U.S. patent application number 10/893428 was filed with the patent office on 2004-12-16 for multi-dentate late transition metal catalyst complexes and polymerization methods using those complexes.
Invention is credited to Boffa, Lisa Saunders, Patil, Abhimanyu Onkar, Schulz, Donald Norman, Sissano, Joseph Anthony, Stibrany, Robert Timothy, Zushma, Stephen.
Application Number | 20040254067 10/893428 |
Document ID | / |
Family ID | 25477208 |
Filed Date | 2004-12-16 |
United States Patent
Application |
20040254067 |
Kind Code |
A1 |
Boffa, Lisa Saunders ; et
al. |
December 16, 2004 |
Multi-dentate late transition metal catalyst complexes and
polymerization methods using those complexes
Abstract
The instant invention provides a late transition metal complex
which can be used with an activating cocatalyst to produce polymers
and copolymers. The invention also provides methods for
polymerizing olefins, as well as copolymers having polar monomers
incorporated therein. More specifically, the invention provides a
composition having the formula LMXZ.sub.n, wherein M is selected
from the group consisting of Cu, Ag and Au; X is selected from the
group consisting of halide, hydride, triflate, acetate, borate,
C.sub.1 through C.sub.12 alkyl, C.sub.1 through C.sub.12 alkoxy,
C.sub.3 through C.sub.12 cycloalkyl, C.sub.3 through C.sub.12
cycloalkoxy, aryl, thiolate, nitrate, sulfate, nitrile, hydroxide
and any other moiety into which a monomer can insert; Z is selected
from the group consisting of halide, hydride, triflate, acetate,
borate, C.sub.1 through C.sub.12 alkyl, C.sub.1 through C.sub.12
alkoxy, C.sub.3 through C.sub.12 cycloalkyl, C.sub.3 through
C.sub.12 cycloalkoxy, aryl, thiolate, carbon monoxide, nitrate,
nitrile, hydroxide, sulfate, olefins, water, any other neutral
coordinating ligand and any other moiety into which a monomer can
insert; n equals 0, 1 or 2; and L is a multi-dentate
nitrogen-containing ligand.
Inventors: |
Boffa, Lisa Saunders;
(Springfield, NJ) ; Patil, Abhimanyu Onkar;
(Westfield, NJ) ; Schulz, Donald Norman;
(Annandale, NJ) ; Stibrany, Robert Timothy; (Long
Valley, NJ) ; Sissano, Joseph Anthony; (Leonardo,
NJ) ; Zushma, Stephen; (Clinton, NJ) |
Correspondence
Address: |
EXXONMOBIL RESEARCH AND ENGINEERING COMPANY
P.O. BOX 900
1545 ROUTE 22 EAST
ANNANDALE
NJ
08801-0900
US
|
Family ID: |
25477208 |
Appl. No.: |
10/893428 |
Filed: |
July 16, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10893428 |
Jul 16, 2004 |
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09941881 |
Aug 28, 2001 |
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6809058 |
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Current U.S.
Class: |
502/167 ;
526/169; 526/319; 526/348.6 |
Current CPC
Class: |
C07F 1/005 20130101;
C08F 110/02 20130101; C08F 210/02 20130101; C08F 10/02 20130101;
C08F 210/02 20130101; C08F 10/02 20130101; C08F 4/54 20130101; C08F
4/54 20130101; C08F 220/10 20130101 |
Class at
Publication: |
502/167 ;
526/319; 526/348.6; 526/169 |
International
Class: |
B01J 031/00 |
Claims
1. A metal complex having the formula LMXZ.sub.n, wherein M is
selected from the group consisting of Cu, Ag and Au; X is selected
from the group consisting of halide, hydride, triflate, acetate,
borate, C.sub.1 through C.sub.12 alkyl, C.sub.1 through C.sub.12
alkoxy, C.sub.3 through C.sub.12 cycloalkyl, C.sub.3 through
C.sub.12 cycloalkoxy, aryl, thiolate, nitrate, sulfate, nitrile,
and hydroxide; Z is selected from the group consisting of halide,
hydride, triflate, acetate, borate, C.sub.1 through C.sub.12 alkyl,
C.sub.1 through C.sub.12 alkoxy, C.sub.3 through C.sub.12
cycloalkyl, C.sub.3 through C.sub.12 cycloalkoxy, aryl, thiolate,
carbon monoxide, nitrate, nitrile, hydroxide, sulfate, olefins, and
water n equals 0, 1 or 2; and L is a tri-dentate
nitrogen-containing ligand selected from the group consisting of
2,2':6',2"-terpyridine, [2,6-bis(1-phenylimino)ethyl]pyridine,
1,4,7-triazacyclononane, and their substituted derivatives.
2. The composition according to claim 1 wherein M is Cu.
3. The metal complex according to claim 1 wherein for each
occurrence of Z, each Z is independently selected from the group
consisting of diethylether, tetrahydrofuran, acetonitrile,
benzonitrile, dioxane, acetone, 2-butanone, phenylisocyanate,
ethylene, carbon monoxide, 1-hexene and norbomene.
4-44. (Cancelled)
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention is directed towards multi-dentate late
transition metal polymerization catalyst complexes and their use in
forming polymers from olefins or polar monomers and copolymers from
olefins and polar monomers.
[0003] 2. Description of the Related Art
[0004] Polymers and copolymers may be formed from olefinic monomers
by using transition metal catalyst technology. Ziegler-Natta
catalysts have been used for many years, while, in more recent
years, metallocene catalysts have been preferred in certain
applications, since the polyolefins produced via metallocene
catalysis often possess superior properties. The most well known
metallocene technology employs catalysts containing early
transition metal atoms, such as Ti and Zr.
[0005] Even though polyolefins formed by such metallocene catalysts
possess certain 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 these, and possibly other, properties.
Unfortunately, polar monomers tend to poison early transition metal
catalysts.
