Note: Descriptions are shown in the official language in which they were submitted.
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LUBRICANTS FROM MIXED ALPHA-OLEFIN FEEDS
FIELD OF THE INVENTION
[0001] The invention relates to lubricant compositions comprising PAO
and/or HVI-PAO basestock made by contacting mixed feed - alpha-olefins with a
catalyst comprising a metallocene.
BACKGROUND OF THE INVENTION
[0002] The viscosity-temperature relationship of a lubricating oil is one of
the critical criteria which must be considered when selecting a lubricant for
a
particular application. Viscosity. Index (VI) is an empirical, unitless number
which indicates the rate of change in the viscosity of an oil within a given
temperature range. Fluids exhibiting a relatively large change in viscosity
with
temperature are said to have a low viscosity index. A low VI oil, for example,
will thin out at elevated temperatures faster than a high VI oil. Usually, the
high
VI oil is more desirable because it has higher viscosity at higher
temperature,
which translates into better or thicker lubrication film and better protection
of the
contacting machine elements. In another aspect, as the oil operating
temperature
decreases, the viscosity of a high VI oil will not increase as much as the
viscosity
of a low VI oil. This is advantageous because the excessive high viscosity of
the
low VI oil will decrease the efficiency of the operating machine. Thus high VI
oil
has performance advantages in both high and low temperature operation. VI is
determined according to ASTM method D 2270-93 [1998]. VI is related to
kinematic viscosities measured at 40 C and 100 C using ASTM Method D 445.
[0003] PAOs comprise a class of hydrocarbons manufactured by the
catalytic oligomerization (polymerization to low molecular weight products) of
linear a-olefins (LAOs) typically ranging from 1-hexene to 1-octadecene, more
typically from 1-octene to 1-dodecene, with 1-decene as the most common and
often preferred material. Such fluids are described, for example, in U.S.
Patent
6,824,671 and patents referenced therein, although polymers of lower olefins
such
as ethylene and propylene may also be used, especially copolymers of ethylene
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with higher olefins, as described in U.S. Patent 4,956,122 or 4,990,709 and
the
patents referred to therein.
[0004] High viscosity index polyalpha-olefin (HVI-PAO) prepared by, for
instance, polymerization of alpha-olefins using reduced metal oxide catalysts
(e.g., chromium) are described, for instance, in U.S. Patent Nos. 4,827,064;
4,827,073; 4,990,771; 5,012,020; and 5,264,642. These HVI-PAOs are
characterized by having a high viscosity index (VI) of about 130 and above,
more
preferably 150 and above, still more preferably 160 and above, yet still more
preferably 200 and above, and one or more of the following characteristics: a
branch ratio of less than 0.19, a weight average molecular weight of between
300
and 45,000, a number average molecular weight of between 300 and 18,000, a
molecular weight distribution of between 1 and 5, and pour point below -15 C.
Measured in carbon number, these molecules range from C30 to C1300.
Viscosities
of the HVI-PAO oligomers measured at 100 C range from 3 centistokes ("cSt") to
15,000 cSt. These HVI-PAOs have been used as basestocks in engine and
industrial lubricant formulations. See also U.S. Patent Nos. 4,180,575;
4,827,064;
4,827,073; 4,912,272; 4,990,771; 5,012,020; 5,264,642; 6,087,307; 6,180,575;
WO 03/09136; WO 2003071369A; U.S. Patent Application No. 2005/0059563;
WO 00/58423; and Lubrication Engineers, 55/8, 45 (1999); and have recently
been found to be useful for industrial oil and grease formulations..
[0005] Another advantageous property of these HVI-PAOs is that, while
lower molecular weight unsaturated oligomers are typically and preferably
hydrogenated to produce thermally and oxidatively stable materials, higher
molecular weight unsaturated HVI-PAO oligomers useful as lubricant are
sufficiently thermally and oxidatively stable to be utilized without
hydrogenation
and, optionally, may be so employed.
[0006] As used herein, the term "polyalpha-olefin" includes PAOs and
HVI-PAOs. Depending on the context, the term "PAO" may include HVI-PAOs
or it may be used to distinguish non-HVI-PAOs from HVI-PAOs. Generally,
when PAO is used alone, it implies the products have properties similar to the
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fluids made from conventional polymerization process using BF3 or A1C13 or
their
modified versions, as described in U.S. Pat. 6,824,671 and references therein.
[0007] Polyalpha-olefins of different viscosity grades are known to be
useful in synthetic and semi-synthetic lubricants and grease formulations.
See, for
instance, Chapters 19 to 27 in Rudnick et al., "Synthetic Lubricants and High-
Performance Functional Fluids", 2nd Ed. Marcel Dekker, Inc., N.Y. (1999).
Compared to the conventional mineral oil-based products, these PAO-based
products have excellent viscometrics, high and low temperature performance.
They usually provide energy efficiency and extended service life.
[0008] In the production of PAOs and HVI-PAOs, the feed is usually
limited to one specific alpha-olefins, usually 1-decene. Occasionally, when 1-
decene is not available in large enough quantity, small to moderate amounts of
1-
octene or 1-dodecene is added to make up the quantity. It is generally thought
that
1-decene is the most preferred feed (see reference "Wide-Temperature Range
Synthetic Hydrocarbon Fluids" by. J. A. Brennen, Ind. Eng. Chem. Prod. Res.
Dev., 19, 2-6 (1980). When mixtures of feed are used, the products tend to be
blocky copolymers rather than random copolymers and/or products produced at
the beginning of the process are different than that produced at the end of
the
process, and the inhomogeneous polymer product will be characterized by poor
viscosity indices (VI). and poor low temperature properties are produced.
Thus, in
the past, PAOs and HVI-PAOs have generally been made using pure C10 feeds.
[0009] There are specific examples of mixed feeds being used. For
instance, in U.S. 6,646,174, a mixture of about 10 to 40 wt. % 1-decene and
about
60 to 90 wt. % 1-dodecene and are co-oligomerized in the presence of an
alcohol
promoter. Preferably 1-decene is added portion-wise to the single
oligomerization
reactor containing 1-dodecene and a pressurized atmosphere of boron
trifluoride.
Product is taken overhead and the various cuts are hydrogenated to give PAO
characterized by a kinematic viscosity of from about 4 to about 6 at 100 C, a
Noack weight loss of from about 4 % to about 9 %, a viscosity index of from
about 130 to about 145, and a pour point in the range of from about -60 C to
about
-50 C. See also U.S. Pat. Nos. 4,950,822; 6,646,174; 6,824,671, 5,382,739 and
U.S. Patent Application No. 2004/0033908. All these copolymers or co-oligomers
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produced by conventional Friedel-Crafts catalysts usually are characterized by
having extra relatively short branches, such as methyl and ethyl short side
chains,
even though the feed olefins do not contain these short branches. This is
because
the Friedel-Crafts catalyst partially isomerizes the starting alpha-olefins
and the
intermediates formed during the oligomerization. The presence of short chain
branches is less desirable for superior lubricant properties, including VI and
volatility. In contrast, the copolymers described in this invention will not
have
extraneous short chain branches. If the feed is propylene and 1-dodecene, the
predominant side chain in the polymers will be methyl and n-C10H23 side
chains.
Except for the contribution of usually less than 5% of the polymer end groups
initiated through the rare allylic hydrogen abstraction of the alpha-olefin
monomers by the active metal centers, the oligomers will not have extra ethyl,
propyl, butyl, etc. side chains that are present in non-metallocene (e.g.
Friedel-
Crafts) methods,.
[0010] Previous patents report the use of mixed alpha-olefins as feeds to
produced co-oligomers or copolymers for use as lubricant components. U.S.
patent 4,827,073 reported the use of a reduced chromium oxide on silica gel as
catalyst to polymerize C6 to C20 alpha-olefins. Although liquid copolymers
were
produced by the process, the copolymer has very different polymer composition
from the monomer ratio in the feed. The reduced chromium oxide on silica gel
catalyst polymerized the lower alpha-olefins, such as 1-butene or 1-hexene, at
a
significantly higher rate than the alpha-olefins of 1-decene, 1-dodecene or
larger
alpha-olefins [see comparative examples in Example section]. As a result, the
copolymer tends to be more blocky or more inhomogeneous in a conventional
synthesis process. Both are detrimental to the product VI and low temperature
properties. Similarly, Ziegler or Ziegler-Natta type catalysts have also been
reported to copolymerize mixed alpha-olefins. Examples are US patents
4,132,663, 5,188,724 and 4,163,712. The problem with using Ziegler or Ziegler-
Natta catalysts is that they can only produce polymers of very high molecular
weights. As a result, the products are used as plastics and additives, but are
not
suitable as high performance base stocks. Furthermore, according to all
literature
reports, Ziegler or Ziegler-Nafta catalysts usually have higher reactivities
toward
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smaller alpha-olefins, such as propylene, 1-butene, 1-pentene or 1-hexene,
than
toward larger alpha-olefins, such as 1-decene, 1-dodecene, or larger 1-olefins
(reference Macromolecular Chemistry and Physics, 195, 2805 (1994) or 195, 3889
(1994)). This difference in catalyst reactivity resulted in heterogeneous
chemical
structures for the copolymers, which are not random copolymers and have high
degree of blockiness. Both characteristics are detrimental for lube
properties.
[0011] It would be highly beneficial if a process could be devised whereby
a homogeneous and uniform PAO and/or HVI-PAO having an excellent viscosity-
temperature relationship could be produced from a wide variety of mixed feed
LAOs.
[0012] The present inventors have discovered an unanticipated method of
producing a uniform PAO and/or HVI-PAO product by contacting a mixed feed of
LAOs of varying carbon numbers with an activated metallocene catalyst.
SUMMARY OF THE INVENTION
[0013] The invention is directed to an improved process for producing
PAOs and HVI-PAOs which employs contacting a feed comprising a mixture of
LAOs with an activated metallocene catalyst, optionally after hydrogenation,
to
produce liquid polymers with superior properties for use as lubricant
components
or as functional fluids.
[0014] This invention is also directed to a copolymer composition made
from at least two alpha-olefins of C3 to C30 range and having monomers
randomly
distributed in the polymers. It is preferred that the average carbon number,
as
defined herein, is at least 4.1. Advantageously, ethylene and propylene, if
present
in the feed, are present in the amount of less than 50 wt% individually or
preferably less than 50 wt% combined. The copolymers of the invention can be
isotactic, atactic, syndiotactic polymers or any other form of appropriate
tacticity.
These copolymers have useful lubricant properties, including excellent VI,
pour
point, low temperature viscometrics when used alone, or as blend fluids with
other
lubricants or other polymers. Furthermore, these copolymers have narrow
molecular weight distributions and excellent shear stability.
[0015] In an embodiment, the mixed feed LAOs comprise at least two and
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up to 26 different linear alpha-olefins selected from C3 to C30 linear alpha-
olefins.
In a preferred embodiment, the mixed feed LAO is obtained from an ethylene
growth process using an aluminum catalyst or a metallocene catalyst.
[0016] In another embodiment, the alpha-olefins can be chosen from any
component from a conventional LAO production facility together with another
LAO available from a refinery or chemical plant, including propylene, 1-
butene,
1-pentene, and the like, or with 1-hexene or 1-octene made from dedicated
production facility. In another embodiment, the alpha-olefins can be chosen
from
the alpha-olefins produced from Fischer-Tropsch synthesis (as reported in U.S.
5,382,739).
[0017] The activated metallocene catalyst can be simple metallocenes,
substituted metallocenes or bridged metallocene catalysts activated or
promoted
by, for instance, MAO or a non-coordinating anion.
[0018] It is an object of the invention to provide a convenient method of
making a new PAO and/or HVI-PAO composition from a variety of feedstocks.
[0019] These and other objects, features, and advantages will become
apparent as reference is made to the following detailed description, preferred
embodiments, examples, and appended- claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] In the accompanying drawings, like reference numerals are used to
denote like parts throughout the several views.
[0021] Figure 1 illustrates the relationship of pour point versus kinematic
viscosity for embodiments according to the present invention in comparison
with
a product produced using a pure Cio feed.
[0022] Figure 2 illustrates the relationship of viscosity index (VI) versus
kinematic viscosity for embodiments according to the present invention
compared
with a product produced using a pure C 1 o feed.
[0023] Figures 3 and 4 show the mole fraction of an olefin component in
the product versus the mole fraction of same monomer in the feed for examples
according to the present invention.
[0024] Figure 5 is a comparison of pour points between the prior art and
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embodiments of the invention
DETAILED DESCRIPTION
[0025] According to the invention, a feed comprising a mixture of LAOs
selected from C3 to C30 LAOs is contacted with an activated metallocene
catalyst
under oligomerization conditions to provide a liquid product, suitable for use
in
lubricant components or as functional fluids, optionally after hydrogenation.
This
invention is also directed to a copolymer composition made from at least two
alpha-olefins of C3 to C30 range and having monomers randomly distributed in
the
polymers. The phrase "at least two alpha-olefins" will be understood to mean
"at
least two different alpha-olefins" (and similarly "at least three alpha-
olefins"
means "at least three different alpha-olefins", and so forth).
[0026] In preferred embodiments, the average carbon number (defined
herein below) of said at least two alpha-olefins in said feed is at least 4.1.
In
another preferred embodiment, the amount of ethylene and propylene in said
feed
is less than 50 wt% individually or preferably less than 50 wt% combined. A
still
more preferred embodiment comprises a feed having both of the aforementioned
preferred embodiments, i.e., a feed having an average carbon number of at
least
4.1 and wherein the amount of ethylene and propylene is less than 50 wt%
individually.
[0027] In embodiments, the product obtained is an essentially random
liquid copolymer comprising the at least two alpha-olefins. By "essentially
random" is meant that one of ordinary skill in the art would consider the
products
to be a random copolymer. Other characterizations of randomness, some of which
are preferred or more preferred, are provided herein. Likewise the term
"liquid"
will be understood by one of ordinary skill in the art, but more preferred
characterizations of the term are provided herein. In describing the products
as
"comprising" a certain number of alpha-olefins (at least two different alpha-
olefins), one of ordinary skill in the art in possession of the present
disclosure
would understand that what is being described in the polymerization (or
oligomerization) product incorporating said certain number of alpha-olefin
monomers. In other words, it is the product obtained by polymerizing or
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oligomerizing said certain number of alpha-olefin monomers.
[0028] The descriptions herein follow the Periodic Table of the Elements
as set out in Chemical and Engineering News, 63(5), 27 (1985).
[0029] LAO Feed
[0030] By "mixture of LAOs" is meant that at least two different linear
alpha-olefins are present in the feed and up to 28 different linear alpha-
olefins are
present in the feed. It is a surprising discovery of the present invention
that the
rate of incorporation of monomers into the polymer backbone is substantially
the
same regardless of the carbon number of the linear alpha-olefin, and it is
further a
surprising discovery that the incorporation of monomers in the polymer chain
is
essentially random. This allows for a tremendous advantage in selecting the
feed
composition to achieve a preselected target product. This also allows the
advantage of producing a new copolymer composition with a substantially random
monomer distribution, resulting in superior viscometric properties at both
high
and low temperature range.
[0031] In embodiments where the feed is selected from C3 to C30 LAOs,
the feed will comprise anywhere from 2 to 28 different LAOs. Thus, the feed
may
comprise at least two, or at least three, or at least four, or at least five,
or at least
six, or at least seven, or at least eight, and so on, different feeds. The
embodiments may be further characterized by having no single LAO present in an
amount greater than 80 wt%, 60 wt %, 50 wt %, or 49 wt %, or 40 wt %, or 33 wt
%, or 30 wt %, or 25 wt %, or 20 wt %.
[0032] The amounts of LAO present in a feed will be specified herein as
percent by weight of the entire amount of LAO in the feed, unless otherwise
specified. Thus, it will be recognized that the feed may also comprise an
inert
(with respect to the oligomerization reaction in question) material, such as a
carrier, a solvent, or other olefin components present that is not an LAO.
Examples are propane, n-butane, iso-butane, cis- or trans-2-butenes, iso-
butenes,
and the like, that maybe present with propylene or with 1-butene feed. Other
examples are the impurity internal olefins or vinylidene olefins that are
present in
the LAO feed.
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[0033] It is preferred that the amount of ethylene in said feed be at least
less than 50 wt% and generally much less than that, e.g., less than 5 wt%,
more
preferably less than 4 wt% or less than 3 wt% or less than 2 wt%, or less than
1
wt%. In preferred embodiment, the amount of both ethylene and propylene, on an
individual basis, should be less than 50 wt% and more preferably the
combination
of ethylene and propylene should be less than 50 wt%, more preferably less
than
40 wt%, or 30 wt%, or 20 wt%, or 10 wt%, or 5 wt%.
[0034] In other embodiments, feeds may be advantageously selected from
C3 to C30 LAOs, C4 to C24 LAOs, C5 to C24, C4 to C16 LAOs, C5, to C18, C5 to
C16,
C6 to C20 LAOs, C4 to C14 LAOs, Cs to C16, C5 to C16, C6 to C16 LAOs, C6 to
C18
LAOs, C6 to C14 LAOs, among other possible LAO feed sources, such as any
lower limit listed herein to any upper limit listed herein. In other
embodiments,
the feed will comprise at least one monomer selected from propylene, 1 -
butene, 1-
pentene, 1-hexene to 1-heptene and at least one monomer selected from C12-C18
alpha-olefins. Optionally one monomer is selected from C$ and C10 alpha-
olefins.
A preferred embodiment is a feed comprising 1-hexene and 1-dodecene, 1-
tetradecene, and mixtures thereof. Another preferred embodiment is a feed
comprising 1-butene and 1-dodecene, 1-tetradecene, and mixtures thereof.
Another preferred embodiment is a feed comprising 1-hexene, 1-decene, 1-
dodecene and 1-tetradecene, and mixtures thereof. Another preferred embodiment
is a feed comprising 1-hexene and 1-octene, 1-dodecene and 1-tetradecene, and
mixtures thereof. Another preferred embodiment is a feed comprising 1-butene
and 1-hexene and 1-dodecene, 1-tetradecene, and mixtures thereof.
[0035] A particularly advantaged feedstock from the standpoint of supply
and availability is 1-hexene. There are many source of 1-hexene. They are
available from conventional LAO processes, and have recently been produced
intentionally in high yield and cheaply from ethylene. Pure 1-Hexene is now
available commercially from Fischer-Tropsch processes . Because of these
diverse sources, there is advantage in using 1-hexene as one of the feeds. The
presence of 1-hexene in the LAO feed from 0 to 95% is suitable. In a preferred
embodiment, 1-hexene is present in the feed in the amount of about 1 wt % or
10
wt% to about 85 wt% or less, 80 wt% or less, 75 wt% or less, 67 wt% or less,
60
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wt % or less, 50 wt % or less, 40 wt % or less, 33 wt % or less, 30 wt % or
less, 20
wt % or less, or 15 wt % or less as preferred embodiments. The same is true
for 1-
octene, which can be produced selectively from 1-heptene isolated from Fischer-
Tropsch synthesis, or from butadiene as described in WO 9210450. Other alpha-
olefins such as propylene or 1-butene or combinations thereof are also very
advantageous because propylene and 1-butene are readily available from
refinery
or from petrochemical plants. The source of propylene can be in pure form (as
in
chemical grade propylene or as in polymer grade propylene) or in PP stream
(propane-propylene stream) or other appropriate forms. The source of 1-butene
can be in pure form (as in chemical grade 1-butene or as in polymer grade 1-
butene) or in "BB stream" (butane-butene stream, such as Raffinate-1 or
Raffinate-2 stream, as discussed, for instance, in U.S. Patent No. 5,859,159),
or
other appropriate form. 1-Pentene can also be used as one of the advantaged
feeds
in the mixed feed. This 1-pentene can be isolated from naphtha steam cracking
unit, from other refinery sources, or from a Fischer-Tropsch synthesis
process.
Similar to 1-hexene, in embodiments the amount of propylene, 1-butene or 1-
pentene can vary from 1 to 95% in the mixed feed, depending on the needs of
the
product properties.
[0036] The source of the LAO is advantageously from ethylene growth
processes, as described in U.S. Patent Nos. 2,889,385; 4,935,569 (and numerous
references cited therein); 6,444,867; and in Chapter 3 of Lappin and Sauer,
Alpha-
olefins Applications Handbook, Marcel Dekker, Inc., NY 1989. The LAO made
from this ethylene growth process contains only even-number olefins. LAO
containing both even- and odd-number olefins can also be made from steam
cracking or thermal cracking of wax, such as petroleum wax, Fischer-Tropsch
wax, or any other readily available hydrocarbon wax. LAO can also be made in a
Fischer-Tropsch synthesis process, as described in U.S. 5,185,378 or U.S.
6,673,845 and references therein. LAO made directly from syngas synthesis
processes, which can produce significant amounts of C3-C15 alpha-olefins,
containing both even- and odd-number olefins.
[0037] In an embodiment, it is advantageous to use a high quality feed
with minimal inert material. However, LAO containing other inert components,
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including saturated hydrocarbons, internal or vinylidene olefins or aromatic
diluents can also be used as feed. In this case, the LAO would be reacted to
give
polymer and inert components will be passed through the reactor unaffected.
The
polymerization process is also a separation process.
[0038] Another advantaged feedstock comprises 1-butene. In certain
embodiments, a mixed feed comprising from 1 wt% to about 80 wt%, preferably 5
wt% to about 75 wt%, more preferably about 25 wt% to about 75 wt% is
advantageous, particularly wherein the average carbon number of said feed is
at
least 4.1. It is particularly advantageous when the feed also comprises at
least 20
wt% or 25 wt% to about 80 wt% or 75 wt% of at least one alpha-olefin selected
from C8 to C24, C10 to C24, C12 to C24, preferably C14 to C18 alpha-olefins.
