Polymerization catalysts

Patent metadata

Field	Value
Publication number	US-9856337-B2
Application number	US-201615081285-A
Country	US
Kind code	B2
Filing date	Mar 25, 2016
Priority date	Mar 25, 2016
Publication date	Jan 2, 2018
Grant date	Jan 2, 2018

Abstract

The present invention relates to processes for polymerizing unsaturated hydrocarbon monomers. The present invention also relates to a precatalyst having the structure of Formula (I):

M{C(SiHAlk 2 ) 3 } 3   (I),

and to a catalyst comprising the structure of Formula (II):

MC(SiHAlk 2 ) 3 X 2   (II),

and methods for preparation thereof.

First claim

What is claimed is:

1. A precatalyst having the structure of Formula (I):
M{C(SiHAlk 2 ) 3 } 3   (I)

wherein
M is a lanthanide or a transition metal; and
Alk is C 1-6 alkyl,

wherein the lanthanide metal is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb; and
wherein the transition metal is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Rf, and Ha; and
wherein if Alk is Me, then M is not Y, La, Ce, or Pr.

2. The precatalyst according to claim 1 , wherein M is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, or Yb.

3. The precatalyst according to claim 1 , wherein M is Nd.

4. The precatalyst according to claim 1 , wherein the precatalyst has the structure of Formula (Ia):

5. The precatalyst according to claim 1 , wherein the precatalyst has the structure of Formula (Ib):

6. A catalyst comprising the structure of Formula (II):
MC(SiHAlk 2 ) 3 X 2   (II),

wherein
M is a lanthanide or a transition metal;
Alk is C 1-6 alkyl;
X is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate, alkoxide, amide, BR 4 , AlR 4 , or alkyl aluminoxane;
R is independently selected at each occurrence thereof from the group consisting of H, C 6 F 5 , phenyl, and C 1-6 alkyl;

wherein the lanthanide metal is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb; and
wherein the transition metal is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Rf, and Ha; and
wherein if Alk is Me, then M is not Y, La, Ce, or Pr.

7. The precatalyst according to claim 6 , wherein M is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, or Yb.

8. The catalyst according to claim 6 , wherein M is Nd.

9. The catalyst according to claim 6 , wherein X is F, Cl, Br, I, O 2 CR 1 , methylaluminoxane (MAO), or [Ph 3 C][B(C 6 F 5 ) 4 ], and wherein R 1 is C 1-12 alkyl.

10. The catalyst according to claim 6 , wherein the catalyst comprises the structure of Formula (IIa):

11. The catalyst according to claim 6 , wherein the catalyst comprises the structure of Formula (IIb):

12. A catalyst according to claim 6 , wherein the catalyst having the structure of Formula (II) is supported by an inert carrier.

13. The catalyst according to claim 12 , wherein the inert carrier is a porous solid selected from the group consisting of talc, a sheet silicate, an inorganic oxide, and a finely divided polymer powder.

14. A process for preparation of a catalyst comprising:
providing a precatalyst having the structure of Formula (I):
M{C(SiHAlk 2 ) 3 } 3   (I),

wherein
M is a lanthanide or a transition metal; and
Alk is C 1-6 alkyl;

wherein the lanthanide metal is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb; and
wherein the transition metal is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Rf, and Ha;
wherein if Alk is Me, then M is not Y, La, Ce, or Pr;
providing a Lewis acid or a halide source; and
forming the catalyst by reacting the precatalyst having the structure of Formula (I) with the Lewis acid or the halide source.

15. The precatalyst according to claim 14 , wherein M is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, or Yb.

16. The process according to claim 14 , wherein M is Nd.

17. The process according to claim 14 , wherein the catalyst is formed with a Lewis acid, said Lewis acid being selected from the group consisting of [Ph 3 C][B(C 6 F 5 ) 4 ], B(C 6 F 5 ) 3 , Ph 3 B, PhB(C 6 H 5 ) 2 , methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, pentylaluminoxane, neopentylaluminoxane, hexylaluminoxane, octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane, phenylaluminoxane, 2,6-dimethylphenylaluminoxane, ethylaluminum sesquichloride, diisobutylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, isobutylaluminum dichloride, dimethylaluminum chloride, isobutylaluminum dichloride, diethylaluminum iodide, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dioctylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, phenylethylaluminum chloride, phenyl-n-propylaluminum chloride, phenylisopropylaluminum chloride, phenylbutylaluminum chloride, phenylisobutylaluminum chloride, phenyloctylaluminum chloride, p-tolylethylaluminum chloride, p-tolylpropylaluminum chloride, p-tolylisopropylaluminum chloride, p-tolylbutylaluminum chloride, p-tolylisobutylaluminum chloride, p-tolyloctylaluminum chloride, benzylethylaluminum chloride, benzylpropylaluminum chloride, benzylisopropylaluminum chloride, benzylbutylaluminum chloride, benzylisobutylaluminum chloride, benzyloctylaluminum chloride, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, isobutylaluminum dichloride, and octylaluminum dichloride.

18. The process according to claim 14 , wherein the catalyst is formed with a halide source, said halide source being Ph 3 C-Hal, N-chlorosuccinimide, [Alk 3 NH][Hal], or an electrophilic chlorine source, wherein Hal is halogen and each Alk is independently selected in each occurrence thereof from C 1-6 alkyl.

19. The process according to claim 14 , wherein said providing a precatalyst comprises:
providing a first intermediate compound having the structure of Formula (III):
MI 3 THF n   (III),

wherein n is 1 to 9; and
reacting the first intermediate compound with a compound having the structure of Formula (IV):
M 1 C(SiHAlk 2 ) 3   (IV),

wherein
M 1 is a metal;

under conditions effective to produce the precatalyst.

20. The process according to claim 19 , wherein M 1 is K and Alk is Me.

21. A catalyst prepared by the process according to claim 14 .

22. A catalyst according to claim 21 , wherein the catalyst is supported by an inert carrier.

23. The catalyst according to claim 22 , wherein the inert carrier is a porous solid selected from the group consisting of talc, a sheet silicate, an inorganic oxide, and a finely divided polymer powder.

24. The process according to claim 14 , wherein the catalyst comprises a structure of Formula (II):
MC(SiHAlk 2 ) 3 X 2   (II),

wherein
X is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate, alkoxide, amide, BR 4 , AlR 4 , or alkyl aluminoxane; and
R is independently selected at each occurrence thereof from the group consisting of H, C 6 F 5 , phenyl, and C 1-6 alkyl.

25. The process according to claim 24 , wherein X is F, Cl, Br, I, O

Assignees

• Univ Iowa State Res Found Inc
• Kumho Petrochemical

Inventors

• Sadow Aaron David
• Kwag Gwanghoon
• Lee Hanbaek
• Pindwal Aradhana
• Schmidt Bradley M

Classifications

• C07F7/082

  Chemistry & Metallurgy · mapped topic

• C08F136/06 Primary

  Butadiene · CPC title

• C07F7/0896

  Compounds with a Si-H linkage · CPC title

• C08F136/08

  Isoprene · CPC title

• C07F7/0803

  Compounds with Si-C or Si-Si linkages · CPC title