[0006] Certain late transition metal complexes, such as those
containing palladium and nickel, are more successful in
incorporating certain polar monomers into polyolefins. However,
most of these catalyst compositions are costly and produce highly
branched polymers (e.g., 85-150 branches/1000 carbon atoms). Also,
the functionalities are not in the chain, but at the ends of
branches. Consequently, they are limited to polar monomer contents
of about 15 mol % or less. Another disadvantage of these
compositions is that they incorporate only a limited number of
polar monomers, such as alkyl acrylates and vinyl ketones.
[0007] Recently, novel late transition organometallic catalysts
have been made to address the aforementioned problems. More
specifically, U.S. Pat. No. 6,037,297 to Stibrany et al.,
incorporated by reference herein, details group 11 (Cu, Ag and Au;
new IUPAC notation) metal-containing catalyst compositions having a
pseudotetrahedral geometry that are useful in forming is polymers
and copolymers having hydrocarbyl polar functionality. Other
examples of group 11 metal-containing catalyst compositions are
known. See, e.g., WO 98/35996 and JPA 11-171915, both to Shibayama,
et al. and both incorporated by reference herein.
[0008] However, there is still a need to explore other group 11
metal complexes for use in polymerization processes. Ideally, these
late transition metal complexes should be capable of forming
olefinic polymers and copolymers containing polar monomers which
are not highly branched, have polymer chain functionality and are
capable of incorporating a wider variety of polar monomers.
SUMMARY OF THE INVENTION
[0009] The instant invention provides a late transition metal
complex which can be used with an activating cocatalyst to produce
polymers and copolymers. Further, the instant invention can be used
to produce polymers and copolymers containing polar monomers. More
specifically, the metal complex may be activated by a cocatalyst
which is then used to polymerize olefins and copolymerize olefins
with polar monomers. Hence, the invention also provides methods for
polymerizing olefins, as well as copolymers having polar monomers
incorporated therein.
[0010] In one embodiment, the invention provides a composition
having the formula LMXZ.sub.n, wherein M is selected from the group
consisting of Cu, Ag and Au; X is selected from the group
consisting of halide, hydride, triflate, acetate, borates, C.sub.1
through C.sub.12 alkyl, C.sub.1 through C.sub.12 alkoxy, C.sub.3
through C.sub.12 cycloalkyl, C.sub.3 through C.sub.12 cycloalkoxy,
aryl, thiolate, nitrate, sulfate, nitrile, hydroxide and any other
moiety into which a monomer can insert; Z is selected from the
group consisting of halide, hydride, triflate, acetate, borate,
C.sub.1 through C.sub.12 alkyl, C.sub.1 through C.sub.12 alkoxy,
C.sub.3 through C.sub.12 cycloalkyl, C.sub.3 through C.sub.12
cycloalkoxy, aryl, thiolate, carbon monoxide, nitrate, nitrile,
hydroxide, sulfate, olefins, water, any other neutral coordinating
ligand and any other moiety into which a monomer can insert; n
equals 0, 1 or 2; and L is a multi-dentate nitrogen-containing
ligand.
[0011] In another embodiment, the invention is a catalyst
composition comprising the reaction product of a metal complex
having the formula LMXZ.sub.n, as defined above, and an activating
cocatalyst. This embodiment of the invention is particularly useful
in polymerization chemistry.
[0012] In yet another embodiment, the invention provides a method
for using the composition to produce polymers and copolymers which
contain polar monomer units. The method includes contacting the
monomers under polymerization conditions with a catalyst
composition comprising a composition having the formula LMXZ.sub.n,
as defined above, and an activating cocatalyst. Optionally, an
oxidizing agent may also be employed during this process.
[0013] In a further embodiment, the instant invention provides a
novel olefin polymerization process based on the use of a group 11
transition metal complex having the formula MXZ.sub.n, as defined
above; a multi-dentate nitrogen-containing ligand L; and an
activating cocatalyst, which are all contacted with monomers in
situ. Unlike Atom Transfer Radical Polymerization (ATRP), the
instant invention does not use an alkyl halide initiator, but
instead uses a cocatalyst, and can be used to prepare homo- and
co-polymers of aliphatic olefins. Further, unlike U.S. Pat. No.
6,037,297, this embodiment of the invention teaches that the use of
a preformed metal complex is not a prerequisite. More specifically,
it is theorized that the metal complex may be formed in situ by
adding the metal compound with a ligand at the same time cocatalyst
is added. Hence, the advantages of the instant invention include an
in situ method for forming an active catalyst composition which is
a step-saving, cost-saving process.
[0014] These and other features, aspects and advantages of the
present invention will become better understood with regard to the
following description and appended claims.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The invention relates to a novel metal complex which, when
used with an activating cocatalyst, provides a novel catalyst
composition. The invention also provides polymerization methods
which utilize the catalyst composition. Generally speaking, the
methods of the invention produce polymers and copolymers containing
polar monomer groups. It should be appreciated by those skilled in
the art that use of the general term "copolymers" includes
terpolymers and other polymers having various combinations of
monomer units.
[0016] In one embodiment, the invention comprises a composition
comprising the formula LMXZ.sub.n, wherein M is selected from the
group consisting of Cu, Ag and Au; X is selected from the group
consisting of halide, hydride, triflate, acetate, borate, C.sub.1
through C.sub.12 alkyl, C.sub.1 through C.sub.12 alkoxy, C.sub.3
through C.sub.12 cycloalkyl, C.sub.3 through C.sub.12 cycloalkoxy,
aryl, thiolate, nitrate, sulfate, nitrile, hydroxide and any other
moiety into which a monomer can insert; Z is selected from the
group consisting of halide, hydride, triflate, acetate, borate,
C.sub.1 through C.sub.12 alkyl, C.sub.1 through C.sub.12 alkoxy,
C.sub.3 through C.sub.12 cycloalkyl, C.sub.3 through C.sub.12
cycloalkoxy, aryl, thiolate, carbon monoxide, nitrate, nitrile,
hydroxide, sulfate, olefins, water, any other neutral coordinating
ligand and any other moiety into which a monomer can insert; n
equals 0, 1 or 2; and L is a multi-dentate nitrogen-containing
ligand. It should be appreciated by those skilled in the art that
the term "multi-dentate" is meant to encompass tri-dentate,
tetra-dentate, penta-dentate, hexa-dentate, etc., ligands. More
specificially, there will be more than 2 coordinating nitrogen
atoms in the ligand.
