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1. (WO2011061151) ETHYLENE COPOLYMERS
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Claims

A process for copolymerizing ethylene, comprising the step of contacting ethylene, one or more non-conjugated cyclic diene and optionally one or more alpha olefins of formula CH2=CHT wherein T is a Ci-C2o alkyl radical under polymerization conditions in the presence of a catalyst system obtainable by contacting:

) a metallocene compound of formula (I)


(I)

Wherein:

M is titanium zirconium or hafnium;

X, equal to or different from each other, is a hydrogen atom, a halogen atom, a R, OR, OR'O, OS02CF3, OCOR, SR, NR2 or PR2 group wherein R is a linear or branched, saturated or unsaturated Ci-C2o-alkyl, C3-C2o-cycloalkyl, C6-C2o-aryl, C7-C2o-alkylaryl or C7-C2o-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; and R' is a Ci-C2o-alkylidene, C6-C2o-arylidene, C7-C2o-alkylarylidene, or C7-C2o-arylalkylidene radical;

R1, equal to or different from each other, are C1-C40 hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements: R2, and R5, equal to or different from each other, are hydrogen atoms, or Ci-C2o alkyl radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements;

R6, equal to or different from each other, are C1-C40 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements;

R3 and R4, form together a condensed saturated or unsaturaded C3-C7-membered ring preferably a C4-C6-membered ring, optionally containing heteroatoms belonging to groups 13-16 of the Periodic Table of the Elements; every atom forming said ring being substituted with R7 radicals; wherein R7, equal to or different from each other, are hydrogen atoms or C1-C40 hydrocabon radicals, optionally containing one or more heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements;

B) an alumoxane or a compound capable of forming an alkyl metallocene cation; and optionally

(C) an organo aluminum compound.

The process according to claim 1 wherein in the compound of formula (I) X is a hydrogen atom, a halogen atom, a OR'O or R group;

The process according to claims 1 or 2 wherein in the compound of formula (I) R1 , equal to or different from each other, is a linear Ci-Cio-alkyl radical;

The process according to anyone of claims 1-3 wherein R2, and R5 are hydrogen atoms The process according to anyone of claims 1-4 wherein the metallocene compound A) has formula (II):

Wherein R1 R2, R5, R6 and R7 have the meaning described in claim 1.

The process according to claim 5 wherein in the compound of formula (II) R7 are hydrogen atoms.

The process according to anyone of claims 1-6 for copolymerizing ethylene, one or more non-conjugated cyclic diene and one or more alpha olefins of formula CH2=CHT wherein T is a C1-C20 alkyl radical comprising the step of contacting ethylene, one or more non-conjugated cyclic diene and one or more alpha olefins of formula CH2=CHT in the presence of the catalyst system of claims 1-6.

The process according to anyone of claims 1 -7 wherein the non-conjugated cyclic diene is a hydrocarbon compound having 6 to 20 carbon atoms.

The process according to claim 8 wherein the non-conjugated cyclic diene is selected from the group consisting of bicyclo[2.2.1]hept-2-ene derivatives having a C1-C10 alkylidene group as susbstitutent and bicyclo[2.2.1]hept-2-ene derivatives having a C1-C10 alkenyl group as susbstitutent.

The process according to claim 9 wherein the non-conjugated cyclic diene is selected from 5-ethylidene-2-norbornene (E/Z-5-ethylidenebicyclo[2.2.1 ]hept-2-ene) and 5-vinyl-2-norbornene.

11. The process according to anyone of claims 1 -10 wherein the alpha olefins of formula CH2=CHT are selected from the group consisting of propylene, 1-butene, 1-pentene, 2- methyl-lpentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 -dodecacene.

12. The process according to anyone of claims 1-1 1 wherein the polymer has an ethylene derived units content ranging from 25.0 to 99.5 % by weight and a content of non- conjugated cyclic diene derived units ranging from 0.5 to 15.0 % by weight.

13. The process according to claim 12 wherein the polymer has content of non-conjugated cyclic diene derived units ranging from 1.0 to 10.0 % by weight.

14. The process according to anyone of claims 1-13 wherein the polymer has an ethylene derived units content ranging from 30.0 to 75.0 % by weight, a non-conjugated cyclic diene derived units ranging from 2.0 to 10.0 % by weight and a content of alpha olefins of formula CH2=CHT derived units ranging from 23.0 to 60.0 % by weight, the sum being 100%.