Process for the preparation of an ethylene/propylene copolymer

Claim 2

A process for the preparation of a predominantly crystalline ethylene/propylene copolymer containing no more than about 10.3 mol % of propylene units, relative to the entire polymer, by polymerization of ethylene and a 1-olefin comprising propylene in a suspending agent, at a temperature of -60° to 90° C., at a pressure of 0.5 to 150 bar, in the presence of a catalyst comprising a metallocene and an aluminoxane of the formula IV ##STR19## in the case of the linear type and/or of the formula V ##STR20## in the case of the cyclic type, in which in formulae IV and V R 20 is a C 1 -C 6 -alkyl group and q is an integer from 2 to 50, which comprises carrying out the polymerization in liquid propylene as suspending agent, in which the ratio of the partial pressure P C2 of ethylene in the gas phase to the partial pressure P C3 of propylene in the gas phase ##EQU2## and the metallocene is a compound of the formula I, II or III ##STR21## in which in formulae I, II and III M 1 is a metal from group IVb, Vb and VIb of the periodic table, R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 -alkyl gruop, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 10 -aryalkenyl group or a halogen atom, R 3 and R 4 are identical or different and are an indenyl or tetrahydroindenyl radical in which the five-memebered rings of the radicals R 3 and R 4 form a sandwich structure with the central atom M 1 , R 5 and R 6 are identical or different, and are substituents in the 3-position of R 3 and R 4 or are radicals of the formulae ##STR22## in which R 2 is silicon, germanium or tin, R 6 , R 9 and R 10 are identical or different and are a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoralkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -alkoxy group, a C 8 -C 40 -arylalkenyl group, a C 7 -C 40 -alkylaryl group, a trihalosilyl group, a C 1 -C 10 -trialkylsilyl group or a C 1 -C 10 -trialkoxysilyl group, R 7 is ##STR23## ═BR 11 , ═AlR 11 , --Ge--, --Sn--, --O--, --S--, ═S═O, ═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P(O)R 11 , where R 11 , R 12 , R 13 and R 14 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 1 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl, group, a C 7 -C 40 -arylakyl gruop, a C 8 -C 40 -arylalkenyl group, or a C 7 -C 40 -alkylaryl group and R 7 together with the radicals R 3 and R 4 forms a ring, R 7 being linked to the radicals R 3 and R 4 in the 1-position of the radicals R 3 and R 4 , R 15 is ##STR24## in which R 16 and R 17 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 6 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 40 -arylalkenyl group or a C 7 -C 40 -alkylaryl group, n is the number 3, 4 or 5 and p is 1, 2 or 3, R 15 together with the radicals R 3 and R 4 forms a ring, R 15 being linked to the radicals R 3 and R 4 in the 1-position of the radicals R 3 and R 4 , Cp is a cyclopentadienyl radical and R 18 and R 19 are identical or different substituents on the cyclopentadienyl radicals and are a C 1 -C 10 -alkyl group, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 -alkylaryl group, a C 8 -C 40 -arylalkenyl group or a halogen atom.

Claim 3

The process as claimed in claim 1, wherein the polymerization is carried out in the presence of a 1-olefin having 4 to 18 carbon atoms.

Claim 4

The process as claimed in claim 1, wherein the metallocene is ethylenebis[1-(3-trimethylsilylindenyl)]-zirconium dichloride.

Claim 5

The process as claimed in claim 1, wherein the metallocene is propylenebis(1-indenyl)zirconium dichloride.

Claim 6

The process as claimed in claim 1, wherein the metallocene is bis(pentamethylcyclopentadienyl)zirconium dichloride.

Claim 7

A process for the preparation of a predominantly crystalline ethylene/propylene copolymer by polymerization of ethylene and a 1-olefin consisting essentially of propylene and, optionally, an additional 1-olefin having 4 to 18 carbon atoms, said process comprising: polymerizing ethylene in liquid propylene, liquid propylene being the dispersing medium as well as a co-monomer, the ethylene being added to the polymerization mixture in such an amount that the ratio of the partial pressure P C2 of ethylene is the gas phase to the partial pressure P C3 of propylene in the gas phase, ##EQU3## is greater than 0.6, the polymerization being carried out at a temperature of -60° to 90° C., at a pressure of 0.5 to 150 bar, in the presence of a catalyst comprising a metallocene and an aluminoxane, such that the resulting ethylene/propylene copolymer is predominantly crystalline and contains propylene units but in an amount not exceeding about 10.3 mol % relative to the entire copolymer, said aluminoxane having the formula IV ##STR25## in the case of the linear type and/or of the formula V ##STR26## in the case of the cyclic type, wherein in formulae IV and V R 20 is a C 1 -C 6 alkyl group and q is an integer from 2 to 50, and said metallocene consisting essentially of a compound of the formula I, II or III ##STR27## in which in formulae I, II and III M 1 is a metal from group IVb, Vb or VIb of the periodic table, R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 -alkyl gruop, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 10 -aryalkenyl group or a halogen atom, R 3 and R 4 are identical or different and are an indenyl or tetrahydroindenyl radical in which the five-memebered rings of the radicals R 3 and R 4 form a sandwich structure with the central atom M 1 , R 5 and R 6 are identical or different, and are substituents in the 3-position of R 3 and R 4 or are radicals of the formulae ##STR28## in which R 2 is silicon, germanium or tin, R 8 , R 9 and R 10 are identical or different and are a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoralkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -alkoxy group, a C 8 -C 40 -arylalkenyl group, a C 7 -C 40 -alkylaryl group, a trihalosilyl group, a C 1 -C 10 -trialkylsilyl group or a C 1 -C 10 -trialkoxysilyl group, R 7 is ##STR29## ═BR 11 , ═AlR 11 , --Ge--, --Sn--, --O--, --S--, ═S═O, ═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P(O)R 11 , where R 11 , R 12 , R 13 and R 14 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 1 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl, group, a C 7 -C 40 -arylakyl gruop, a C 8 -C 40 -arylalkenyl group, or a C 7 -C 40 -alkylaryl group and R 7 together with the radicals R 3 and R 4 forms a ring, R 7 being linked to the radicals R 3 and R 4 in the 1-position of the radicals R 3 and R 4 , R 15 is ##STR30## in which R 16 and R 17 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 6 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 40 -arylalkenyl group or a C 7 -C 40 -alkylaryl group, n is the number 3, 4 or 5 and p is 1, 2 or 3, R 15 together with the radicals R 3 and R 4 forms a ring, R 15 being linked to the radicals R 3 and R 4 in the 1-position of the radicals R 3 and R 4 , Cp is a cyclopentadienyl radical and R 18 and R 19 are identical or different substituents on the cyclopentadienyl radicals and are a C 1 -C 10 -alkyl group, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 -alkylaryl group, a C 8 -C 40 -arylalkenyl group or a halogen atom.