[0017] When the metal composition is reacted with an activating
cocatalyst, such as methylaluminoxane ("MAO"), an activated
catalyst composition is created. Thus, in another embodiment, the
invention is an activated catalyst composition comprising the
reaction product of: (a) a metal complex having the formula
LMXZ.sub.n, wherein M is selected from the group consisting of Cu,
Ag and Au; X is selected from the group consisting of halide,
hydride, triflate, acetate, borate, C.sub.1 through C.sub.12 alkyl,
C.sub.1 through C.sub.12 alkoxy, C.sub.3 through C.sub.12
cycloalkyl, C.sub.3 through C.sub.12 cycloalkoxy, aryl, thiolate,
nitrate, sulfate, nitrile, hydroxide and any other moiety into
which a monomer can insert; Z is selected from the group consisting
of halide, hydride, triflate, acetate, borate, C.sub.1 through
C.sub.12 alkyl, C.sub.1 through C.sub.12 alkoxy, C.sub.3 through
C.sub.12 cycloalkyl, C.sub.3 through C.sub.12 cycloalkoxy, aryl,
thiolate, carbon monoxide, nitrate, nitrile, hydroxide, sulfate,
olefins, water, a neutral coordinating ligand, and any other moiety
into which a monomer can insert; n equals 0, 1 or 2; and L is a
multi-dentate nitrogen-containing ligand; and (b) an activating
cocatalyst.
[0018] In a preferred embodiment, L is a nitrogen-containing
multi-dentate ligand selected from the group consisting of aromatic
compounds, aliphatic compounds or a combination of aromatic and
aliphatic compounds. The aromatic or aliphatic compounds can be
acyclic compounds or they can be connected to form cyclic
compounds. Examples of nitrogen-containing aromatic compounds
include, but are not limited to, heterocycles, such as a
substituted or unsubstituted 2,2':6'2"-terpyridine and a
substituted or unsubstituted 2,6-diaryliminopyridine. Each sample
heterocycle is shown below. 1
[0019] For the terpyridine structure shown above, R is
independently selected from the group consisting of hydrogen,
C.sub.1 to C.sub.20 alkyl, C.sub.4 to C.sub.24 cycloalkyl and
C.sub.5 to C.sub.30 aromatic groups which, optionally, contain
heteroatoms. Although only three R groups are shown, there could be
as many as 11 or more R groups, depending upon the size of the
aromatic rings. 2
[0020] For the [2,6-bis(l-phenylimino)ethyl]pyridine structure
shown above, R and R' are independently selected from the group
consisting of hydrogen, C.sub.1 to C.sub.20 alkyl, C.sub.4 to
C.sub.24 cycloalkyl, and C.sub.5 to C.sub.30 aromatic groups which,
optionally, contain heteroatoms. Although only three R groups and
two R' groups are shown, there could be as many as 15 or more R and
R' groups, depending upon the size of aromatic rings.
[0021] Similarly, examples of nitrogen-containing aliphatic
compounds include, but are not limited to, substituted or
unsubstituted diethylenetriamine or cyclic amine, as illustrated
below: 3
[0022] For the structures above, R is independently selected from
the group consisting of hydrogen, C.sub.1 to C.sub.20 alkyl,
cycloalkyl and aromatic groups which, optionally, contain
heteroatoms. Furthermore, m is from 1 to 5, and n is from 0 to
5.
[0023] Specific examples of nitrogen-containing ligands include
456
[0024] In yet another preferred embodiment, L may be a pyrazolyl
borate compound, as taught in U.S. Pat. No. 5,627,164 to Gorun, et
al., incorporated by reference herein.
[0025] In a preferred embodiment, M is copper. Among the options
for X, halogens are preferred. Suitable non-halide options for X
include, but are not limited to, triflate, trifluoroacetate,
perfluorotetraphenyl borate, tetrafluoro borate, hydride, alkyl
groups or any other moiety into which a monomer can insert, such as
an atom, or group of atoms, covalently or ionically bonded to
M.
[0026] For each occurrence of Z, each Z is preferably independently
selected from the group consisting of halogens, triflate,
trifluoroacetate, perfluorotetraphenyl borate, tetrafluoro borate,
hydride, alkyl, diethylether, tetrahydrofuran, acetonitrile,
benzonitrile, dioxane, acetone, 2-butanone, phenylisocyanate,
ethylene, carbon monoxide, 1-hexene and norbornene, or any other
moiety into which a monomer can insert.
[0027] Advantageously, the catalysts of 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 olefinic 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). One of skill in the art will
know that the hydrocarbyl polar functional groups mentioned above
include ethers, esters, ketones, alcohols, and carboxylic acids,
among others.
[0028] Examples of the activating cocatalysts used above include,
but are not limited to, aluminum compounds containing an Al--O
bond, such as the alkylaluminoxanes, specifically methylaluminoxane
("MAO") and isobutyl modified methylaluminoxane; aluminum alkyls;
aluminum halides; alkylaluminum halides; alkylaluminum alkoxides;
alkylaluminum aryloxides; Lewis acids other than any of the
foregoing list; and mixtures of the foregoing can also be used in
conjunction with alkylating agents, such as dimethyl magnesium,
methyl magnesium chloride and methyl lithium. Examples of such
Lewis acids are those compounds corresponding to the formula:
R"".sub.3B, wherein R"", independently each occurrence, is selected
from hydrogen, silyl, hydrocarbyl, halohydrocarbyl, alkoxide,
aryloxide, amide or combinations thereof, said R"" having up to 30
non-hydrogen atoms.
[0029] It is to be appreciated by those skilled in the art that the
above formula for the preferred Lewis acids represents an empirical
formula, and that many Lewis acids exist as dimers or higher
oligomers in solution or in the solid state. Other Lewis acids
which are useful in the catalyst compositions of this invention
will be apparent to those skilled in the art.
