Substantially linear copolymers

Details Substantially linear copolymers Substantially linear copolymers

1999-11-05

2002-07-09

Lipman, Bernard (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S164000, C526S319000, C526S324000, C526S320000, C526S329700, C526S327000

Reexamination Certificate

active

06417303

ABSTRACT:

FIELD OF THE INVENTION
The invention is directed towards tetrahedral and pseudo-tetrahedral late transition metal polymerization catalyst complexes and their use in forming homopolymers from olefins or polar monomers and copolymers from olefins and polar monomers.
BACKGROUND
Polymers and copolymers may be formed from olefinic monomers by using transition metal metallocene catalyst technology. This well-known technology uses catalysts containing early transition metal atoms such as Ti and Zr.
Even though polyolefins formed by such metallocene catalysts posses enhanced properties over polyolefins produced by conventional Ziegler-Natta catalysts, further improvements in properties such as wettability and adhesiveness may be possible. It is believed that including polar monomers in an olefinic polymer or copolymer would improve wettability and adhesiveness in those materials. Unfortunately, polar monomers tend to poison early transition metal catalysts.
Certain late transition metal complexes of palladium and nickel incorporate some polar monomers. However, such catalyst systems are costly. Also, the polymers so produced are highly branched (85-150 branches/1000 carbon atoms) and the functionalities are not in the chain but at the ends of branches. Consequently, they are limited to polar monomer contents≦about 15 mol%. Another disadvantage of these systems is that they incorporate only a limited number of polar monomers (e.g. alkyl acrylates and vinyl ketones). Methyl methacrylate and n-butyl vinyl ether are mildly inhibiting or inert.
Certain functional ethylene copolymers can also be made by free radical polymerization. In commercial practice, these materials also have significant short-chain and some long-chain branching (E. F. McCord, W. H. Shaw, Jr. and K A. Hutchinson,
Macromolecules
, 1997, 30, 246-256). Furthermore, some functional monomers (e.g. n-butyl vinyl ether) do not readily incorporate under free radical conditions (K. W. Doak, Encyclopedia of Polymer Science and Technology, 2nd Ed. H. F. Mark, Ed John Wiley and Sons, New York, 1986, Vol. 6, pp 387-429.
Consequently, there remains a need for a polymerization catalyst capable of forming olefinic polymers and copolymers and that are effective polymerization catalysts in the presence of polar monomers.
SUMMARY OF THE INVENTION
In one embodiment, the invention is a substantially linear copolymer represented by the formula:
where A is a segment derived from an acyclic aliphatic olefin of 2 to about 20 carbon atoms;
R is H or CH
3
;
X is —OR
1
or —COOR
1
;
R
1
is an alkyl group of 1 to 24 carbon atoms; and Y is from about 0.02 to about 0.95
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of the invention comprises comprises a substantially linear copolymers having the formula:
where A is a segment derived from an acyclic aliphatic olefin of 2 to about 20 carbon atoms; R is H or CH
3
; x is —OR
1
or —COOR
1
; R
1
is an alkyl group of 1 to 24 carbon atoms and y is from about 0.02 to about 0.95 and preferably y is from about 0.18 to about 0.85.
These copolymers have polar functional monomer segments,
which are substantially in the chain rather than at ends of branches.
In the case where —A— is a polymer segment derived from ethylene, the branch content of which is below about 15 branches/1000 carbon atoms, for example from about 0.5 to less than 15 branches.
In another embodiment, the invention comprises a substantially linear copolymer having a polymer chain of the formula:
where A is a segment derived from an acyclic aliphatic olefin of 2 to about 20 carbon atoms. R is H or CH
3
. X is —OR
1
or —COOR
1
. R
1
is an alkyl group of 1 to about 24 carbon atoms and y is from 0.18 to 0.85.
In yet another embodiment, the invention comprises a substantially linear copolymer having a polymer chain comprising the formula:
where A is a segment derived from ethylene. R is H or CH
3
. X is —OR
1
or —COOR
1
. R
1
is an alkyl group of 4 carbon atoms and y is from 0.18 to 0.85.
In another embodiment, the invention comprises a substantially linear copolymer having a polymer chain comprising the formula:
wherein y 0.02-0.95.
In another embodiment, the invention comprises a substantially linear copolymer having a polymer chain comprising the formula:
wherein y=0.02-0.95.
In another embodiment, the invention comprises a substantially linear copolymer having a polymer chain comprising the formula:
wherein y=0.02-0.95.
In another embodiment, the invention comprises a substantially linear copolymer having a polymer chain comprising the formula:
wherein y=0.02-0.95.
The catalyst used in the process to form this invention is a complex having the formula LMX
1
X
2
, wherein L is a nitrogen-containing bidentate ligand represented by the formula:
[AZA′]
and
[AA′],
wherein A and A′ are independently selected from the group consisting of
wherein R1 is independently selected from the group consisting of hydrogen, C
1
through C
12
straight chain or branched alkyl, C
3
through C
12
cycloalkyl, aryl, and trifluoroethane;
R2 and R3 are independently selected from the group consisting of hydrogen, C
1
through C
12
straight chain or branched alkyl, C
3
through C
12
cycloalkyl, C
1
through C
12
alkoxy, F, Cl, SO
3
, C
1
through C
12
perfluoroalkyl, and N(CH
3
)
2
;
Z is selected from the group consisting of non-substituted C
1
through C
12
straight chain or branched alkyl, C
3
through C
12
cycloalkyl; methoxy; amino; halo; and C
1
through C
12
haloalkyl substituted straight chain or branched alkyl or cycloalkyl of up to 12 carbon atoms or C
1
-C
40
aryl or alkylaryl groups.
X
1
and X
2
are independently selected from the group consisting halogens, hydride, triflate, acetate, trifluoroacetate, tris ([perfluorotetraphenyl) borate, and tetrafluoro borate, C
1
through C
12
straight chain or branched alkyl or alkoxy, C
3
through C
12
cycloalkyl or cycloalkoxy, and aryl or any other ligand with which a monomer can insert;
Accordingly, some of the ligands of the present invention have the structures:
For compactness, some bonds are shown without termination; these bonds are terminated by methyl groups.
The metal M is selected from Cu, Ag, and Au. Among Cu, Ag, and Au, Cu is preferred; among X
1
and X
2
, halogens are preferred.
Suitable non-halide X
1
and X
2
include triflate, tifluoroacetate, tris perfluorotetraphenyl borate, or tetrafluoro borate, hydride, alkyl groups or any other ligand into which a monomer can insert. Among the metal complexes of the present invention, those having the 1,1′bis(1-methylbenzimidazol-2yl)1″ methoxyethane ligand or the 3,3′(1-ethylbenzimidazol-2yl) pentane ligand, or 2,2′bis[2-(1-alkylbenzimidazol-2yl)] biphenyl, where the alkyl group is from C
1
-C
20
, and X
1
=X
2
=chloride are particularly preferred.
1,1′bis(1-methylbenzimidazol-2yl)1″ methoxyethane ligands with copper as the metal and chlorine as X
1
and X
2
have the structure
3,3′(1-ethylbenzimidazol-2yl) pentane ligands with copper as the metal and chlorine as X
1
and X
2
have the structure
2,2′bis[2-(1-alkylbenzimidazol-2yl)]biphenyl ligands with copper as the metal and chlorine as X
1
and X
2
, and C
1
-C
20
as R
1
, have the structure
Advantageously, the catalysts used to form the present invention are not poisoned by compounds containing hydrocarbyl polar functional groups when used in the formation of polymers and copolymers synthesized all or in part from olefinic monomers. As such, the catalysts of the present invention are useful in preparing polymers and copolymers formed from olefinic monomers, such as polyethylene; polymers and copolymers formed from monomers containing hydrocarbyl polar functional groups such as poly(methyl methacrylate); and copolymers derived from olefins and monomers containing hydrocarbyl polar functional groups such as poly (ethylene-co-methyl methacrylate).
A process used to form the present invention employs a metal complex having

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