Modified catalyst supports

Patent metadata

Field	Value
Publication number	US-9403920-B2
Application number	US-201113816100-A
Country	US
Kind code	B2
Filing date	Aug 16, 2011
Priority date	Aug 13, 2010
Publication date	Aug 2, 2016
Grant date	Aug 2, 2016

Abstract

A supported catalyst system includes a coprecipitated silica- and titania-containing support, alumoxane, and a metallocene. The supported catalyst system has a Ti content of at least 0.1 wt %.

First claim

The invention claimed is:

1. A supported catalyst system comprising a coprecipitated silica- and titania-containing support comprising an alumoxane and at least one metallocene, wherein the supported catalyst system has a Ti content of from 0.1 wt % to 10 wt %, and wherein the alumoxane is deposited on the coprecipitated silica- and titania-containing support.

2. The supported catalyst system according to claim 1 , wherein the alumoxane is an oligomeric, linear or cyclic alumoxane selected from
R—(Al(R)—O) x —AlR 2   (III)

for oligomeric, linear alumoxanes; or
(—Al(R)—O—) y   (IV)

for oligomeric, cyclic alumoxanes
wherein x is 1-40; wherein y is 3-40; and wherein each R is independently selected from a C 1 -C 8 alkyl.

3. The supported catalyst system according to claim 1 , wherein a molar ratio of aluminum, provided by the alumoxane, to transition metal, provided by the at least one metallocene, of the supported catalyst system is between 20 and 200.

4. The supported catalyst system according to claim 1 , wherein the coprecipitated silica- and titania-containing support is an MAO-modified support, wherein MAO is methylaluminoxane.

5. A process for preparing a supported catalyst system comprising a coprecipitated silica- and titania-containing support comprising an alumoxane and at least one metallocene, wherein the supported catalyst system has a Ti content of from 0.1 wt % to 10 wt %, the process comprising the following steps:
a) coprecipitating precursors of titania and silica in solution in order to generate a gel;
b) aging the gel;
c) washing the gel to remove undesirable salts;
d) drying the gel to obtain the coprecipitated silica and titania containing support; and
e) treating the coprecipitated silica and titania containing support with the alumoxane.

6. The process according to claim 5 , wherein the precursor of titania is selected from one or more of the compounds having the general formula R n Ti(OR′) m or (RO) n Ti(OR′) m , wherein R and R′ are the same or different and are selected from the group consisting of hydrocarbyl groups containing from 1 to 12 carbon, halogens and hydrogen, and wherein n is 0 to 4, m is 0 to 4 and m+n equals 4.

7. The process according to claim 5 , wherein the precursor of titania is selected from one or more of the group consisting of tetraalkoxides of titanium having the general formula Ti(OR′) 4 wherein each R is the same or different and is an alkyl or cycloalkyl group each having from 3 to 5 carbon atoms.

8. The process according to claim 5 , wherein the precursor of silica is one or more selected from the group consisting of silicate salts and compounds having the general formula R n Si(OR′) m or (RO) n Si(OR′) m , wherein R and R′ are the same or different and are selected from the group consisting of hydrocarbyl groups containing from 1 to 12 carbon, halogens and hydrogen, and wherein n is 0 to 4, m is 0 to 4 and m+n equals 4.

9. The process according to claim 5 , wherein treating the coprecipitated silica and titania containing support with the alumoxane comprises depositing the alumoxane on the coprecipitated silica and titania containing support.

10. The process according to claim 9 , wherein treating the coprecipitated silica and titania containing support with the alumoxane comprises mixing the alumoxane in an inert diluent/solvent with the coprecipitated silica and titania containing support, wherein alumoxane deposition occurs at a temperature between 60° C. and 120° C.

11. The process according to claim 5 , further comprising treating the coprecipitated silica and titania containing support with the at least one metallocene either during treatment with the alumoxane or after treatment with the alumoxane.