[0030] Other examples of such cocatalysts include salts of group 13
element complexes (new IUPAC notation). These and other examples of
suitable cocatalysts and their use in organometallic polymerization
are discussed in U.S. Pat. No. 5,198,401 and PCT patent documents
WO 97/48736 and WO 96/40805, all incorporated by reference
herein.
[0031] Preferred activating cocatalysts include trimethylaluminum,
triisobutylaluminum, methylaluminoxane, ethylaluminoxane,
chlorodiethyaluminum, dichloroethylaluminum, triethylboron,
trimethylboron, triphenylboron and halogenated, especially
fluorinated, triphenyl boron compounds.
[0032] The most highly preferred activating cocatalysts include,
but are not limited to, triethylaluminum, methylaluminoxane,
fluoro-substituted tetra-aryl borates, such as
triphenylmethyl[tetrakis(pentafluorophenyl)bo- rate], sodium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and
dimethylanilinium[tetrakis(pentafluorophenyl)borate], and
fluoro-substituted triarylboranes, such as
tris(4-fluorophenyl)boron, tris(2,4-difluorophenyl)boron,
tris(3,5-bis(trifluoromethyl)phenyl)boron,
tris(pentafluorophenyl)boron, (pentafluorophenyl-diphenyl)boron,
and bis(pentafluorophenyl)phenylboron. Such fluoro-substituted
triarylboranes may be readily synthesized according to techniques
such as those disclosed in Marks, et al., J. Am. Chem. Soc., 113,
3623-3625 (1991), which is herein incorporated by reference.
[0033] Furthermore, the equivalent ratio of metal to activating
cocatalyst is preferably in arange from 1:0.5 to 1:10.sup.4,
morepreferably from 1:0.75 to 1:10.sup.3. In most polymerization
reactions, the equivalent ratio of catalyst:polymerizable compound
employed is from 10.sup.-12:1 to 10.sup.-1:1, more preferably from
10.sup.-9:1 to 10.sup.-4:1.
[0034] The catalyst can be utilized by forming the metal complex
LMXZ.sub.n, as defined above, and, where required, combining the
activating cocatalyst with the metal complex in a diluent.
Optionally, an oxidizing agent may also be utilized in conjunction
with the cocatalyst. Oxidizing agents may include, but are not
limited to, NOBF.sub.4, 1,4-benzoquinone,
tetrachloro-1,4-benzoquinone, AgClO.sub.4,
Ag(C.sub.6F.sub.5).sub.4B, ferricinium (C.sub.6F.sub.5).sub.4B,
(3,5-(CF.sub.3).sub.2--(C.sub.6H.sub.4)B)Cp.sub.2Fe.sup.+, and
(3,5-(CF.sub.3).sub.2--(C.sub.6H.sub.4)B)Cp*.sub.2Fe.sup.+. The
preparation may be conducted in the presence of one or more
polymerizable monomers, if desired. Preferably, the catalysts are
Prepared at a temperature within the range from -100.degree. C. to
300.degree. C., preferably from 0.degree. C. to 250.degree. C., and
most preferably from 0.degree. C. to 100.degree. C. Suitable
solvents include liquid or supercritical gases, such as CO.sub.2;
straight- and branched-chain hydrocarbons, such as chlorobenzene,
dichlorobenzene, and perfluorinated C.sub.2-10 alkanes; and
aromatic and alkyl-substituted aromatic compounds, such as benzene,
toluene and xylene. Suitable solvents also include liquid olefins
which may act as monomers or comonomers, including ethylene,
propylene, butadiene, 1-hexene, 3-methyl-1-pentene,
4-methyl-1-pentene, 1-octene, 1-decene, and 4-vinylcylohexane
(including all isomers alone or in mixtures). Other solvents
include anisole, methyl chloride, methylene chloride, chloroform,
2-pyrrolidone and N-methylpyrrolidone. Preferred solvents are
aliphatic hydrocarbons and aromatic hydrocarbons, such as
toluene.
[0035] Olefinic monomers useful in forming homopolymers and
copolymers with the catalyst of the invention include, but are not
limited to: (a) aliphatic olefins; (b) olefins having a hydrocarbyl
polar functionality; and (c) mixtures of (i) at least one olefin
having a hydrocarbyl polar functional group and (ii) at least one
aliphatic olefin. Olefinic monomers include ethylenically
unsaturated monomers, nonconjugated dienes, oligomers, and higher
molecular weight, vinyl-terminated macromers. Examples include
C.sub.2-20 olefins, vinylcyclohexane, tetrafluoroethylene, and
mixtures thereof. Preferred monomers include the C.sub.2-10
.alpha.-olefins, especially ethylene, propylene, isobutylene,
1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene or mixtures of
the same.
[0036] Monomers having hydrocarbyl polar functional groups useful
in forming homopolymers and copolymers with the catalyst of the
invention are vinyl ether and C.sub.1 to C.sub.20 alkyl vinyl
ethers, such as n-butyl vinyl ether; acrylates, such as C.sub.1 to
C.sub.24 alkyl acrylates, preferably t-butyl acrylate and lauryl
acrylate; and methacrylates, such as methyl methacrylate.
[0037] In another embodiment, the invention provides one method for
polymerizing olefinic monomers selected from the aforementioned
group. The method of this embodiment comprises contacting the
olefinic monomers under polymerization conditions with an activated
catalyst compound comprising the reaction product of: (a) a metal
complex having the formula LMXZ.sub.n, as defined above; and (b) an
activating cocatalyst. Furthermore, by controlling the temperature,
catalyst loading, ligand structure and residence time, product
selectivity can be adjusted to produce individual polymers and
copolymers with high selectivity.
[0038] A further embodiment comprises a method for polymerizing the
aforementioned olefinic monomers in situ. This method includes
contacting in situ under polymerization conditions compound
MXZ.sub.n, compound L, an activating cocatalyst, and one or more of
the olefinic monomers. In this situation, the equivalent ratio of
compound L to compound MXZ.sub.n is preferably from 0.25:1 to 4:1,
and more preferably from 0.5:1 to 2:1.