[0039] It is preferred that the average carbon number of the feed is at least
4.1. While the upper limit of average carbon number is not a critical
characteristic
of the feed (and will be more naturally limited by the characterization of the
product as an "essentially random liquid polymer"), a useful upper limit may
be
given as C20-C24 alpha-olefins, C18 or C16 or C14, or other preferred upper
limits
given herein below. Average carbon number, as used herein, refers to the
average
carbon number of the C3 to C30 alpha-olefins in the feed. Another preferred
embodiment is to select a mixed feed, which may be a mixed feed as described
in
any one of the aforementioned embodiments or as otherwise described herein,
having an average carbon number of between about 4.1 carbon atoms and 14
carbon atoms, and more preferably from greater than 5 carbon atoms to less
than
12 carbon atoms, and more preferably from greater than 5.5 carbon atoms to
less
than 11 carbon atoms. The average value of the carbon number ("average carbon
number") is defined as the total sum of the mole fraction of each alpha-olefin
times the carbon number in the alpha-olefins (Cap, = I (mole fraction)1 x
(number
of carbons)1). There are many possible combinations to achieve this preferred
average carbon numbers of the LAO feeds. Examples of the possible
combinations are summarized in Table A. Note that in Table A, "eq. mo" feed
comprises equimolar amounts of even-numbered alpha-olefins from C6 to C18. All
of the average carbon numbers listed in Table A are preferred feeds, and
preferred
feeds also include a range of average carbon numbers from any lower amount
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listed in Table A to any higher amount listed in Table A.
[00401 A particular advantage of the present invention is that it allows for
the production of a product that closely mirrors the properties of an
oligomerization process using a single feed of 1-decene without actually using
an
appreciable amount of 1 -decene or the commonly used 1 -decene-equivalent,
Table
A.
Image
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which often contains about equal molar of 1-octene and 1-dodecene. Thus, in an
embodiment, the feed used in the present invention does not contain 1-decene,
or
contains 1-decene in an amount less than about 1' wt %, or less than about 5
wt %,
or less than about 10 wt %, or less than about 20 wt %, or less than 30%, or
less
than 50%, or less than 60%, or less than 70%, and also an embodiment wherein
the feed from one of these preferred embodiments not having an appreciable
amount of 1-decene is used to produce a product having substantially similar
properties as a product produced using a feed comprising substantially all 1-
decene, or 90 wt % 1-decene. Preferred embodiments include feeds where any
one of 1-octene, 1-decene, and 1-dodecene is less then 70%, 50 wt %, or 40 wt
%,
or 33 wt %, or 30 wt %, or 25 wt %, or 20 wt %, or 10 wt %, or 5 wt %, and/or
wherein the total of 1-octene, ,1-decene, and 1-dodecene is present in the
aforementioned amounts.
[0041] One of the advantages of the present invention is that a feed may
be taken directly from another process without laborious, time-consuming,
and/or
expensive isolation of one or more monomers. Thus, for example, a preferred
embodiment is a feed used directly, with minimum isolation, from an ethylene
growth process. Usually, LAO processes produce C6 to C20 LAO with small
amounts of C20+ LAO. In typical production processes, each individual C6 to
C18
LAO is isolated from the crude mixture by careful fractionation. Usually each
LAO has it unique application. This fractionation step adds cost and
complexicity
to the LAO production. In the present invention, the whole range of C4 to C20+
LAO directly from the oligomerization process can be used as feed, with only a
separation of the light gases. There is no need to separate each individual
fraction.
Or, a wide range of LAO from C6 to C20 distilled in one fraction to separate
it
from the heavy C20+ bottom can be used as feed in this invention. Or, a wide
range of LAO from C6 to C18 distilled in one fraction from the remaining heavy
LAOs can be used as feed. And so forth for any range LAO desired. This whole
range or wide range LAO which requires no or minimum or simple isolation is a
superior feed for this invention. To be able to use this whole range or wide
range
LAO offers economic advantage and furthermore, the product properties are
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superior.
[00421 Under certain reaction conditions, ethylene may be used as a
"growth reagent" to produce alpha-olefins which are low molecular weight
polymers (oligomers) of the growth reagent. Such reactions are described, for
instance, in U.S. Patent Nos. 2,889,385; 4,935,569 (and numerous references
cited
therein); 6,444,867; and in Chapter 3 of Lappin and Sauer, Alpha-olefins
Applications Handbook, Marcel Dekker, Inc., NY 1989. The entire mixture of
olefins produced by one of such processes, comprising, for example, nine
different
alpha-olefm oligomers of ethylene having from 4 to 20 carbon atoms, may be
used
directly in the process of the present invention with minimum isolation of the
bulk
of the alpha-olefins but without the necessity of separating the each
individual
oligomer. Mixtures of linear alpha-olefins (LAO) produced by other processes
such as steam/thermal cracking of petroleum-based slack wax or more desirably
from the steam/thermal cracking of wax derived from Fischer-Tropsch (FT)
synthesis as described in the paper "Gas-to-Liquids Technology Provides New
Hope for Remote Fields" published in Lubricant World, October 2000, page 30.
By properly selecting the cracking conditions, alpha-olefins ranging from C5
to
C18 can be produced in high yields, as described in US Pat. Nos. 5,136,118;
5,146,002; and 5,208,403. In all these cracking processes, the wax derived
from
GTL process is the most desirable feed because of its high purity, lack of
sulfur,
nitrogen or other heteroatoms, and its low aromatics, naphthenics, and
branched
paraffins, content.
[00431 Mixtures of LAOs can also be produced directly from Fischer-
Tropsch synthesis using special catalysts, usually cobalt or iron based FT
catalysts, in combination with a synthesis gas with a low H2/CO ratio. The
mixture of alpha-olefins with only even carbon numbers or with both odd and
even carbon numbers can be used with minimum separation as feed for this
invention, or can be separated into different fractions. Fractions with no
other
special use can be used as feed in this invention process to yield high
quality
synthetic fluids. This approach provides a method to optimize total LAO value.
Examples of the feed compositions are summarized in Table A. In many cases,
the preferred feeds are chosen from C3- to C7 alpha-olefins in combination
with
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another olefin or olefins chosen from C12 to C20 alpha-olefins. This approach
leaves out the C8 and Clo LAOs or uses only minimum amounts of them. The C8
and C10 LAOs are usually in high demand from other applications, such as for
use
as co-monomers for polyethylene plastic synthesis or used in BF3 or A1C13-
based
oligomerization processes, which prefer 1-decene as feed. Or if C8 and Clo
alpha-
olefins are available, then they can be added as part of the feed.
[0044] In addition to LAO used in this process, other alpha-olefins
containing branches that are at least two carbons away from the olefinic
double
bonds can also be used as one of the mixture components. Examples of these
alpha-olefins include 4-methyl-l-pentene, or other slightly branched alpha-
olefins
produced from Fischer-Tropsch synthesis process or from wax-cracking process.
These slightly branched alpha-olefins can be used together with the LAOs
described above as feeds.
[0045] Polymerization Catalyst System
[0046] This improved process employs a catalyst system comprising a
metallocene compound (Formula 1, below) together with an activator such as a
non-coordinating anion (NCA) activator (Formula 2, below, is one example) or
methylaluminoxane (MAO) (Formula 3, below).
B(C6F5)a
Me Formula 2
A\ /MX 2 H Me
Formula 1 NCA
~ ~$ Formula 3
cN3
MAO
[0047] The term "catalyst system" is defined herein to mean a catalyst
precursor/activator pair, such as a metallocene/activator pair. When "catalyst
system" is used to describe such a pair before activation, it means the
unactivated
catalyst (precatalyst) together with an activator and, optionally, a co-
activator
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(such as a trialkyl aluminum compound). When it is used to describe such a
pair
after activation, it means the activated catalyst and the activator or other
charge-
balancing moiety. Furthermore, this activated "catalyst system" may optionally
comprise the co-activator and/or other charge-balancing moiety.
[0048] The metallocene is selected from one or more compounds
according to Formula 1, above. In Formula 1, M is selected from Group 4
transition metals, preferably zirconium (Zr), hafnium (Hf) and titanium (Ti),
L1
and L2 are independently selected from cyclopentadienyl ("Cp"), indenyl, and
fluorenyl, which may be substituted or unsubstituted, and which may be
partially
hydrogenated, A is an optional bridging group which if present, in preferred
embodiments is selected from dialkylsilyl, dialkylmethyl, ethenyl (-CH2-CH2-),
alkylethenyl (-CR2-CR2-), where alkyl can be independently hydrogen radical,
C1
to C16 alkyl radical or phenyl, tolyl, xylyl radical and the like, and wherein
each of
the two X groups, Xa and Xb, are independently selected from halides, OR (R is
an
alkyl group, preferably selected from C1 to C5 straight or branched chain
alkyl
groups), hydrogen, Cl to C16 alkyl or aryl groups, haloalkyl, and the like.
Usually
relatively more highly substituted metallocenes give higher catalyst
productivity
and wider product viscosity ranges and are thus often more preferred.
[0049] In using the terms "substituted or unsubstituted cyclopentadienyl
ligand", "substituted or unsubstituted indenyl ligand", and "substituted or
unsubstituted tetrahydroindenyl ligand", "substituted or unsubstituted
fluorenyl
ligand", and "substituted or unsubstituted tetrahydrofluorenyl or
octahydrofluorenyl ligand" the substitution to the aforementioned ligand may
be
hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl,
silylcarbyl, or germylcarbyl. The substitution may also be within the ring
giving
heterocyclopentadienyl ligands, heteroindenyl ligands or
heterotetrahydoindenyl
ligands, each of which can additional be substituted or unsubstituted.
[0050] For purposes of this invention and the claims thereto the terms
"hydrocarbyl radical," "hydrocarbyl" and hydrocarbyl group" are used
interchangeably throughout this document. Likewise the terms "group",
"radical"
and "substituent" are also used interchangeably in this document. For purposes
of
this disclosure, "hydrocarbyl radical" is defined to be C1-C1oo radicals, that
may be
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linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic, and
include substituted hydrocarbyl radicals, halocarbyl radicals, and substituted
halocarbyl radicals, silylcarbyl radicals, and germylcarbyl radicals as these
terms
are defined below.
[0051] Substituted hydrocarbyl radicals are radicals in which at least one
hydrogen atom has been substituted with at least one functional group such as
NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3,
PbR*3 and the like or where at least one non-hydrocarbon atom or group has
been
inserted within the hydrocarbyl radical, such as -0-, -S-, -Se-, -Te-, -N(R*)-
, =N-,
-P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Si(R*)2-,
-Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2- and the like, where R* is independently a
hydrocarbyl or halocarbyl radical, and two or more R* may join together to
form a
substituted or unsubstituted saturated, partially unsaturated or aromatic
cyclic or
polycyclic ring structure.
[0052] Halocarbyl radicals are radicals in which one or more hydrocarbyl
hydrogen atoms have been substituted with at least one halogen (e.g. F, Cl,
Br, I)
or halogen-containing group (e.g. CF3).
[0053] Substituted halocarbyl radicals are radicals in which at least one
halocarbyl hydrogen or halogen atom has been substituted with at least one
functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*,
BR*2, SiR*3, GeR*3, SnR*3, PbR*3 and the like or where at least one non-carbon
atom or group has been inserted within the halocarbyl radical such as -0-, -5-
,
-Se-, -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-
,
=B-, -Si(R*)2-, -Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2- and the like, where R* is
independently a hydrocarbyl or halocarbyl radical provided that at least one
halogen atom remains on the original halocarbyl radical. Additionally, two or
more R* may join together to form a substituted or unsubstituted saturated,
partially unsaturated or aromatic cyclic or polycyclic ring structure.
[0054] Silylcarbyl radicals (also called silylcarbyls) are groups in which
the silyl functionality is bonded directly to the indicated atom or atoms.
Examples
include SiH3, SiH2R*, SiHR*2, SiR*3, SiH2(OR*), SiH(OR*)2, Si(OR*)3,
SiH2(NR*2), SiH(NR*2)2, Si(NR*2)3, and the like where R* is independently a
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hydrocarbyl or halocarbyl radical and two or more R* may join together to form
a
substituted or unsubstituted saturated, partially unsaturated or aromatic
cyclic or
polycyclic ring structure.
[0055] Germylcarbyl radicals (also called germylcarbyls) are groups in
which the germyl functionality is bonded directly to the indicated atom or
atoms.
Examples include GeH3, GeH2R*, GeHR*2, GeR*3, GeH2(OR*), GeH(OR*)2,
Ge(OR*)3, GeH2(NR*2), GeH(NR*2)2, Ge(NR*2)3, and the like where R* is
independently a hydrocarbyl or halocarbyl radical and two or more R* may join
together to form a substituted or unsubstituted saturated, partially
unsaturated or
aromatic cyclic or polycyclic ring structure.
[0056] Polar radicals or polar groups are groups in which the heteroatom
functionality is bonded directly to the indicated atom or atoms. They include
heteroatoms of groups 1-17 of the Periodic Table either alone or connected to
other elements by covalent or other interactions such as ionic, van der Waals
forces, or hydrogen bonding. Examples of functional heteroatom containing
groups include carboxylic acid, acid halide, carboxylic ester, carboxylic
salt,
carboxylic anhydride, aldehyde and their chalcogen (Group 14) analogues,
alcohol
and phenol, ether, peroxide and hydroperoxide, carboxylic amide, hydrazide and
imide, amidine and other nitrogen analogues of amides, nitrile, amine and
imine,
azo, nitro, other nitrogen compounds, sulfur acids, selenium acids, thiols,
sulfides,
sulfoxides, sulfones, phosphines, phosphates, other phosphorus compounds,
silanes, boranes, borates, alanes, aluminates. Functional groups may also be
taken
broadly to include organic polymer supports or inorganic support material such
as
alumina, and silica. . Preferred examples of polar groups include NR*2, OR*,
SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SnR*3, PbR*3 and the like where
R* is independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl or
substituted halocarbyl radical as defined above and two R* may join together
to
form a substituted or unsubstituted saturated, partially unsaturated or
aromatic
cyclic or polycyclic ring structure.
[0057] In some embodiments, the hydrocarbyl radical is independently
selected from methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl,
hexyl,
heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl,
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hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,
tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,
triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,
decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl,
hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,
docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl,
octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl,
heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl,
tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl,
nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl,
pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl,
triacontynyl,
butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, and
decadienyl. Also included are isomers of saturated, partially unsaturated and
aromatic cyclic and polycyclic structures wherein the radical may additionally
be
subjected to the types of substitutions described above. Examples include
phenyl,
methylphenyl, dimethylphenyl, ethylphenyl, dethylphenyl, propylphenyl,
dipropylphenyl, benzyl, methylbhnzyl, naphthyl, anthracenyl, cyclopentyl,
cyclopentenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl,
cycloheptenyl, norbornyl, norbomenyl, adamantyl and the like. For this
disclosure, when a radical is listed, it indicates that radical type and all
other
radicals formed when that radical type is subjected to the substitutions
defined
above. Alkyl, alkenyl and alkynyl radicals listed include all isomers
including
where appropriate cyclic isomers, for example, butyl includes n-butyl, 2-
methylpropyl, 1-methylpropyl, tent-butyl, and cyclobutyl (and analogous
substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-
methylbutyl, 2-
methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and analogous
substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-
butenyl, 2-butenyl, 3-butenyl, 1-methyl-i-propenyl, 1-methyl-2-propenyl, 2-
methyl-1-propenyl and 2-methyl-2-propenyl (and cyclobutenyls and
cyclopropenyls). Cyclic compound having substitutions include all isomer
forms,
for example, methylphenyl would include ortho-methylphenyl, meta-
methylphenyl and para-methylphenyl; dimethylphenyl would include 2,3-
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dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,
3,4-dimethylphenyl, and 3,5-dimethylphenyl.
[0058] Examples of cyclopentadienyl and indenyl ligands are illustrated
below as anionic ligands. The ring numbering scheme is also illustrated.
1 7
6
0 2 2
4 5
3 4 3
Cydopentadienyl Indenyl
[0059] A similar numbering and nomenclature scheme is used for
heteroindenyl as illustrated below where Z and Q independently represent the
heteroatoms 0, S, Se, or Te, or heteroatom groups, NR', PR', AsR', or SbR'
where
R' is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl,
substituted
halocarbyl, silylcarbyl, or germylcarbyl substituent. The number scheme shown
below is for heteroindenyl ligands that are bridged to another ligand via a
bridging
group-
4 3 4 3
O
5 (Q:1() 2 5 Z O 2
Z
6 1 6 1
Examples include: Examples include:
Cyclopenta[b]thienyl (Z=S) Cyclopenta[c]thienyl(Z=S)
Cyclopenta[b]furanyl (Z=O) Cyclopenta[c]furanyl (Z=O)
Cyclopenta[b]selenophenyl (Z=Se) Cyclopenta[c]selenophenyl (Z=S e)
Cyclopenta[b]tellurophenyl (Z=Te) Cyclopenta[c]tellurophenyl (Z=Te)
6-Methyl-cyclopenta[b]pyrrolyl (Z=N-Me) SMethyl-cyclopenta[c]pyrrolyl (Z=N-Me)
6-Methyl-cyclopenta[b]phospholyl (Z=P-Me) 5 Methyl-cyclopenta[c]phospholyl
(Z=P-Me)
6-Methyl-cyclopenta[b]arsolyl (Z=As-Me) 5 Methyl-cyclopenta[c]arsolyl (Z=As-
Me)
6-Methyl-cyclopenta[b]stibolyl (Z=Sb-Me) 5 Methyl-cyclopenta[c]stibolyl (Z=Sb-
Me)
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[0060] A similar numbering and nomenclature scheme is used for
heterocyclopentadienyl rings as illustrated below where G and J independently
represent the heteroatoms N, P, As, Sb or B. For these ligands when bridged to
another ligand via a bridging group, the one position is usually chosen to be
the
ring carbon position where the ligand is bonded to the bridging group, hence a
numbering scheme is not illustrated below.
G 00
Examples include:
Azacy. clopentadiene (G = N)
Phosphacyclopentadiene (G = P)
Stibacyclopentadiene (G = Sb)
Arsacyclopentadiene (G As)
Boracyclopentadiene (G = B)
[0061] Depending on the position of the bridging ligand, the numbering
for the following ligands will change; 1,3 and 1,2 are only used in this case
to
illustrate the position of the heteroatoms relative to one another.
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GO/ J G
Examples include: Examples include:
1,3-Diazacyclopentadiene (G = J = N) 1,2 Diazacyclopentadiene (G = J = N)
1,3-Diphosphacyclopentadiene (G = J = P) 1,2 Diphosphacyclopentadiene (G = J =
P)
1,3-Distibacyclopentadiene (G= J = Sb) 1,2 Distibacyclopentadiene (G= J = Sb)
1,3-Diarsacyclopentadiene (G = J As) 1,2 Diarsacyclopentadiene (G = J = As)
1,3-Diboaacyclopentadiene (G = J B) 1,2-Diboracyclopentadiene (G = J= B)
1,3-Azaphosphacyclopentadiene (G = N; J P) 1,2 Azaphosphacyclopentadiene (G =
N; J P)
1,3-Azastibacyclopentadiene (G =N; J = Sb) 1,2 Azastibacyclopentadiene (G = N;
J = Sb)
1,3-Azarsacyclopentadiene (G = N; J = As) 1,2 Azarsacyclopentadiene (G = N; J
= As)
1,3-Azaboracyclopentadiene (G = N; J = B) 1 ,2 Azaboracyclopentadiene (G = N;
J = B)
1,3-Arsaphosphacyclopentadiene (G = As; J = P) 1,2 Arsaphosphacyclopentadiene
(G = As; J = P)
1,3-Arsastibacyclopentadiene (G = As; J = Sb) 1,2-Arsastibacyclopentadiene (G
= As; J = Sb)
1,3-Arsaboracyclopentadiene (G =As; J = B) 1,2 Arsaboracyclopentadiene (G As;
J = B)
1,3-Boraphosphacyclopentadiene (G = B; J =P) 1,2-B oraphosphacyclopentadiene
(G = B; J =P)
1,3-Borastibacyclopentadiene (G = B; J = Sb) 1,2-B orastibacyclopentadiene (G
= B; J = Sb)
1,3-Phosphastibacyclopentadiene (G = P; J = Sb) 1,2
Phosphastibacyclopentadiene (G = P; J = Sb)
[0062] A "ring heteroatom" is a heteroatorn that is within a cyclic ring
structure. A "heteroatorn substituent is heteroatom containing group that is
directly bonded to a ring structure through the heteroatom. A "bridging
heteroatom substituent" is a heteroatom or heteroatom group that is directly
bonded to two different ring structures through the heteroatom. The terms
"ring
heteroatom", "heteroatom substituent", and "bridging heteroatom substituent"
are
illustrated below where Z and R' are as defined above. It should be noted that
a
"heteroatom substituent" can be a "bridging heteroatom substituent" when R' is
additionally defined as the ligand "A".
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Z
"ring heteroatom"
OP
b Z
coo
b ZR'
"heteroatom substituent" "bridging heteroatom substituent"
[0063] A "ring carbon atom" is a carbon atom that is part of a cyclic ring
structure. By this definition, an indenyl ligand has nine ring carbon atoms; a
cyclopentadienyl ligand has five ring carbon atoms. Transition metal compounds
have symmetry elements and belong to symmetry groups. These elements and
groups are well established and can be referenced from Chemical Applications
of
Group Theory (2nd Edition) by F. Albert Cotton, Wiley-Interscience, 1971.
Pseudo-symmetry, such as a pseudo C2-axis of symmetry refers to the same
symmetry operation, however, the substituents on the ligand frame do not need
to
be identical, but of similar size and steric bulk. Substituents of similar
size are
typically within 4 atoms of each other, and of similar shape. For example,
methyl,
ethyl, n-propyl, n-butyl and iso-butyl substituents (e.g. C1-C4 primary bonded
substituents) would be considered of similar size and steric bulk. Likewise,
iso-
propyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl and 1-methylpentyl substituents
(e.g. C3-C6 secondary bonded substituents) would be considered of similar size
and steric bulk. Tert-butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1-
dimethylpentyl and 1-ethyl-1 -methylpropyl (e.g. C4-C7 tertiary bonded
substituents) would be considered of similar size and steric bulk. Phenyl,
tolyl,
xylyl, and mesityl substituents (C6-C9 aryl substituents) would be considered
of
similar size and steric bulk. Additionally, the bridging substituents of a
compound
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with a pseudo C2-axis of symmetry do not have to be similar at all since they
are
far removed from the active site of the catalyst. Therefore, a compound with a
pseudo C2-axis of symmetry could have for example, a Me2Si, MeEtSi or MePhSi
bridging ligand, and still be considered to have a pseudo C2-axis of symmetry
given the appropriate remaining ligand structure.
[0064] For purposes of this disclosure, the term oligomer refers to
compositions having 2-75 mer units and the term polymer refers to compositions
having 76 or more mer units. A mer is defined as a unit of an oligomer or
polymer that originally corresponded to the olefin(s) used in the
oligomerization
or polymerization reaction. For example, the mer of polydecene would be
decene.
