Process for producing propylene copolymers in gas phase

Patent metadata

Field	Value
Publication number	US-10364307-B2
Application number	US-201515510030-A
Country	US
Kind code	B2
Filing date	Sep 11, 2015
Priority date	Sep 12, 2014
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

Abstract

A process for the preparation of a heterophasic copolymer of propylene and ethylene comprising polymerizing propylene and ethylene in the gas phase in the presence of a solid particulate catalyst free from an external carrier comprising: (i) a symmetrical complex of formula (I), wherein M is zirconium or hafnium; each X is a sigma ligand; L is a divalent bridge selected from —R′ 2 C—, —R′ 2 C—CR′2-, —R′ 2 Si—, —R′ 2 Si—SiR′ 2 —, —R′ 2 Ge—, wherein each R′ is independently a hydrogen atom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl; R 2 is a C1-C20 hydrocarbyl radical; R 5 is a C1-C20 hydrocarbyl radical; R 6 is a tertiary C4-C20 hydrocarbyl radical; R 7 is a hydrogen atom or a C 1-10 -hydrocarbyl radical; n is 0 to 3; R 1 is a C1-C20 hydrocarbyl radical and optionally two adjacent R 1 groups taken together can form a further mono or multicyclic ring condensed to Ph ring optionally substituted by one or two groups R 4 ; and R 4 is a C1-C10 alkyl radical and (ii) a cocatalyst, preferably comprising an organometallic compound of a Group 13 metal; wherein the xylene soluble fraction (XS) of the heterophasic copolymer of propylene and ethylene has an intrinsic viscosity of at least 1.5 dl/g and an ethylene content of 10 to 70 wt %.

First claim

The invention claimed is:

1. A process for the preparation of a heterophasic copolymer of propylene and ethylene comprising:
(I) in a first stage polymerising propylene and optionally ethylene in the presence of a solid particulate catalyst free from an external carrier, said catalyst comprising:
(i) a symmetrical complex of formula (I):

wherein
M is zirconium or hafnium;
each X is a sigma ligand;
L is a divalent bridge selected from —R′ 2 C—, —R′ 2 C—CR′ 2 —, —R′ 2 Si—, —R′ 2 Si—SiR′ 2 —, —R′ 2 Ge—, wherein each R′ is independently a hydrogen atom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl;
R 2 is a C1-C20 hydrocarbyl radical;
R 5 is a C1-C20 hydrocarbyl radical;
R 6 is a tertiary C4-C20 hydrocarbyl radical;
R 7 is a hydrogen atom or a C 1-10 -hydrocarbyl radical;
n is 0 to 3;
R 1 is a C1-C20 hydrocarbyl radical and optionally two adjacent R 1 groups taken together can form a further mono or multicyclic ring condensed to Ph ring optionally substituted by one or two groups R 4 ; and
R 4 is a C1-C10 alkyl radical
and (ii) a cocatalyst; and

(II) in a second subsequent stage polymerising propylene and ethylene in the gas phase in the presence of the product of step (I) and in the presence of the catalyst from step (I) to produce said heterophasic copolymer of propylene and ethylene;
wherein the xylene soluble fraction (XS) of the heterophasic copolymer of propylene and ethylene has an intrinsic viscosity of at least 1.5 dl/g and an ethylene content of 10 to 70 wt %; and
wherein the xylene soluble fraction (XS) is at least 15 wt % of the heterophasic copolymer of propylene and ethylene.

2. A process as claimed in claim 1 wherein the catalyst is formed by obtaining a complex of formula (I) and a cocatalyst;
forming a liquid/liquid emulsion system, which comprises a solution of catalyst components (i) and (ii) dispersed in a solvent, and solidifying said dispersed droplets to form solid particles.

3. A process as claimed in claim 1 wherein step (I) produces a propylene homopolymer.

4. A process as claimed in claim 1 wherein all polymerisation steps of the process other than any prepolymerisation step take place at a temperature of at least 60° C.

5. A process as claimed in claim 1 wherein the ethylene content of the xylene soluble fraction of the heterophasic copolymer of propylene and ethylene is at least 14 wt %.

6. A process as claimed claim 1 wherein R 2 is branched 13 to the cyclopentadienyl ring.

7. A process as claimed in claim 1 wherein the complex is of formula (II)

wherein
M is Zr or Hf;
R 2 is CH 2 -Ph, CH 2 —C(R 3 ) 3-q (H) q wherein R 3 is a C 1-6 -alkyl group or together two R 3 groups form a C 3-7 -cycloalkyl ring wherein said ring is optionally substituted by a C 1-6 alkyl group and q can be 1 or 0;
L is methylene, ethylene or SiR 8 2 ;
R 8 is C1-10 alkyl, C 6-10 -aryl, C 7-12 -alkylaryl, or C 7-12 -arylalkyl;
each X is a hydrogen atom, benzyl, OR, a halogen atom, or an R group;
R is C 1-10 alkyl or C 6-10 aryl;
each R 7 is H or C 1-3 -alkyl;
n is 0 to 2;
R 1 is C 1-10 -alkyl;
R 5 is C 1-10 alkyl; and
R 6 is tertiary C 4-10 -alkyl;
and wherein the two ligands forming the complex are identical.

8. A process as claimed in claim 1 wherein the complex is of formula (III)

in which:
M is Zr or Hf
each R 2 is CH 2 -Ph, CH 2 —C(R 3 ) 3-q (H) q wherein R 3 is a C 1-6 -alkyl group or together two R 3 groups form a C 3-7 -cycloalkyl ring wherein said ring is optionally substituted by a C 1-6 alkyl group and q can be 1 or 0;
L is SiR 8 2 ;
R 8 is C 1-8 alkyl;
each X is a halogen atom, methoxy, benzyl or methyl;
n is 0 or 1;
R 5 is C 1-6 alkyl;
R 6 is tertiary C 4-10 alkyl; and
R 1 is C 1-6 alkyl;
and wherein the two ligands forming the complex are identical.

9. A process as claimed in claim 1 wherein the complex is of formula (IV)

wherein L is SiR 8 2 ;
R 8 is C 1-8 alkyl;
R 2 is CH 2 -Ph, CH 2 —C(R 3 ) 3-q (H) q wherein R 3 is a C 1-6 -alkyl group or together two R 3 groups form a C 3-7 -cycloalkyl ring wherein said ring is optionally substituted by a C 1-6 alkyl group and q can be 1 or 0;
each X is a halogen atom, methoxy, benzyl or methyl;
M is Zr; or Hf;
R 5 is C 1-6 alkyl; and
R 6 is tertiary C 4-10 alkyl;
and wherein the two ligands forming the complex are identical.

10. A process as claimed in claim 1 wherein the complex is of formula (V)

wherein L is SiR 8 2 ;
R 8 is C 1-8 alkyl;
each X is a halogen atom, methoxy, benzyl or methyl; and
M is Zr.

11. A process as claimed in claim 1 wherein the XS fraction of the heterophasic copolymer of propylene and ethylene is at least 20 wt-%.

12. A process as claimed in claim 1 wherein the cocatalyst comprises an organometallic compound of a Group 13 metal.

13. A process as claimed in claim 1 wherein the complex is

Assignees

• Borealis Ag

Inventors

• Resconi Luigi
• Hafner Norbert
• Töltsch Wilfried

Classifications

• C08F210/06 Primary

  Propene · CPC title

• C08F2500/17

  Viscosity · CPC title

• C08F210/02

  Ethene · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F2/34

  Polymerisation in gaseous state · CPC title