Polymerization of olefins

Details Polymerization of olefins Polymerization of olefins

2001-05-31

2003-04-01

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S171000, C526S172000, C526S178000, C526S348000, C526S352000, C502S155000, C502S167000

Reexamination Certificate

active

06541585

ABSTRACT:

FIELD OF INVENTION
Olefins including polar vinyl monomers, in particular acrylate monomers, are (co)polymerized using as catalysts selected transition metal complexes that have a Lewis acid in close proximity to the metal center.
TECHNICAL BACKGROUND
The polymerization of olefins such as ethylene and propylene is a very important commercial activity, and such polymers in various forms are made in enormous quantities for numerous uses. Various methods are known for polymerizing olefins, such as free radical polymerization of ethylene, and coordination polymerization using catalysts such as Ziegler-Natta-type and metallocene-type catalysts. Nevertheless, given the importance of polyolefins, new catalysts are constantly being sought for such polymerizations, to lower the cost of production and/or make new, and hopefully improved, polymer structures. More recently so-called single-site catalysts using late transition metal complexes have been developed, and they have proved in many instances to give polymers different in structure than those produced by the earlier known early transition metal catalysts.
Another type of useful polyolefin is one that contains polar comonomers, such as acrylates. One of the advantages of some late transition metal catalysts is that they can incorporate polar vinyl olefins, including acrylates, in copolymerizations with other polymerizable olefins, particularly ethylene.
It has been discovered that (co)polymers of olefins, including polar vinyl olefins, are produced especially well by transition metal complexes that contain ligands that are capable of binding a Lewis acid in close proximity to the transition metal center.
In general, Lewis acids are often added as activators to olefin polymerizations, e.g., for the purpose of transforming a halide or similar group on the metal into an alkyl group active for olefin insertion, for converting the metal complex into a cation species active for olefin polymerization, for protecting/deactivating the polar group of a monomer, and for scavenging impurities. In particular, the use of Lewis acids to activate late metal complexes for the copolymerization of ethylene and polar monomers and to protect the polar monomers has been reported; however, ligands that were capable of binding both a Lewis acid and a transition metal were not used in these copolymerizations. See, for example, U.S. Pat. No. 6,174,975; WO99/05189; M. M. Marques et. al.,
Polym. Int.
(2001), 50, 579-587; and M. M. Marques, et. al.
Macromol. Chem. Phys.
(2000), 201, 2464-2468. Lewis acids have been added as activators for olefin polymerization to catalyst systems containing ligands that were capable of binding to the Lewis acid through a Lewis acid/Lewis base interaction (see for example, WO9840374, U.S. Pat No. 6,103,658 and WO9847933); however, no polar monomers were used in any of the copolymers made and, in addition, the ligand in these instances was not capable of binding the Lewis acid in close proximity to the metal center.
SUMMARY OF THE INVENTION
The invention concerns a process for polymerizing an olefin component comprising one or more polymerizable olefins, comprising the step of contacting, under polymerizing conditions, said olefin component with a polymerization catalyst system comprising a group 3-11 transition metal or lanthanide, a coordinating ligand, and a Lewis acid component, wherein the Lewis acid component is:
(a) neutral and covalently bound to said coordinating ligand, or
(b) positively charged and bound to a Lewis basic site of said coordinating ligand.
Ethylene and H
2
C═CH—(CH
2
)
t
—H where t is an integer of 1 to 20 are more preferred olefins and ethylene is especially preferred.
In a preferred embodiment of the invention, the transition metal is Fe, Co, Ni, Pd or Cu; more preferably Ni. Preferably the polymerizable olefin is one or more of ethylene, H
2
C═CH—(CH
2
)
t
—H, H
2
C═CH—R
100
—G, norbornene, substituted norbornene, cyclopentene, or substituted cyclopentene; where t is an integer of 1 to 20, and R
100
is a covalent bond or alkylene or substituted alkylene, and G is an inert functional group. Ethylene, H
2
C═CH—(CH
2
)
t
—H, and H
2
C═CH—R
100
—G are more preferred, and ethylene is especially preferred. It is preferred that R
100
is a covalent bond or —(CH
2
)
q
—, G is C(O)Y, Y is —OH, —NR
101
R
102
, —OR
103
, or —SR
104
, wherein R
101
and R
102
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, R
103
and R
104
are each hydrocarbyl or substituted hydrocarbyl, and q is an integer of 1 to 20. Especially preferred are R
100
is a covalent bond, Y is —OR
103
and R
103
is an alkyl or substituted alkyl.
Preferably ethylene is homopolymerized or copolymerized with H
2
C═CH—(CH
2
)
t
H and/or H
2
C═CH—R
100
G. It is especially preferred that ethylene is copolymerized with H
2
C═CH—R
100
G.
In another embodiment, the ligand is capable of holding said Lewis acid in close proximity to said metal component. Preferably the Lewis acid is bound to the complex within a Lewis Acid Interaction Cone of about 130° or less; more preferably about 90° or less.
In another embodiment, the ligand is of the formula
wherein BX, BY and BZ are each independently a Lewis base; L is independently LA or BX; LA is a Lewis acid; CA is a connecting atom selected from the group consisting of carbon, nitrogen, sulfur, silicon, boron, and phosphorus; f and r are independently an integer of 1 or more; e is zero or an integer of 1 or more; g is an integer of 2 or more; and dashed lines are bridges, single or multiple bonds.
In another embodiment, Formula (I) or (II) is
wherein:
R
1
and R
2
are each independently hydrocarbyl, substituted hydrocarbyl or a functional group;
Y is CR
11
R
12
, S(T), S(T)
2
, P(T)Q, NR
36
or NR
36
NR
36
;
X is —O—, —CR
5
R
6
— or NR
5
;
A is O, S, Se, N, P or As;
Z is O, S, Se, N, P or As;
each Q is independently hydrocarbyl or substituted hydrocarbyl;
R
3
, R
4
, R
5
, R
6
, R
11
and R
12
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R
7
is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that when Z is O, S or Se, R
7
is not present;
each R
8
and R
9
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R
10
is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R
11
and R
12
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
each T is independently ═O or ═NR
30
;
R
30
is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
each R
31
and R
32
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, provided that R
31
and R
32
taken together may form a ring;
R
33
and R
34
are each independently hydrocarbyl or substituted hydrocarbyl, provided that each is aryl substituted in at least one position vicinal to the free bond of the aryl group, or each has an E
S
of −1.0 or less;
R
35
is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, provided that when A is O, S or Se, R
35
is not present;
R
36
is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
m is 0 or 1;
s is 0 or 1;
n is 0 or 1; and
q is 0 or 1;
provided that:
any two of R
3
, R
4
, R
5
, R
6
, R
8
, R
9
, R
11
and R
12
bonded to the same carbon atom taken together may form a functional group;
any two of R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
11
, R
12
, R
31
, R
32
, R
33
, R
34
, R
35
and R
36
bonded to the same atom or vicinal to one another taken together may form a ring.
In another preferred embodiment, Formula (III) is
wherein:
each R
52
is independently hydrocarbyl or substituted hydrocarbyl, provided that each R
52
is aryl substituted in one position vicinal to the free bond of the aryl group or each independently has an E
S
of −1.0 or less.
each R
50
is independently substituted hydrocarbyl; and
each R
51
is independently hydrogen, hydrocarbyl or su

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