[0065] The metallocene compounds (pre-catalysts), useful herein are
preferably cyclopentadienyl derivatives of titanium, zirconium and hafnium. In
general, useful titanocenes, zirconocenes and hafnocenes may be represented by
the following formulae 4 and 5:
(Cp-A'-Cp*)MXaXl (4)
(CpCP*)MXaXb (5)
wherein:
M is the metal center, and is a Group 4 metal preferably Titanium, zirconium
or
hafnium, preferably zirconium or hafnium; Cp and Cp* are the same or different
cyclopentadienyl rings substituted with from zero to four or five substituent
groups S", each substituent group S" being, independently, a radical group
which
is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl,
silylcarbyl or germylcarbyl, or Cp and Cp* are the same or different
cyclopentadienyl rings in which any two adjacent S" groups are joined to form
a
substituted or unsubstituted, saturated, partially unsaturated, or aromatic
cyclic or
polycyclic substituent;
A' is a bridging group;
Xa and Xb are, independently, hydride radicals, hydrocarbyl radicals,
substituted
hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals,
silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals,
or
substituted germylcarbyl radicals; or both X are joined and bound to the metal
atom to form a metallacycle ring containing from about 3 to about 20 carbon
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atoms; or both together can be an olefin, diolefin or aryne ligand; or when
Lewis-
acid activators, such as methylaluminoxane or trialkylaluminum or
trialkylboron,
etc., which are capable of donating a hydrocarbyl ligand as described above to
the
transition metal component, are used, both X may, independently, be a halogen,
alkoxide, aryloxide, amide, phosphide or other univalent anionic ligand or
both X
can also be joined to form a anionic chelating ligand.
[0066] In a preferred embodiment the metallocene is racemic which means
in a preferred embodiment, that the compounds represented by formula (4) have
no plane of symmetry containing the metal center, M; and have a C2-axis of
symmetry or pseudo C2-axis of symmetry through the metal center. Preferably in
the racemic metallocenes represented by formula (1) A' is selected from R'2C,
R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R'C=CR',
R'C=CR'CR'2, R'2CCR'=CR'CR'2, R'C=CR'CR'=CR', R'C=CR'CR'2CR'2,
R'2CSiR'2, R'2SiSiR'2, R'2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2,
R'2CGeR'2, R'2GeGeR'2, R'2CGeR'2CR'2, R'2GeCR'2GeR'2, R'2SiGeR'2,
R'C=CR'GeR'2, R'B, R'2C BR', R'2C BR'-CR'2a R'N, R'P, 0, S, Se, R'2C-O-
CR'2, R'2CR'2C-O-CR'2CR'2, R'2C-0-CR'2CR'2a R'2C-O-CR'=CR', R'2C-S-
CR'2, R'2CR'2C-S-CR'2CR'2, R'2C-S-CR'2CR'2, R'2C-S-CR'=CR', R'2C-Se-
CR'2, R'2CR'2C-Se-CR'2CR'2, R'2C-Se-CR'2CR'2, R'2C-Se-CR'=CR', R'2C-
N=CR', R'2C-NR'-CR'2, R'2C-NR'-CR'2CR'2, R'2C-NR'-CR' =CR',
R'2CR'2C-NR'-CR'2CR'2, R'2C-P=CR', and R'2C-PR'-CR'2 and when Cp is
different than Cp*, R' is a C1-C5-containing hydrocarbyl, substituted
hydrocarbyl,
halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent,
and
when Cp is the same as Cp*, R' is a C1-C20-containing hydrocarbyl, substituted
hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl
substituent and optionally two or more adjacent R' may join to form a
substituted
or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic
substituent.
Similarly, C1 metallocenes can also be used for this invention. All these
catalysts
usually produce polyalpha-olefins with high degree of isotacticity or highly
isotactic polymers. See J. Am. Chem. Soc. 1988, 110, 6225 for a review of the
effect of catalyst structure on polymer tacticity, In addition to catalyst
structures,
the degree of isotacticity depends on other factors, such as catalyst purity,
ligand
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types, reaction conditions, etc. The polymers with various degrees of
tacticity are
useful as synthetic lube base stocks or functional fluids.
[0067] In another preferred embodiment the metallocene is the meso form
which means that the compounds represented by formula (4) have plane of
symmetry containing the metal center, M. In other words, the metallocenes
containing a C2,, symmetry are also suitable for this application. This class
of
catalysts usually produces atactic polyalpha-olefins. In many cases,
metallocene
catalysts without any bridging between the cyclopentadienyl ligands, as in
formula (5), also produce atactic polyalpha-olefins. In another preferred
embodiment, the metallocenes with C, symmetry or minor variations thereof can
also be used for this invention. These types of metallocenes when activated
usually produced syndiotactic polyalpha-olefins. In the present invention, the
polyalpha-olefins can be made from at least two alpha-olefins mixture using
any
one class of the catalysts to produce isotactic, atactic or syndiotactic
polymer or
combinations of these different tacticities in varying amounts. The PAO
products
made from mixed alpha-olefin feeds and with predominantly isotactic, atactic
or
syndiotactic compositions or combinations of these different tacticities in
varying
amounts all have superior VI and low temperature properties. Using mixed alpha-
olefins as feeds is more advantageous than using pure olefins, especially in
improving low temperature viscosities. Other appropriate forms of catalysts
which may produce combinations of these different tacticities, in a block or
semi-
block manner are also suitable for this invention.
[0068] Another important characteristic of these metallocene catalysts is
that they copolymerize the two or more alpha-olefins at comparable reaction
rates.
Metallocene catalysts differ from conventional Ziegler-Natta or supported
metal
oxide on silica gel catalysts. These conventional catalysts usually polymerize
smaller olefins, e.g., C3 or C4, much faster than the larger LAOs, such as
C12, C14a
etc. This is not the case for the metallocene catalysts of the present
invention,
where the reactivities of C3 and C18 alpha-olefins are relatively similar.
Because
of this uniform reactivity toward all the alpha-olefin feeds, the co- or
terpolymer
products by metallocene are random. This randomness of monomer distribution is
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important for imparting the resultant polymer with the desired lube basestock
properties discussed earlier.
[0069] Table B depicts representative constituent moieties for the
metallocene components of formulas 4 and 5. The list is for illustrative
purposes
only and should not be construed to be limiting in any way. A number of final
components may be formed by permuting all possible combinations of the
constituent moieties with each other. When hydrocarbyl radicals including
alkyl,
alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl and aromatic radicals
are
disclosed in this application the term includes all isomers. For example,
butyl
includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl;
pentyl includes n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-
ethylpropyl, neopentyl, cyclopentyl and methylcyclobutyl; butenyl includes E
and
Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l-propenyl, 1-methyl-2-
propenyl, 2-methyl-l-propenyl and 2-methyl-2-propenyl. This includes when a
radical is bonded to another group, for example, propylcyclopentadienyl
include
n-propylcyclopentadienyl, isopropylcyclopentadienyl and
cyclopropylcyclopentadienyl. In general, the ligands or groups illustrated in
Table
B include all isomeric forms. For example, dimethylcyclopentadienyl includes
1,2-dimethylcyclopentadienyl and 1,3-dimethylcyclopentadienyl; methylindenyl
includes 1-methylindenyl, 2-methylindenyl, 3-methylindenyl, 4-methylindenyl, 5-
methylindenyl, 6-methylindenyl and 7-methylindenyl; methylethylphenyl includes
ortho-methylethylphenyl, meta-methylethylphenyl and para-methylethylphenyl.
Examples of specific invention catalyst precursors take the following formula
where some components are listed in Table B. To illustrate members of the
transition metal component, select any combination of the species listed in
Tables
B. For nomenclature purposes, for the bridging group, A', the words "silyl"
and
"silylene" are used interchangeably, and represent a diradical species. For
the
bridging group A', "ethylene" refers to a 1,2-ethylene linkage and is
distinguished
from ethene-1,l-diyl. Thus, for the bridging group A', "ethylene" and "1,2-
ethylene" are used interchangeably. For compounds having a bridging group, A',
the bridge position on the cyclopentadienyl-type ring is always considered the
1-
position. The numbering scheme previous defined for the indenyl ring is used
to
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indicate the bridge position; if a number is not specified, it is assumed that
the
bridge to the indenyl ligand is in the one position.
TABLE B -
A' Cp, Cp*
dimethylsilylene cyclopentadienyl
diethylsilylene methylcyclopentadienyl
dipropylsilylene dimethylcyclopentadienyl
dibutylsilylene trimethylcyclopentadienyl
dipentylsilylene tetramethylcyclopentadienyl
dihexylsilylene ethylcyclopentadienyl
diheptylsilylene diethylcyclopentadienyl
dioctylsilylene propylcyclopentadienyl
dinonylsilylene dipropylcyclopentadienyl
didecylsilylene butylcyclopentadienyl
diundecylsilylene dibutylcyclopentadienyl
didodecylsilylene pentylcyclopentadienyl
ditridecylsilylene dipentylcyclopentadienyl
ditetradecylsilylene hexylcyclopentadienyl
dipentadecylsilylene dihexylcyclopentadienyl
dihexadecylsilylene heptylcyclopentadienyl
diheptadecylsilylene diheptylcyclopentadienyl
dioctadecylsilylene octylcyclopentadienyl
dinonadecylsilylene dioctylcyclopentadienyl
dieicosylsilylene nonylcyclopentadienyl
diheneicosylsilylene dinonylcyclopentadienyl
didocosylsilylene decylcyclopentadienyl
ditricosylsilylene didecylcyclopentadienyl
ditetracosylsilylene undecylcyclopentadienyl
dipentacosylsilylene dodecylcyclopentadienyl
dihexacosylsilylene tridecylcyclopentadienyl
diheptacosylsilylene tetradecylcyclopentadienyl
dioctacosylsilylene pentadecylcyclopentadienyl
dinonacosylsilylene hexadecylcyclopentadienyl
ditriacontylsilylene heptadecylcyclopentadienyl
dicyclohexylsilylene octadecylcyclopentadienyl
dicyclopentylsilylene nonadecylcyclopentadienyl
dicycloheptylsilylene eicosylcyclopentadienyl
dicyclooctylsilylene heneicosylcyclopentadienyl
dicyclodecylsilylene docosylcyclopentadienyl
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dicyclododecylsilylene tricosylcyclopentadienyl
dinapthylsilylene tetracosylcyclopentadienyl
diphenylsilylene pentacosylcyclopentadienyl
ditolylsilylene hexacosylcyclopentadienyl
dibenzylsilylene heptacosylcyclopentadienyl
diphenethylsilylene octacosylcyclopentadienyl
di(butylphenethyl)silylene nonacosylcyclopentadienyl
methylethylsilylene triacontylcyclopentadienyl
methylpropylsilylene cyclohexylcyclopentadienyl
methylbutylsilylene phenylcyclopentadienyl
methylhexylsilylene diphenylcyclopentadienyl
methylphenylsilylene triphenylcyclopentadienyl
ethylphenylsilylene tetraphenylcyclopentadienyl
ethylpropylsilylene tolylcyclopentadineyl
ethylbutylsilylene benzylcyclopentadienyl
propylphenylsilylene phenethylcyclopentadienyl
dimethylgermylene cyclohexylmethylcyclopentadienyl
diethylgermylene napthylcyclopentadienyl
diphenylgermylene methylphenylcyclopentadienyl
methylphenylgermylene methyltolylcyclopentadienyl
cyclotetramethylenesilylene methylethylcyclopentadienyl
cyclopentamethylenesilylene methylpropylcyclopentadienyl
cyclotrimethylenesilylene methylbutylcyclopentadienyl
cyclohexylazanediyl methylpentylcyclopentadienyl
butylazanediyl methyleexylcyclopentadienyl
methylazanediyl methylheptylcyclpentadienyl
phenylazanediyl methyloctylcyclopentadienyl
perfluorophenylazanediyl methylnonylcyclopentadienyl
methylphosphanediyl methyldecylcyclopentadienyl
ethylphosphanediyl vinylcyclopentadienyl
propylphosphanediyl propenylcyclopentadienyl
butylphosphanediyl butenylcyclopentadienyl
cyclohexylphosphanediyl Tetrahydroindenyl
phenylphosphanediyl indenyl
methylboranediyl methylindenyl
phenylboranediyl dimethylindenyl
methylene trimethylindenyl
dimethylmethylene tetramethylindenyl
diethylmethylene pentamethylindenyl
dibutylmethylene methylpropylindenyl
dipropylmethylene dimethylpropylindenyl
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diphenylmethylene methyldipropylindenyl
ditolylmethylene methylethylindenyl
di(butylphenyl)methylene methylbutylindenyl
di(trimethylsilylphenyl)methylene ethylindenyl
di(triethylsilylphenyl)methylene propylindenyl
dibenzylmethylene butylindenyl
cyclotetramethylenemethylene pentylindenyl
cyclopentamethylenemethylene hexylindenyl
ethylene heptylindenyl
methylethylene octylindenyl
dimethylethylene nonylindenyl
trimethylethylene decylindenyl
tetramethylethylene phenylindenyl
cyclopentylene (fluorophenyl)indenyl
cyclohexylene (methylphenyl)indenyl
cycloheptylene biphenylindenyl
cyclooctylene (bis(trifluoromethyl)phenyl)indenyl
propanediyl napthylindenyl
methylpropanediyl phenanthrylindenyl
dimethylpropanediyl benzylindenyl
tmmethylpropanediyl benzindenyl
tetramethylpropanediyl cyclohexylindenyl
pentamethylpropanediyl methylphenylindenyl
hexamethylpropanediyl ethylphenylindenyl
tetramethyldisiloxylene propylphenylindenyl
vinylene methylnapthylindenyl
ethene- 1, 1 -diyl ethylnapthylindenyl
divinylsilylene Propylnapthylindenyl
dipropenylsilylene (methylphenyl)indenyl
dibutenylsilylene (dimethylphenyl)indenyl
methylvinylsilylene (ethylphenyl)indenyl
methylpropenylsilylene (diethylphenyl)indenyl
methylbutenylsilylene (propylphenyl)indenyl
dimethylsilylmethylene (dipropylphenyl)indenyl
diphenylsilylmethylene methyltetrahydroindenyl
dimethylsilylethylene ethyltetrahydroindenyl
diphenylsilylethylene propyltetrahydroindenyl
dimethylsilylpropylene butyltetrahydroindenyl
diphenylsilylpropylene phenyltetrahydroindenyl
dimethylstannylene (diphenylmethyl)cyclopentadienyl
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diphenylstannylene dimethyltetrahydroindenyl
trimethylsilylcyclopentadienyl
triethylsilylcyclopentadienyl
Xt or X2 trimethylgermylcyclopentadienyl
chloride trifluromethylcyclopentadienyl
bromide cyclopenta[b]thienyl
iodide cyclopenta[b]furanyl
fluoride cyclopenta[b]selenophenyl
hydride cyclopenta[b]tellurophenyl
methyl cyclopenta[b]pyrrolyl
ethyl cyclopenta[b]phospholyl
propyl cyclopenta[b]arsolyl
butyl cyclolienta[b]stibolyl
peetyl methylcyclopenta[b]thienyl
hexyl methylcyclopenta[b]furanyl
heptyl methylcyclopenta[b]selenophenyl
octyl methylcyclopenta[b]tellurophenyl
nonyl methylcyclopenta[b]pyrrolyl
decyl methylcyclopenta[b]phosphoryl
undecyl methylcyclopenta[b]arsolyl
dodecyl methylcyclopenta[b]stibolyl
tridecyl dimethylcyclopenta[b]thienyl
tetradecyl dimethylcyclopenta[b]furanyl
pentadecyl dimethylcyclopenta[b]pyrrolyl
hexadecyl dimethylcyclopenta[b]phosphoryl
heptadecyl trimethylcyclopenta[b]thienyl
octadecyl trimethylcyclopenta[b]furanyl
nonadecyl trimethylcyclopenta[b]pyrrolyl
eicosyl trimethylcyclopenta[b]phosphoryl
heneicosyl ethylcyclopenta[b]thienyl
docosyl ethylcyclopenta[b]furanyl
tricosyl ethylcyclopenta[b]pyrrolyl
tetracosyl ethylcyclopenta[b]phosphoryl
pentacosyl diethylcyclopenta[b]thienyl
hexacosyl diethylcyclopenta[b]furanyl
heptacosyl diethylcyclopenta[b]pyrrolyl
octacosyl diethylcyclopenta[b]phosphoryl
nonacosyl triethylcyclopenta[b]thienyl
triacontyl triethylcyclopenta[b]furanyl
phenyl triethylcyclopenta[b]pyrrolyl
benzyl triethylcyclopenta[b]phosphoryl
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phenethyl propylcyclopenta[b]thienyl
tolyl propylcyclopenta[b]furanyl
methoxy propylcyclopenta[b]pyrrolyl
ethoxy propylcyclopenta[b]phosphoryl
propoxy dipropylcyclopenta[b]thienyl
butoxy dipropylcyclopenta[b]thianyl
dimethylamido dipropylcyclopenta[b]pyrrolyl
diethylamido dipropylcyclopenta[b]phosphory
methylethylamido tripropylcyclopenta[b]thienyl
phenoxy tripropylcyclopenta[b]furanyl
benzoxy tripropylcyclopenta[b]pyrrolyl
allyl tripropylcyclopenta[b]phosphoryl
butylcyclopenta[b]thienyl
butylc yclop enta [b ] furanyl
XI and X2 together butylcyclopenta[b]pyrrolyl
methylidene butylcyclopenta[b]phosphoryl
ethylidene dibutylcyclopenta[b]thienyl
propylidene dibutylcyclopenta[b]furanyl
tetramethylene dibutylcyclopenta[b]pyrrolyl
pentamethylene dibutylcyclopenta[b]phosphorylphospholyl
hexamethylene tributylcyclopenta[b]thienyl
ethylenedihydroxy tributylcyclopenta[b]furanyl
butadiene tributylcyclopenta[b]pyrrolyl
methylbutadiene tributylcyclopenta[b] phospholyl phospholyl
dimethylbutadiene ethylmethylcyclopenta[b]thienyl
pentadiene ethylmethylcyclopenta[b]furanyl
methylpentadiene ethylmethylcyclopenta[b]pyrrolyl
dimethylpentadiene ethylmethylcyclopenta[b]phosphoryl
hexadiene methylpropylcyclopenta[b]thienyl
methylhexadiene methylpropyleyclopenta[b]furanyl
dimethylhexadiene methylpropylcyclopenta[b]pyrrolyl
methylpropylcyclopenta[b] phosphoryl
butylmethylcyclopenta[b]thienyl
M butylmethylcyclopenta[b]furanyl
titanium butylmethylcyclopenta[b]pyrrolyl
zirconium butylmethylcyclopenta[b]phosphoryl
hafnium cyclopenta[c]thienyl
cyclopenta[c]furanyl
cyclopenta[c] selenophenyl
cyclopenta[c] tellurophenyl
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cyclopenta[c]pyrrolyl
cyclopenta[c]phosphoryl
cyclopenta[c]arsolyl
cyclopenta[c] stibolyl
methylcyclopenta[c]thienyl
methylcyclopenta [c] furanyl
methylcyclopenta[c] selenophenyl
methylcyclopenta[c]tellurophenyl
methylcyclopenta[c]pyrrolyl
methylcyclopenta[c]phosphoryl
methylcyclopenta [c] ars olyl
methylcyclopenta[c]stibolyl
dimethylcyclopenta[c]thienyl
dimethylcyclop enta [c] furanyl
dimethylcyclopenta[c]pyrrolyl
dimethylcyclopenta[cjphosphoryl
trimehylcyclopenta[c]thienyl
trimethylcyclopenta[c] furanyl
trimethylcyclopenta[c]pyrrolyl
trimethylcyclopenta[c]phosphoryl
ethylcyclopenta[c]thienyl
ethylcyclop enta [ c] furanyl
ethylcyclopenta[c]pyrrolyl
ethylcyclopenta[c]phosphoryl
diethylcyclop enta [c] thienyl
diethylcyclop enta [c] furanyl
diethylcyclopenta[c]pyrrolyl
diethylcyclopenta[c]phosphoryl
triethylcyclopenta[c]thienyl
triethylc yc lop enta [c] furanyl
triethylcyclopenta[c]pyrrolyl
triethylcyclopenta[c]phosphoryl
propylcyclopenta[c]thienyl
propylcyc lop enta [c] furanyl
propylcyclopenta[c]pyrrolyl
propylcyclopenta[c]phosphoryl
dipropylcyclopenta[c]thienyl
dipropylcyclopenta[c]furanyl
dipropylcyclopenta[c]pyrrolyl
dipropylcyclopenta[c]phosphoryl
tripropylcyclopenta[c]thienyl
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tripropylcyclop enta [c] furanyl
tripropylcyclopenta[c]pyrrolyl
tripropylcyclopenta[c]phosphorylphosphorylphospholyl
butylcyclopenta[c]thienyl
butylcyclopenta[c]furanyl
butylcyclopenta[c]pyrrolyl
butylcyclopenta[c]phosphoryl
dibutylcyclopenta[c]thienyl
dibutylcyclopenta[c]furanyl
dibutylcyclopenta[c]pyrrolyl
dibutylcyclopenta[c]phosphoryl
tributylcyclopenta[c]thienyl
tributylcyclopenta[c] furanyl
tributylcyclopenta[c]pyrrolyl
tributylcyclopenta[c]phosphoryl
etylmethylcyclopenta[c]thienyl
ethylmethylcyclopenta[c] furanyl
ethylmethylcyclopenta[c]pyrrolyl
ethylmethylcyclopenta[c]phosphoryl
methylpropylcyclopenta[c]thienyl
methylpropylcyclopenta[c]furanyl
methylpropylcyclopenta[c]pyrrolyl
methylpropylcyclop enta [c] pho sphoryl
butylmethylcyclopenta[c]thienyl
butylmethylcyclopenta[c]furanyl
butylmethylcyclopenta[c]pyrrolyl
butylmethylcyclopenta[c]phosphoryl
[0070] In a preferred embodiment of the invention, Cp is the same as Cp*
and is a substituted or unsubstituted cyclopentadienyl, indenyl or
tetrahydroindenyl ligand or fluorenyl. In another preferred embodiment of the
invention, Cp is different from Cp* and is a substituted or unsubstituted
cyclopentadienyl, indenyl or tetrahydroindenyl ligand or fluorenyl.
