Metal complexes of salan-type ligands and uses thereof as catalysts for polymerization of alpha-olefins

Patent metadata

Field	Value
Publication number	US-9493587-B2
Application number	US-201213980920-A
Country	US
Kind code	B2
Filing date	Jan 19, 2012
Priority date	Jan 20, 2011
Publication date	Nov 15, 2016
Grant date	Nov 15, 2016

Abstract

Use of homogeneous catalytic systems which include as a pre-catalyst a complex of a group 4 metal and a Salan ligand in the polymerization of alpha-olefins, is disclosed. The Salan ligand is characterized by a sequential diamino-containing skeleton unit which is non-symmetric, and the pre-catalysts can also be such that are devoid of a symmetry element. The disclosed polymerization results in alpha-olefin polymers such as polypropylene which are characterized by high levels of tacticity. Also disclosed are novel Salan ligands and novel complexes thereof with group 4 metals.

First claim

What is claimed is:

1. A process of polymerizing an alpha-olefin, the process comprising contacting the alpha-olefin with a catalyst system which comprises:
(i) a pre-catalyst comprising a group 4 element being in coordination with a Salan ligand, said Salan ligand comprising two substituted or unsubstituted phenol moieties and a sequential diamino-containing skeleton unit linking said phenol moieties, wherein said sequential diamino-containing skeleton unit is non-symmetric and said pre-catalyst is devoid of a symmetry element; and
(ii) a co-catalyst,
thereby polymerizing the alpha-olefin.

2. The process of claim 1 , wherein said pre-catalyst is represented by general Formula II:

wherein:
Q is MXn,
whereas M is a group 4 element; X is a labile group; and n is 0, 1, 2, 3 or 4;
Z and Y are each independently a substituted or unsubstituted alkylene chain being from 1 to 5 carbon atoms in length, such that Z and Y form together an alkylene chain that is 2 to 10 carbon atoms in length;
each of R 1 -R 8 is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, halogen, alkoxy, aryloxy, heteroalicyclic, heteroaryl, and nitro, provided that at least one of R 1 -R 4 is other than hydrogen; and
each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl, provided that at least one of R and R′ is hydrogen; and provided that when R and R′ are the same. Y is different from Z; and
(ii) a co-catalyst,
thereby polymerizing the alpha-olefin.

3. The process of claim 2 , wherein each of R 1 -R 4 is independently halogen.

4. The process of claim 2 , wherein at least one of R 1 -R 4 is a bulky substituent.

5. The process of claim 4 , wherein said bulky substituent comprises a bulky rigid group.

6. The process of claim 4 , wherein R 1 is adamantyl.

7. The process of claim 2 , wherein Z is selected from the group consisting of (CRaRb), (CRaRb)(CRcRd) and (CRaRb)(CRcRd)(CReRf), and Y is selected from the group consisting of (CRgRh), (CRgRh)(CRiRj) and (CRgRh)(CRiRj)(CRkRp),
wherein each of Ra-Rp is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, halogen, alkoxy, aryloxy, and/or at least two of Ra-Rp, R′ and R form together a five-or six-membered, aromatic or non-aromatic ring.

8. The process of claim 2 , wherein R′ is hydrogen.

9. The process of claim 8 , wherein R is alkyl.

10. The process of claim 1 , wherein said alpha-olefin is propylene.

11. A process of polymerizing an alpha-olefin, the process comprising contacting the alpha-olefin with a catalyst system which comprises:
(i) a pre-catalyst comprising a group 4 element being in coordination with a Salan ligand, said Salan ligand comprising two substituted or unsubstituted phenol moieties and a sequential diamino-containing skeleton unit linking said phenol moieties, wherein said sequential diamino-containing skeleton unit is non-symmetric and said pre-catalyst is devoid of a symmetry element; and
(ii) a co-catalyst,
thereby polymerizing the alpha-olefin,
wherein said pre-catalyst is represented by general Formula II:

wherein:
Q is MXn,
whereas M is a group 4 element; X is a labile group; and n is 0, 1, 2, 3 or 4;
Z and Y are each independently a substituted or unsubstituted alkylene chain being from 1 to 5 carbon atoms in length, such that Z and Y form together an alkylene chain that is 2 to 10 carbon atoms in length;
each of R 1 -R 4 is independently halogen;
each of R 5 -R 8 is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, halogen, alkoxy, aryloxy, heteroalicyclic, heteroaryl, and nitro; and
each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl, provided that at least one of R and R′ is hydrogen; and provided that when R and R′ are the same, Y is different from Z.

12. A process of polymerizing an alpha-olefin, the process comprising contacting the alpha-olefin with a catalyst system which comprises:
(i) a pre-catalyst comprising a group 4 element being in coordination with a Salan ligand, said Salan ligand comprising two substituted or unsubstituted phenol moieties and a sequential diamino-containing skeleton unit linking said phenol moieties, wherein said sequential diamino-containing skeleton unit is non-symmetric and said pre-catalyst is devoid of a symmetry element; and
(ii) a co-catalyst,
thereby polymerizing the alpha-olefin,
wherein said pre-catalyst is represented by general Formula II:

wherein:
Q is MXn,
whereas M is a group 4 element; X is a labile group; and n is 0, 1, 2, 3 or 4;
Z and Y are each independently a substituted or unsubstituted alkylene chain being from 1 to 5 carbon atoms in length, such that Z and Y form together an alkylene chain that is 2 to 10 carbon atoms in length;
each of R 1 -R 8 is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, halogen, alkoxy, aryloxy, heteroalicyclic, heteroaryl, and nitro,
provided that at least one of R 1 -R 4 is a bulky substituent which comprises a bulky rigid group; and
each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl, provided that at least one of R and R′ is hydrogen; and provided that when R and R′ are the same, Y is different from Z.

13. A process of polymerizing an alpha-olefin, the process comprising contacting the alpha-olefin with a catalyst system which comprises:
(i) a pre-catalyst comprising a group 4 element being in coordination with a Salan ligand, said Salan ligand comprising two substituted or unsubstituted phenol moieties and a sequential diamino-containing skeleton unit linking said phenol moieties, wherein said sequential diamino-containing skeleton unit is non-symmetric and said pre-catalyst is devoid of a symmetry element; and
(ii) a co-catalyst,
thereby polymerizing the alpha-olefin,
wherein said pre-catalyst is represented by general Formula II:

wherein:
Q is MXn,
whereas M is a group 4 element; X is a labile group; and n is 0, 1, 2, 3 or 4;
Z and Y are each independently a substituted or unsubstituted alkylene chain being from 1 to 5 carbon atoms in length, such that Z and Y form together an alkylene chain that is 2 to 10 carbon atoms in length;
R 1 is adamantyl;
each of R 2 -R 8 is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, halogen, alkoxy, aryloxy, heteroalicyclic, heteroaryl, and nitro; and
each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl, provided that at least one of R and R′ is hydrogen; and provided that when R and R′ are the same, Y is different from Z.

Assignees

• Kol Moshe
• Press Konstantin
• Ramot At Tel-Aviv Univ Ltd

Inventors

• Kol Moshe
• Press Konstantin

Classifications

• B01J27/24

  Nitrogen compounds · CPC title

• C07F7/00

  Compounds containing elements of Groups 4 or 14 of the Periodic Table · CPC title

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F2500/03

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

• C08F2500/15

  Isotactic · CPC title