12. A supported catalyst system comprising a coprecipitated silica- and titania-containing support comprising an alumoxane and at least one metallocene, wherein the supported catalyst system has a Ti content of from 0.1 wt % to 10 wt %;
wherein the at least one metallocene is selected from formula (I) or (II):
(Ar) 2 MQ 2   (I)

R″(Ar) 2 MQ 2   (II)

wherein the metallocenes according to formula (I) are non-bridged metallocenes and the metallocenes according to formula (II) are bridged metallocenes;
wherein said metallocene according to formula (I) or (II) has two Ar bound to M which are the same or different from each other;
wherein Ar is an aromatic ring, group or moiety and wherein each Ar is selected independently from an indenyl or a tetrahydroindenyl, wherein each of said groups may be optionally substituted with one or more substituents each independently selected from the group consisting of hydrogen, halogen and a hydrocarbyl having 1 to 20 carbon atoms and wherein said hydrocarbyl optionally contains one or more atoms selected from the group consisting of B, Si, S, O, F and P;
wherein M is a transition metal selected from the group consisting of titanium, zirconium, hafnium and vanadium;
wherein each Q is independently selected from the group consisting of halogen; a hydrocarboxy having 1 to 20 carbon atoms; and a hydrocarbyl having 1 to 20 carbon atoms and wherein said hydrocarbyl optionally contains one or more atoms selected from the group consisting of B, Si, S, O, F and P; and
wherein R″ is a divalent group or moiety bridging the two Ar groups and is selected from the group consisting of a C 1 -C 20 alkylene, a germanium, a silicon, a siloxane, an alkylphosphine and an amine, and wherein said R″ is optionally substituted with one or more substituents each independently selected from the group consisting of a hydrocarbyl having 1 to 20 carbon atoms and wherein said hydrocarbyl optionally contains one or more atoms selected from the group consisting of B, Si, S, O, F and P.

13. A process for preparing a polyolefin comprising the step of polymerising an olefin in the presence of a supported catalyst system comprising a coprecipitated silica- and titania-containing support comprising an alumoxane and at least one metallocene, wherein the supported catalyst system has a Ti content of from 0.1 wt % to 10 wt %, wherein polymerization is carried out in a gas phase reactor and/or in a slurry phase reactor.

14. The process according to claim 13 , wherein the olefin is ethylene or propylene.

15. The process of claim 13 , wherein the polyolefin is polyethylene having a molecular weight distribution (Mw/Mn) measured by GPC analysis of from 2 to 10; a density measured according to ISO 1183 of from 0.920 to 0.970 g/cm 3 ; and a melt flow index (MI 2 ) measured according to ISO 1133, condition D, at 190° C. and 2.16 kg of from 0.1 to 50 g/10 min.

16. A process for preparing a polyolefin comprising the step of polymerising an olefin in the presence of a supported catalyst system comprising a coprecipitated silica- and titania-containing support comprising an alumoxane and at least one metallocene, wherein the supported catalyst system has a Ti content of from 0.1 wt % to 10 wt %, wherein the polyolefin is polypropylene and wherein the process comprises the step of polymerising propylene in a bulk process.

17. A process for preparing a polyolefin comprising the step of polymerising an olefin in the presence of a supported catalyst system comprising a coprecipitated silica- and titania-containing support comprising an alumoxane and at least one metallocene, wherein the supported catalyst system has a Ti content of from 0.1 wt % to 10 wt %, wherein the polyolefin is polypropylene having a density measured according to ISO 1183 of from 0.920 to 0.970 g/cm 3 ; and a melt flow index (Mb) measured accordi

Assignees

• Willocq Christopher
• Vantomme Aurélien
• Slawinski Martine
• Total Res & Technology Feluy

Inventors

• Willocq Christopher
• Vantomme Aurélien
• Slawinski Martine

Classifications

• C08F4/025

  Metal oxides · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C08F210/00 Primary

  Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title