[0071] Preferred metallocene compounds (pre-catalysts) which, according
to the present invention, provide catalyst systems, which are specific to the
production of poly-a-olefins having high catalyst productivity and convert C3
to
C30 alpha-olefins with comparable reactivities. These compounds can have any
one of the symmetry groups classified as C2, pseudo-C2, C2V, or CS symmetry,
and
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include the racemic and meso versions of. bis(indenyl)zirconium dichloride,
bis(indenyl)zirconium dimethyl, bis(methylindenyl)zirconium dichloride,
bis(methylindenyl)zirconium dimethyl,
bis(dimethylindenyl)zirconium dichloride, bis(dimethylindenyl)zirconium
dimethyl,
bis(alkyllindenyl)zirconium dichloride, bis(alkylindenyl)zirconium dimethyl,
bis(dialkylindenyl)zirconium dichloride, bis(dialkylindenyl)zirconium
dimethyl,
dimethylsilylbis(indenyl) zirconium dichloride, dimethylsilylbis(indenyl)
zirconium dimethyl, diphenylsilylbis(indenyl) zirconium dichloride,
diphenylsilylbis(indenyl) zirconium dimethyl, methylphenylsilylbis(indenyl)
zirconium dichloride,
methylphenylsilylbis(indenyl) zirconium dimethyl, ethylenebis(indenyl)
zirconium dichloride, ethylenebis(indenyl) zirconium dimethyl,
methylenebis(indenyl) zirconium dichloride, methylenebis(indenyl) zirconium
dimethyl, dimethylsilylbis(indenyl) hafnium dichloride,
dimethylsilylbis(indenyl)
hafnium dimethyl, diphenylsilylbis(indenyl) hafnium dichloride,
diphenylsilylbis(indenyl) hafnium dimethyl, methylphenylsilylbis(indenyl)
hafnium dichloride, methylphenylsilylbis(indenyl) hafnium dimethyl,
ethylenebis(indenyl) hafnium dichloride, ethylenebis(indenyl) hafnium
dimethyl,
methylenebis(indenyl) hafnium dichloride, methylenebis(indenyl) hafnium
dimethyl, dimethylsilylbis(tetrahydroindenyl) zirconium dichloride,
dimethylsilylbis(tetrahydroindenyl) zirconium dimethyl,
diphenylsilylbis(tetrahydroindenyl) zirconium dichloride,
diphenylsilylbis(tetrahydroindenyl) zirconium dimethyl,
methylphenylsilylbis(tetrahydroindenyl) zirconium dichloride,
methylphenylsilylbis(tetrahydroindenyl) zirconium dimethyl,
ethylenebis(tetrahydroindenyl) zirconium dichloride,
ethylenebis(tetrahydroindenyl) zirconium dimethyl,
methylenebis(tetrahydroindenyl) zirconium dichloride,
methylenebis(tetrahydroindenyl) zirconium dimethyl,
dimethylsilylbis(tetrahydroindenyl) hafnium dichloride,
dimethylsilylbis(tetrahydroindenyl) hafnium dimethyl,
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diphenylsilylbis(tetrahydroindenyl) hafnium dichloride,
diphenylsilylbis(tetrahydroindenyl) hafnium dimethyl,
methylphenylsilylbis(tetrahydroindenyl) hafnium dichloride,
methylphenylsilylbis(tetrahydroindenyl) hafnium dimethyl,
ethylenebis(tetrahydroindenyl) hafnium dichloride,
ethylenebis(tetrahydroindenyl)
hafnium dimethyl, methylenebis(tetrahydroindenyl) hafnium dichloride,
methylenebis(tetrahydroindenyl) hafnium dimethyl, dimethylsilylbis(4,7-
dimethylindenyl) zirconium dichloride, dimethylsilylbis(4,7-dimethylindenyl)
zirconium dimethyl, diphenylsilylbis(4,7-dimethylindenyl) zirconium
dichloride,
diphenylsilylbis(4,7-dimethylindenyl) zirconium dimethyl,
methylphenylsilylbis(4,7-dimethylindenyl) zirconium dichloride,
methylphenylsilylbis(4,7-dimethylindenyl) zirconium dimethyl, ethylenebis(4,7-
dimethylindenyl) zirconium dichloride, ethylenebis(4,7-dimethylindenyl)
zirconium dimethyl, methylenebis(4,7-dimethylindenyl) zirconium dichloride,
methylenebis(4,7-dimethylindenyl) zirconium dimethyl, dimethylsilylbis(4,7-
dimethylindenyl) hafnium dichloride, dimethylsilylbis(4,7-dimethylindenyl)
hafnium dimethyl, diphenylsilylbis(4,7-dimethylindenyl) hafnium dichloride,
diphenylsilylbis(4,7-dimethylindenyl) hafnium dimethyl,
methylphenylsilylbis(4,7-dimethylindenyl) hafnium dichloride,
methylphenylsilylbis(4,7-dimethylindenyl) hafnium dimethyl, ethylenebis(4,7-
dimethylindenyl) hafnium dichloride, ethylenebis(4,7-dimethylindenyl) hafnium
dimethyl, methylenebis(4,7-dimethylindenyl) hafnium dichloride,
methylenebis(4,7-dimethylindenyl) hafnium dimethyl, dimethylsilylbis(2-methyl-
4-napthylindenyl) zirconium dichloride, dimethylsilylbis(2-methyl-4-
napthylindenyl) zirconium dimethyl, diphenylsilylbis(2-methyl-4-
napthylindenyl)
zirconium dichloride, dimethylsilylbis(2,3-dimethylcyclopentadienyl) zirconium
dichloride, dimethylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dimethyl,
diphenylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dichloride,
diphenylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dimethyl,
methylphenylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dichloride,
methylphenylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dimethyl,
ethylenebis(2,3-dimethylcyclopentadienyl) zirconium dichloride,
ethylenebis(2,3-
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dimethylcyclopentadienyl) zirconium dimethyl, methylenebis(2,3-
dimethylcyclopentadienyl) zirconium dichloride, methylenebis(2,3-
dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis(2,3-
dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylbis(2,3
dimethylcyclopentadienyl) hafnium dimethyl, diphenylsilylbis(2,3-
dimethylcyclopentadienyl) hafnium dichloride, diphenylsilylbis(2,3-
dimethylcyclopentadienyl) hafnium dimethyl, methylphenylsilylbis(2,3-
dimethylcyclopentadienyl) hafnium dichloride, methylphenylsilylbis(2,3-
dimethylcyclopentadienyl) hafnium dimethyl, ethylenebis(2,3-
dimethylcyclopentadienyl) hafnium dichloride, ethylenebis(2,3-
dimethylcyclopentadienyl) hafnium dimethyl, methylenebis(2,3-
dimethylcyclopentadienyl) hafnium dichloride, methylenebis(2,3-
dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylbis(3-
trimethylsilylcyclopentadienyl) zirconium dichloride, dimethylsilylbis(3-
trimethylsilylcyclopentadienyl) zirconium dimethyl, diphenylsilylbis(3-
trimethylsilylcyclopentadienyl) zirconium dichloride, diphenylsilylbis(3-
trimethylsilylcyclopentadienyl) zirconium dimethyl, methylphenylsilylbis(3-
trimethylsilylcyclopentadienyl) zirconium dichloride, methylphenylsilylbis(3-
trimethylsilylcyclopentadienyl) zirconium dimethyl, ethylenebis(3-
trimethylsilylcyclopentadienyl) zirconium dichloride, ethylenebis(3-
trimethylsilylcyclopentadienyl) zirconium dimethyl, methylenebis(3-
trimethylsilylcyclopentadienyl) zirconium dichloride, methylenebis(3-
trimethylsilylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis(3-
trimethylsilylcyclopentadienyl) hafnium dichloride, dimethylsilylbis(3-
trimethylsilylcyclopentadienyl) hafnium dimethyl, diphenylsilylbis(3-
trimethylsilylcyclopentadienyl) hafnium dichloride, diphenylsilylbis(3-
trimethylsilylcyclopentadienyl) hafnium dimethyl, methylphenylsilylbis(3-
trimethylsilylcyclopentadienyl) hafnium dichloride, methylphenylsilylbis(3-
trimethylsilylcyclopentadienyl) hafnium dimethyl, ethylenebis(3-
trimethylsilylcyclopentadienyl) hafnium dichloride, ethylenebis(3-
trimethylsilylcyclopentadienyl) hafnium dimethyl, methylenebis(3-
trimethylsilylcyclopentadienyl) hafnium dichloride, and methylenebis(3-
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trimethylsilylcyclopentadienyl) hafnium dimethyl. Another set of preferred
metallocene catalysts include substituted unbridged bis(R1,R2aR3,R4,R5-
cyclopentadienyl) zirconium dichlorides or dimethyls where the R1 to R5 groups
can be same or different and can be independently chosen from H, C1 to C20
hydrocarbyl radicals. These metallocenes when activated with MAO or NCA co-
catalysts and optionally with co-activators have high catalyst productivity
and
more importantly have comparable reactivity for all alpha-olefins with C3 to
C30
range. Specific examples are bis(alkylcyclopentadienyl) zirconium dichlorides
(alkyl = C1 to C20-alkyl group, specially, methyl, ethyl, n-propyl, n-butyl, n-
pentyl, n-hexyl, etc. and iso-propyl, isobutyl, t-butyl groups, etc.), bis(1,2-
dimethylcyclopentadienyl) zirconium dichloride, bis(1,3-
dimethylcyclopentadienyl) zirconium dichloride, bis(l-methyl-3-n-
propylcyclopentadienyl) zirconium dichloride, bis(1-methyl-3-
ethylcyclopentadienyl) zirconium dichloride, bis(l-methyl-3-n-
propylcyclopentadienyl) zirconium dichloride,bis(1-methyl-2-n-
butylcyclopentadienyl) zirconium dichloride, bis(1-methyl-2-n-
propylcyclopentadienyl) zirconium dichloride, bis(l-methyl-2-
ethylcyclopentadienyl) zirconium dichloride, bis(1,2,3-
trimethylcyclopentadienyl)
zirconium dichloride, bis(1,2,4-trimethylcyclopentadienyl) zirconium
dichloride,
bis(1,2-dimethyl-4-ethylcyclopentadienyl) zirconium dichloride, bis(1,2-
dimethyl-
4-n-propylcyclopentadienyl) zirconium dichloride, bis(1,2-dimethyl-4-n-
butylcyclopentadienyl) zirconium dichloride, bis(tetramethylcyclopentadienyl)
zirconium dichloride, bis(pentamethylcyclopentadienyl) zirconium dichloride,
etc.
[00721 Particularly preferred species are the racemic and meso versions of:
dimethylsilylbis(indenyl) zirconium dichloride, dimethylsilylbis(indenyl)
zirconium dimethyl, ethylenebis(indenyl) zirconium dichloride,
ethylenebis(indenyl) zirconium dimethyl, dimethylsilylbis(tetrahydorindenyl)
zirconium dichloride, dimethylsilylbis(tetrahydorindenyl) zirconium dimethyl,
ethylenebis(tetrahydorindenyl) zirconium dichloride,
ethylenebis(tetrahydorindenyl) zirconium dimethyl, dimethylsilylbis(4,7-
dimethylindenyl) zirconium dichloride, dimethylsilylbis(4,7-dimethylindenyl)
zirconium dimethyl, ethylenebis(4,7-dimethylindenyl) zirconium dichloride,
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ethylenebis(4,7-dimethylindenyl) zirconium dimethyl, dimethylsilylbis(indenyl)
hafnium dichloride, dimethylsilylbis(indenyl) - hafnium dimethyl,
ethylenebis(indenyl) hafnium dichloride, ethylenebis(indenyl) hafnium
dimethyl,
dimethylsilylbis(tetrahydorindenyl) hafnium dichloride,
dimethylsilylbis(tetrahydorindenyl) hafnium dimethyl,
ethylenebis(tetrahydorindenyl) hafnium dichloride,
ethylenebis(tetrahydorindenyl)
hafnium dimethyl, dimethylsilylbis(4,7-dimethylindenyl) hafnium dichloride,
dimethylsilylbis(4,7-dimethylindenyl) hafnium dimethyl, ethylenebis(4,7-
dimethylindenyl) hafnium dichloride, and ethylenebis(4,7-dimethylindenyl)
hafnium dimethyl. Other preferred catalysts include
diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, iso-
propylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, iso-
propylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconium dichloride,
ethylenebis(9-fluorenyl)zirconium dichloride, dimethylsilylbis(9-
fluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(9-
fluorenyl)zirconium dichloride, diphenylsilyl(cyclopentadienyl)(9-
fluorenyl)zirconium dichloride, their analogs of dimethyls or the analogs of
hafnium metallocenes.
[0073] The metallocene compounds, when activated by a per se commonly
known activator such as methyl aluminoxane, form active catalysts for the
polymerization or oligomerization of olefins. Activators that may be used
include
aluminoxanes such as methyl aluminoxane (or MAO, shown in Formula II,
above), modified methyl aluminoxane, ethyl aluminoxane, iso-butyl aluminoxane
and the like, Lewis acid activators including triphenyl boron, tris-
perfluorophenyl
boron, tris-perfluorophenyl aluminum and the like, ionic activators including
dimethylanilinium tetrakis perfluorophenyl borate, triphenyl carbonium
tetrakis
perfluorophenyl borate, dimethylanilinium tetrakis perfluorophenyl aluminate,
and
the like, and non-coordinating anions such as shown in Formula III.
[0074] A co-activator is a compound capable of alkylating the transition
metal complex, such that when used in combination with an activator, an active
catalyst is formed. Co-activators include aluminoxanes such as methyl
aluminoxane, modified aluminoxanes such as modified methyl aluminoxane, and
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aluminum alkyls such trimethyl aluminum, tri-isobutyl aluminum, triethyl
aluminum, and tri-isopropyl aluminum, tri-n-hexyl aluminum, tri-n-octyl
aluminum, tri-n-decyl aluminum or tri-n-dodecyl aluminum. Co-activators are
typically used in combination with Lewis acid activators and ionic activators
when the pre-catalyst is not a dihydrocarbyl or dihydride complex. Sometimes
co-activators are also used as scavengers to deactivate impurities in feed or
reactors.
[0075] The aluminoxane component useful as an activator typically is
preferably an oligomeric aluminum compound represented by the general formula
(R"-Al-O),,, which is a cyclic compound, or R" (R"-Al-O)õ A1R"2, which is a
linear
compound. The most common aluminoxane is a mixture of the cyclic and linear
compounds. In the general aluminoxane formula, R" is independently a CI-C20
alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl, isomers
thereof,
and the like, and "n" is an integer from 1-50. Most preferably, R" is methyl
and
"n" is at least 4. Methyl aluminoxane and modified methyl aluminoxanes are
most preferred. For further descriptions see, EP 0 279 586, EP 0 594 218, EP 0
561 476, W094/10180 and US Pat. Nos. 4,665,208, 4,874,734, 4,908,463,
4,924,018, 4,952,540, 4,968,827, 5,041,584, 5,091,352, 5,103,031, 5,157,137,
5,204,419, 5,206,199, 5,235,081, 5,248,801, 5,329,032, 5,391,793, and
5,416,229.
[0076] When an aluminoxane or modified aluminoxane is used, the catalyst-
precursor-to-activator molar ratio (based on the metals, e.g., Zr or Hf to Al)
is
from about 1:3000 to 10:1; alternatively, 1:2000 to 10:1; alternatively 1:1000
to
10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively
1:250 to
1:1, alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively
1:50 to 1:1;
alternatively 1:10 to 1:1. When the activator is an aluminoxane (modified or
unmodified), some embodiments select the maximum amount of activator at a
5000-fold molar excess over the catalyst precursor (per metal catalytic site).
The
preferred minimum activator-to-catalyst-precursor ratio is 1:1 molar ratio.
[0077] Ionic activators (which in embodiments may be used in combination
with a co-activator) may be used in the practice of this invention. Ionic
activators,
sometimes referred to as non-coordinating anion (NCA) activators, usually
refer
to those activators that have distinctive ionic character in their active
states, even
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though these activators are neutral chemical compounds. They are exemplified
by
Formula 2, above, which a preferred ionic activator. Preferably, discrete
ionic
activators such as [Me2PhNH][B(C6F5)4], [R3NH][B(C6F5)4], [R2NH2][B(C6F5)4],
[RNH3][B(C6F5)4], [R4N][B(C6F5)4], [Ph3C][B(C6F5)4], [Me2PhNH][B((C6H3-3,5-
(CF3)2))4], [Ph3C][B((C6H3-3,5-(CF3)2))4], [NH4] or Lewis acidic
activators such as B(C6F5)3 or B(C6H5)3 can be used, where Ph is phenyl and Me
is methyl, R=C1 to C16 alkyl groups. Preferred co-activators, when used, are
aluminoxanes such as methyl aluminoxane, modified aluminoxanes such as
modified methyl aluminoxane, and aluminum alkyls such as tri-isobutyl
aluminum, and trimethyl aluminum, triethyl aluminum, and tri-isopropyl
aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum or
tri-n-dodecyl aluminum. The preferred ionic activators are N,N-
dimethylanilinium tetrakis(pentafluorophenyl)borate, tetra-methylanilinium
tetrakis(pentafluorophenyl)borate, tetradecylanilinium
tetrakis(pentafluorophenyl)borate, tetrahexadecylanilinium
tetrakis(pentafluorophenyl)borate, [Ph3C][B(C6F5)4], B(C6F5)3.
[0078] It is within the scope of this invention to use an ionizing or
stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium
tetrakis
(pentafluorophenyl) borate, a tris(perfluorophenyl) boron metalloid precursor
or a
tris(perfluoronaphthyl) boron metalloid precursor, polyhalogenated
heteroborane
anions (e.g., WO 98/43983), boric acid (e.g., U.S. Patent No. 5,942,459) or
combination thereof.
[0079] Examples of neutral stoichiometric activators include tri-substituted
boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three
substituent groups are each independently selected from alkyls, alkenyls,
halogen,
substituted alkyls, aryls, arylhalides, alkoxy and halides. Preferably, the
three
groups are independently selected from halogen, mono- or multicyclic
(including
halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof,
preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having
1
to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups
having 3 to 20 carbon atoms (including substituted aryls). More preferably,
the
three groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl or
mixtures
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thereof. Even more preferably, the three groups are halogenated, preferably
fluorinated, aryl groups. Most preferably, the neutral stoichiometric
activator is
tris(perfluorophenyl) boron or tris(perfluoronaphthyl) boron.
[0080] Ionic stoichiometric activator compounds may contain an active
proton, or some other cation associated with, but not coordinated to, or only
loosely coordinated to, the remaining ion of the ionizing compound. Such
compounds and the like are described in European publications EP-A-0 570 982,
EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-
0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197,
5,241,025, 5,384,299 and 5,502,124 and U.S. Patent Application Serial No.
08/285,380, filed August 3, 1994.
[0081] Ionic catalysts can be prepared by reacting a transition metal
compound with an activator, such as B(C6F6)3, which upon reaction with the
hydrolyzable ligand (X') of the transition metal compound forms an anion, such
as ([B(C6F5)3(X')]-), which stabilizes the cationic transition metal species
generated by the reaction. The catalysts can be, and preferably are, prepared
with
activator components which are ionic compounds or compositions. However
preparation of activators utilizing neutral compounds is also contemplated by
this
invention.
[0082] Compounds useful as an activator component in the preparation of
the ionic catalyst systems used in the process of this invention comprise a
cation,
which is preferably a Bronsted acid capable of donating a proton, and a
compatible non-coordinating anion which anion is relatively large (bulky),
capable of stabilizing the active catalyst species which is formed when the
two
compounds are combined and said anion will be sufficiently labile to be
displaced
by olefinic, diolefinic, and acetylenically unsaturated substrates or other
neutral
Lewis bases such as ethers, nitriles and the like. Two classes of compatible
non-
coordinating anions have been disclosed in EP- 277,003 and EP 277,004
published 1988: 1) anionic coordination complexes comprising a plurality of
lipophilic radicals covalently coordinated to, and shielding, a central charge-
bearing metal or metalloid core, and 2) anions comprising a plurality of boron
atoms such as carboranes, metallacarboranes and boranes.
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[0083] In a preferred embodiment, the stoichiometric activators include a
cation and an anion component, and maybe represented by the following formula:
(L**_H)d+ (A'-)
wherein L** is an neutral Lewis base;
H is hydrogen;
(L**-H) + is a Bronsted acid
Ad- is a non-coordinating anion having the charge d-
d is an integer from 1 to 3.
[0084] The cation component, (L**-H)d+ may include Bronsted acids such as
protons or protonated Lewis bases or reducible Lewis acids capable of
protonating
or abstracting a moiety, such as an alkyl or aryl, from the precatalyst after
alkylation. The activating cation (L**-H)d+ may be a Bronsted acid, capable of
donating a proton to the alkylated transition metal catalytic precursor
resulting in a
transition metal cation, including ammoniums, oxoniums, phosphoniums,
silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline,
dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine,
triethylamine, NN-dimethylaniline, methyldiphenylamine, pyridine, p-bromo
N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from
triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from
ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane,
sulfoniums from thioethers, such as diethyl thioethers and
tetrahydrothiophene,
and mixtures thereof. The activating cation (L**-H)d+ may also be a moiety
such
as silver, tropylium, carbeniums, ferroceniums and mixtures, preferably
carboniums and ferroceniums; most preferably triphenyl carbonium.
[0085] The anion component Ad" include those having the formula [Mk+Q,:]d-
wherein k is an integer from 1 to 3; n is an integer from 2-6; n - k = d; M is
an
element selected from Group 13 of the Periodic Table of the Elements,
preferably
boron or aluminum, and Q is independently a hydride, bridged or unbridged
dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted
hydrocarbyl,
halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals,
said
Q having up to 20 carbon atoms with the proviso that in not more than one
occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl
group
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having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl
group,
and most preferably each Q is a pentafluoryl aryl group. Examples of suitable
Ad"
also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895.
