Polymerisation of propylene

Patent metadata

Field	Value
Publication number	US-2024368317-A1
Application number	US-202218558372-A
Country	US
Kind code	A1
Filing date	May 6, 2022
Priority date	May 7, 2021
Publication date	Nov 7, 2024
Grant date	—

Abstract

A process for the polymerisation of propylene is described, in which the resulting polypropylene is high molecular weight atactic polypropylene. Also described is high molecular weight and ultra-high molecular weight atactic polypropylene.

First claim

1 . A process for the preparation of a polypropylene, the process comprising contacting propylene with a compound having a structure according to Formula I shown below:

wherein
R 1 and R 2 are each independently selected from the group consisting of hydrogen, (1-6C)alykyl, (1-6C)haloalkyl, (1-6C)alykoxy, (2-6C)alykenyl, (2-6C)alykynyl, —NR 3 R 4 and —(O) n —(CR 5 R 6 ) m —R 7 , where n is 0 or 1, m is 0 or 1, R 3 and R 4 are independently selected from hydrogen and (1-3C)alykyl, R 5 and R 6 are each independently hydrogen or (1-2C)alykyl, and R 7 is selected from the group consisting of aryl, heteroaryl, carbocyclyl and heterocyclyl, and where each R 7 is independently optionally substituted with one or more groups R 8 selected from the group consisting of halo, hydroxy, (1-4C)alykyl, (1-4C)haloalkyl and (1-3C)alykoxy;
R a and R b are each independently selected from (1-4C)alykyl, (2-4C)alykenyl and aryl;
each Y is independently selected from the group consisting of hydride, halo, (1-5C)alykyl, (1-5C)alykoxy, —(CH 2 ) p Si(R 9 ) 3 , —NR 10 R 11 , and —(O) q —(CR 12 R 13 ), —R 14 , where p is 1 or 2, q is 0 or 1, r is 0 or 1, each R 9 is independently (1-3C)alykyl, R 10 and R 11 are independently selected from hydrogen and (1-3C)alykyl, R 12 and R 13 are independently selected from hydrogen and (1-2C)alykyl, and R 14 is selected from the group consisting of aryl, heteroaryl, carbocyclyl and heterocyclyl, and where each R 14 is independently optionally substituted with one or more groups R 15 selected from the group consisting of halo, hydroxy, (1-4C)alykyl, (1-4C)haloalkyl and (1-3C)alykoxy.

2 . The process of claim 1 , wherein R 1 and R 2 are each independently selected from the group consisting of hydrogen, (1-5C)alykyl, (1-5C)alykoxy and —(O) n —(CR 5 R 6 ) m —R 7 .

3 . The process of claim 1 or 2 , wherein R 7 is selected from the group consisting of phenyl and 5-6 membered heteroaryl, wherein said 5-6 membered heteroaryl contains 1 or 2 nitrogen heteroatoms.

4 . The process of claim 1, 2 or 3 , wherein R 7 is phenyl.

5 . The process of any one of the preceding claims , wherein R 8 is selected from the group consisting of halo and (1-3C)alykyl.

6 . The process of claim 1 , wherein R 1 and R 2 are each independently selected from the group consisting of hydrogen, methyl, tert-butyl and —C(CH 3 ) 2 Ph, where Ph denotes phenyl.

7 . The process of any one of the preceding claims , wherein R a and R b are methyl.

8 . The process of any one of the preceding claims , wherein each Y is independently selected from the group consisting of hydride, chloro, bromo, iodo, (1-3C)alykyl, (1-3C)alykoxy, —(CH 2 ) p Si(R 9 ) 3 , —NR 10 R 11 , and —(O) q —(CR 12 R 13 ), —R 14 .

9 . The process of any one of the preceding claims , wherein p is 1 and R 9 is methyl, R 10 and R 11 are independently selected from (1-3C)alykyl, and R 12 and R 13 are hydrogen.

10 . The process of any one of the preceding claims , wherein R 14 is selected from the group consisting of phenyl and 5-6 membered heteroaryl, wherein said 5-6 membered heteroaryl contains 1 or 2 nitrogen heteroatoms.

11 . The process of any one of the preceding claims , wherein R 15 is selected from the group consisting of (1-4C)alykyl.

12 . The process of any one of the preceding claims , wherein each Y is independently selected from the group consisting of chloro, bromo, iodo, methyl, —CH 2 Si(CH 3 ) 3 , —N(CH 3 ) 2 and —O-2,6-diisopropylphenyl.

13 . The process of any one of the preceding claims , wherein Y is chloro.

14 . The process of any one of the preceding claims , wherein the compound of Formula I has a structure according to Formula I-A shown below:

wherein R 1 , R 2 and Y are as defined in any one of the preceding claims .

15 . The process of any one of the preceding claims , wherein the compound of Formula I has a structure according to Formula I-B shown below:

wherein R 1 , R 2 , R a and R b are as defined in any one of claims 1 to 24 .

16 . The process of any one of the preceding claims , wherein the compound of Formula I has a structure according to Formula I-C shown below:

wherein R 1 and R 2 are as defined in any one of claims 1 to 24 .

17 . The process of any one of the preceding claims , wherein the compound of Formula I is supported on a supporting substrate, wherein the supporting substrate is solid polymethylaluminoxane.

18 . Atactic polypropylene having a molecular weight (M w ) greater than 500,000 g mol −1 .

19 . The polypropylene of claim 18 , wherein the polypropylene has a degree of crystallinity of <1% (e.g., is amorphous) when analysed by DSC and/or has no detectable melting enthalpy (ΔH f ) when analysed by DSC.

20 . The polypropylene of claim 18 , wherein the polypropylene has a molecular weight (M w ) of greater than 700,000 g mol −1 , or greater than 900,000 g mol −1 .

21 . The polypropylene of claim 18 , wherein the polypropylene has a molecular weight (M w ) of greater than 1,100,000 g mol −1 .

22 . The polypropylene of any one of claims 18 to 21 , wherein the polydispersity index (PDI) of the polypropylene is less than 3.0.

23 . The polypropylene of any one of claims 18 to 21 , wherein the polydispersity index (PDI) of the polypropylene is less than 2.6.

24 . The polypropylene of any one of claims 18 to 21 , wherein the polydispersity index (PDI) of the polypropylene is less than 2.2.

25 . The polypropylene of any one of claims 18 to 24 , wherein the polypropylene has a Pr of 0.45-0.55.

Assignees

• Univ Oxford Innovation Ltd

Inventors

• O'Hare Dermot
• Buffet Jean-Charles
• Turner Zoe
• Collins Rice Clement

Classifications

• C08F2420/07

  Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title

• C08F2500/01

  High molecular weight, e.g. >800,000 Da. · CPC title

• C08F2500/35

  Crystallinity, e.g. soluble or insoluble content as determined by the extraction of the polymer with a solvent · CPC title

• C08F2420/02

  Cp or analog bridged to a non-Cp X anionic donor · CPC title