Note: Descriptions are shown in the official language in which they were submitted.
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QLEFIN Ol IGoMERizATloN PROCFSS AND CATALYST
TECHNICAL FIELD
This invention relates generally to the preparation of alpha-olefin
oligomers which are useful as synthetic lubricants and functional fluids, and
5 more particularly to a novel catalyst system and a novel catalytic process for conducting such oligomerizations.
BACKGROUND
Alpha-olefin oligomers and their use as synthetic lubricants are well-
known. The oligomers are usualiy hydrogenated in order to improve their
10 stability. Hydrogenated oligomers produced from 1-alkenes, especially linear
1-alkenes, having in the range of about 8 to about 14 carbon atoms are
generally deemed most suitable for use as synthetic lubricants and fluids.
Hydrogenated oligomer oils with viscosities of about 2-10 cSt at 100~C are
typically used for general lubricating oil applications. These materials are, in15 general, mixtures of different percentages of dimer, trimer, tetramer,
pentamer and, in the case of the higher viscosity products in this range,
higher oligomers as well. For some lubricant applications, hydrogenated
oligomers with still higher viscosities are desired.
While various types of alpha-olefin oligomerization catalysts have been
20 disclosed, catalysts based on boron trifluoride have proven most useful.
Patent literature on BF3-based alpha-olefin oligomerization includes U.S. Pat
Nos. 2,806,072; 3,149,178; 3,382,291; 3,769,363; 3,997,621; 4,172,855;
4,218,330; 4,436,947; 4,982,026; 5,068,487; 5,191,140; 5,396,013; and
5,420,373. As indicated in these disclosures, a suitable promoter is used
25 with the BF3 to render it suitably effective for effecting the oligomerization.
Although the boron trifluoride-based catalyst systems exemplified by
the above patents are effective, they are not without drawbacks or
deficiencies. Chief among these are the problems of recovery and disposal
of the catalyst residues. See for example U.S. Pat Nos. 4,213,001;
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WO 97/21651 PCT/US96/19988
4,263,467; 4,308,414; 4,384,162; 4,394,2g6; 4,433,197; 4,4~4,366; and
4,981,578 which describe various ways of coping with these problems.
U.S. Pat No. 5,288,677 discloses immobilized Lewis acid catalysts and
their use as catalysts for the polymerization of isobutylene, mixed butenes
and copolymerization of monomers including 1-butene, ethyiene and 1-
hexene. One of the catalysts used for polymerization of isobutylene is
hydroxylated polybutene-1 copolymer which has been reacted with BF3 in a
manner to form a sigma (cs) bond between the boron and oxygen atoms. For
ease of description this copolymer is depicted in simplified form in the patent
as PB-O-BF2 ("PB" referring to polybutene). Additional experiments have
been conducted using PP-O-BF2 catalyst systems, such as:
PP-O-BF2/n-BuOH;
Pp-o-BF2ln-Buoi-~/cH2cl2;
PP-O-BF2/HCI;
Pp-o-BF2lHcllcH2cl2;
PP-O-BF2/HCI;
PP-O-BF2/t-BuCI; and
PP-O-BF2/BF3 (gaseous BF3~
where "PP" refers to polypropylene, n-BuOH is n-butanol, CH2CI2 is
methylene chloride, and t-BuCI is tertiary butyl chloride, and where the BF3
was in gaseous form. This work has shown that all of these additional
systems show good reactivity in polymerizing isobutylene and styrene.
Unfortunately, all of these systems showed no reactivity to 1-octene.