[00861 Illustrative, but not limiting examples of boron compounds which
may be used as an activating cocatalyst in combination with a co-activator in
the
preparation of the improved catalysts of this invention are tri-substituted
ammonium salts such as: trimethylammonium tetraphenylborate,
triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,
tri(fn-butyl)ammonium tetraphenylborate, tri(tert-butyl)ammonium
tetraphenylborate, NN-drmethylanilinium tetraphenylborate, N,N-
diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)
tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate,
triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium
tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium
tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)
tetrakis(pentafluorophenyl)borate, trimethylammonium tetralds-(2,3,4,6-
tetrafluorophenyl) borate, triethylammonium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, tripropylammonium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, NN-dimethylanilinium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, NN-dimethyl-(2,4,6-trimethylanilinium) tetrakis-
(2,3,4,6-tetrafluorophenyl)borate, trimethylammonium
tetrakis(perfluoronaphthyl)borate, triethylammonium
tetrakis(perfluoronaphthyl)borate, tripropylammonium
tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium
tetrakis(perfluoronaphthyl)borate, tri(tert-butyl)arnmonium
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tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium
tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium
tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)
tetrakis(perfluoronaphthyl)borate, trimethylammonium
tetrakis(perfluorobiphenyl)borate, triethylammonium
tetrakis(perfluorobiphenyl)borate, tripropylammonium
tetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium
tetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammonium
tetrakis(perfluorobiphenyl)borate, NN-dimethylanilinium
tetrakis(perfluorobiphenyl)borate, N,N-diethylanilinium
tetrakis(perfluorobiphenyl)borate, NN-dimethyl-(2,4,6-trimethylanilinium)
tetrakis(perfluorobiphenyl)borate, trimethylammonium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, triethylammonium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, tripropylammonium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammonium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, N,N-dimethylanilinium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, N,N-diethylanilinium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkyl ammonium salts
such
as: di-(iso-propyl)ammonium tetrakis(pentafluorophenyl)borate, and
dicyclohexylammonium tetrakis(pentafluorophenyl)borate; and other salts such
as
tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-
dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tropylium
tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium
tetraphenylborate, triethylsilylium tetraphenylborate,
benzene(diazonium)tetraphenylborate, tropylium
tetrakis(pentafluorophenyl)borate, triphenylcarbenium
tetrakis(pentafluorophenyl)borate, triphenylphosphonium
tetrakis(pentafluorophenyl)borate, triethylsilylium
tetrakis(pentafluorophenyl)borate, benzene(diazonium)
tetrakis(pentafluorophenyl)borate, tropylium tetrakis-(2,3,4,6-
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tetrafluorophenyl)b orate, triphenylcarbenium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, triphenylphosphonium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, triethylsilylium tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, benzene(diazonium) tetrakis-(2,3,4,6-
tetrafluorophenyl)borate, tropylium tetrakis(perfluoronaphthyl)borate,
triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylphosphonium
tetrakis(perfluoronaphthyl)borate, triethylsilylium
tetrakis(perfluoronaphthyl)borate, benzene(diazonium)
tetrakis(perfluoronaphthyl)borate, tropylium
tetrakis(perfluorobiphenyl)borate,
triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylphosphonium
tetrakis(perfluorobiphenyl)borate, triethylsilylium
tetrakis(perfluorobiphenyl)borate, benzene(diazonium)
tetrakis(perfluorobiphenyl)borate, tropylium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, triphenylphosphonium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, triethylsilylium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, and benzene(diazonium) tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate.
[0087] Most preferably, the ionic stoichiometric activator (L**-H)d+ (Ad") is
NN-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium
tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium
tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, triphenylcarbenium
tetrakis(perfluoronaphthyl)borate, triphenylcarbenium
tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-
bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium
tetra(perfluorophenyl)borate.
[0088] The catalyst precursors can also be activated with cocatalysts or
activators that comprise non-coordinating anions containing metalloid-free
cyclopentadienide ions. These are described in U.S. Patent Publication
2002/0058765 Al, published on 16 May 2002, and for the instant invention,
require the addition of a co-activator to the catalyst pre-cursor.
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[0089] "Compatible" non-coordinating anions are those which are not
degraded to neutrality when the initially formed complex decomposes. Further,
the anion will not transfer an anionic substituent or fragment to the cation
so as to
cause it to form a neutral transition metal compound and a neutral by-product
from the anion. Preferred non-coordinating anions useful in accordance with
this
invention are those that are compatible, stabilize the transition metal
complex
cation in the sense of balancing its ionic charge at +1, yet retain sufficient
lability
to permit displacement by, an ethylenically or acetylenically unsaturated
monomer
during polymerization. These types of cocatalysts are sometimes used with
scavengers. They have the general compositions of R1, R2, R3-Al where R1, R2
and R3 can be H or any of C1 to C20 hydrocarbyl radicals. Examples of the
trialkylaluminum compounds include but are not limited to tri-iso-butyl
aluminum, tri-n-octyl aluminum, tri-n-hexyl aluminum, triethylaluminum or
trimethylaluminum, tri-n-decyl aluminum, tri-n-dodecyl aluminum.
[0090] Invention processes also can employ cocatalyst compounds or
activator compounds that are initially neutral Lewis acids but form a cationic
metal complex and a noncoordinating anion, or a zwitterionic complex upon
reaction with the alkylated transition metal compounds. The alkylated
metallocene compound is formed from the reaction of the catalyst pre-cursor
and
the co-activator. For example, tris(pentafluorophenyl) boron or aluminum act
to
abstract a hydrocarbyl ligand to yield an invention cationic transition metal
complex and stabilizing noncoordinating anion, see EP-A-0 427 697 and EP-A-0
520 732 for illustrations of analogous Group-4 metallocene compounds. Also,
see
the methods and compounds of EP-A-0 495 375. For formation of zwitterionic
complexes using analogous Group 4 compounds, see U.S. Patents 5,624,878;
5,486,632; and 5,527,929.
[0091] Additional neutral Lewis acids are known in the art and are suitable
for abstracting formal anionic ligands. See in particular the review article
by E.
Y.-X. Chen and T.J. Marks, "Cocatalysts for Metal-Catalyzed Olefin
Polymerization: Activators, Activation Processes, and Structure-Activity
Relationships", Chen. Rev., 100, 1391-1434 (2000).
[0092] When the cations of noncoordinating anion precursors are Bronsted
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acids such as protons or protonated Lewis bases (excluding water), or
reducible
Lewis acids such as ferrocenium or silver cations, or alkali or alkaline earth
metal
cations such as those of sodium, magnesium or lithium, the catalyst-precursor-
to-
activator molar ratio may be any ratio. Combinations of the described
activator
compounds may also be used for activation.
[00931. When an ionic or neutral stoichiometric NCA-type activator is used,
the catalyst-precursor-to-activator molar ratio is from 1:10 to 1:1; 1:10 to
10:1;
1:10to2:1; 1:10to3:1; 1:10to5:1; 1:2 to 1.2:1; 1:2 to 10:1; 1:2to2:1;
1:2to3:1;
1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5
to 1:1; 1:5
to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2. The catalyst-
precursor-to-
co-activator molar ratio is from 1:500 to 1:1, 1:100 to 100:1; 1:75 to 75:1;
1:50 to
50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1, 1:2 to 2:1; 1:100
to 1:1;
1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1-' 1:10 to 1:1; 1:5 to 1:1;
1:2 to 1:1;
1:10 to 2:1.
[0094] Preferred activators and activator/co-activator combinations include
methylaluminoxane, modified methylaluminoxane, mixtures of
methylaluminoxane with dimethylanilinium tetrakis(pentafluorophenyl)borate or
tris(pentafluorophenyl)boron, and mixtures of trialkyl aluminum, preferable
any
one of tri-isobutyl aluminum, triethyl aluminum, tri-n-alkyl aluminum or
trimethyl
aluminum or their combination, with dimethylanilinium
tetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron or their
analogs.
[0095] In some embodiments, scavenging compounds are used with
stoichiometric activators. Typical aluminum or boron alkyl components useful
as
scavengers are represented by the general formula R" JZ2 where J is aluminum
or
boron, R" is as previously defined above, and each Z is independently R" or a
different univalent anionic ligand such as halogen (Cl, Br, I), alkoxide (OR")
and
the like. R" is a H or any radical chosen from the C1 to C20 hydrocarbyl
radicals.
Most preferred aluminum alkyls include triethylaluminum, diethylaluminum
chloride, tri-iso-butylaluminum, tri-n-octylaluminum. tri-n-hexylaluminum,
trimethylaluminum and the like. Preferred boron alkyls include triethylboron.
Scavenging compounds may also be aluminoxanes and modified aluminoxanes
including methylaluminoxane and modified methylaluminoxane. The scavenger
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can be the same or different from the co-activator used for the catalyst
system.
[0096] An active catalyst solution can be prepared by dissolving metallocene,
activator including methylaluminoxane or NCA, co-activator and/or scavenger in
proper pre-purified solvent individually. Then combine all the component
solutions in any one of the following orders to give active catalyst solution.
Method (a) - add metallocene solution to co-activator and/or scavenger
solution,
followed by addition of activator. Method (b) - combine metallocene solution
with activator solution and add this mixture into co-activator and/or
scavenger
solution. Method (c) - add activator solution to co-activator and/or scavenger
solution, followed by, metallocene solution. Sometimes, co-activator and/or
scavenger solution can be added in two separate stages in method (a) to (c).
[0097] Sometimes, preparation of stock solutions is not necessary. All
components are mixed directly into proper pre-purified solvent. One method
[method (d)] to prepare catalyst solution is to first add co-activator and/or
scavenger to solvent, followed by addition of metallocene solution or solid,
followed by activator solution or solid. Another method [method (e)] is to
first
add metallocene solution or solid to solvent, followed by co-activator and/or
scavenger, followed by activator. Another method [method (f)] is to first add
co-
activator and/or scavenger solution or liquid to solvent, followed metallocene
solution or solid, followed by activator solution or solid. Another method
[method (g)] is to first add co-activator and/or scavenger solution or liquid
to
solvent, followed activator solution or solid, followed by metallocene
solution or
solid. All these methods produce active catalyst solutions. Usually, method
(a)
and method (d) are the most preferred methods. All solvents used in the
catalyst
preparation are pre-purified by passing through purifiers, which include
molecular
sieves and/or activated de-oxygenation catalysts. Sometimes, a small amount of
co-activator and/or scavenger tri-alkylaluminum or aluminoxane is added to all
the solvents to remove impurities.
[0098] In a preferred embodiment, the catalyst system includes a support.
The solubility of invention catalyst precursors allows for the ready
preparation of
supported catalysts. To prepare uniform supported catalysts, the catalyst
precursor preferably dissolves in the chosen solvent. The term "uniform
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supported catalyst" means that the catalyst precursor, the activator and or
the
activated catalyst approach uniform distribution upon the support's accessible
surface area, including the interior pore surfaces of porous supports. Some
embodiments of supported catalysts prefer uniform supported catalysts; other
embodiments show no such preference.
[0099] Useful supported catalyst systems may be prepared by any method
effective to support other coordination catalyst systems, effective meaning
that the
catalyst so prepared can be used for oligomerizing or polymerizing olefin in a
heterogeneous process. The catalyst precursor, activator, co-activator if
needed,
suitable solvent, and support may be added in any order or simultaneously.
[00100] By one method, the activator, dissolved in an appropriate solvent such
as toluene may be stirred with the support material for 1 minute to 10 hours.
The
total solution volume may be greater than the pore volume of the support, but
some embodiments limit the total solution volume below that needed to form a
gel
or slurry (about 90% to 400 %, preferably about 100-200% of the pore volume).
The mixture is optionally heated from 30-200 C during this time. The catalyst
precursor may be added to this mixture as a solid, if a suitable solvent is
employed
in the previous step, or as a solution. Or alternatively, this mixture can be
filtered,
and the resulting solid mixed with a catalyst precursor solution. Similarly,
the
mixture may be vacuum-dried and mixed with a catalyst precursor solution. The
resulting catalyst mixture is then stirred for 1 minute to 10 hours, and the
supported catalyst is filtered from the solution and the solvent removed,
either by
vacuum-drying or evaporation alone.
[00101] Alternatively, the catalyst precursor and activator may be combined
in solvent to form a solution. Then the support is added, and the mixture is
stirred
for 1 minute to 10 hours. The total solution volume may be greater than the
pore
volume of the support, but some embodiments limit the total solution volume
below that needed to form a gel or slurry (about 90% to 400 %, preferably
about
100-200% of the pore volume). After stirring, the residual solvent is removed
under vacuum, typically at ambient temperature and over 10-16 hours. But
greater or lesser times and temperatures are possible.
[00102] The catalyst precursor may also be supported absent the activator; in
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that case, the activator (and co-activator if needed) is added to a slurry
process's
liquid phase. For example, a solution of catalyst precursor may be mixed with
a
support material for a period of about 1 minute to 10 hours. The resulting
precatalyst mixture may be filtered from the solution and dried under vacuum,
or
evaporation alone removes the solvent. The total catalyst-precursor-solution
volume may be greater than the support's pore volume, but some embodiments
limit the total solution volume below that needed to form a gel or slurry
(about
90% to 400 %, preferably about 100-200% of the pore volume).
[00103] Additionally, two or more different catalyst precursors may be placed
on the same support using any of the support methods disclosed above.
Likewise,
two or more activators or an activator and co-activator may be placed on the
same
support.
[00104] Suitable solid particle supports are typically comprised of polymeric
or refractory oxide materials, each being preferably porous. Any support
material
that has an average particle size greater than 10 gm is suitable for use in
this
invention. Various embodiments select a porous support material, such as for
example, talc, inorganic oxides, inorganic chlorides, for example magnesium
chloride and resinous support materials such as polystyrene polyolefin or
polymeric compounds or any other organic support material and the like. Some
embodiments select inorganic oxide materials as the support material including
Group-2, -3, -4, -5, -13, or -14 metal or metalloid oxides. Some embodiments
select the catalyst support materials to include silica, alumina, silica-
alumina, and
their mixtures. Other inorganic oxides may serve either alone or in
combination
with the silica, alumina, or silica-alumina. These are magnesia, titania,
zirconia,
and the like. Lewis acidic materials such as montmorillonite and similar clays
may also serve as a support. In this case, the support can optionally double
as an
activator component. But additional activator may also be used. In some cases,
a
special family of solid support commonly known as MCM-41 can also be used.
MCM-41 is a new class of unique crystalline support and can be prepared with
tunable pore size and tunable acidity when modified with a second component. A
detailed description of this class of material and their modification can be
found in
US 5,264,203.
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[00105] The support material may be pretreated by any number of methods.
For example, inorganic oxides may be calcined, chemically treated with
dehydroxylating agents such as aluminum alkyls and the like, or both.
[00106] As stated above, polymeric carriers will also be suitable in
accordance with the invention, see for example the descriptions in WO 95/15815
and U.S. patent 5,427,991. The methods disclosed may be used with the catalyst
compounds, activators or catalyst systems of this invention to adsorb or
absorb
them on the polymeric supports, particularly if made up of porous particles,
or
may be chemically bound through functional groups bound to or in the polymer
chains.
[00107] Useful catalyst carriers may have a surface area of from 10-700
m2/g, and or a pore volume of 0.1-4.0 cc/g and or an average particle size of
10-
500 m. Some embodiments select a surface area of 50-500 m2/g, and or a pore
volume of 0.5-3.5 cc/g, and or an average particle size of 20-200 m. Other
embodiments select a surface area of 100-400 m2/g, and or a pore volume of 0.8-
3.0 cc/g, and or an average particle size of 30-100 m. Carriers of this
invention
typically have a pore size of 10-1000 angstroms, alternatively 50-500
angstroms,
or 75-350 angstroms.
[00108] The metallocenes and or the metallocene/activator combinations
are generally deposited on the support at a loading level of 10-100 micromoles
of
catalyst precursor per gram of solid support; alternately 20-80 micromoles of
catalyst precursor per gram of solid support; or 40-60 micromoles of catalyst
precursor per gram of support. But greater or lesser values may be used
provided
that the total amount of solid catalyst precursor does not exceed the
support's pore
volume.
[00109] The metallocenes and or the metallocene/activator combinations
can be supported for bulk, or slurry polymerization, or a fixed bed reactor or
otherwise as needed. Numerous support methods are known for catalysts in the
olefin polymerization art, particularly aluminoxane-activated catalysts; all
are
suitable for use herein. See, for example, U.S. Patents 5,057,475 and
5,227,440.
An example of supported ionic catalysts appears in WO 94/03056. U.S. Patent
5,643,847 and WO 96/04319A which describe a particularly effective method.
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Both polymers and inorganic oxides may serve as supports, see U.S. Patents
5,422,325, 5,427,991, 5,498,582 and 5,466,649, and international publications
WO 93/11172 and WO 94/07928.
[00110] In another preferred embodiment, the metallocene and or activator
(with or without a support) are combined with an alkyl aluminum compound,
preferably a trialkyl aluminum compound, prior to entering the reactor.
Preferably the alkyl aluminum compound is represented by the formula: R3A1,
where each R is independently a Cl to C20 alkyl group, preferably the R groups
are independently selected from the group consisting of methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, n-butyl, pentyl, isopentyl, n-pentyl, hexyl,
isohexyl, n-
hexyl, heptyl, octyl, isocotyl, n-octyl, nonyl, isononyl, n-nonyl, decyl,
isodecyl,
n-cecyl, undecyl, isoundecyl, n-undecyl, dodecyl, isododecyl, and n-dodecyl,
preferably isobutyl, n-octyl, n-hexyl, and n-dodecyl. Preferably the alkyl
aluminum compound is selected from tri-isobutyl aluminum, tri n-octyl
aluminum, tri-n-hexyl aluminum, and tri-n-dodecyl aluminum.
[00111] Polymerization process
[00112] Many polymerization/oligomerization processes and reactor types
used for metallocene-catalyzed polymerization or oligomerization such as
solution, slurry, or bulk polymerization or oligomerization processes can be
used
in this invention. In another embodiment, if a solid or supported catalyst is
used,
a slurry or continuous fixed bed or plug flow process is suitable. In a
preferred
embodiment, the monomers are contacted with the metallocene compound and
the activator in the solution phase, bulk phase, or slurry phase, preferably
in a
continuous stirred tank reactor, continuous tubular reactor, a semi-continuous
reactor, or a batch reactor. In a preferred embodiment, the temperature in any
reactor used herein is from -10 C to 250 C, preferably from 30 C to 220 C,
preferably from 50 C to 180 C, preferably from 60 C to 170 T. In a preferred
embodiment, the pressure in any reactor used herein is from 0.1 to 100
atmospheres, preferably from 0.5 to 75 atmospheres, preferably from 1 to 50
atmospheres. In another embodiment, the monomers, metallocene and activator
are contacted for a residence time of from 1 second to 100 hours, preferably
30
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seconds to 50 hours, preferably 2 minutes to 6 hours, preferably 1 minute to 4
hours. In another embodiment solvent or diluent is present in the reactor and
is
preferably selected from the group consisting of butanes, pentanes, hexanes,
heptanes, octanes, nonanes, decanes, undecanes, dodecanes, tridecanes,
tetradecanes, pentadecanes, hexadecanes, benzene, toluene, o-xylenes, m-
xylenes,
p-xylenes, ethylbenzene, isopropylbenzene, and n-butylbenzene, preferably
toluene and or xylenes and or ethylbenzene, NorparTM or IsoparTM solvent.
These
solvents or diluents may be pre-treated in same manners as the feed olefins.
[00113] Typically in the processes of this invention, one or more transition
metal compounds, one or more activators, and one or more feeds according to
the
present invention are contacted to produce polymer or oligomer. These
catalysts
may be supported and as such will be particularly useful in the known slurry,
solution, or bulk operating modes conducted in single, series, or parallel
reactors.
If the catalyst or activator or co-activator is a soluble compound, the
reaction can
be carried out in a solution mode. Even if one of the components is not
completely soluble in the reaction medium or in the feed solution, either at
the
beginning of the reaction or during or at the later stage of the reaction, a
solution
or slurry type operation is still applicable. In any case, the catalyst
components in
solvents, such as toluene or other conveniently available aromatic solvents,
or in
aliphatic solvent, or in the feed alpha-olefin stream are fed into the reactor
under
inert atmosphere (usually nitrogen or argon blanketed atmosphere) to allow the
reaction to take place. In this process, the feed alpha-olefins can be charged
individually or pre-mixed in a mixture, or one stream contains mixture of feed
olefins and another stream contains one olefin feed, such as in the case when
one
of the feed olefins is gaseous or liquefied gas propylene or 1-butene or mixed
butene stream. The reaction can be run in a batch mode where all the
components are added into a reactor and allowed to react to a pre-designed
degree
of conversion, either partial conversion or full conversion. Then the catalyst
is
deactivated by any possible means, such as exposure to air, water, or by
addition
of alcohols or solvents containing deactivator agents. The reaction can also
be
carried out in a semi-continuous operation, where feeds and catalyst
components
are continuously and simultaneously added to the reactor so to maintain a
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constant ratio of catalyst system and feed olefins. When all feeds and
catalyst
components are added, the reaction is allowed to proceed to a pre-determined
stage. Then the reaction is discontinued in the same manner as described in
the
batch operation. The reaction can also be carried out in a continuous
operation,
where feeds and catalyst are continuously and simultaneously added to the
reactor
so to maintain a constant ratio of catalyst system and feed olefins. The
reaction
product is continuously withdrawn from the reactor, as in a typical continuous
stirred tank reactor (CSTR) operation. The residence times of the reactants
are
controlled by a pre-determined degree of conversion. The withdrawn product is
then typically quenched in the separate reactor in a similar manner as other,
operation. In a preferred embodiment, any of the processes to prepare PAO's
described herein are continuous processes. Preferably the continuous process
comprises the steps of a) continuously introducing a feed stream comprising at
least 10 mole % of the one or more C3 to C24 alpha-olefins into a reactor, b)
continuously introducing the metallocene compound and the activator into the
reactor, and c) continuously withdrawing the polyalpha-olefin from the
reactor.
In another embodiment, the continuous process comprises the step of
maintaining
a partial pressure of hydrogen in the reactor of 200 psi (1379 kPa) or less,
based
upon the total pressure of the reactor, preferably 150 psi (1034 kPa) or less,
preferably 100 psi (690 kPa) or less, preferably 50 psi (345 kPa) or less,
preferably 25 psi (173 kPa) or less, preferably 10 psi (69 kPa) or less.
[001141 One or more reactors in series or in parallel may be used in the
present invention. The transition metal compound, activator and when required,
co-activator, may be delivered as a solution or slurry in a solvent or in the
alpha-
olefin feed stream, either separately to the reactor, activated in-line just
prior to
the reactor, or preactivated and pumped as an activated solution or slurry to
the
reactor. Polymerizations/oligomerizations are carried out in either single
reactor
operation, in which monomer, or several monomers, catalyst/activator/co-
activator, optional scavenger, and optional modifiers are added continuously
to a
single reactor or in series reactor operation, in which the above components
are
added to each of two or more reactors connected in series. The catalyst
components can be added to the first reactor in the series. The catalyst
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component may also be added to both reactors, with one component being added
to first reaction and another component to other reactors. In one preferred
embodiment, the precatalyst is activated in the reactor in the presence of
olefin.
