Aluminum alkyls with pendant olefins on clays

Patent metadata

Field	Value
Publication number	US-10676547-B2
Application number	US-201615744475-A
Country	US
Kind code	B2
Filing date	Aug 10, 2016
Priority date	Aug 31, 2015
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

This invention relates to organoaluminum compounds, organoaluminum activator systems, preferably supported, to polymerization catalyst systems containing these activator systems, and to polymerization processes utilizing the same. In particular, this invention relates to catalyst systems comprising ion-exchange layered silicate, a catalyst compound, an activator and an aluminum compound represented by formula: Al(R′)3−v(R″)v, wherein each R′, independently, is a C1-C30 hydrocarbyl group; each R″, independently, is a C4-C20 hydrocarbenyl group; and v is from 0.1 to 3.

First claim

What is claimed is:

1. A catalyst system comprising ion-exchange layered silicate, a catalyst compound, and an aluminum compound composition represented by formula:
Al(R′) 3-v (R″) v

wherein each R′, independently, is a C1-C30 hydrocarbyl group;
each R″, independently, is a linear C4-C20 hydrocarbenyl group, having an end-vinyl group; and
v is from 0.1 to 3.

2. The catalyst system of claim 1 , wherein R″ is butenyl, pentenyl, heptenyl, or octenyl.

3. The catalyst system of claim 1 , wherein R″ is octenyl.

4. The catalyst system of claim 1 , wherein the aluminum compound composition contains less than 20 weight percent of dimer.

5. The catalyst system of claim 1 , wherein the aluminum compound composition comprises diisobutyl(oct-7-en-1-yl)aluminum and/or isobutyldi(oct-7-en-1-yl)aluminum.

6. The catalyst system of claim 1 , wherein the aluminum compound composition comprises tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum, isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, isobutyl-di(non-8-en-1-yl)-aluminum, isobutyl-di(hept-6-en-1-yl)-aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-8-en-1-yl)aluminum, diisobutyl(dodec-10-en-1-yl)aluminum, or a mixture thereof.

7. The catalyst system of claim 1 , wherein the ion-exchange layered silicate is natural or synthetic montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, stevensite, vermiculite, halloysite, aluminate oxides, bentonite, kaolinite, dickite, smectic clays, mica, magadiite, kenyaite, octosilicate, kanemite, makatite, attapulgite, sepiolite, zeolitic layered materials or a mixture thereof.

8. The catalyst system of claim 1 , wherein R′ is methyl, ethyl, propyl, isobutyl, or butyl.

9. The catalyst system of claim 1 , wherein R′ is isobutyl.

10. The catalyst system of claim 1 , wherein v is about 2.

11. The catalyst system of claim 1 , wherein the aluminum compound composition contains less than 1 weight percent of dimer.

12. The catalyst system of claim 1 , wherein the catalyst compound is represented by the formula:
T j L A L B L c i MDE
where, M is a group 3, 4, 5, or 6 transition metal atom, or a lanthanide metal atom, or actinide metal atom; L A is a substituted or unsubstituted monocyclic or polycyclic arenyl pi-bonded to M; L B is as defined for L A or is J, a hetero-atom ancillary ligand bonded to M through the heteroatom; the L A and L B ligands are optionally covalently bridged together through a bridging group, T, wherein j is 0 or 1; L c i is an optional neutral, non-oxidizing ligand having a dative bond to M; i equals 0, 1, 2 or 3; D and E are independently mono-anionic labile ligands, each having a sigma-bond to M, optionally bridged to each other or to L A , L B or L c , and T is a bridging group represented by the formula R′ 2 C, R′ 2 Si, R′ 2 Ge, R′ 2 CCR′ 2 , R′ 2 CCR′ 2 CR′ 2 , R′ 2 CCR′ 2 CR′ 2 CR′ 2 , R′ C═CR′, R′ 2 CSiR′ 2 , R′ 2 SiSiR′ 2 , R′ 2 CSiR′ 2 CR′ 2 , R′ 2 SiCR′ 2 SiR′ 2 , R′ 2 CGeR′ 2 , R′ 2 GeGeR′ 2 , R′ 2 CGeR′ 2 CR′ 2 , R′ 2 GeCR′ 2 GeR′ 2 , R′ 2 SiGeR′ 2 , R′B, R′ 2 C—BR′, R′ 2 C—BR′—CR′ 2 , R′ 2 C—O—CR′ 2 , R′ 2 C—S—CR′ 2 , R′ 2 C—Se—CR′ 2 , R′ 2 C—NR′—CR′ 2 , or R′ 2 C—PR′—CR′ 2 where R′ is hydrogen or a C 1 -C 20 containing hydrocarbyl or substituted hydrocarbyl and optionally two or more adjacent R′ optionally join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent.

