forming compound selected from the group consisting of an activator compound:

(A) represented by the general formula

(L ^* -H) _d ⁺ A ^d- or

(B) which is a salt of an oxidizing cation and a non-coordinating compatible anion represented by the formula

(Ox ^{e +} ) _d (A ^d- ) _e , or

(C) which is a salt of a silylium ion and a non-coordinating compatible anion represented by the formula

R ₃ Si ⁺ A ^-

where L * represents a neutral Lewis base;

(L ^* -H) ⁺ is Bronstad acid;

Ox ^{e +} is a cationic oxidizing agent having an e ⁺ charge;

d takes integer values from 1 to 3;

e takes integer values from 1 to 3;

A ^d- is a non-coordinating compatible anion having a charge of d-,

R represents C _1-10 -hydrocarbyl;

A ^- is a non-coordinating compatible anion having a charge of -1; combinations of the activator compounds listed above.

4. The composition of the metal complex catalysts according to claim 1, in which the metal complex in accordance with formulas I) and II) contains one of the following metal atoms lanthanide metal.

5. The composition of the metal complex catalysts according to claim 1, in which the metal complex in accordance with formulas I) and II) contains neodymium.

6. The composition of the metal complex catalysts according to claim 1, where only one of the indices a, b, c, d, e, g, h, i, r, s, t, u, v is not equal to zero, and R ¹ is identical to R ² ; R ³ is identical to R ⁴ ; R ¹⁴ is identical to R ¹⁵ ; R ²⁵ is identical to R ²⁶ ; R ²⁷ is identical to R ²⁸ .

7. The composition of the metal complex catalysts according to claim 1, in which the metal complex is one of the following complexes:

where Z represents (CR ₂ ) ₂ , (SiR ₂ ) ₂ , (CR ₂ ) O (CR ₂ ), (SiR ₂ ) O (SiR ₂ ) or a 1,2-disubstituted aromatic ring system; R, R ¹⁴ , R ¹⁷ , R ²⁰ , R ²³ , R ²⁷ , selected independently from each other, represent a hydrogen atom, alkyl, benzyl, aryl, silyl, stannyl; X represents a fluorine, chlorine or bromine atom; b, c are 1 or 2; f is 1 or 2; M 'represents Li, Na, K, and

where M, R, X, Z have the meanings defined above.

8. The composition of the metal complex catalysts according to claim 1, where the metal complex is one of the following complexes:

where (C ₆ H ₄ ) represents a 1,2-substituted aromatic ring and Me means methyl, Ph means phenyl, THF (THF) means tetrahydrofuran, and n is a number from 1 to 1000.

9. The metal complex catalyst compositions of claim 1, wherein the metal complex is prepared by the reaction of neodymium trichloride, adduct of neodymium trichloride and dimethoxyethane, adduct of neodymium trichloride and triethylamine or adduct of neodymium trichloride and tetrahydrofuran with one of the following metal compounds:

10. The metal complex catalyst compositions of claim 1, wherein the activator compound contains methylaluminoxane (MAO) or triisobutylaluminum modified methylaluminoxane or isobutylaluminoxane.

11. The composition of the metal complex catalysts according to claim 3, in which the activator compound is represented by the following general formula

(L ^* -H) _d ⁺ A ^d- ,

where L * and (L ^* -H) ⁺ have the meanings defined in paragraph 2, and A ^d- corresponds to the formula

[M * Q ₄ ],

where M * represents boron or aluminum in a formal oxidation state of +3; and Q represents a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy or fluorinated silyl hydrocarbyl group containing up to 20 non-hydrogen atoms, provided that no more than one of the available Q is hydrocarbyl; or

the activator compound is a salt of a cationic oxidizing agent and a non-coordinating compatible anion represented by the formula

(Ox ^{e +} ) _d (A ^d- ) _e ,

where Ox ^{e +} , d and e have the same meanings as defined in claim 2, and A ^d- is tetrakis (pentafluorophenyl) borate.

12. The composition of the metal complex catalysts according to claim 11, in which each of the available Q represents a fluorinated aryl group.

13. The composition of the metal complex catalysts according to claim 1, in which the transition metal halide compound c) is present in the composition and contains a metal atom of group 3-10, a lanthanide metal or actinoid metal bonded to one to six halogen atoms selected from the group including fluorine, chlorine, bromine or iodine atoms.

14. The metal complex catalyst compositions of claim 13, wherein the transition metal halide compound c) is one of the following compounds: ScCl ₃ , TiCl ₂ , TiCl ₃ , TiCl ₄ , TiCl ₂ * 2LiCl, ZrCl ₂ , ZrCl ₂ * 2LiCl, ZrCl ₄ , VCl ₃ , VCl ₅ , CrCl ₂ , CrCl ₃ , CrCl ₅ and CrCl ₆ .

15. The metal complex catalyst composition of claim 13, wherein the transition metal halide compound c) is present in the composition and is a compound obtained by reacting the transition metal halide compound c) of paragraph 13 or 14 with a Lewis base.

16. The metal complex catalyst compositions of claim 15, wherein the transition metal halide compound c) is a compound obtained by reacting the transition metal halide compound c) of claims 13 or 14 with one of n-butyl lithium, tert-butyl lithium compounds, methyl lithium, diethyl magnesium or ethyl magnesium halide.

17. The metal complex catalyst compositions of claim 1, wherein the optional catalyst modifier d) is present in the composition and is a neutral Lewis acid selected from C _1-30 hydrocarbyl substituted compounds of group 13 or their halogenated (including perhalogenated) derivatives.

18. The metal complex catalyst compositions of claim 17, wherein the optional modifier catalyst d) is selected from (hydrocarbyl) aluminum compounds and their halogenated (including perhalogenated) derivatives containing from 1 to 20 carbon atoms in each hydrocarbyl or halogenated hydrocarbyl group, where (hydrocarbyl) aluminum compounds are selected from trialkylaluminum and alkylaluminum hydrides.

19. The metal complex catalyst compositions of claim 17, wherein the activator compound b) is a tri (hydrocarbyl) boron compound containing from 1 to 20 carbon atoms in each hydrocarbyl group, and the catalyst modifier d) is a trialkyl aluminum compound containing from 1 to 4 carbon atoms in each alkyl group.

20. The composition of the metal complex catalysts according to claim 1, in which the carrier material e) is present in the composition and

represents clay, silicon dioxide, charcoal, graphite, expanded clay, swollen graphite, carbon black, layered silicates or alumina.

21. The method of producing polydienes, characterized in that the production of polydienes is carried out using the composition of metal complex catalysts according to any one of the preceding paragraphs.

22. The method of producing polydienes according to item 21, where the molar ratio of the activator compound b) to the central metal in the metal complex a) is in the range from 11:10 to 5000: 1.

23. The method of producing polydienes according to item 21, where the molar ratio of the transition metal halide compound c) to the central metal in the metal complex a) is in the range from 1: 100 to 1000: 1.

24. The method of producing polydienes according to item 21, where the diolefin (e) monomer (s) is selected (s) from the group comprising 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3- dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene, 1,3-cyclooctadiene, norbornadiene.

25. The method of producing polydienes according to paragraph 24, where the ratio of the catalyst complex on the carrier to the carrier material e) is in the range from about 0.5 to 100000.