In another embodiment, the precatalyst such as the dichloride form of the
metallocenes is pre-treated with alkylalumum reagents, especially,
triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum, followed by
charging into the reactor containing other catalyst component and the feed
olefins, or followed by pre-activation with the other catalyst component to
give
the fully activated catalyst, which is then fed into the reactor containing
feed
olefins. In another alternative, the pre-catalyst metallocene is mixed with
the
activator and/or the co-activator and this activated catalyst is then charged
into
reactor, together with feed olefin stream containing some scavenger or co-
activator. In another alternative, the whole or part of the co-activator is
pre-
mixed with the feed olefins and charged into the reactor at the same time as
the
other catalyst solution containing metallocene and activators and/or co-
activator.
The catalyst compositions can be used individually or can be mixed with other
known polymerization catalysts to prepare polymer or oligomer blends.
Monomer and catalyst selection allows polymer or oligomer blend preparation
under conditions analogous to those using individual catalysts. Polymers
having
increased MWD are available from polymers made with mixed catalyst systems
can thus be achieved.
[00115] Generally, when using metallocene catalysts, it is important to pre-
treat the feed components to remove any impurities in olefins, solvents, or
diluents or the inert gases (nitrogen or argon) used to blanket the reactor.
The
feed pre-treatment is usually conducted by passing the liquid or gaseous feed
stream over at least one bed of activated molecular sieves, such as 13X, 5A,
4A,
3A molecular sieve. Sometimes, two beds of the same or different molecular
sieves are used. Sometimes, a special oxygenate removal catalyst bed is also
employed. Such oxygenate removal catalysts include various reduced copper
oxide catalyst or reduced copper chromite catalyst. After careful pre-
treatment of
feed olefins, solvents, diluents and after careful precaution to keep the
catalyst
component stream(s) and reactor free of any impurities, as would be recognized
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by one of ordinary skill in the art, the reaction should proceed well. In a
preferred embodiment, particularly in the case where the metallocene catalyst
is
immobilized on a support, the complete catalyst system will additionally
comprise one or more scavenging compounds. Here, the term scavenging
compound means a compound that removes polar impurities from the reaction
environment. These impurities adversely affect catalyst activity and
stability.
Typically, purifying steps are used before introducing reaction components to
a
reaction vessel. But such steps will rarely allow polymerization or
oligomerization without using some scavenging compounds. Normally, the
polymerization process will still use at least small amounts of scavenging
compounds.
[00116] Typically, the scavenging compound will be an organometallic
compound such as the Group-13 organometallic compounds of U.S. Patents
5,153,157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132,
and that of WO 95/07941. Exemplary compounds include triethyl aluminum,
triethyl borane, tri-iso-butyl aluminum, diisobutylaluminum hydride, methyl
aluminoxane, iso-butyl aluminoxane, and tri-n-octyl aluminum. Those
scavenging compounds having bulky or C6-C20 linear hydrocarbyl substituents
connected to the metal or metalloid center usually minimize adverse
interaction
with the active catalyst. Examples include triethylaluminum, but more
preferably, bulky compounds such as tri-iso-butyl aluminum, tri-iso-prenyl
aluminum, and long-chain linear alkyl-substituted aluminum compounds, such as
tri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum. When
aluminoxane is used as the activator, any excess over that needed for
activation
will scavenge impurities and additional scavenging compounds may be
unnecessary. Aluminoxanes also may be added in scavenging quantities with
other activators, e.g., methylaluminoxane, [Me2HNPh]+[B(pfp)4]- or B(pfp)3,
where pfp is perfluorophenyl (C6F5) Me is methyl and Ph is phenyl.
[00117] The process according to the invention may also be accomplished
in a homogeneous solution processes. Generally this involves polymerization or
oligomerization in a continuous reactor in which the polymer formed and the
starting feed according to the invention and catalyst materials according to
the
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invention are agitated to reduce or avoid concentration or temperature
gradients.
Temperature control in the reactor is generally obtained by balancing the heat
of
polymerization and with reactor cooling by reactor jackets or cooling coils or
a
cooled side-stream of reactant to cool the contents of the reactor, auto
refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent,
monomers or solvent) or combinations of all the above methods. Adiabatic
reactors with pre-chilled feeds may also be used. The reactor temperature
depends on the catalyst used and the product desired. Higher temperatures tend
to give lower molecular weights and lower temperatures tend to give higher
molecular weights, however this is not a hard and fast rule. In general, the
reactor temperature preferably can vary between about 0 C and about 300 C,
more preferably from about 10 C to about 250 C, and most preferably from
about 25 C to about 230 C. Usually, it is important to control the reaction
temperature as pre-determined. In order to produce fluids with narrow
molecular
distribution, such as to promote the highest possible shear stability, it is
useful to
control the reaction temperature to obtain minimum of temperature fluctuation
in
the reactor or over the course of the reaction time. If multiple reactors are
used in
series or in parallel, it is useful to keep the temperature constant in a pre-
determined value to minimize any broadening of molecular weight distribution.
In order to produce fluids with broad molecular weight distribution, one can
adjust the reaction temperature swing or fluctuation, or as in series
operation, the
second reactor temperature is preferably higher than the first reactor
temperature.
In parallel reactor operation, the temperatures of the two reactors are
independent.
Or one can use two types of metallocene catalysts.
[00118] While reaction conditions may generally be determined by one of
ordinary skill in the art in possession of the present disclosure, typical
conditions
will now be discussed.
[00119] The pressure in any reactor used herein can vary typically from
about 0.1 atmosphere to 100 atmosphere (1.5 psi to 1500 psi), preferably from
0.5
bar to 75 atm (8 psi-1125 psi), most preferably from 1.0 to 50 atm (15 psi to
750
psi). The reaction pressure is usually higher than atmospheric pressure when
light olefins with high vapor pressures, such as propylene or butenes, are
used as
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one of the feed olefins. The reaction can be carried out under the atmosphere
of
nitrogen or with some hydrogen. Sometimes a small amount of hydrogen is
added to the reactor to improve the catalyst productivity. The amount of
hydrogen is preferred to keep at such a level to improve catalyst
productivity, but
not induce any hydrogenation of olefins, especially the feed alpha-olefins
because
the conversion of alpha-olefins into saturated paraffins is very detrimental
to the
efficiency of the process. The amount of hydrogen partial pressure is
preferred to
be kept low, less than 100 psi, preferably less than 50 psi, preferably less
than 25
psi, preferably less than 10psi, preferably less than 5 psi, preferably less
than 1
psi. In a particularly preferred embodiment in any of the process described
herein
the concentration of hydrogen in the reactant phase is less than 100 ppm,
preferably less than 50 ppm, preferably less than 10 ppm, preferably less than
1
ppm. In a particularly preferred embodiment in any of the process described
herein the concentration of hydrogen in the reactor is kept at a partial
pressure of
200 psi (1379 kPa) or less, based upon the total pressure of the reactor,
preferably
150 psi (1034 kPa) or less, preferably 100 psi (690 kPa) or less, preferably
50 psi
(345 kPa) or less, preferably 10 psi (69 kPa) or less.
[00120] The reaction time or reactor residence time is usually dependent on
the type of catalyst used, the amount of catalyst system used, and the desired
conversion level. Different metallocenes have different activity. Usually,
higher
degree of alkyl substitution on the cyclopentadienyl ring, or bridging
improves
catalyst productivity. Catalysts such as 1,2,3,4-
tetramethylcyclopentadienylzirconium dichloride or 1,2,4-tri
methylcyclopentadienylzirconium dichloride, or pentamethylcyclopentadienyl
zirconium dichloride or their dialkyl analogs have desirable high productivity
and
stability than unsubstituted metallocenes. Certain bridged and bridged with
substitution catalysts, such as the di-halides or dialkyls of
dimethylsilylbis[cyclopentadienyl] zirconium,
dimethylsilylbis[indenyl]zirconium
or dimethylsilylbis[tetrahydro-indenyl]zirconium, dimethylsilylbis[1-
methylindenyl] zirconium, ethylidenebis[indenyl]zirconium,
ethylidenebis[tetrahydroindenyl]zirconium, ethylidenebis[ 1-
methylindenyl]zirconium, or their hafnium analogs, etc. Usually the amount of
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catalyst components used is determinative. A high catalyst loading tends to
gives
high conversion at short reaction time. However, high catalyst usage makes the
production process uneconomical and difficult to manage the reaction heat or
to
control the reaction temperature. Therefore, it is useful to choose a catalyst
with
maximum catalyst productivity to minimize the amount of metallocene and the
amount of activators needed. When the catalyst system is metallocene plus
methylaluminoxane, the range of methylaluminoxane used is typically in the
range of 0.01 milligram (mg) to 500 mg/g of alpha-olefin feed. A more
preferred
range is from 0.02 mg to 10 mg/g of alpha-olefin feed. Furthermore, the molar
ratios of the aluminum to metallocene (Al/M molar ration) range from 2 to
4000,
preferably 10 to 2000, more preferably 50 to 1000, and most preferably 100 to
500. When the catalyst system is metallocene plus a Lewis acid or an ionic
promoter with NCA component, the metallocene use is typically in the range of
0.01 microgram to 500 micrograms of metallocene component/gram of alpha-
olefin feed. Usually the preferred range is from 0.1 microgram to 100
microgram
of metallocene component per gram of alpha-olefin feed. Furthermore, the molar
ratio of the NCA activator to metallocene is in the range from 0.1 to 10,
preferably 0.5 to 5, more preferably 0.5 to 3. If a co-activator of
alkylaluminum
compound is used, the molar ratio of the Al to metallocene is in the range
from 1
to 1000, preferably 2 to 500, more preferably 4 to 400, even more preferably 4
to
100, or most preferably 10 to 50.
[001211 Typically, the highest possible conversion (close to 100%) of feed
alpha-olefin in the shortest possible reaction time is preferred. However, in
CSTR operation, it is sometimes optimal to run the reaction at slightly less
than
100% conversion. There are also occasions when partial conversion is more
desirable, namely when the narrowest possible MWD of the product is desirable
because partial conversion can avoid a MWD broadening effect. Typically, the
conversions of the total feed olefins are in the range of 20% to 100%, more
desirably in the range of 50% to 100%, and most desirably in the range of 80
to
99%. If the reaction is conducted to less than 100% conversion of the alpha-
olefin, the unreacted starting material after separation from other product
and
solvents/diluents can be recycled to increase the total process efficiency.
When
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the catalyst system is metallocene and MAO, the catalyst productivity is
usually
in the range of 20 to 50,000 gram total product per gram of MAO, preferably
greater than 100 gram total product per gram of MAO, most preferably greater
than 500 gram total product per gram of MAO.. When the catalyst is metallocene
and a Lewis acid or an ionic promoter with NCA component, the catalyst
productivity is typically 1000 to 10,000,000 gram total product per gram of
metallocene catalyst, preferably 10,000 gram, more preferably 50,000 gram of
total product per gram of metallocene catalyst. The catalyst productivity is
in the
same range for grams of total product per grams of Lewis acid or ionic
promoter
with NCA component.
[00122] Desirable residence times for any process described herein may
likewise be determined by one of ordinary skill in the art in possession of
the
present disclosure, and will typically range from 1 minute to 20 hours, or
more
typically 5 minutes to 10 hours.
[00123] Each of these processes may also be employed in single reactor,
parallel or series reactor configurations. The liquid processes comprise
contacting olefin monomers with the above described catalyst system,
preferably
in a suitable diluent, solvent, recycle, or mixture thereof, and allowing the
reaction to occur for a sufficient time to produce the desired polymers or
oligomers. Hydrocarbon solvents both aliphatic and aromatic are suitable.
Aromatics such as benzene, toluene, xylenes, etylbenzene, propylbenzene,
cumene, t-butylbenzene are suitable. Alkanes, such as hexane, heptane,
pentane,
isopentane, and octane, NorparTM fluids or IsoparTM fluids from ExxonMobil
Chemical Company in Houston, Texas are also suitable. Generally, toluene is
most suitable to dissolve catalyst components. Norpar fluids or Isopar fluids
or
hexanes (or mixtures thereof) are preferred as reaction diluents. Oftentimes,
a
mixture of toluene and Norpar fluids or Isopar fluids is used as diluent or
solvent.
[00124] The process can be carried out in a continuous stirred tank reactor,
batch reactor, or plug flow reactor, or more than one reactor operated in
series or
parallel. These reactors may have or may not have internal cooling and the
monomer feed may or may not be refrigerated. See, for instance, U.S. patent
5,705,577 for typical process conditions.
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[00125] When a solid supported catalyst is used for the conversion, a slurry
polymerization/oligomerization process generally operates in the similar
temperature, pressure and residence time range as described previously. In a
slurry polymerization or oligomerization, a suspension of solid catalyst,
promoters, monomer and comonomers are added. The suspension including
diluent is intermittently or continuously removed from the reactor. The
catalyst is
then separated from the product by filtration, centrifugation, or settlement.
The
fluid is then distilled to remove solvent, any unreacted components, and light
product. A portion or all of the solvent and unreacted component or light
components can be recycled for reuse.
[00126] If the catalyst used is un-supported, solution catalyst, when the
reaction is complete as in the batch mode, or when the product is withdrawn
from
the reactor as in a CSTR, the product may still contain soluble or suspended
catalyst components. These components are preferably deactivated and/or
removed. Any of the usual catalyst deactivation methods or aqueous wash
methods can be used to remove the catalyst component. Typically, the reaction
is
deactivated by addition of stoichiometric amount or excess of air, moisture,
alcohol, isopropanol, etc. The mixture is then washed with dilute sodium
hydroxide or with water to remove catalyst components. The residual organic
layer is then subjected to distillation to remove solvent, which can be
recycled for
reuse. The distillation can further remove any light reaction product from C18
and
less. These light components can be used as diluent for further reaction. Or
they
can be used as olefmic raw material for other chemical synthesis, as these
light
olefin product have vinylidene unsaturation, most suitable for further
functionalization to convert in high performance fluids. Or these light olefin
products can be hydrogenated to be used as high quality paraffinic solvents.
[00127] Polymerization or oligomerization in absence of hydrogen is also
advantageous to provide polymers or oligomers with high degree of unsaturated
double bonds. These double bonds can be easily converted into functionalized
fluids with multiple performance features. Examples for converting these
polymers with molecular weight greater than 300 can be found in the
preparation
of ashless dispersants, by reacting the polymers with maleic anhydride to give
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PAO-succinic anhydride which can then reacted with amines, alcohols, polyether
alcohols to convert into dispersants. Examples for such conversion can be
found
in the book "Lubricant Additives: Chemistry and Application," ed. by Leslie R.
Rudnick, p. 143-170.
[00128] 'In a typical process to produce high performance fluids from mixed
LAO over metallocene catalyst system, the polymerization step usually produces
some light ends with less than C24 carbons. The amount of the light fraction
usually depends on the reaction temperature, catalyst used, residence time,
and
the desired fluid viscosity or molecular weight. Usually, a lower viscosity
process produces higher amount of light fraction and high viscosity (>10 cSt)
process produces almost exclusively >C24 fraction, with little or no light
fractions.
For example, the light fraction can range from 0.1 wt% to 30 wt% of total
product
for a 150 cSt fluid to 6 cSt fluid, respectively, from mixed LAO. It is
usually
more desirable to produce the least amount of light fraction. The amount of
light
fraction can be minimized by careful control of the process temperature,
residence time, stable and homogeneous catalyst, etc.
[00129] Polymerization can also be carried out in the presence of hydrogen.
The advantages of polymerization in the presence of H2 are increased catalyst
productivity and reduced degree of unsaturation, which under proper conditions
can be so low that no further hydrogenation step is needed. When the reaction
is
carried out in the presence of hydrogen, hydrogen pressure is advantageously
kept low to achieve highest productivity. High hydrogen pressure will have the
disadvantage of hydrogenating the alpha-olefins into alkanes, thus reducing
the
total product yields. Typically, hydrogen partial pressure should be kept
below
200 psi, preferably below 50 psi more preferably below 30 psi or most
preferably
below 20 psi. In a static, batch operation, the molar ratio of olefins to
hydrogen is
advantageously kept below 5, preferably below 10, more preferably below 20, or
most preferably below 50. One of ordinary skill in the art in possession of
the
present disclosure can determine the appropriate hydrogen level without more
than routine experimentation.
[00130] The polyalpha-olefins produced from the above polymerization
process using a mixed alpha-olefins as feed contain unsaturated double bond,
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sometimes rich in vinylidene contents with some 1,2-disubstituted olefins.
These
unsaturated polymers are most suitable for further functionalization reaction.
Examples of such functionalization are alkylation with aromatics compounds,
such as benzene, toluene, xylene, naphthalene, phenol or alkylphenols. The
polymer olefins can also react with maleic anhydride to give polyalpha-olefin
succinic anhydride, which can be further converted with amines or alcohols to
corresponding succinimide or succinate esters. These imides and esters are
superior dispersants. Because of the use of PAO as the hydrocarbon moiety, the
finished dispersant will have much better viscometrics than the conventional
dispersants made from polyisobutylene.
[00131] In an embodiment, the product of the process according to the
invention, comprising polyalpha-olefins, is hydrogenated. In particular the
polyalpha-olefin product is preferably treated to reduce heteroatom catalyst
components to less than 600 ppm, and then contacted with hydrogen and a
hydrogenation catalyst to produce a polyalpha-olefin having a bromine number
less than 1.8. Usually, the bromine number is below 1.8. Lower bromine number
is more desirable, as it indicates an improved thermal/oxidative stability. In
a
preferred embodiment, the treated polyalpha-olefin comprises 100 ppm of
heteroatom catalyst components or less, preferably 10 ppm of heteroatom
catalyst
components or less. Preferably the hydrogenation catalyst is selected from the
group consisting of supported Group 7, 8, 9, and 10 metals, preferably the
hydrogenation catalyst selected from the group consisting of one or more of
Ni,
Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo, and W, supported on silica, alumina, clay,
titania, zirconia, or mixed metal oxide supports. A preferred hydrogenation
catalyst is nickel supported on kieselguhr, or platinum or palladium supported
on
alumina, or cobalt-molydenum supported on alumina. Usually, a high nickel
content catalyst, such as 60% Ni on Keiselguhr catalyst is used, or a
supported
catalyst with high amount of Co-Mo loading.
[00132] In a preferred embodiment the polyalpha-olefin product is
contacted with hydrogen and a hydrogenation catalyst at a temperature from 25
to
350 C, preferably 100 to 300 C. In another preferred embodiment the polyalpha-
olefin is contacted with hydrogen and a hydrogenation catalyst for a time
period
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from 5 minutes to 100 hours, preferably from 5 minutes to 24 hours. In another
preferred embodiment the polyalpha-olefin is contacted with hydrogen and a
hydrogenation catalyst at a hydrogen pressure of from 25 psi to 2500 psi,
preferably from 100 to 2000 psi. In another preferred embodiment the
hydrogenation process reduces the number of mm triad groups in a polyalpha-
olefin by 1 to 80 %. Hydrogenation of PAO's per se is well-known. See, for
instance, U.S. 5,573,657 and "Lubricant Base Oil Hydrogen Refining Processes"
(page 119 to 152) in Lubricant Base Oil and Wax Processing, by Avilino
Sequeira, Jr., Marcel Dekker, Inc., NY, 1994.
[00133] The hydrogenation process can be accomplished in a slurry reactor
in a batch operation or in a continuous stirred tank reactor (CSTR), where the
catalyst concentration is 0.001 wt% to 20 wt% of the PAO (or HVI-PAO)
product, or preferably 0.01 to 10 wt% of the product. Hydrogen and feed are
added continuously to the reactor to allow for a certain residence time,
usually 5
minutes to 10 hours, to allow complete hydrogenation of the unsaturated
olefins
and to allow proper conversion. The amount of catalyst added is usually in
slight
excess, to compensate for the catalyst deactivation. The catalyst and
hydrogenated PAO and/or HVI-PAO are continuously withdrawn from the
reactor. The product mixture was then filtered, centrifuged or settled to
remove
the solid hydrogenation catalyst. The catalyst can be regenerated and reused.
The hydrogenated PAO can be used as is or further distilled or fractionated to
the
right component if necessary. In some cases, when the hydrogenation catalyst
show no catalyst deactivation over long term operation, the stir tank
hydrogenation process can be carried out in a manner where a fixed amount of
catalyst is maintained in the reactor, usually 0.1 wt% to 10% of the total
reactant,
and only hydrogen and PAO feed are continuously added at certain feed rate and
only hydrogenated PAO was withdrawn from the reactor.
[00134] The hydrogenation process can also be accomplished by a fixed
bed process, in which the solid catalyst is packed inside a tubular reactor
and
heated to reactor temperature. Hydrogen and PAO and/or HVI-PAO feed can be
fed through the reactor simultaneously from the top or bottom or
countercurrently
to maximize the contact between hydrogen, PAO/HVI-PAO and catalyst, and to
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allow best heat management. The feed rate of the PAO and hydrogen are
adjusted to give proper residence to allow complete hydrogenation of the
unsaturated olefins in the feed and to allow desirable conversion of mm triads
in
the process. The hydrogenated PAO fluid can be used as is or further distilled
or
fractionated to give the right component, if necessary.
[00135] Polymer Product Composition.
[00136] This invention provides a liquid polyalpha-olefin composition
which in embodiments may be characterized as comprising at least two types of
branches with average branch length of at least 2.1, ranging from 2.1 to 12,
preferably 3 to 11, more preferably 4 to 10, more preferably 4.5 to 9.5, more
preferably 5 to 9, more preferably 5.5 to 8.5, more preferably 6 to 8, and
most
preferably 7 to 8. The product is a liquid. For the purposes of this
invention, a
"liquid" is defined to be a fluid that has no distinct melting point above 0
C,
preferably no distinct melting point above -20 C, and has a kinematic
viscosity at
100 C of 3000 cSt or less, preferably 1000 cSt or less and/or a kinematic
viscosity at 40 C of 35,000 cSt or less, preferably 10,000 cSt or less.
[00137] The polymers may be further characterized as having a random
monomer distribution along the polymer backbone. This randomness can be
characterized by either nuclear magnetic resonance spectroscopy (NMR) or mass
spectrometry (MS) methods or by gas chromotagraphic (GC) analysis of light
oligomer fractions.