[0039] In general, the polymerization may be accomplished at
conditions well known in the art for Ziegler-Natta or Kaminsky-Sinn
type polymerization reactions, that is, temperatures from
-100.degree. C. to 250.degree. C., preferably from 0.degree. C. to
250.degree. C., and pressures from atmospheric to 2000 atmospheres
(200 Mpa). Suitable polymerization conditions include those known
to be useful for metallocene catalysts when activated by aluminum
or boron compounds. Suspension, solution, slurry, gas phase or
other process conditions may be employed, if desired. The catalysts
may be supported, and such supported catalysts may be employed in
the polymerizations of this invention. Preferred supports include
alumina, silica, polymeric supports and meso-porous materials.
[0040] The polymerization typically will be conducted in the
presence of a solvent. Suitable solvents include those previously
described as useful in the preparation of the catalyst. Indeed, the
polymerization may be conducted in the same solvent used in
preparing the catalyst. Optionally, of course, the catalyst may be
separately prepared in one solvent and used in another.
[0041] The polymerization will be conducted for a time sufficient
to form the polymer, and the polymer is recovered by techniques
well known in the art and illustrated in the following non-limiting
examples which help to further described the invention.
EXAMPLES
Example 1
Synthesis of
(2,6-Bis-[1-(2,6-dimethylphenylimino)ethyl]-pyridine)CuCl.sub- .2
("I")
[0042] A 93 mg (0.56 mmol) quantity of CuCl.sub.2.(H.sub.2O).sub.2
mg, was dissolved in 10 mL anhydrous acetonitrile in a 100 mL
Schlenk flask equipped with a stirbar and reflux condenser. Then, 2
mL of triethyl orthoformate was added and the clear green solution
was heated to 84.degree. C. Next, 202 mg (0.56 mmol) of
2,6-bis-[1-(2,6-dimethylphenyli- mino)ethyl]-pyridine was dissolved
in a mixture of 10 mL anhydrous acetonitrile and 0.6 mL toluene at
70.degree. C. and added to the copper chloride solution through the
top of the condenser. The solution slowly became brown and, after 1
minute, a brown precipitate began to form. The mixture was stirred
at 84.degree. C. for an additional 20 minutes and cooled to room
temperature. The brown precipitate was collected by filtration,
rinsed with additional acetonitrile, and dried under vacuum (90 mg,
32% yield, FW 504.0 g/mol). IR (KBr): 3400 (w, residual O--H), 3080
(m), 2945 (m), 2909 (m), 1618 (m, Cu--Cl), 1565 (C.dbd.N), 1470
(s), 1373 (m), 1265 (s), 1223 (s), 1101 (w), 1034 (m), 814 (m), 770
(m), 744 (sh) cm.sup.-1.
Example 2
Preparation of
(2,6-Bis-[1-(2,6-dimethylphenylimino)ethyl]-pyridine)CuCl
("II")
[0043] A 67 mg (0.0.68 mmol) quantity of CuCl (rinsed with aqueous
HCl and dried) was slurried in 20 mL anhydrous THF in a Schlenk
flask equipped with a stirbar and reflux condenser under argon.
Next, 2 mL of triethyl orthoformate was added and the slurry was
heated to 60.degree. C. The
2,6-bis-[1-(2,6-dimethylimino)ethyl]-pyridine (250 mg, 0.0.68 mmol)
was dissolved in anhydrous THF and cannulated into the warm slurry.
The CuCl began to dissolve and the mixture was allowed to reflux
under argon for several hours, after which it had assumed a dark
brown color. The solvent was removed by cannula and the remaining
solids rinsed with a small amount of anhydrous acetonitrile and
dried under vacuum. Approximately 50 mg (16% yield, FW 468.5 g/mol)
was recovered in the drybox as a brown powder. NMR
(d.sub.3-acetonitrile): .delta. 8.29 (app. d, 2 H, Py-m), 8.27
(app. t, 1 H, Py-p), 7.14 (d, J=7.6 Hz, 4 H, aniline m), 7.02 (t,
J=7.4 Hz, 2 H, aniline p), 2.27 (s, 6 H, N.dbd.CMe), 2.05 (s, 12 H,
aniline Me). IR (KBr): 3450 (w), 3063 (w), 3017 (w), 2972 (m), 2917
(m), 1928 (w), 1620 (m), 1588 (s), 1468 (vs), 1368 (m), 1250 (s),
1206 (s), 1092 (m), 1036 (w), 988 (w), 810 (m), 770 (s)
cm.sup.-1.
Example 3
Preparation of
(N,N,N',N",N"-Pentamethyldiethylenetriamine)CuCl.sub.2 ("III")
[0044] An 8.12 g (0.0952 mol) quantity of
CuCl.sub.2.(H.sub.2O).sub.2 was dissolved in 250 mL ethanol in a
500 mL flask equipped with a stirbar and reflux condenser. Then, 50
mL of diethylene orthoformate was added, and the solution was
stirred for 15 minutes. Next, a 7.5 g (FW 173.30, 0.0866 mol)
quantity of N,N,N',N",N"-pentamethyldiethylenetriamine was added.
The mixture was refluxed for 30 minutes and cooled to room
temperature. The flask was sealed and cooled in a refrigerator for
crystallization to occur. The blue crystals were collected by
filtration, rinsed with additional ethanol, and dried under a
vacuum resulting in 2.13 g of the complex.
Example 4
Ethylene Polymerization
[0045] In an argon glovebox, 1.416 g of a 30 wt % methylaluminoxane
solution in toluene (Albemarle, stored at -35.degree. C., 425 mg
MAO, 7.32 mmol) was weighed into a soap-washed and oven-dried 300
mL Parr glass liner. Then, 25 mL of chlorobenzene (distilled from
CaH.sub.2) and 25 mL of toluene (dried by passage over alumina and
Q5 copper catalyst) were added followed by 45.6 mg (0.090 mmol) of
I, the copper complex formed in Example 1. The liner was then
placed into a 300 mL Hasteloy Parr reactor (soap-washed and
oven-dried), which was quickly assembled, sealed and removed from
the glove box. The reactor was heated to 80.degree. C. and the
contents were stirred at approximately 350 rpm with an air-driven
stirring shaft. After a quick nitrogen purge of the connected
lines, the reactor was pressurized to 600 psi with ethylene (passed
through drying columns of molecular sieves and Q5 copper catalyst).
