Modified catalyst supports

Patent metadata

Field	Value
Publication number	US-10233268-B2
Application number	US-201113807559-A
Country	US
Kind code	B2
Filing date	Jul 1, 2011
Priority date	Jul 1, 2010
Publication date	Mar 19, 2019
Grant date	Mar 19, 2019

Abstract

The invention covers a supported catalyst system prepared according to a process comprising the following step:
i). impregnating a silica-containing catalyst support having a specific surface area of from 150 m 2 /g to 800 m 2 /g, preferably 280 m 2 /g to 600 m 2 /g, with one or more titanium compounds of the general formula selected from R n Ti(OR′) m and (RO) n Ti(OR′) m , wherein R and R′ are the same or different and are selected from hydrocarbyl groups containing from 1 to 12 carbon and halogens, and wherein n is 0 to 4, m is 0 to 4 and m+n equals 4, to form a titanated silica-containing catalyst support having a Ti content of at least 0.1 wt % based on the weight of the Ti-impregnated catalyst support

wherein the supported catalyst system further comprises an alumoxane and a metallocene.

First claim

The invention claimed is:

1. A process for preparing a supported catalyst system comprising:
i). impregnating a silica-containing catalyst support having a specific surface area of from 150 m 2 /g to 800 m 2 /g, with a mixture of titanium compounds of 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 hydrocarbyl groups containing from 1 to 12 carbon and halogens, and wherein n is 0 to 4, m is 0 to 4 and m+n equals 4, to form a titanated silica-containing catalyst support having a Ti content of at least 0.1 wt % based on the weight of the Ti-impregnated catalyst support;
wherein the supported catalyst system further comprises an alumoxane and a metallocene, and wherein the metallocene comprises a transition metal;
ii). drying the Ti-impregnated catalyst support prior to the addition of alumoxane and metallocene on the Ti-impregnated catalyst support;
iii). adding the alumoxane on the Ti-impregnated catalyst support prior to or during the addition of metallocene;
wherein the molar ratio of aluminum from the alumoxane to transition metal of the supported catalyst system is between 30 and 100 and
wherein the silica-containing catalyst support is not contacted with a halogenated compound other than the metallocene.

2. The process according to claim 1 , wherein the titanated silica-containing catalyst support has a Ti content of 0.1 to 60 wt % based on the weight of the Ti-impregnated catalyst support.

3. The process according to claim 1 , wherein the titanated silica-containing catalyst support has a Ti content of 0.1 to 12 wt % based on the weight of Ti-impregnated catalyst support and an atomic molar ratio Ti/M, wherein M is a transition metal selected from one or more of zirconium, hafnium and vanadium, of 0.13 to 500.

4. The process according to claim 1 , wherein the titanium compounds in the mixture of titanium compounds are selected from 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.

5. The process according to claim 1 , wherein the titanium compounds in the mixture of titanium compounds comprise Ti(OC 4 H 9 ) 4 and Ti(OC 3 H 7 ) 4 , and wherein the ratio of Ti(OC 4 H 9 ) 4 and Ti(OC 3 H 7 ) 4 is about 20/80.

6. The process according to claim 1 , wherein the alumoxane is methylaluminoxane (MAO).

7. The process according to claim 1 , wherein the 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 independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, 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 comprising 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 comprising B, Si, S, O, F and P; and
wherein R″ is a divalent group or moiety bridging the two Ar groups and 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 comprising a hydrocarbyl having 1 to 20 carbon atoms and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F and P.

8. The process according to claim 7 , wherein each Ar is selected independently from an indenyl or a tetrahydroindenyl.

9. The process 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.

10. The process according to claim 1 , wherein the titanium compounds in the mixture of titanium compounds are selected from the group consisting of tetraalkoxides of titanium having the general formula Ti(OR′) 4 ;
wherein each R′ is the same or different, wherein each R′ is an alkyl group having from 3 to 5 carbon atoms, a cycloalkyl group having from 3 to 5 carbon atoms, or mixtures thereof;
wherein the impregnation of the support by the mixture of titanium compounds is performed by introducing the mixture of titanium compounds in the form of a suspension in a diluent, or by introducing the mixture of titanium compounds dissolved in an aqueous solvent.

11. The process according to claim 1 , wherein the mixture of titanium compounds comprises Ti(OC 4 H 9 ) 4 or Ti(OC 3 E 7 ) 4 .

12. The process according to claim 1 , wherein the titanium compounds in the mixture of titanium compounds are of the general formula R n Ti(OR′) m , wherein R and R′ are the same or different and are selected from hydrocarbyl groups containing from 1 to 12 carbon and halogens, and wherein n is 0 to 4, m is 0 to 4 and m+n equals 4.

13. The process according to claim 1 , wherein the titanium compounds in the mixture of titanium compounds are of the general formula (RO) n Ti(OR′) m , wherein R and R′ are the same or different and are selected from hydrocarbyl groups containing from 1 to 12 carbon and halogens, and wherein n is 0 to 4, m is 0 to 4 and m+n equals 4.

14. The process according to claim 1 , wherein impregnation of the silica-containing catalyst support with the mixture of titanium compounds forms Si—O—Ti—OH on a surface of pores within the silica-containing catalyst support prior to addition of the alumoxane to the Ti-impregnated catalyst support.

15. The process according to claim 1 , wherein drying the Ti-impregnated catalyst support prior to the addition of alumoxane and metallocene on the Ti-impregnated catalyst support comprises heating the Ti-impregnated catalyst support to a temperature of at least 100° C. in an atmosphere of dry and inert gas, air, or combinations thereof.

16. The process according to claim 1 , wherein adding the alumoxane to the Ti-impregnated catalyst support comprises mixing the alumoxane in an inert diluent or solvent with the Ti-impregnated catalyst support, wherein deposition of the alumoxane on the Ti-impregnated catalyst support occurs at a temperature between 60° C. and 120° C.

17. The process of according to claim 1 , wherein the alumoxane is added on the Ti-impregnated catalyst support prior to addition of metallocene, and wherein adding the metallocene to the Ti-impregnated catalyst support comprises mixing the metallocene with the Ti-impregnated catalyst support.

18. The process according to claim 1 , wherein the mixtu

Assignees

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

Inventors

• Willocq Christopher
• Vantomme Aurélien
• Slawinski Martine

Classifications

• B01J2531/56

  Vanadium · CPC title

• B01J2531/49

  Hafnium · CPC title

• B01J31/122

  Metal aryl or alkyl compounds · CPC title

• B01J31/0212

  Alkoxylates · CPC title

• C08F110/06

  Propene · CPC title