[00138] In MS, the degree of randomness (x) is defined as the sum of
Markovian P-matrix elements, x=PAB + PBA, where A and B are comonomers or
combination of comonomers (see reference Mass Spectrometry of Polymers,
edited by G. Montaudo and R. P. Lattimer, CRC Press, Boca Raton, Fl, 2002,
Chapter 2, p. 72 to 85). For an ideal random copolymer x=1. X for this
inventive
polymer is usually between 0.7 to 1.4, preferably between 0.8 to 1.2,
preferably
between 0.9 and 1.1. The MS method is carried out as following. MS technique
is
based on a combination of field desorption mass spectrometry (FDMS) and
Markovian statistics. In FDMS, samples are dissolved in methylene chloride
with
0.1 to 10% (w/v) concentration. 1 to 5 l of the solution is deposited on to
the FD
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emitter. The emitter was inserted into the ion source of a mass spectrometer
in 10-
to 10-6 torn vacuum. A high electric voltage (10 to 13 kV) is applied between
the
emitter and a pair of extraction rod. A high field strength of 107 to 108 v/cm
can
be reached. One or more electrons were removed from the molecules via a
quantum tunneling effect. Vibration excitation is minimal and thus intact
molecular ions are formed, generating molecular ion mass spectra for the PAO
oligomers. Markovian statistics were developed to calculate PAO oligomer
distributions based on transition probability matrix (P-matrix). A theoretical
mass
spectrum was determined by summation of all oligomer distribution and was
compared against the experimental mass spectrum in the molecular weight range
between 10 to 10,000 g/mol, preferably between 100 to 5000 g/mol, preferably
between 400 and 1000 g/mol . The P-matrix was adjusted in an iterative process
to minimize the differences between the theoretical and experimental mass
spectral data. The product composition and structure (degree of randomness)
can
then be calculated from the optimized P-matrix elements. Other parameters such
as run length and feed reactivity ratio can also be deduced from the Markovian
statistics. For product described in this invention, zero order Markovian (or
Bernoullian random) distribution showed the best fit with experimental data
with
x ranges from 0.93 to 1.05.
[00139] The NMR method to characterize the material is described below.
Typically, proton NMR spectroscopy - because of its intrinsically limited
spectral
dispersion - provides decreasing utility for determining the composition of
the
polymers as the lengths of the comonomers increase. The greater resolution in
the
carbon spectra often provides multiple opportunities for determining the
monomer composition. For example, in polymerizations of 1-butene with
comonomers longer than or equal to C10, we calculated the composition in two
ways: the lB2 (10.7 ppm) and 1B3+ (14.1 ppm) methyl resonances, and the
backbone S methylenes between the branches. The methyl integral calculation
is a direct measurement from the peak integrals, and may suffer from endgroup
errors (e.g. initiating butenes would appear in the comonomer region). The S""
methylene region (41-39 ppm), while also susceptible to end group effects in
low
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molecular weight materials, shows three S methylene peaks that were assigned
to the C,,-C,,, Cn C4, and C4-C4 structures. The integrals of the three peaks
were
fit by least squares minimization to a Bernoullian model for monomer addition.
The Bernoullian model defines the likelihood of finding a specific monomer at
any position in the chain as proportional to the overall molar concentration
of that
monomer and independent of the identity of neighboring monomers. The
excellent fit of the S methylene peak areas with Bernoullian distribution
indicates very little deviation from random monomer addition. The adjustable
parameter for the fits is the mole-percentage C4, which can be converted to a
weight-percentage. The fitting process is carried out by normalizing the sum
of
the S methylene integrals to 1Ø Least squares minimization seeks to minimize
the square root of the sum of the squares (Diff) of the differences between
the
experimental dyad mole fractions (e.g. [AA]exp) and the mole fractions
predicted
by the Bernoullian model (e.g. [AA]Bem), where the two comonomers in the
polymer are A and B. The formula for Diff is given below.
Diff = ([AA]exp -[AA]Bern)2 +([AB+BA]exp -[AB+BA]Berõ)2 +([BB]ex, -[BB]Bern)2
[00140] In cases where multiple LAOs are used, and signals from longer
LAO's are not resolved, analysis can be performed with the non-resolved
monomers lumped into an aggregate A and/or an aggregate B monomer,
depending on where their resonances appear. The minimized Diff will then
address the randomness of aggregate A versus aggregate B.
[00141] When the feed composition contains more than two alpha-olefins,
the analytical method and mathematics to analyze the data become very complex
for both the NMR method and the MS method. In this case, one may consider
analyzing the polymer compositional randomness by lumping the feed olefins
into two groups with averaged properties to simplify the compositional
analysis.
The conclusion should be within the scope of the two component analysis.
Another method to deduce the randomness of the polymer composition is to
analyze the rates of consumption of the starting alpha-olefins during
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polymerization. The relative ratio of the fastest reacting monomer should not
be
more than 5 times faster than the slowest reacting monomer. A more preferred
ratio is less than 3, and the most preferred ratio is less than 2. As a ratio
of 1
usually indicates a random copolymer, another possible method for deducing the
randomness of the polymer composition is to calculate the ratio of the amount
of
one alpha-olefin in the product to the same alpha-olefin in the feed For the
polymers in the present invention, this ratio is within 0.5 to 3, and
preferably 0.8
to 2, with the ratio of 1 as a completely random polymer.
[00142] The gas chromatographic (GC) method can also be extended to
analyzing the whole or partial polymer composition using an internal standard
method. The gas chromatograph is a HP model equipped with a 60 meter DB1
capillary column. A 1 microliter sample was injected into the column at 70 C,
held for 0 minutes, program-heated at 10 C per minute to 300 C and held for 15
minutes. The content of the dimer, trimer, tetramer of total carbon numbers
less
than 50 can be analyzed quantitatively using the gc method. The distribution
of
the composition from dimer, trimer and tetramer and/or pentamer can be fit to
a
Bernoullian distribution and the randomness can be calculated from the
difference between the GC analysis and best fit calculation.
[00143] In another embodiment, any of the polyalpha-olefins described
herein have an MW (weight average molecular weight) of 100,000 or less,
preferably between 200 and 80,000, more preferably between 250 and 60,000,
more preferably between 280 and 50,000, and most preferably between 336 and
40,000 g/mol. (Preferred M, 's include those from 224 to 55,100, preferably
from
392 to 30,000, more preferably 800 to 24,000, and most preferably 2,000 to
37,5000 g/mol. Alternately preferred M, 's include 224 to about 6790, and
preferably 224 to about 2720).
[00144] In another embodiment, any of the alpha-olefins described herein
preferably have a number average molecular weight (Mn) of 50,000 or less, more
preferably between 200 and 40,000, more preferably between 250 and 30,000, or
most preferably between 500 and 20,000 g/mol. More preferred Mn ranges
include 280 to 10,000, 280 to 4,000, 200 to 20,900, 280 to 10,000, 200 to
7000,
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200 to 2000, 280 to 2900, 280 to 1700, and 200 to 500.
[00145] In another embodiment, any of the polyalpha-olefins described
herein preferably have an M,,,/Mõ or molecular weight dispersity (MWD) of
greater than 1 and less than 5, preferably less than 4, more preferably less
than 3,
more preferably less than 2.5, and most preferably less than 2.
[00146] The MW and Mõ are measured by GPC method using polystyrene as
calibration standard. The Mõ is correlated with the fluid viscosity according
to a
power equation Mõ = A x (V)B, where V is kinematic viscosity measured at
100 C according to the ASTM D 445 method, A and B are constants which vary
slightly depending on the type of olefin feeds. For example, when a set PAO
made from a mixed feed of 33 wt% C6 and 67 wt% C12 LAOs was analyzed by
GPC, the relationship of Mõ versus 100 C viscosity was as follows: Mõ = 344.96
x )0.4921
[00147] In a preferred embodiment of this invention, any PAO described
herein may have a pour point of less than 10 C (as measured by ASTM D 97).
Pour point of any fluid is usually a function of fluid viscosity. Within a
class of
fluids, usually high viscosity fluids have high pour points, and low viscosity
fluids have low pour points. The pour point of the PAOs of this invention have
pour points of less than 10 C, preferably less than 0 C, more preferably less
than
-10 C, more preferably less than -20 C, more preferably less than -25 C,
more
preferably less than -30 C, more preferably less than -35 C, more preferably
less
than -50 C, and most preferably less than -70 C.
[00148] In a preferred embodiment of this invention, any PAO
described herein may have a kinematic viscosity at 40 C from about 4 to about
80,000 centi-Stokes (cSt) as measured by ASTM D 445 method, preferably from
about 5 cSt to about 50,000 cSt at 40 C.
[00149] In another embodiment according to the present invention,
any polyalpha-olefin described herein may have a kinematic viscosity at 100 C
from about 1.5 to about 5,000 centi-Stokes (cSt), preferably from about 2 cSt
to
about 3,000 cSt, more preferably from about 3 cSt to about 1,000 cSt, and yet
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more preferably from about 8 cSt to about 500 cSt. The PAOs have viscosities
in
the range of 2 to 500 cSt at 100 C in one embodiment, and from 2 to 3000 cSt
at
100 C in another embodiment, and from 3.2 to 300 cS in another embodiment.
(All viscosities are measured by ASTM D 445 method at 100 C, except when
specified at other temperatures.).
[00150] In another embodiment according to the present invention any
polyalpha-olefin described herein may have a kinematic viscosity at 100 C from
3 to 10 cSt and a flash point of 130 C or more (as measured by the ASTM D 92
method).
[00151] The PAOs prepared herein, particularly those of low viscosity
(such as those with a KVioo of 10 cSt or less), are especially suitable as
base
stocks for high performance automotive engine oil formulation by themselves or
by blending with other fluids, such as Group 1, II, Group II+, Group III,
Group
III+ (Note: Group II+ and Group III+ are names often used in trade journals,
and
thus known to one of ordinary skill in the art; they usually denote base
stocks that
have properties better than Gr II or III, but can not fully meet the next
level of
specification; as used herein, each of the per se well know API
classifications I
through V will include their "+" basestock, if available, unless the "+"
basestock
is specifically recited; in the claims the "+" form is considered part of the
API
group denoted), or lube base stocks derived from hydroisomerization of wax
fraction from Fischer-Tropsch hydrocarbon synthesis from CO/H2 syn gas, or
other Group IV or Group V base stocks. PAOs having KVioo s from 3 cSt to 8
cSt are also preferred grades for high performance automotive engine oil or
industrial oil formulations. The PAOs of 40 to 1000 cSt made in this invention
and especially some high KVio0 grades up to 5000 cSt are specially desirable
for
use as blend stock with Gr 1, II, III, III+, IV, V, or GTL derived Tube base
stocks
for use in industrial and automotive engine or gear oil. They are also
suitable for
use in personal care application, such as blends with soap, detergents, other
emollients, for use in personal care cream, lotion, sticks, shampoo,
detergents,
etc. In another embodiment the PAOs have KVioo s ranging from about 10 to
about 3045 cSt. In another embodiment the PAOs have KVloo's ranging from
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about 20 to about 1500 cSt.
[00152] In another embodiment according to the present invention any
polyalpha-olefin described herein may have a viscosity index (VI) of from 80
to
400, alternatively from 100 to 380, alternatively from 100 to 300,
alternatively
from 140 to 380, alternatively from 180 to 306, alternatively from 252 to 306,
alternatively the viscosity index is at least about 165, alternatively at
least about
187, alternatively at least about 200, alternatively at least about 252. VI
usually
is a function of fluid viscosity. For many lower viscosity (KVioo of 3 to 10
cSt)
fluids made from 1-decene equivalent feeds, the preferred VI range is from 100
to
180. Other embodiments include ranges from 140 to 380, 120 to 380, and 100-
400. Higher viscosity fluid usually have higher VI. Viscosity index is
determined according to ASTM Method D 2270-93 [1998] and the VI is related
to kinematic viscosities measured at 40 C and 100 C using ASTM Method D 445
method. All kinematic viscosity values reported for fluids herein are measured
at
100 C unless otherwise noted. Dynamic viscosity can then be obtained by
multiplying the measured kinematic viscosity by the density of the liquid. The
units for kinematic viscosity are m2/s, commonly converted to cSt. or
centistokes
(1cSt. =10-6 m2/s or 1 cSt = 1 mm2/sec). Lube VI and pour point are dependent
on lube viscosity. For the most valid comparison of VI and pour point, it is
best
to compare fluids with similar viscosities at the same temperature.
[00153] One embodiment according to the present invention is a new class
of polyalpha-olefins having a unique chemical composition which is
characterized by a high percentage of unique tail-to-tail connections at the
end
position of the polymer. The new poly-alpha-olefins after hydrogenation, when
used by themselves or blended with another fluid, have unique lubrication
properties. Or these new poly-alpha-olefins without hydrogenation can be
further
functionalized at the unsaturation position with other reagents, such as
aromatics,
maleic anhydride, etc. The term "tail-to-tail connection" refers to a
connection
formed in the PAO oligomer in which the linear alpha-olefins incorporated into
an oligomer are connected to one another via the alpha carbon, i.e., the
methylene
vinyl carbon of a linear alpha-olefin. The polyalpha-olefins synthesized from
the
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polymerization reaction contain unsaturation, which can be conveniently
measured by bromine number (ASTM D 1159 or equivalent method) or NMIR
methods. Typically the bromine number will change as a function of the polymer
molecular size or viscosity. The bromine number for the polymer will range
from
70 to 0. When the bromine number is below 1 or 2, the product can be used as
is,
without further hydrogenation. In many cases, when there is a need to reduce
to
bromine number to below 2, or to below 0.3, or to tailor the tacticity of the
polymer, the polymers are then further hydrogenated with a hydrogenation
catalyst and a high pressure of hydrogen gas to reduce the unsaturation to
give
product with a bromine number less than 0.3
[00154] Another embodiment according to the present invention is a new
class of hydrogenated polyalpha-olefins having a unique chemical composition
which is characterized by a high percentage of unique tail-to-tail connection
at
the end position of the polymer and by a reduced degree of isotacticity
compared
to the product before hydrogenation.
[00155] The PAOs produced according to this invention are typically
dimer, trimer, tetramer or higher oligomers of any two monomers from C3 to C30
linear alpha-olefins. Alternatively, an alpha-olefin with alkyl substituent at
least
2 carbons away from the olefinic double bond, such as 4-methyl-l-pentene, can
also be used or alpha-olefins containing aromatic substituents two carbons
away
from the olefins. Examples are 4-phenyl-l-butene or 6-phenyl-l-hexene, etc.
Typically the PAOs produced herein are usually a mixture of many different
oligomers. The smallest oligomers from these alpha-olefins have carbon numbers
ranging from C6 to C20. These small oligomers are usually too light for most
high
performance fluids application. They are usually separated from the higher
oligomers with carbon number of greater than C20 (for example C24 and higher
are more preferred as high performance fluids). These separated C10 to C20
oligomer olefins or the corresponding paraffins after hydrogenation can be
used
in specialty applications, such as drilling fluids, solvents, paint thinner,
etc., with
excellent biodegradability, toxicity, viscosities, etc. The fraction of C20 to
C60, or
preferably C24 to C50, or more preferably C28 to C45, or most preferably C30
to C40
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can be used as high performance fluids. Typically, they have superior
performance attributes, making them beneficial for specific applications: such
as
lower viscosity for better fuel economy, better biodegradability, better low
temperature flow properties, or lower volatility.
[00156] The higher viscosity products usually have much higher average
degree of polymerization, and have very low amounts of C24 and lower
components. These high viscosity fluids are excellent blend stocks for lube
application to improve the viscosity. Because of their usually narrow
molecular
weight distribution, they have superior shear stability. Because of their
unique
chemical composition, they have excellent viscometrics and unexpected low
traction properties. These higher viscosity PAOs can be used as superior blend
stocks. They, can be blend stocks with any of the Group 1, 11, 111, 111+, GTL
and
Group V fluids, to give optimum viscometrics, solvency, high- and low-
temperature lubricity, etc. When further blended with proper additives,
including
antioxidants, antiwear additives, friction modifiers, dispersants, detergents,
corrosion inhibitors, defoamants, extreme pressure additives, seal swell
additives,
and optionally viscosity modifiers, etc., the finished formulated lubes can be
used
as automotive engine oils, gear oils, industrial oils, or grease. Description
of
typical additives and synthetic lubricants can be found in the book "Lubricant
Additives" Chemistry and Applications, ed. L. R. Rudnick, Marcel Dekker, Inc.,
New York, 2003, and Synthetic Lubricants and High-Performance Functional
Fluids, 2d ed. By L R. Rudnick and R. L. Shubkin, Marcel Dekker, Inc., New
York, 1999.
[00157] Experimental
[00158] The following examples are meant to illustrate the present
invention and provide a comparison with other methods and the products
produced therefrom. Numerous modifications and variations are possible and it
is to be understood that within the scope of the appended claims, the
invention
may be practiced otherwise than as specifically described herein.
[00159] The alpha-olefins used for all the experiments, either individually or
pre-mixed, were purified by mixing 1 liter of un-treated raw material with 20
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grams of activated 13X molecular sieve and 10 grams of de-oxygenation catalyst
(a reduced copper catalyst) for at least two days inside a glove box. The
molecular sieve and de-ox catalyst were then removed by filtration. This
treated
individual alpha-olefins were than combined to give the desirable composition.
Similarly, this purification can be carried out by pumping a stream of the
alpha-
olefins, either alone or pre-mixed, through a bed of activated 13X molecular
sieve
alone, or through a bed of activated 13X molecular siever followed by a bed of
de-oxygenated catalyst, prior to entering reactor. Sometimes for convenience,
this purification can be carried out by pumping a stream of the alpha-olefins,
either alone or pre-mixed, through a bed of activated 13X molecular sieve
followed by a bed of activated alumina, prior to entering the reactor.
[00160] To test the flowability of the fluid after it is subjected to low
temperature, a test was developed wherein a 10-30 ml liquid sample of polymer
was soaked in crushed dry ice for at least two hours, followed by a slow
warming
to room temperature. Some materials may remain solid even after warming to
room temperature, whereas others will become free-flowing liquids after warm-
up to room temperature. This test is reproducible and provides a convenient
method for comparing low-temperature behavior of the fluids.
[00161] Example 1. An olefin mixture containing 18.4% 1-hexene, 22.3% 1-
octene, 21.6% 1-decene, 16.8% 1-dodecene, 10.4% 1-tetradecene, 6.4% 1-
hexadecene and 4% 1-octadecene was used as feed. This composition is similar
to the linear alpha-olefins produced from a typical LAO plant. 30 grams of
this
olefin mixture and 0.522 gram of a toluene solution containing 20 mg of
triisobutylaluminum (TIBA)/g of toluene were charged into a reactor. A
catalyst
solution containing 11 grams toluene, 0.0133 grams TIBA stock solution,
0.30798 mg rac-dimethylsilylbis(tetrahydroindenyl) zirconium dichloride (A)
and
0.5408 mg N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (B) was
added to the reactor with stirring while maintaining a temperature of 30 C.
After
19 hours reaction time, the reaction was terminated by addition of 3 ml
isopropanol, followed by washing with 120 ml 5% sodium hydroxide solution in
water. The isolated organic layer was distilled at 160 C/i millitorr vacuum
for
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two hours to remove light ends and to isolate the lube fraction. The total
lube
yield was 85%. The recovered lube properties are summarized in Table 1.
[00162] Example 2. Similar to Example 1, except a metallocene containing
70% meso- and 30% racemic-dimethylsilylbis(tetrahydroindenyl) zirconium
dichloride (C) was used in the preparation.
[00163] Example 3. Similar to Example 1, except the reaction was carried out
at 60 C.
[00164] Example 4. Similar to Example 2, except the reaction was carried out
at 60 C.
[00165] Example 5. An olefin mixture containing 33.6 grams 1-octene, 42.0
grams 1-decene and 50.4 grams 1-dodecene was charged into a round bottom
flask and heated to 70 C under an N2 atmosphere. A catalyst solution
containing
2.34 grams 10 wt% MAO in toluene solution, 60 grams toluene and 3.7 mg of
Catalyst A was added slowly to the olefin mixture while maintaining constant
temperature. The reaction was continued for 4 hours. Gas chromatography
showed that 94% of the starting olefins were converted. The reaction was
quenched by addition of 3 ml isopropanol, followed by washing with 120 ml 5%
sodium hydroxide solution in water. The isolated organic layer was distilled
at
160 C/1 millitorr vacuum for two hours to remove any light ends. The lube
properties are summarized in Table 1.
[00166] Example 6 is a comparative example. An identical reaction was
carried out as Example 5, except a pure 1-decene was used as feed. The lube
properties are summarized in Table 1. This fluid in the lab flowability test
remained a solid after warming up to room temperature.
[00167] Examples 1-5 demonstrated that one can produce lube base stocks of
wide viscosity ranges with superior VI and pour points from wide range of
mixed
alpha-olefins, ranging from C8-C12 to C6-C18. Compared with Example 6, the
fluids made from mixed alpha-olefins as described in Example 1-5 had
distinctly
better flowability. These two examples demonstrated the advantages of using
mixed alpha-olefins as feeds for this metallocene chemistry.
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[00168] Example 7. An olefin mixture containing 7.1% 1-hexene, 9.5% 1-
octene, 11.9% 1-decene, 14.3% 1-dodecene, 16.7% 1-tetradecene, 19.1% 1-
hexadecene and 21.4% 1 -octadecene was used as feed. 30 grams of this feed was
charged into a reactor at 31 C. A catalyst solution containing 0.195 grams of
10
wt% MAO in toluene, 9.7 grams toluene, and 0.308 mg of catalyst A, was added
to the reactor. After 3 days, the reaction was worked up in a manner similar
to
the previous example. The lube product properties are listed in Table 1.
[00169] Example 8. Similar to Example 1, except the feed composition was as
described in Example 7.
[00170] Example 9. Similar to Example 7, except Catalyst C was used
[00171] Example 10, Similar to Example 1, except the feed composition was
as described in Example 7, and the catalyst was Catalyst C.
[00172] Example 11. Similar to Example 7, except the reaction temperature
was 60 C
[00173] Example 12. Similar to Example 8, except the catalyst was catalyst C
and the reaction temperature was 60 C.