The reactor was sealed off from all gas lines and stirred at
80.degree. C. overnight, after which it was cooled to room
temperature and vented. The contents were poured into a large
excess (approx. 1 L) of 5% HCl in methanol. The white insoluble
polymer was collected by filtration, rinsed with a small volume of
additional methanol, and dried in a vacuum oven overnight at
75.degree. C. to yield 112 mg of the polymer. IR (KBr): 2917 (s),
2851 (s), 1472 (m), 729 (w), 719 (w) cm.sup.-1. Melting point (DSC,
2.sup.nd heat): 134.9.degree. C.
Example 5
Polymerization of Ethylene
[0046] In an argon glovebox, 0.357 g of a 30 wt % methylaluminoxane
solution in toluene (Albemarle, stored at -35.degree. C., 107 mg
MAO, 1.84 mmol) was weighed into a soap-washed and oven-dried 300
mL Hasteloy Parr reactor. Then, 100 mL of toluene (dried by passage
over alumina and Q5 copper catalyst) was added followed by 45.6 mg
(0.090 mmol) of I, the copper complex formed in Example 1. The
reactor was quickly assembled, sealed, removed from the glove box,
and heated to 80.degree. C., and its contents were stirred at
approximately 350 rpm with an air-driven stirring shaft. After a
quick nitrogen purge of the connected lines, the reactor was
pressurized to 600 psi with ethylene (passed through drying columns
of molecular sieves and Q5 copper catalyst). The reactor was sealed
off from all gas lines and stirred for two days at 80.degree. C.,
after which it was cooled to room temperature and vented. The
contents were poured into a large excess (approx. 1 L) of 5% HCl in
methanol. The white insoluble polymer was collected by filtration,
rinsed with a small volume of additional methanol, and dried in a
vacuum oven overnight at 75.degree. C. to yield 226 mg of the
polymer.
Example 6
Polymerization of Ethylene
[0047] In an argon glovebox, 0.354 g of a 30 wt % methylaluminoxane
solution in toluene (Albemarle, stored at -35.degree. C., 106 mg
MAO, 1.83 mmol) was weighed into a soap-washed and oven-dried 300
mL Parr glass liner. Next, 25 is mL of chlorobenzene (distilled
from CaH.sub.2) and 25 mL of toluene (dried by passage over alumina
and Q5 copper catalyst) were added, followed by 45.6 mg (0.090
mmol) of I, the copper complex from Example 1. The liner was placed
into a 300 mL Hasteloy Parr reactor (soap-washed and oven-dried),
which was quickly assembled, sealed and removed from the glove box.
The reactor was heated to 80.degree. C. and the contents were
stirred at ca. 350 rpm with an air-driven stirring shaft. After a
quick nitrogen purge of the connected lines, the reactor was
pressurized to 600 psi with ethylene (passed through drying columns
of molecular sieves and Q5 copper catalyst). The reactor was sealed
off from all gas lines and stirred overnight at 80.degree. C.,
after which it was cooled to room temperature and vented. The
contents were poured into a large excess (approx. 1 L) of 5% HCl in
methanol. The white insoluble polymer was collected by filtration,
rinsed with a small volume of additional methanol, and dried in a
vacuum oven overnight at 75.degree. C. to yield 91 mg of the
polymer.
Example 7
Polymerization of Ethylene
[0048] A glass-lined Parr reactor was loaded in an argon glove box
with 100 mL of toluene and 10.53 g of 30 wt % MAO solution in
toluene, and 0.0112 g of III, the copper complex formed in Example
3, was added. The Parr reactor was then sealed, placed in a fume
hood and pressurized with 750 psig ethylene at 60.degree. C. for 24
hours. The reactor was cooled, vented and its contents poured into
a solution of MeOH/HCl (300 mL MeOH/100 mL 10% HCl). The mixture
was stirred for 24 hours to remove catalyst residues. The polymer
was isolated by filtration and dried under vacuum at 60.degree. C.
for 24 hours. The yield of the polyethylene was 120 mg. The IR
spectrum (film) of the product showed the characteristic linear
crystalline polyethylene doublet absorption at 719 and 729
cm.sup.-1.
Example 8
Polymerization of n-Butyl Acrylate
[0049] In an argon glovebox, a 30 mL septum bottle was loaded with
a 0.01 g (FW 309.75, 0.0322 mmol) quantity of III, the copper
complex formed in Example 3, and 15 mL of toluene. A 0.77 g
quantity of 30 wt % MAO solution in toluene was then added. The
yellow solution turned colorless upon the MAO addition. Then, 5 g
(FW 128.17, 0.039 mol) of n-butyl acrylate was added. The bottle
was sealed in the glovebox and placed into a fume hood. The
solution was stirred for 72 hours at 25.degree. C. The viscous
solution was added to a solution of MeOH/HCl (300 mL MeOH/100 mL
10% HCl solution to precipitate the polymer. The product was washed
with water, then methanol, and dried in vacuum oven for 24 hours at
60.degree. C. The yield of the poly(n-butyl acrylate) was 3.26 g.
The IR spectrum (film) of the product showed the characteristic
polymer ester absorption peak at 1736 cm.sup.-1. On polymerization,
the monomeric ester absorption peak shifts from 1728 cm.sup.-1 to
the polymeric ester absorption at 1736 cm.sup.-1. The
characteristic double bond absorption peaks at 1637 and 812
cm.sup.-1 also disappear on polymerization. The GPC data (solvent:
THF, polystyrene standard) gave a M.sub.n of 119,600 and a M.sub.w
of 204,780. .sup.13C NMR (ppm, CDCl.sub.3): 13.7 [s,
--CH.sub.2--CH(COOCH.su- b.2CH.sub.2CH.sub.2CH.sub.3)--], 19.1 [s,
--CH.sub.2--CH (COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 30.7 [s,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 34-37 [m,
--CH.sub.2CH(COOCH.sub.2 CH.sub.2 CH.sub.2CH.sub.3)--], 41-42 [m,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 64.5 [s,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 174-175 [m,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--]. There were
no resonances due to olefin from the monomer.