Claim 8

A process for the preparation of a predominantly crystalline ethylene/propylene copolymer by polymerization of ethylene and a 1-olefin consisting essentially of propylene and, optionally, an additional 1-olefin having 4 to 18 carbon atoms, said process comprising: polymerizing ethylene in liquid propylene, liquid propylene being the dispersing medium as well as a co-monomer, the ethylene being added to the polymerization mixture in such an amount that the ratio of the partial pressure P C2 of ethylene is the gas phase to the partial pressure P C3 of propylene in the gas phase, ##EQU3## is greater than 0.6, the polymerization being carried out at a temperature of -60° to 90° C., at a pressure of 0.5 to 150 bar, in the presence of a catalyst comprising a metallocene and an aluminoxane, such that the resulting ethylene/propylene copolymer is predominantly crystalline and contains propylene units but in an amount not exceeding about 10.3 mol % relative to the entire copolymer, said aluminoxane having the formula IV ##STR25## in the case of the linear type and/or of the formula V ##STR26## in the case of the cyclic type, wherein in formulae IV and V R 20 is a C 1 -C 6 alkyl group and q is an integer from 2 to 50, and said metallocene consisting essentially of a compound of the formula I, II or III ##STR27## in which in formulae I, II and III M 1 is a metal from group IVb, Vb or VIb of the periodic table, R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 -alkyl gruop, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 10 -aryalkenyl group or a halogen atom, R 3 and R 4 are identical or different and are an indenyl or tetrahydroindenyl radical in which the five-memebered rings of the radicals R 3 and R 4 form a sandwich structure with the central atom M 1 , R 5 and R 6 are identical or different, and are substituents in the 3-position of R 3 and R 4 or are radicals of the formulae ##STR28## in which R 2 is silicon, germanium or tin, R 8 , R 9 and R 10 are identical or different and are a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoralkyl group, a C 6 -C 10 - aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -alkoxy group, a C 8 -C 40 -arylalkenyl group, a C 7 -C 40 -alkylaryl group, a trihalosilyl group, a C 1 -C 10 -trialkylsilyl group or a C 1 -C 10 -trialkoxysilyl group, R 7 is ##STR29## ═BR 11 , ═AlR 11 , --Ge--, --Sn--, --O--, --S--, ═S═O, ═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P(O)R 11 , where R 11 , R 12 , R 13 and R 14 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 1 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl, group, a C 7 -C 40 -arylakyl gruop, a C 8 -C 40 -arylalkenyl group, or a C 7 -C 40 -alkylaryl group and R 7 together with the radicals R 3 and R 4 forms a ring, R 7 being linked to the radicals R 3 and R 4 in the 1-position of the radicals R 3 and R 4 , R 15 is ##STR30## in which R 16 and R 17 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 6 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 40 -arylalkenyl group or a C 7 -C 40 -alkylaryl group, n is the number 3, 4 or 5 and p is 1, 2 or 3, R 15 together with the radicals R 3 and R 4 forms a ring, R 15 being linked to the radicals R 3 and R 4 in the 1-position of the radicals R 3 and R 4 , Cp is a cyclopentadienyl radical and R 18 and R 19 are identical or different substituents on the cyclopentadienyl radicals and are a C 1 -C 10 -alkyl group, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 -alkylaryl group, a C 8 -C 40 -arylalkenyl group or a halogen atom.

Claim 9

The process as claimed in claim 6, wherein said additional 1-olefin is present during the polymerization.

Claim 10

The process as claimed in claim 6, wherein the ratio P C2 /P C3 is greater than 0.9.

Claim 11

The process as claimed in claim 6, wherein the polymerization is carried out under temperature and pressure conditions of 20° to 70° C. and 14.5 to 120 bar.

Claim 12

The process as claimed in claim 6, wherein the concentration of said metalocene, relative to the transition metal, is 10 -3 to 10 -8 mole of transition metal per dm 3 of liquid propylene.

Claim 13

The process as claimed in claim 6, wherein R 1 and R 2 are hydrogen, chlorine, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 6 -C 8 aryl, C 6 -C 8 -aryloxy, C 2 -C 4 -alkenyl, C 7 -C 10 arylalkyl, C 7 -C 12 -alkylaryl, or C 8 -C 12 -arylalkenyl.