13. The catalyst system of claim 1 , wherein the catalyst compound is one or more of:
rac-dimethylsilylbis[(2-methyl-4-phenyl)indenyl] zirconiumdimethyl;
rac-dimethylsilylbis[(2-methyl)indenyl] zirconiumdimethyl;
rac-dimethylsilyl-bis(indenyl)hafniumdimethyl;
rac-dimethylsilyl-bis(indenyl)hafniumdichloride;
rac-dimethylsilyl-bis(indenyl)zirconiumdimethyl;
rac-dimethylsilyl-bis(indenyl)zirconiumdichloride;
rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)hafniumdimethyl;
rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)hafniumdichloride;
rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)zirconiumdimethyl;
rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)zirconiumdichloride;
rac-dimethylsilyl-bis(2-methyl-benzindenyl)hafniumdimethyl;
rac-dimethylsilyl-bis(2-methyl-benzindenyl)hafniumdichloride;
rac-dimethylsilyl-bis(2-methyl-benzindenyl)zirconiumdimethyl;
rac-dimethylsilyl-bis(2-methyl-benzindenyl)zirconiumdichloride;
bis(1-methyl,4-butylcyclopentadienyl)zirconiumdichloride;
bis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethyl;
bis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethoxide;
bis(1-methyl,4-butylcyclopentadienyl)zirconiumdibenzyl;
bis(1-methyl,4-butylcyclopentadienyl)zirconiumdifluoride;
bis(1-methyl,4-butylcyclopentadienyl)zirconiumdiamide;
bis(1-methyl,4-ethylcyclopentadienyl)zirconiumdichloride;
bis(1-methyl,4-ethylcyclopentadienyl)zirconiumdimethyl;
bis(1-methyl,4-benzylcyclopentadienyl)zirconiumdichloride;
bis(1-methyl,4-benzylcyclopentadienyl)zirconiumdimethyl;
bis(1-methyl,3-butylcyclopentadienyl)zirconiumdichloride;
bis(1-methyl,3-butylcyclopentadienyl)zirconiumdimethyl;
bis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdichloride;
bis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdimethyl;
1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium dimethyl;
dimethylsilylene(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium dimethyl;
dimethylsilylene(cyclopentadienyl)(3,6-di-tert-butyl-fluoren-9-yl)hafnium dimethyl;
diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium dimethyl;
diphenylmethylene(cyclopentadienyl)(3,6-di-tert-butyl-fluoren-9-yl)hafnium dimethyl;
isopropylidene(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium dimethyl;
isopropylidene(cyclopentadienyl)(3,6-di-tert-butyl-fluoren-9-yl)hafnium dimethyl;
dimethylsilylene(cyclopentadienyl)(2,7-dimethylfluoren-9-yl)hafnium dimethyl;
dimethylsilylene(cyclopentadienyl)(3,6-dimethylfluoren-9-yl)hafnium dimethyl;
diphenylmethylene(cyclopentadienyl)(2,7-dimethylfluoren-9-yl)hafnium dimethyl;
diphenylmethylene(cyclopentadienyl)(3,6-dimethylfluoren-9-yl)hafnium dimethyl;
dimethyl silylene(cyclopentadienyl)(fluoren-9-yl)hafnium dimethyl;
isopropylidene(cyclopentadienyl)(fluoren-9-yl)hafnium dimethyl;
diphenylmethylene(cyclopentadienyl)(fluoren-9-yl)hafnium dimethyl; and
1,1′-bis(4-triethylsilylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium dimethyl.

14. The catalyst system of claim 1 , wherein the catalyst compound is Me 2 Si(2,3,4,5-tetramethylCp)(Cp)ZrMe 2 ; (1,3-Me-nBuCp) 2 ZrCl 2 ; and/or rac-Me 2 Si(H 4 Ind) 2 ZrCl 2 .

15. The catalyst system of claim 1 , wherein the ion-exchange layered silicate is montmorillonite.

16. The catalyst system of claim 1 , further comprising an activator.

17. The catalyst system of claim 16 , wherein the activator comprises an alumoxane.

18. The catalyst system of claim 16 , wherein the activator comprises a non-coordinating anion.

19. The catalyst system of claim 16 , wherein the activator comprises one or more of:
trimethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)bor

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Holtcamp Matthew W
• Day Gregory S
• Hagadorn John R
• Palafox Patrick J
• Mathialagan Ramyaa
• Canich Jo Ann M

Classifications

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F4/642

  Component covered by group C08F4/64 with an organo-aluminium compound {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title