Example 9
Copolymerization of Ethylene and t-Butyl Acrylate
[0050] A glass-lined Parr reactor was loaded in an argon glove box
with 100 mL of toluene and 10.53 g of 30 wt % MAO solution in
toluene. Then, a 0.0112 g quantity of III, the complex formed in
Example 3, was added followed by 5 g of tert-butyl acrylate. The
Parr reactor was sealed, placed in a fume hood and pressurized with
350 psig ethylene and heated to 60.degree. C. with stirring. The
ethylene pressure was then increased to 700 psig and the reactor
continued to stir for 18 hours at 60.degree. C. The reactor was
cooled, vented and its contents poured into a solution of MeOH/HCl
(300 mL MeOH/100 mL 10% HCl). The mixture was stirred for 24 hours
to remove catalyst residues. The polymer was isolated by filtration
and dried under vacuum at 60.degree. C. for 24 hours. The yield of
the copolymer was 310 mg. The IR spectrum of the product showed the
characteristic ester absorption peak at 1728 cm.sup.-1.
Example 10
Polymerization of Ethylene
[0051] In an argon glove box, a glass-lined Parr reactor was loaded
with 120 mL of toluene and 2.84 g of 30 wt % MAO solution in
toluene. A 10.6 mg quantity of CuCl.sub.2.2H.sub.2O (FW 170.48,
6.218.times.10.sup.-2 mmol) was then added (Al/Cu ratio of 234)
followed by a 10.4 mg quantity of
N,N,N',N",N"-pentamethyldiethylenetriamine (FW 173.30,
6.00.times.10.sup.-2 mmol) ligand. The Parr reactor was sealed,
placed in a fume hood and pressurized with 750 psig ethylene, and
polymerized at 60.degree. C. for 20 hours. The reactor was cooled,
vented and quenched with methanol. The polymer was soaked in a
MeOH/HCl (300 mL MeOH/100 mL 10% HCl) mixture for 24 hours to
remove catalyst residues. The polymer was isolated by filtration
and dried under vacuum at 60.degree. C. for 24 hours. The yield of
the polyethylene was 50 mg. The IR spectrum (film) of the product
showed the characteristic linear crystalline polyethylene doublet
absorption at 719 and 729 cm.sup.-1.
Example 11
Polymerization of t-Butyl Acrylate
[0052] In an argon glovebox, a 30 mL septum bottle was loaded with
a 0.003 g quantity of CuCl.sub.2.2H.sub.2O (FW 170.48, 0.02 mmol)
and 15 mL of toluene. A 0.00315 g quantity of
N,N,N',N',N"-pentamethyldiethylenetriami- ne ligand was then added,
resulting in the formation of a yellow solution. Next, a 0.88 g
quantity of 30 wt % MAO solution in toluene was added. The yellow
solution turned colorless upon MAO addition. Then, 5 g of t-butyl
acrylate (FW 128.17, 0.039 mol) was added. The bottle was sealed in
the glove box and placed in a fume hood. The solution was heated at
60.degree. C. for 3 hours. The viscous solution was cooled to room
temperature and was added to a MeOH/HCl (300 mL MeOH/100 mL 10%
HCl) solution to precipitate the polymer. The product was washed
with water, then methanol, and dried in vacuum oven at 60.degree.
C. for 24 hours. The yield of the poly(t-butyl acrylate) was 400
mg. The IR spectrum (film) of the product showed the characteristic
ester peak at 1734 cm.sup.-1. .sup.13C NMR (ppm, CDCl.sub.3): 27.7
(s, --CH.sub.2--CH(COOC(CH.sub.3).sub.3--), 35.9 and 37.1 (m,
--CH.sub.2--CH(COOC(CH.sub.3).sub.3), 42.3 (m,
--CH.sub.2--CH(COOC(CH.sub- .3).sub.3--), 79.6 (s,
--CH.sub.2--CH(COOC(CH.sub.3).sub.3--), 173.3 (s,
--CH.sub.2--CH(COOC(CH.sub.3).sub.3--). There were no resonances
due to olefin from the monomer.
Example 12
Copolymerization of Ethylene and t-Butyl Acrylate
[0053] In an argon glove box, a 0.0062 g quantity of
CuCl.sub.2.2H.sub.2O (FW 170.48, 0.04 mmol) and 100 mL of toluene
were loaded into a glass-lined Parr reactor. Then, a 0.0068 g
quantity of N,N,N',N",N"-pentamethyldiethylenetriamine ligand was
added, which cause the solution to turn yellow. Next, a 1.53 g
quantity of 30 wt % MAO solution in toluene was added. Then, a 5 g
quantity of t-butyl acrylate (FW 128.17, 0.039 mol) was added. The
Parr reactor was then sealed, placed in a fume hood, and
pressurized with 750 psig ethylene, and polymerized at 60.degree.
C. for 20 hours. The reactor was cooled, vented and quenched with
methanol. The polymer was soaked in a MeOH/HCl mixture (300 mL
MeOH/100 mL 10% HCl) for 24 hours to remove catalyst residues. The
polymer was isolated by filtration and dried under vacuum at
60.degree. C. for 24 hours. The yield of the product was 250 mg.
.sup.13C NMR spectra of the product showed EAE, EAA/AAE and AAA
triads and a copolymer composition of 56% ethylene (E) and 46%
acrylate (A).
