# US 8,785,575 B2 · Process for the preparation of ethylene propylene copolymers

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- Number: US 8,785,575 B2
- Document ID: US8785575B2
- Status: Granted
- Kind: B2
- Application number: 12/226,385
- Filed: 2007-04-06
- Published: 2009-08-06
- Granted: 2014-07-22
- Earliest claimed: 2006-04-21
- Assignees: Basell Polyolefine GmbH
- Applicants: Luigi Resconi; Francesca Focante
- Inventors: Luigi Resconi; Francesca Focante
- Web page: https://patentgrep.com/patent/US8785575B2

## CPC

- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A polymerization process comprising contacting under polymerization conditions ethylene and at least propylene to obtain a copolymer containing from 96% by mol to 71% by mol of ethylene derived units, in the presence of a catalyst system obtainable by contacting: b) at least a metallocene compound of formula (I), b) alumoxane or a compound capable of forming an alkyl metallocene cation; and optionally c) an organo aluminum compound; wherein the groups R1-R4, L, M and W are described in the text.

## Claims

### Claim 1

A polymerization process comprising contacting under polymerization conditions ethylene and propylene to obtain an ethylene-propylene copolymer comprising from 96% by mol to 71% by mol of ethylene derived units in presence of a catalyst system obtained by contacting:
a) at least a metallocene compound of formula (I)
and
b) alumoxane or a compound capable of forming an alkyl metallocene cation;
wherein:
M is an atom of a transition metal selected from group 3, 4, or the lanthanide or actinide groups in the Periodic Table of Elements;
X equal to or different from each other, is hydrogen, halogen, R, OR, OR′O, OSO2CF3, OCOR, SR, NR2 or PR2;
R is a linear or branched, cyclic or acyclic, C1-C40-alkyl, C2-C40 alkenyl, C2-C40alkynyl, C6-C40-aryl, C7-C40-alkylaryl or C7-C40-arylalkyl radical, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R′ is a C1-C20-alkylidene, C6-C20-arylidene, C7-C20-alkylarylidene, or C7-C20-arylalkylidene radical;
L is a divalent bridging group selected from C1-C20 alkylidene, C3-C20 cycloalkylidene, C6-C20 arylidene, C7-C20 alkylarylidene, or C7-C20 arylalkylidene radicals, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or a silylidene radical comprising up to 5 silicon atoms;
R1 is a linear C1-C40 hydrocarbon radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R2 and R3 are part of 4-7 membered ring condensed to the benzene ring of the indenyl moiety, said ring optionally comprising at least one heteroatom belonging to groups 13-16 of the Periodic Table of Elements, wherein the valence of each atom forming the ring being filled with R18 radicals;
R18 equal to or different from each other, are hydrogen or C1-C40 hydrocarbon radicals;
R4 is hydrogen;
W is an aromatic 5 or 6 membered ring optionally comprising at least one heteroatom belonging to groups 13-16 of the Periodic Table of Elements, wherein the valence of each atom of the ring is substituted with hydrogen or is optionally substituted with at least one R5 group; and
R5 equal to or different from each other, are C1-C40 hydrocarbon radicals optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.

### Claim 2 (depends on 1)

The process according to claim 1, wherein R1 is selected from methyl, ethyl, an alpha branched aryl, and an arylalkyl radical comprising from 2 to 20 carbon atoms and optionally comprising O, N, S, P or Se atoms.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the catalyst system further comprises c) an organo aluminum compound.

### Claim 4 (depends on 1)

The process according to claim 1, wherein
M is zirconium, titanium or hafnium;
X is hydrogen, halogen, OR′O, or R;
L is Si(R11)2;
R11is a linear or branched, cyclic or acyclic, C1-C40-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40-aryl, C7-C40-alkylaryl or C7-C40-arylalkyl radical; and
R1 is a C1-C10-alkyl radical.

### Claim 5 (depends on 1)

The process according to claim 1, wherein R2 and R3 are part of 5-6 membered ring condensed to the benzene ring of the indenyl moiety, the ring being substituted with R18 radicals; wherein R18 is hydrogen or a linear or branched, C1-C20-alkyl radical.

### Claim 6 (depends on 1)

The process according to claim 1, wherein W is selected from the group consisting of the following moieties of formula (Wa), (Wb) and (Wc):
wherein the * represents the point in which the moiety is bound to the indenyl moiety of the compound of formula (I);
R6, R7, R8, R9 and R10, equal to or different from each other, are hydrogen or C1-C40 hydrocarbon radicals optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
Z1 is nitrogen or a CR10 group;
Z2 is nitrogen or a CR6 group;
Z3 is nitrogen or a CR7 group;
Z4 is nitrogen or a CR8 group;
Z5 is nitrogen or a CR9 group, with the proviso that not more than 2 groups among Z1, Z2, Z3, Z4 and Z5 are nitrogen atoms;
Z6 is oxygen, sulfur, a NR13 group or a CR13 group;
Z7 is oxygen, sulfur, a NR14 group or a CR14 group;
Z8 is oxygen, sulfur, a NR15 group or a CR15 group;
Z9 is oxygen, sulfur, a NR16 group or a CR16 group;
z10 is nitrogen or carbon, with the proviso that not more than 1 group among Z6, Z7, Z8, Z9 or Z10 sulfur, oxygen, or a nitrogen-containing group atom selected from nitrogen, NR13, NR14, NR15, and NR16; and
R13, R14, R15 and R16, equal to or different from each other, are hydrogen or C1-C40 hydrocarbon radicals optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the compound of formula (I) comprises formula (IIa), (IIb) or (IIc):
wherein
M is an atom of a transition metal selected from group 3, 4, or the lanthanide or actinide groups in the Periodic Table of Elements;
X equal to or different from each other, is hydrogen, halogen, R, OR, OR′O, OSO2CF3, OCOR, SR, NR2 or PR2;
R is a linear or branched, cyclic or acyclic, C1-C40-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40-aryl, C7-C40-alkylaryl or C7-C40-arylalkyl radical, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R′ is a C1-C20-alkylidene, C6-C20-arylidene, C7-C20-alkylarylidene, or C7-C20-arylalkylidene radical;
L is a divalent bridging group selected from C1-C20 alkylidene, C3-C20 cycloalkylidene, C6-C20 arylidene, C7-C20 alkylarylidene, or C7-C20 arylalkylidene radicals, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or a silylidene radical comprising up to 5 silicon atoms;
R1 is a linear C1-C40 hydrocarbon radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R4 is hydrogen;
R5 is a C1-C40 hydrocarbon radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R6, R7, R8, R9 and R10, equal to or different from each other, are hydrogen or C1-C40 hydrocarbon radicals optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R14,R15and R16, equal to or different from each other, are hydrogen or C1-C40 hydrocarbon radicals optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; and
R11 and R12 equal to or different from each other, are hydrogen or C1-C40 hydrocarbon radicals optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.

### Claim 8 (depends on 1)

The process according to claim 1, wherein the process is carried out at a temperature ranging from 60° C. to 200° C.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the copolymer comprises from 75% by mol to 90% by mol of ethylene derived units.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the process is carried out in solution.