Preparation of catalyst system

Patent metadata

Field	Value
Publication number	US-12312368-B2
Application number	US-202017614747-A
Country	US
Kind code	B2
Filing date	May 20, 2020
Priority date	May 29, 2019
Publication date	May 27, 2025
Grant date	May 27, 2025

Abstract

Improved preparation process for silica supported catalyst systems, which comprise a specific class of metallocene complexes in combination with a boron containing cocatalyst and an aluminoxane cocatalyst and use of the new, improved catalyst system.

First claim

The invention claimed is:

1. A process for the preparation of a supported catalyst system, wherein the catalyst system comprises:
(i) a metallocene complex;
(ii) a cocatalyst system comprising a boron containing cocatalyst and an aluminoxane cocatalyst; and
(iii) a porous inorganic support;
whereby the process comprises the steps of:
a) reacting the porous inorganic support with a first portion of the aluminoxane cocatalyst in a first hydrocarbon solvent to obtain an aluminoxane cocatalyst treated support;
b) reacting the metallocene complex with a second portion of the aluminoxane cocatalyst in a second hydrocarbon solvent,
wherein the first portion of the aluminoxane cocatalyst added in step a) is from 75.0 to 97.0 wt % of the total amount of the aluminoxane cocatalyst and the second portion of the aluminoxane cocatalyst added in step b) is from 3.0 to 25.0 wt % of the total amount of aluminoxane cocatalyst;
c) adding the boron containing cocatalyst to the solution obtained in step b) to obtain a solution of the metallocene complex, boron containing cocatalyst, and aluminoxane cocatalyst, wherein the metallocene complex includes a metal ion M and whereby the boron containing cocatalyst is added in an amount such that the molar ratio of boron/M is in the range of from 0.1:1 to 10:1;
d) adding the solution obtained in step c) to the aluminoxane cocatalyst treated support obtained in step a) to form the supported catalyst system; and optionally
e) drying the so obtained supported catalyst system.

2. The process as claimed in claim 1 , wherein the metallocene complex is of formula (I)-(III):

wherein
each X independently is a sigma-donor ligand;
M is Ti, Zr, Hf, Y, Sc, La, or an element from the lanthanides;
each Cp independently is an unsubstituted or substituted cyclopentadienyl containing ligand or an unsubstituted or substituted fused cyclopentadienyl containing ligand;
Q is —O or —NW or —PW;
W is an organic group or H;
L is a carbon, silicon or germanium based bridge in which one to four backbone atoms link the ligands; and
r is an integer such that the oxidation state of the metal is satisfied.

3. The process as claimed in claim 1 , wherein the metallocene complex is of formula (VI):

wherein
each X independently is a sigma-donor ligand;
M is a group 4 metal;
L is a carbon, silicon, or germanium based bridge in which one to four backbone atoms link the ligands; and
each Ind is a substituted or unsubstituted indenyl, or a substituted or unsubstituted fused indenyl.

