US 6,596,827 B2Granted

Method for catalytic polymerization of alpha-olefin monomers using an ultra-high activity non-metallocene pre-catalyst

AssigneesRamot at Tel-Aviv University Ltd., Bar Ilanresearch and Development Company Ltd.

InventorsMoshe Kol, Edit Y. Tshuva, Zeev Goldschmidt

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Abstract

Disclosed are olefin polymerization methods comprising the use of the following compounds: wherein M is a metal atom, R1-R8 are univalent radicals, X1 and X2 are univalent ligands, X3 is a divalent ligand, and (RnY—T) is an optional donor or non-donor group. The relatively stable and simply synthesized pre-catalyst is activated by a co-catalyst under mild reaction conditions, producing exceptionally reactive polymerization of a wide variety of alpha-olefin monomers, and forming a variety of poly(alpha-olefin) products, having high molecular weight and low molecular weight distribution (PDIs close to 1). Living polymerization is performed at or above room temperature, along with achieving block co-polymerization of alpha-olefin monomers at room temperature, and producing polymers and oligomers having a wide range of molecular weights. The catalyst formed during reaction remains ‘alive’ for as long as 31 hours, for producing a polymer with a molecular weight as high as 450,000 grams/mole.

Claims130

Dependent claims

A method for catalytic polymerization of an alpha-olefin monomer comprising the steps of:

(a) providing a particular form of an amine bis(phenolate) pre-catalyst having a general structure selected from the group consisting of:
wherein:
a solid line represents a covalent bond;
a dashed line represents a bond having a varying degree of covalency and a varying degree of coordination;
M is a metal atom covalently bonded to each said O atom and bonded with varying degrees of covalency and coordination to said N atom;
X1 and X2 are each a univalent anionic ligand covalently bonded to said metal atom;
X3 is a single divalent anionic ligand covalently bonded to said metal atom;
R1 through R4 are each a univalent radical covalently bonded to first said (C6) aromatic group;
R5 through R8 are each a univalent radical covalently bonded to second said (C6) aromatic group;
and
(RnY—T) is an optional group selected from the group consisting of a non-donor group covalently bonded to said N atom, wherein said non-donor group, said T is a covalent bridging group between said N atom and said Y, said Y is a group covalently bonded to said T, and, each of at least one said Rn is selected from the group consisting of a saturated substituent covalently bonded to said Y, an unsaturated substituent covalently bonded to said Y, and a univalent radical covalently bonded to said Y, and a donor group covalently bonded to said N atom, wherein said donor group, said T is a covalent bridging group between said N atom and said Y, said Y is a heteroatom covalently bonded to said T and bonded with varying degrees of covalency and coordination to said metal atom, and, optional said Rn substituents are selected from the group consisting of at least one saturated substituent covalently bonded to said Y, and at least one unsaturated substituent covalently bonded to said Y;
(b) preparing a first chemical entity featuring said particular form of said amine bis(phenolate) pre-catalyst of step (a);
(c) providing a co-catalyst suitable for activating said particular form of said amine bis(phenolate) pre-catalyst;
(d) preparing a second chemical entity featuring said provided co-catalyst of step (c);
(e) forming a catalytic polymerization reaction by mixing (i) said first chemical entity featuring said particular form of said amine bis(phenolate) pre-catalyst, with (ii) said second chemical entity of said provided co-catalyst, with (iii) the alpha-olefin monomer to be catalytically polymerized, whereby said co-catalyst activates said pre-catalyst, whereby combination of said pre-catalyst and said co-catalyst becomes a catalyst for effecting the catalytic polymerization of the alpha-olefin monomer and for producing at least one poly(alpha-olefin) product;
(f) allowing said catalytic polymerization reaction to progress;
(g) terminating said catalytic polymerization reaction;
and
(h) isolating said at least one poly(alpha-olefin) product formed by said catalytic polymerization reaction.

16 more elements

A method for catalytic polymerization of an alpha-olefin monomer comprising the steps of:

(a) providing a particular form of an amine bis(phenolate) catalyst having a general structure selected from the group consisting of:
wherein:
a solid line represents a covalent bond;
a dashed line represents a bond having a varying degree of covalency and a varying degree of coordination;
M is a metal atom covalently bonded to each said O atom and bonded with varying degrees of covalency and coordination to said N atom;
X1 and X2 are each a univalent anionic ligand covalently bonded to said metal atom;
X3 is a single divalent anionic ligand covalently bonded to said metal atom;
R1 through R4 are each a univalent radical covalently bonded to first said (C6) aromatic group;
R5 through R8 are each a univalent radical covalently bonded to second said (C6) aromatic group;
and
(RnY—T) is an optional group selected from the group consisting of a non-donor group covalently bonded to said N atom, wherein said non-donor group, said T is a covalent bridging group between said N atom and said Y, said Y is a group covalently bonded to said T, and, each of at least one said Rn is selected from the group consisting of a saturated substituent covalently bonded to said Y, an unsaturated substituent covalently bonded to said Y, and a univalent radical covalently bonded to said Y, and a donor group covalently bonded to said N atom, wherein said donor group, said T is a covalent bridging group between said N atom and said Y, said Y is a heteroatom covalently bonded to said T and bonded with varying degrees of covalency and coordination to said metal atom, and, optional said Rn substituents are selected from the group consisting of at least one saturated substituent covalently bonded to said Y, and at least one unsaturated substituent covalently bonded to said Y;
(b) preparing a first chemical entity featuring said particular form of said amine bis(phenolate) catalyst of step (a);
(c) forming a catalytic polymerization reaction by mixing (i) said first chemical entity featuring said particular form of said amine bis(phenolate) catalyst, with (ii) the alpha-olefin monomer to be catalytically polymerized, whereby said amine bis(phenolate) catalyst effects the catalytic polymerization of the alpha-olefin monomer for producing at least one poly(alpha-olefin) product;
(d) allowing said catalytic polymerization reaction to progress;
(e) terminating said catalytic polymerization reaction;
and
(f) isolating said at least one poly(alpha-olefin) product formed by said catalytic polymerization reaction.

14 more elements

A method for living catalytic polymerization of an alpha-olefin monomer comprising the steps of:

(a) providing a particular form of an amine bis(phenolate) pre-catalyst having a general structure selected from the group consisting of:
wherein:
a solid line represents a covalent bond;
a dashed line represents a bond having a varying degree of covalency and a varying degree of coordination;
M is a metal atom covalently bonded to each said O atom and bonded with varying degrees of covalency and coordination to said N atom;
X1 and X2 are each a univalent anionic ligand covalently bonded to said metal atom;
X3 is a single divalent anionic ligand covalently bonded to said metal atom;
R1 through R4 are each a univalent radical covalently bonded to first said (C6) aromatic group;
R5 through R8 are each a univalent radical covalently bonded to second said (C6) aromatic group;
and
(RnY—T) is an optional group selected from the group consisting of a non-donor group covalently bonded to said N atom, wherein said non-donor group, said T is a covalent bridging group between said N atom and said Y, said Y is a group covalently bonded to said T, and, each of at least one said Rn is selected from the group consisting of a saturated substituent covalently bonded to said Y, an unsaturated substituent covalently bonded to said Y, and a univalent radical covalently bonded to said Y, and a donor group covalently bonded to said N atom, wherein said donor group, said T is a covalent bridging group between said N atom and said Y, said Y is a heteroatom covalently bonded to said T and bonded with varying degrees of covalency and coordination to said metal atom, and, optional said Rn substituents are selected from the group consisting of at least one saturated substituent covalently bonded to said Y, and at least one unsaturated substituent covalently bonded to said Y;
(b) preparing a first chemical entity featuring said particular form of said amine bis(phenolate) pre-catalyst of step (a);
(c) providing a co-catalyst suitable for activating said particular form of said amine bis(phenolate) pre-catalyst;
(d) preparing a second chemical entity featuring said provided co-catalyst of step (c);
(e) forming a living catalytic polymerization reaction by mixing (i) said first chemical entity featuring said particular form of said amine bis(phenolate) pre-catalyst, with (ii) said second chemical entity of said provided co-catalyst, with (iii) the alpha-olefin monomer to be catalytically polymerized, whereby said co-catalyst activates said pre-catalyst, whereby combination of said pre-catalyst and said co-catalyst becomes a catalyst for effecting the living catalytic polymerization of the alpha-olefin monomer and for producing at least one poly(alpha-olefin) product;
(f) allowing said living catalytic polymerization reaction to progress;
(g) terminating said living catalytic polymerization reaction;
and
(h) isolating said at least one poly(alpha-olefin) product formed by said living catalytic polymerization reaction.

16 more elements

Dependencies are inferred from the claim text.

Facts

Application: 09/903,660Filed 13 Jul 2001 · continuation in part
Priority: 10 Sep 1999
Published: US 2002/0019503 A114 Feb 2002
Granted: 22 Jul 2003
Term ends: Not estimatedThe source records don’t support an estimate.

Classification12 codes

C08F 297/08
Using a catalyst of the coordination type: polymerising mono-olefins
C07F 7/003
Compounds containing elements of Groups 4 or 14 of the Periodic Table: without C-Metal linkages
C08F 4/545
Together with other compounds thereof: rare earths being present, e.g. triethylaluminium + neodymium octanoate
C08F 10/00
Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double