Metallocene catalyst based on a transition metal of groups 4 or 5 of the periodic table immobilized on a support modified with soluble hybrid silica, method for producing and using same

Patent metadata

Field	Value
Publication number	US-9822199-B2
Application number	US-201415101710-A
Country	US
Kind code	B2
Filing date	Dec 4, 2014
Priority date	Dec 5, 2013
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

The present invention pertains to a metallocene catalyst based on a transition metal of groups 4 or 5 of the periodic table prepared by the immobilization of a metallocene complex on a support modified with hybrid soluble silica, prepared by a non-hydrolytic sol-gel process. There is also described a process for preparing said catalyst.
The supported metallocene catalyst of the present invention has the advantages of high catalytic activity, morphology, besides the fact of producing copolymers of ethylene with alpha-olefins having molecular behavior that will bring benefits in mechanical properties, such as resistance to tearing, piercing and impact, as well as improved optical and weldability properties.

First claim

What is claimed is:

1. A metallocene catalyst based on a transition metal of groups 4 or 5 of the periodic table immobilized on a support modified with soluble hybrid silica, comprising:
(a) at least one metallocene derived from a compound of formula 1:
[L] 2 -MQ 2   formula 1

wherein
M is a transition metal of groups 4 or 5;
Q's, which are the same or different, are halogen radical, aryl radical, alkyl radical containing from 1 to 5 carbon atoms or alkoxy radical containing from 1 to 5 carbon atoms; and
L is a bulky ligand of the cyclopentadienyl, indenyl or fluorenyl type, optionally substituted by alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl, linked to the transition metal by bonding:
(b) a hybrid soluble silica;
(c) an inorganic catalyst support; and
(d) at least one aluminum-containing organometallic reagent.

2. The catalyst according to claim 1 , wherein the hybrid soluble silica is obtained by the non-hydrolytic sol-gel route and has a structure consisting of siloxane groups (SiOSi), alkoxy groups and aliphatic organic groups, covalently bonded to the silicon atoms.

3. The catalyst according to claim 1 , wherein the inorganic catalyst support is an oxide compound.

4. The catalyst according to claim 1 , wherein the organometallic reagent containing aluminum is an aluminoxane compound selected from methylaluminoxane type (MAO), etylaluminoxane (EAO) or a compound of formula 2
Cl x Al(C) y   Formula 2

wherein:
C is an aliphatic organic group containing 1 to 6 carbon atoms;
Al is aluminum;
x is an integer from 0 to 1; and
y is an integer from 2 to 3.

5. The catalyst according to claim 1 , wherein the hybrid soluble silica is physically adsorbed or chemically bonded on the surface of the inorganic catalyst support.

6. The catalyst according to claim 1 , wherein the content of C, from the aliphatic organic groups of the hybrid soluble silica, in the catalyst is between 0.5% to 20% relative to the mass of inorganic support.

7. The catalyst according to claim 1 , wherein the content of Al, from the organometallic reagent, ranges from 1 to 20% relative to the catalyst mass.

8. The catalyst according to claim 1 , wherein the content of transition metal, from the metallocene complex of formula 1, ranges from 0.1 to 6% relative to the catalyst mass.

9. A process for obtaining a supported metallocene catalyst as defined in claim 1 , comprising the following steps:
(a) Preparing a hybrid soluble silica;
(b) Reacting the hybrid soluble silica obtained in step (a) with an inorganic support;
(c) Removing the solvent from the reaction product obtained in step (b);
(d) Reacting the product obtained in step (c) with an organometallic reagent containing aluminum;
(e) Removing the solvent from the reaction product obtained in step (d);
(f) Reacting the product obtained in step (e) with a metallocene complex; and
(g) Removing the solvent from the reaction product obtained in step (f).

10. The process according to claim 9 , wherein step (a) comprises the following steps:
i) Preparing a suspension of a metal halide in an organic solvent;
ii) Adding silicon tetrachloride on the suspension prepared in step (i);
iii) Preparing a mixture containing an alkoxysilane, an organo-alkoxysilane and an organic solvent;
iv) Adding the mixture prepared in step (iii) on the suspension obtained in step (ii); and
v) Chemical reaction between the reagents present in the mixture prepared in step (iv).

11. The process according to claim 9 , wherein in step (b) the inorganic support can be used in its form in natura or calcined up to a temperature limit of 800° C.

12. The process according to claim 9 , wherein the hybrid soluble silica added to the inorganic support in step (b) ranges from 0.5% to 20% by mass of carbon per mass of inorganic support.

13. The process according to claim 9 , wherein the solvent is removed from the product of step (b) by a technique selected from nitrogen gas flow evaporation, settling/siphoning, evaporation by reduced pressure or evaporation by heating, used in isolation or in combination.

14. The process according to claim 9 , wherein the organometallic reagent containing aluminum added in step (d) is an aluminoxane compound of the methylaluminoxane type, ethylaluminoxane or a compound of formula 2
Cl x Al(C) y   formula 2

wherein:
C is an aliphatic organic group containing 1 to 6 carbon atoms;
Al is aluminum;
x is an integer from 0 to 1; and
y is an integer from 2 to 3.

15. The process according to claim 9 , wherein the content of organometallic reagent containing aluminum added to the product of step (c) ranges from 0.1% to 20% by mass of aluminum per mass of product of step (c).

16. The process according to claim 9 , wherein the solvent is removed from the reaction product obtained in step (d) by a technique selected from nitrogen gas flow evaporation, settling/siphoning, evaporation by reduced pressure or evaporation by heating, used in isolation or in combination.

17. The process according to claim 9 , wherein the metallocene used in step (f) comprises a derivative compound of the following formula:
[L] 2 -MQ 2   formula 1

wherein
M is a transition metal of groups 4 or 5;
Q's, which are the same or different, are halogen radical, aryl radical, alkyl radical containing from 1 to 5 carbon atoms or alkoxy radical containing from 1 to 5 carbon atoms; and
L is a bulky ligand of the cyclopentadienyl, indenyl or fluorenyl type, optionally substituted by alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl, linked to the transition metal by bonding.

18. The process according to claim 9 , wherein the content of metallocene added in step (f) ranges from 0.1 to 6% by mass of transition metal per mass of supported catalyst.

19. The process according to claim 9 , wherein the solvent is removed from the reaction product obtained in step (f) by a technique selected from nitrogen gas flow evaporation, settling/siphoning, evaporation by reduced pressure or evaporation by heating, used in isolation or in combination.

20. A process of copolymerization of ethylene and an alpha-olefin in the presence of the supported metallocene catalyst according to claim 1 .

Assignees

• Braskem Sa

Inventors

• Brambilla Rodrigo
• Miranda Marcia Silva Lacerda
• Moreira Ana Cristina Fontes
• Rocha Etienne Marcos De Almeida
• Gollmann Maria Angelica Cardoso

Classifications

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/02

  Carriers therefor · CPC title

• C08F210/02

  Ethene · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title