Example 13
Polymerization of Ethylene
[0054] A glass-lined Parr reactor was loaded in an argon glove box
with 120 mL of toluene and 2.84 g of a 30 wt % MAO solution in
toluene. A 11.0 mg quantity of CuCl.sub.2.2H.sub.2O (FW 170.48,
6.452.times.10.sup.-2 mmol) was then added (Al:Cu ratio of 227:1)
followed by a 10.0 mg quantity of
1,4,7-trimethyl-1,4,7-triazacyclononane (FW 171.29,
5.84.times.10.sup.-2 mmol) ligand. The Parr reactor was then
sealed, placed in a fume hood, and pressurized with 750 psig
ethylene, and polymerized at 60.degree. C. for 16 hours. The
reactor was cooled, vented and quenched with methanol. The polymer
was soaked in a MeOH/HCl mixture (300 mL MeOH/100 mL 10% HCl) for
24 hours to remove catalyst residues. The polymer was isolated by
filtration and dried under vacuum at 60.degree. C. for 24 hours.
The yield of the polyethylene was 110 mg. The IR spectrum (film) of
the product showed the characteristic linear crystalline
polyethylene doublet absorption at 719 and 729 cm.sup.-1.
Example 14
Polymerization of n-Butyl Acrylate
[0055] In an argon glovebox, a 30 mL septum bottle was loaded with
a 0.0061 g quantity of CuCl.sub.2.2H.sub.2O (FW 170.98,
3.57.times.10.sup.-2 mmol) and 15 mL of toluene. Then, a 0.0056 g
quantity of 1,4,7-trimethyl-1,4,7-triazacyclononane (FW 171.29,
3.327.times.10.sup.-2 mmol) ligand was added, resulting in a yellow
solution. A 0.77 g quantity of 30 wt % MAO solution in toluene was
then added. The yellow solution turned colorless upon MAO addition.
Next, a 5 g quantity of n-butyl acrylate (FW 128.17, 0.039 mol) was
added. The bottle was sealed in the glove box and placed in a fume
hood. The solution was stirred at 25.degree. C. for 72 hours. The
viscous solution was added to a MeOH/HCl (300 mL MeOH/100 mL 10%
HCl) solution to precipitate the polymer. The product was washed
with water, then methanol, and dried in a vacuum oven at 60.degree.
C. for 24 hours. The yield of the poly(n-butyl acrylate) was 4.12
g. The IR spectrum (film) of the product showed the characteristic
polymer ester absorption peak at 1736 cm.sup.-1. After
polymerization, the monomeric ester absorption peak shifted from
1728 cm.sup.-1 to the polymeric ester absorption at 1736 cm.sup.-1.
The characteristic double bond absorption peaks at 1637 cm.sup.-1
and 812 cm.sup.-1 also disappeared upon polymerization. The GPC
data (solvent: THF, polystyrene standard) gave a M.sub.n of 112,200
and a M.sub.w of 160,700. .sup.13C NMR (ppm,CDCl.sub.3): 13.6 [s,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 19.1 [s,
--CH.sub.2--CH (COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 30.7 [s,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 34-37 [m,
--CH.sub.2CH(COOCH.sub.2 CH.sub.2 CH.sub.2CH.sub.3)--], 41-42 [m,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 64.5 [s,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 174-175 [m,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--]. There were
no resonances due to olefin from the monomer.
Example 15
Polymerization of n-Butyl Acrylate
[0056] In an argon glovebox, a 30 mL septum bottle was loaded with
a 0.0061 g quantity of CuCl.sub.2.2H.sub.2O (FW 170.98, 0.0357
mmol) and 15 mL of toluene. Then, a 0.0130 g quantity of
4.4',4"-tri-tert-butyl-2,2':6- ",2'-terpyridine (FW 401.60, 0.0324
mmol) ligand was added resulting in the formation of a yellow
solution. A 0.77 g quantity of 30 wt % MAO solution in toluene was
then added. The yellow solution turned colorless upon MAO addition.
Next, 5 g of n-butyl acrylate (FW 128.17, 0.039 mol) was added. The
bottle was sealed in the glove box and placed in a fume hood. The
solution was stirred at 25.degree. C. for 72 hours. The viscous
solution was added to a MeOH/HCl (300 mL MeOH/100 mL 10% HCl)
solution to precipitate the polymer. The product was washed with
water, then methanol, and dried in vacuum oven at 60.degree. C. for
24 hours. The yield of the poly(n-butyl acrylate) was 3.12 g. The
IR spectrum (film) of the product showed the characteristic polymer
ester absorption peak at 1736 cm.sup.-1. On polymerization, the
monomeric ester absorption peak shifted from 1728 cm.sup.-1 to the
polymeric ester absorption at 1736 cm.sup.-1. The characteristic
double bond absorption peaks at 1637 cm.sup.-1 and 812 cm.sup.-1
also disappeared upon polymerization. The GPC data (solvent: THF,
polystyrene standard) gave a M.sub.n of 124,100 and a M.sub.w of
214,600 .sup.13C NMR (ppm,CDCl.sub.3): 13.7 [s,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 19.1 [s,
--CH.sub.2--CH (COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 30.7 [s,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 34-37 [m,
--CH.sub.2CH(COOCH.sub.2 CH.sub.2 CH.sub.2CH.sub.3)--], 41-42 [m,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 64.5 [s,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--], 174-175 [m,
--CH.sub.2--CH(COOCH.sub.2CH.sub.2CH.sub.2CH.sub.3)--]. There were
no resonances due to olefin from the monomer.
[0057] The foregoing examples clearly demonstrate that the novel
composition of the instant invention can be used as an effective
polymerization catalyst to make polymers and copolymers, including
copolymers having polar functionality. More specifically, the
examples show how polar monomers can be readily polymerized without
poisoning the catalyst. Also, the chain, as opposed to the
branches, contains a significant quantity of the polar monomers.
Furthermore, the polymers formed are not highly branched.
Additionally, the examples show that the polymers formed have a
high percent of polar monomer content (e.g., greater than about 15
mol %). Finally, there are a variety of polar monomers which may be
incorporated into the olefinic polymer and copolymer products.
These features overcome the disadvantages of most organometallic
catalyst technology used today, as discussed above in the
background section.
* * * * *