[00174] Figures 1 and 2 compare the VI and pour points of the lubes made
from mixed olefms with those made from 1-decene. This graph shows that the
mixed-olefin lubes have VI and pour points similar to the 1-decene-derived
lubes.
The examples in Table 1 further demonstrate that these mixed-olefin-derived
lube
products demonstrated flowable behavior in the cooling/warming cycle test.
These results are not expected from prior art. These fluids can be used as
lubricant base stocks or as blend stocks with other lube base stocks to
improve
the properties of the latter.
[00175] In summary, the examples in this patent memo demonstrate that one
can use a broad spectrum of LAOs as feeds to produce high quality lubricant
base
stocks using metallocene polymerization catalysts. This invention
significantly
broadens the options for feed sources for generating high quality synthetic
fluids.
Furthermore, these examples demonstrate that we can use the whole mixture of
LAO from an ethylene growth process (Scheme 1). This process scheme may
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significantly improve the synthetic base stock process economics. These
examples demonstrate that the lube products made from mixed LAO feeds have
unexpected, superior, flow properties.
[00176] Scheme 1.
1-C6=
1-Cg: =
C2H4 1-C10- High VI Poly-Alpha-Olefins
1-CI8
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00 N 3
N 01 M O
M N
00 116 00
- .-~ O O
v~ M N r"i
kn 00
~ M M- M O
cn N N
ON O N M
- 1
N p~ 01 `~
00 N N
M N
00
V'i O1
N kn en -t O
M d N 4~+
M en
":t 6 00 ,-'
N 00 =- M +~
N O N I Z
O N
In
N O
N O1
00
M N m 0
N O
N N en N
con m
O O O1 N
a r- N N N
O L N
i
i o 0 0
Ua~ n 0U O
W a (~j hYi a 0 w
F~1 ./
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[00177] Example 13. Similar to Example 7, except 0.308 mg of a catalyst meso-
ethylenebis(1-indenyl)zirconium dichloride (Catalyst D) was used and reaction
was carried
out at 30 C. The lube product properties were summarized in Table 2.
[00178] Example 14. Similar to Example 13, except the reaction was carried out
at
60 C.
[00179] Example 15. Similar to Example 13, except 0.308 mg of a catalyst rac-
ethylenebis(1-indenyl)zirconium dichloride (Catalyst E) was used.
[00180] Example 16. Similar to Example 15, except the reaction was carried out
at
60 C.
[00181] Examples 13 to 16 demonstrated that other metallocene catalysts are
just as
effective for polymerization of mixed alpha-olefins to give high VI fluids.
Table 2
Example 13 Example 14 Example 15 Example 16
Kv at 100 C, cSt 804.16 917.13 727.84 648.15
Kv at 100 C, cSt 8292.3 9870.2 7878.9 7336.7
VI 302 306 290 278
[00182] Examples 17 to 21. Similar to Example 1 or Example 5, except a mixture
of 1-
hexene and 1-tetradecene was used as feed. By adjusting the reaction
temperature, we
obtained 12-15 cSt fluids. Their properties and process data are summarized in
Table 3.
Examples 17 to 20 are polymers from mixed linear alpha-olefins (C6 and C14),
and have
superior VI and pour points. The reaction conversions were high and
selectivity to lube
products were above 75%. All these lube products have much higher VI than lube
Example
21 made from pure 1-hexene.
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Table 3.
Example 17 18 19 20 21 - comparative example
Catalyst Type A+MAO A+MAO A+B A+B A+B
Wt% C6 75.0 60.5 60.5 30.0 100.0
Wt% C14 25.0 39.5 39.5 70.0 0.0
Average C, 7 7.75 7.75 10 6
Reaction Temp, 'C 140 140 100 100 120
Kv 100 C, cSt 14.62 14.96 14.04 13.52 12.02
Kv 40 C, cSt 110.18 107.89 99.62 85.67 96.66
VI 126 134 133 150 105
Pour Point, C -48 -36 -36 -18 -43
Conversion, wt% 86.6 84.2 93.9 92.9 na
Wt% Selectivity to lube 76.6 81.6 82.0 91.4 na
[00183] In Table 4, Examples 23 to 25 used 1-hexene and 1-dodecene as feed.
Example
26 used 1-hexene and 1-hexadecene as feed. In all cases, the product lubes
have excellent
VI and pour points, exceeding the VI obtained with pure 1-hexene feed.
Table 4
Exam le 23 24 25 Example 26
Catalyst Type A+MAO A+B A+B Catalyst Type A+B
Wt% C6 60.0 40.4 20.0 Wt% C6 77.1
Wt% C12 40.0 59.6 80.0 Wt% C16 22.9
Average C,; 7.5 8.55 10 Average C, 7
Reaction Tem, C 140 100 100 Reaction Tem, C 100
Kv 100 C, cSt 15.71 16.03 17.18 Kv 100 C, cSt 19.13
Kv 40 C, cSt 118.92 111 115.9 Kv 40 C, cSt 161.22
VI 130 144 152 VI 126
Pour Point, C -57 -54 -39 Pour Point, C -30
Conversion, wt% 87.4 84.5 91.2 Conversion, wt% 83.2
Wt% Selectivity to lube 74 91.1 94.3 Wt% Selectivity to lube 86.6
[00184] In Table 5, Examples 27 to 30 used 1-hexene, 1-dodecene and 1-
tetradecene as
feeds. Again, the products have superior VI and pour point properties, much
better than
comparative example 21 made from pure 1-hexene.
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Table 5
Example 27 28 29 30
Catalyst A+B A+B A+B A+MAO
Wt% C6 64.9 30.4 24 40
Wt% C12 16.2 60.8 48 20
Wt% C14 18.9 8.8 28 40
Average C,, 7.4 9.3 10 8.13
Reaction Tem4 C 100 100 100 140
Kv 100 C, cSt 17.48 15.46 13.21 11.44
Kv 40 C, cSt 135.94 106.05 87.17 69.58
VI 132 146 150 147
Pour Point, C -55 -42 -33 -24
Conversion, wt% 84.6 86.7 91.2 na
Wt% selectivity to lube 84.9 92.6 91.4 na
[001851 Similar runs using mixed olefins as feed produced high viscosity
products
with excellent VI and pour points. Results are summarized in Table 6.
Table 6
Example no. 31 K60.0 33 34 35 36 37 38
+MA +MA A+B A+B A+B A+B A+B
Wt% C6 60.0 60.5 30.0 41.7 60.5 100.0 100.0
1-Cn olefin, n= 12 14 14 14 14 0 0
Wt% Cn 40.0 40.0 39.5 70.0 58.3 39.5 0.0 0.0
-Average C, 7.5 7.5 7.75 10 9 7.75 6 6
Rxn Temp, 'C 100 50 100 70 60 50 80 45
Kv 100 C, cSt 42.19 661.55 45.6 70.2 295.72 625.2 53.57 269.21
Kv 40 C, cSt 409.2 11288 454.3 667.5 3841.8 10424 661.4 4900.3
VI 147 235 148 174 215 234 132 176
Pour Point, C -43 -24 -39 -18 -30 -24 -40 -24
Mn 1892 na 2025 3045 5875 na 1613 na
MWD 1.68 na 1.715 1.832 2.089 na 1.67 na
% Conversion 92.6 96.7 89.1 92.5 92.8 96 93.5
% Lube Selectivity 92.3 100 95 98.2 100 100 95
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[00186] Example 39. To a 600 ml autoclave dried under nitrogen, was charged
16.7
grams of a mixture containing 60% 1-butene and 40% 2-butene and a solution
containing 90
grains 1-dodecene, 0.262 gram triisobutyaluminum (TIBAL) and 1.72 mg catalyst
A. The
autoclave was heated to 60 C. A solution containing 20 gram toluene and 2.305
mg catalyst
B was added into the autoclave. The reaction was continued for 6 hours and
then quenched
by addition of 1 ml isopropanol and 10 gram of activated alumina. The lube
product was
isolated by filtering and distillation under high vacuum to remove any light
ends boiling
below 150 C at 0.1 millitorr. The final product weighed 88 grams and
properties are
summarized in Table 7.
[001871 Examples 40 to 42. Similar to Example 39, except different amounts of
feeds
were used.
[00188] Example 43. Similar to Example 39, except 1-tetradecene was used as
feed.
[00189] Example 44. Similar to Example 39, except 76.2 grams 1-hexadecene and
40
grams of a butene mixture containing 60% 1 -butene and 40% 2-butene were used
as feed.
[00190] Example 45. Similar to Example 39, except 73.2 grams 1-octadecene and
44.7
grams of a butene mixture containing 60% 1 -butene and 40% 2-butene were used
as feed.
[00191] Examples 46 and 47. Similar to Examples 42 and 43, except different
amounts of pure 1-dodecene or 1-tetradecene and pure 1-butene were used as
feeds. Data
from Examples 39 to 47 are summarized in Table 7. These data demonstrate
several key
points: 1. high quality fluids with high VI and superior point points were
prepared by mixed
feed from two LAOs, wherein one of them is an abundant 1-butene. 2. The mixed-
olefin
feeds can comprise LAO in and other internal olefins, such as Examples 39 to
45
demonstrate, that a mixed butene stream can be used just as well as a pure 1-
butene
(Examples 46 and 47). 3. The 13C and 1H NMR analysis of the product polymers
demonstrated that the polymers are random copolymers with a random
distribution index
greater than 90%. 4. The product monomer compositions as calculated from 1H
and 13C-
NMR spectral data, and from the calculated Bernoullian compositions agree with
each other,
and with the feed olefin composition. Such polymers are said to possess a high
degree of
randomness in the monomer distribution. This randomness in a polyalpha-olefin
is novel
and contributes to the superior low temperature viscosity viscometrics.
Conventional Ziegler
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or Ziegler-Natta or supported chromium oxide catalysts usually would not have
such high
degree of randomness. 5. Proton NMR analysis of these samples showed that a
significant
amount (10 to 20%) of the olefins are 1,2-disubstituted olefins. The formation
of such
olefins most likely stems from tail-to-tail termination of the growing
polyalpha-olefins. This
unusual termination creates a unique unsaturation which may be beneficial for
subsequent
functionalization reactions or for providing a less branched lube component
(after
hydrogenation) with more desirable lube properties.
Table 7
Example no. 39 40 41 42 43 44 45 46 47
60% 1-Butene/40%2-butenes + LAO Feed pure 1-C4 feed
mole% C4 in feed 25.0 50.0 75.0 34.6 46.7 55.7 62.2 50.0 80.0
1-Cõ olefin, n= 12 12 12 12 14 16 18 12 14
Rxn Temp, 'C 60 60 60 60 60 60 60 60 60
% Conversion 89.3 93.2 95.4 91.1 89.4 94.9 88.1 92.1 94.6
Product Properties
Kv 100 C, cSt 133.8 187.4 175.6 113.3 118.2 101.1 99.1 143.3 212.0
Kv 40 C, cSt 1664.9 2835.3 3297.1 1270.0 1429.0 1205.1 1177.9 1840.5 3733.3
VI 176 174 151 178 173 166 165 176 166
Pour Point, C -36 -27 -24 -39 -15 3 9 -33 -24
End Group Vinylidene Distribution, mole%
C4 49 60 77 40 50 62 67 49 71
Cõ 51 40 23 60 50 38 33 51 29
Product Composition, mole %
by H NMR (CH3 deconvolution)
C4 47.3 61.0 74.0 40.4 51.1 65.6 65.7 54.1 71.8
Cõ 52.7 39.0 26.0 59.6 48.9 34.4 34.3 45.9 28.2
by 13 C NMR (CH3 integration)
C4 47.5 58.3 74.2 37.9 49.5 57.3 63.2 47.7 70.0
Cõ 52.5 41.7 25.8 62.1 50.5 42.7 36.8 52.3 30.0
by C NMR (S CH2 Bemoulian fit)
C4 53.6 63.6 77.9 45.0 57.2 64.6 71.2 55.3 75.3
Cõ 46.4 36.4 22.1 55.0 42.8 35.4 28.8 44.7 24.7
Diff after Minimization 0.01 0.012 0.005 0.023 0.02 0.006 0.008 0.024 0.013
Ratio of av. Calculated C4 in 1.98 1.22 1.01 1.18 1.13 1.12 1.07 1.05 0.91
product to C4 in feed
Olefin Distribution (mole%), olefins per 1000 Carbons
vinyl 0 1 0.9 0.5 0.9 2.1 1.7 0.8 0.9
1,2-disub 14.7 16.2 9.3 16.8 14.4 12.3 17.4 16.5 12.6
trisub 15.6 15.2 15.3 14.2 16.2 18.6 19.8 17.2 19.8
vinylidene 69.6 67.6 74.5 68.5 68.5 67.1 61.1 65.5 66.7
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[001921 The smaller the Diff number (defined earlier in this text), the closer
the Tube polymer to an ideal Bernoullian random copolymer. These numbers are
usually much less than 0.1 for the present invention, indicative of very
random
polymers. Furthermore, the amount of butene and alpha-olefins in the product
compositions as analyzed by either 13C NMR, or by 1H NMR are very similar to
the feed compositions, which again is indicative of a highly random polymer
composition. This is confirmed by the ratio of 1-butene mole% in polymer to
the
1-butene mole% in the feed ranging from 0.91 to 1.98.
[001931 Furthermore, using Field-Desorption Mass Spectroscopy, we
analyzed the lube samples from Examples 17, 18, 19, 20, 33 and 34 and found
that the alpha-olefin content in the polymers is very similar to the feed
composition, as shown in Table 8. Similarly, we calculated the random
distribution index for this series of copolymers and found that they have very
high degree of randomness, with the RD index ranging from 75% to 91%.
Furthermore, the calculated mole fractions of 1-hexene and 1-tetradecene in
polymer composition correlate closely with the mole fractions of 1-hexene and
1-
tetradecene in the feeds, as shown in Figure 3. This high degree of
correlation is
an excellent indication of high degree of randomness of the polymers.
Table 8.
Example No. 17 18 19 20 33 34
Average C, 7 7.75 7.75 10 7.75 10
Mole fraction of Feed
1-Hexene 0.875 0.778 0.778 0.5 0.778 0.5
1-Tetradecene 0.125 0.222 0.222 0.5 0.222 0.5
Calculated Mole fraction*
1-Hexene 0.85 0.73 0.74 0.5 0.76 0.5
1-Tetradecene 0.15 0.27 0.26 0.5 0.24 0.5
Calculated Best Fit P-Matrix*
PHH 0.85 0.75 0.73 0.48 0.77 0.53
PTT 0.13 0.32 0.22 0.48 0.28 0.53
Calculated Randonmess factor*
1.02 0.93 1.05 1.04 0.95 0.94
* Calculation was discussed in the detailed description of the invention
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[00194] From the data in Table 8, it is clear that the polymers made in this
invention have a degree of randomness, x, very close to 1, ranging from 0.93
to
1.05.
[00195] In Examples 48 to 51, polyalpha-olefins of 40 to 90 cSt were made
from 1-hexene and 1-dodecene. The reaction conditions and lube properties are
summarized in Table 9. The 1-hexene and 1-dodecene contents in the polymer
product were analyzed by 13C NMR, and the results are also summarized in Table
9. The mole fraction of 1-hexene in the products correlates very well with the
mole fraction of 1-hexene in feed composition (Figure 4). This high degree of
correlation indicates that the polymers are highly random copolymers. These
random copolymers have excellent VI and pour points.
Table 9
Catalyst Type A+MA A+B A+B A+B
Example 48 49 50 51
Co, n= 12 12 12 12
Average CX 7.5 9 10 10.5
Wt% C6 60.0 33.3 20.0 14.3
mole % C6 in feed 75 50 33.3 25
Kv 100 C, cSt 42.19 85.68 77.73 91.17
Kv 40 C, cSt 409.2 851.1 701.3 845.1
VI 147 178 185 190
Pour Point, C -43 -42 -39 -27
by 13C NMR
Mole % hexene in pobrmer 66.7 49.6 32.6 26.3
mole% dodecene in polymer 33.3 50.4 67.4 73.7
[00196] Comparison with prior art examples. In these experiments, an
alpha-olefin mixture of same composition as Example 1 was polymerized at 35,
50 and 70 C in the same procedures as Example 1 to produce fluid with
properties summarized in Example 52 to 54 in Table 10.
Example No. 52 53 54
Reaction Temp, oC 70 50 35
Kv 100oC, cS 88.79 515.59 688.59
Kv 40oC, cS 844.71 6123.36 8533.71
VI 185 258 271
PP, C -45 -30
I -27
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[00197] Example 52 to 54 fluids were made from feed compositions similar
to Example 21 A to D of prior art US Patent 4827073. Figure 5 compares the
pour points of the Example 52-54 fluids vs. prior art example 21 A to D. This
graph shows that at the same viscosity, the fluids of this invention have much
lower pour points. The prior art examples have at least 10 C higher pour
points.
This is a clear indication that fluids made from this invention have more
uniform
monomer distribution and are advantageous than prior art samples.
[00198] Table 11 summarizes the wt% conversion of C6 to C18 alpha-
olefins and the relative conversion to 1-hexene by different metallocene
catalyst
systems. This wt% conversion was calculated from the amount of unreacted
alpha-olefins in crude mixture analyzed by gas chromograph equipped with a 60
meter boiling point capillary column. As these data demonstrated that the
conversions of 1-C6 to 1-C18 olefin in each example were very similar to each
other over a very wide range of conversions from 14% to 72% average
conversion. The relative conversions rates of C6 to C18 alpha-olefins to 1-
hexene range from 0.65 to 1.21 for all these catalyst systems over a wide
range of
conversions. This indicated that all the alpha-olefins, irrespective of their
size,
have similar reactivity. These data support our previous conclusion that the
monomers are incorporated into the polymer at equal rates and that the
monomers
are distributed randomly in the polymers.
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Table 11
Example Example Example Example Example Example
7 8 9 10 13 15
Reaction Time, 3.0 4.2 17.5 5.0 6.0 5.0
Hours
Wt% Conversion of Each Individual
Olefins
1-C6 33.4 53.6 50.5 29.5 16.7 74.6
1-C8 29.1 44.9 47.1 30.9 15.5 72.6
1-Cl0 29.5 44.2 48.3 35.8 14.0 74.0
1-C12 27.6 41.9 47.6 35.2 13.6 71.6
1-C14 27.7 41.6 48.5 34.3 15.3 69.4
1-C16 27.6 43.8 50.7 32.8 12.1 72.1
1-C18 29.3 42.3 52.1 31.5 10.8 69.6
Average 29.2 44.6 49.3 32.9 14.0 72.0
Conversion
Relative Conversion to 1-
Hexene
1-C6 1.00 1.00 1.00 1.00 1.00 1.00
1-C8 0.87 0.84 0.93 1.05 0.93 0.97
1-C10 0.88 0.83 0.96 1.21 0.84 0.99
1-C12 0.83 0.78 0.94 1.19 0.82 0.96
1-C14 0.83 0.78 0.96 1.16 0.92 0.93
1-C16 0.83 0.82 1.00 1.11 0.73 0.97
1-C18 0.88 0.79 1.03 1.07 0.65 0.93
Average 0.87 0.83 0.97 1.11 0.84 0.96
Conversion
[00199] Thus, numerous specific examples of the production of high
performance PAO fluids from mixed feed olefins, including substantial amounts
of olefins other than pure 1-decene or traditional decene-substitutes such as
1-
octene and 1-dodecene, have been set forth above.
[00200] The advantages of using these mixed olefin feeds will be
immediately apparent to one of ordinary skill in the art in possession of the
present disclosure. Among other advantages, it significantly increases the
availability and the range of feed stocks useful for the PAO production, so
that
PAO production is not exclusively dependent on 1-decene supply. Second, the
use of wide-range mixed olefins as feeds with metallocene catalyst system
allows
production of a broad product slate, from PAO to HVI-PAO fluids. Third, the
use
of mixed olefins as feeds yields new fluids with superior properties as
lubricant or
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functional fluids. In embodiments, the superior properties include one or more
of: high VI, wide viscosity range, low pour points and other excellent low-
temperature properties, low traction, superior oxidative stability, lubricant
film-
forming properties and superior shear stability, and the like. Surprisingly,
some
of these properties cannot even be achieved using fluids made from pure 1-
decene. Furthermore, the fluids made from the mixed olefins are excellent base
stocks for use as the major components (for example, greater than 50%) in the
formulation of automotive engine lubricants, transmission, and gear
lubricants,
industrial lubricants (including circulation lubricants, gear lubricants,
hydraulic
fluids, turbine oils, pump/compressor oils, refrigeration lubricants, metal-
working
fluids), aerospace lubricants and greases, etc.
[002011 The fluids made in this invention are also superior blend stocks
(from 0.1 wt% to 95%, preferably 20 wt% to 80 wt %) with Group Ito Group V
fluids, and/or with GTL basestocks to give full-synthetic, semi-synthetic or
part-
synthetic lubricants for use in all possible lubricant applications, including
automotive lubricants, industrial lubricants, and greases, as mentioned above.
Because of their intrinsically superior properties, these inventive fluids can
impart, sometimes synergistically, high performance properties to the finished
blend product. Examples are the high shear stability, high VI, high film-
forming
properties, low-temperature viscosity, low traction, superior oxidative
properties
of the finished lubricants. The PAOs disclosed in this invention are used in
formulating lubricant compositions and greases, as described above. Whether in
minor or in major amounts, they are further combined with an effective
concentration of additives selected from typical lubricant composition
additives
such as antioxidants, antiwear agents, rust inhibitors, extreme pressure
agents,
anti-foamants, dispersants and VI improvers. Greases are formulated by
combining the base stock with a thickener such as a lithium soap or a polyurea
compound and one or more grease additives selected from antioxidants, antiwear
agents, extreme pressure agent and dispersants. More examples for formulations
for products can be found in Lubricants and Lubrication, Ed. By T. Mang and W.
Dresel, by Wiley-VCH GmbH, Weinheim 2001.
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[00202] Trademarks used herein are indicated by a TM symbol or
symbol, indicating that the names may be protected by certain trademark
rights,
e.g., they may be registered trademarks in various jurisdictions.
[00203] When numerical lower limits and numerical upper limits are listed
herein, ranges from any lower limit to any upper limit are contemplated. While
the illustrative embodiments of the invention have been described with
particularity, it will be understood that various other modifications will be
apparent to, and can be readily.made, by those skilled in the art without
departing
ftozn the spirit and scope of the invention.
[002041 The invention has been described above with reference to
numerous embodiments and specific examples. Many variations will suggest
themselves to those skilled in this art in light of the above detailed
description.