4. The process as claimed in claim 1 , wherein the metallocene complex is of formula (IV):

wherein
each X independently is a sigma-donor ligand;
M is Zr or Hf,
L is a carbon, silicon, or germanium based divalent bridge in which one or two backbone atoms link the ligands;
each Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms;
each R 1 independently is hydrogen, a linear or branched C 1 -C 6 -alkyl group, a C 7-20 -arylalkyl group, a C 7-20 -alkylaryl group, a C 6-20 -aryl group, or an OY group, wherein Y is a C 1-10 -hydrocarbyl group, or wherein two adjacent R 1 groups taken together with the phenyl carbons to which they are bonded form a ring;
each R 2 independently is a CHR 8′ —R 8 group, with R 8 being H, a linear or branched C 1-6 -alkyl group, a C 3-8 -cycloalkyl group, a C 6-10 -aryl group, or a heteroaryl group having 3 to 20 carbon atoms optionally substituted by one to three groups R 11 , and R 8′ is H or a C 1-6 alkyl;
R 3 is a linear or branched C 1 -C 6 -alkyl group, a C 7-20 -arylalkyl group, a C 7-20 -alkylaryl group, or C 6 -C 20 -aryl group;
R 4 is a C(R 9 ) 3 group, with each R 9 independently being a linear or branched C 1 -C 6 -alkyl group;
R 5 and R 6 are each independently hydrogen or an aliphatic C 1 -C 20 -hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements, or wherein R 5 and R 6 taken together form a 5 membered saturated carbon ring which is optionally substituted by n groups R 10 , n being from 0 to 4, and each R 10 independently is a C 1 -C 20 -hydrocarbyl group, or a C 1 -C 20 -hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements;
R 7 is H, a linear or branched C 1 -C 6 -alkyl group, or an aryl or heteroaryl group having 3 to 20 carbon atoms optionally substituted by one to three groups R 11 ; and
each R 11 independently is hydrogen, a linear or branched C 1 -C 6 -alkyl group, a C 7-20 -arylalkyl group, a C 7-20 -alkylaryl group, a C 6-20 -aryl group, or an OY group, wherein Y is a C 1-10 -hydrocarbyl group.

5. The process as claimed in claim 1 , wherein the metallocene complex is of formula (IX):

wherein
each X independently is a sigma-donor ligand;
M is a group 4 metal;
L is a carbon, silicon, or germanium based divalent bridge in which one or two backbone atoms link the ligands;
R 2 and R 2′ are, independently from each other, H, —OSi(C 1-10 -hydrocarbyl) 3 , or CHR 8′ —R 8 group;
R 8 being H, a linear or branched C 1-6 -alkyl group, a C 3-8 -cycloalkyl group, a C 6-10 -aryl group, or an optionally substituted heteroaryl group having 3 to 20 carbon atoms;
R 8′ is H or a C 1-6 alkyl;
R 5 -R 6 are each independently hydrogen or a C 1 -C 20 -hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements, or R 5 and R 6 taken together form a 5 membered saturated carbon ring which is optionally substituted by n groups R 10 , n being from 0 to 4;
R 5′ —R 6′ are each independently hydrogen or a C 1 -C 20 -hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements, or R 5′ and R 6′ taken together form a 5 membered saturated carbon ring which is optionally substituted by n groups R 10 , n being from 0 to 4;
each R 10 is independently a C 1 -C 20 -hydrocarbyl group, or a C 1 -C 20 -hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements;
Ar and Ar′ are independently phenyl, naphthyl, anthracenyl, pyridyl, thiophenyl, 2-alkylthiophenyl, benzothiophenyl, pyrrolyl, furanyl, or 2-alkylfuranyl optionally substituted by up to 5 groups R 1 ; and
each R 1 independently is hydrogen, a linear or branched C 1 -C 6 -alkyl group, a C 7-20 -arylalkyl group, a C 7-20 -alkylaryl group, C 6-20 -aryl group, or an OY group, wherein Y is a C 1-10 -hydrocarbyl group.

6. The process as claimed in claim 1 wherein the porous inorganic support is a silica support and the metallocene complex is of formula (V):

wherein
M is Zr or Hf;
each X independently is a sigma-donor ligand;
L is a divalent bridge selected from —R′ 2 C—, —R′ 2 C—CR′ 2 -, —R′ 2 Si—, —R′ 2 Si—SiR′ 2 —, and —R′ 2 Ge—, wherein each R′ is independently a hydrogen atom or a C 1 -C 20 -hydrocarbyl group optionally containing one or

Assignees

• Borealis Ag

Inventors

• Reznichenko Alexander
• Virkkunen Ville
• Resconi Luigi

Classifications

• C08F2800/10

  as molar percentages · CPC title

• C08F2500/17

  Viscosity · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F10/06 Primary

  Propene · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title