SUMMARY OF THE INVENTION
This invention in one of its embodiments provides a new catalytic
process for producing 1-olefin oligomers which utilizes a stable catalvst
system that is very reactive at relatively high temperatures, and that is reas~ly
recoverabie and reusable in further oligomerization reactions. In accordance
with this embodiment, a 1-olefin having in the range of about 8 to about 20,
and preferably about 8 to about 14 carbon atoms, or a mixture of two or more
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such 1-olefins, is oligomerized by contact with a cataiyst system formed from
(i) a solid olefin polymer having a linear backbone and a plurality of pendant
omega-hydroxyalkyl groups, and (ii) a boron trihalide, most pre~erably boron
trifluoride, and, optionally, (iii) an organomagnesium halide. Studies have
indicated that the components (i) and (ii) form a complex under ordinary
ambient temperature conditions. The oligomerization process of this
invention is very easy to carry out. Oligomerization proceeds readily in short
reaction periods and at convenient reaction temperatures, including room
temperature.
0 This invention in another of its embodiments provides a new
heterogeneous catalyst system formed form (i) a solid olefin polymer having a
linear ~ackbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) an
organomagnesium halide, and (iii) a boron trihalide, most preferably boron
trifluoride. The available chemical evidence supports the view that the
unification of these components results in the formation under ordinary
ambient room temperature conditions of a novel complex which, using
polypropylene having a plurality of pendant substituents as a typical example,
may be depicted as follows:
(-CH-CH2-)~ (-CH-C~2-)y
1 1
(CH2)n CH3
,0~ (~
X2B 'MgX
~X~
where X is halide, x is an integer representing the number of the substituted
polypropylene units in the molecule, y is an integer representing the nurnber
of unsubstituted polypropylene units in the molecule, and n is an integer
30 representing the length of the carbon chain of the pendant substituents.
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This catalyst system or complex is readily prepared by combining a
Grignard reagent with a solid olefin polymer having pendant omega-
hydroxyalkyl groups and then combining a boron trihalide, preferably boron
trifluoride, with the resultant product. Both steps are preferably conducted in
a suitable anhydrous medium, such as a hydrocarbon diluent, under an inert
atmosphere, using the substituted olefin polymer in finely-divided or
particulate form. Both steps can be conducted at room temperature. The
process for producing the catalyst system or complex forms still another
embodiment of this invention.
0 One important advantage of the invented process and catalyst system
is that the solid catalyst system or components can be recovered and reused
repeatedly in batch-type operations and can be used for long periods of time
in continuous or semi-continuous operations. Thus, in a batch-type process,
the solid catalyst material can be readily separated from the product by
filtration or like physical separation procedure, and used in ensuing
operations. In continuous and semi-continuous operations the solid catalyst
material can be used as a bed through which the olefin is passed. When
using a catalyst formed from solid olefn polymer having a linear backbone
and a plurality of pendant omega-hydroxyalkyl groups and a boron trihalide
20 without organomagnesium halide, boron trihalide is periodically introduced tothe oligomerization at intervals sufficient to maintain the catalytic activity of
the catalyst system. When using catalyst formed from the olefin polymer,
boron trihalide and organomagnesium halide, the solid catalyst complex is
kept in an anhydrous, inert environment when not in use. In oligomerizations
25 utilizing the catalyst complex, a fresh charge of boron trihalide is completely
unnecessary, at least during the extended periods of time during which the
catalyst retains suitable catalytic activity. However, a fresh charge of boron
trihalide can be introduced into the mixture at any suitable time, if desired.
Another feature of this invention is the fact that by utilizing appropriate
30 combinations of reaction time and temperature, oligomer product mixtures
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having different proportions of dimers, trimers, tetramers, etc., can be formed.For example, by increasing the temperature products having higher
proportions of dimer and trimer and smaller proportions of tetramer and
higher oligomers can be formed. Similarly, by keeping the temperature
5 relatively iow and increasing the reaction period the proportion of dimer in the
product mixture can be decreased.
The above and other embodiments and features of this invention will
become still further apparent from the ensuing description and appended
claims.
FURTHER DESCRIPTION
Olefins for Oligomerization
The olefins used in making the oligomers are predominately (at least
50 mole %) C8-C20 and preferably predominately C8-C14 straight chain (i.e.,
linear) monoolefinically unsaturated hydrocarbons in which the olefinic
unsaturation exists in the 1- or alpha-position of the straight chain. Such
alpha-olefins are available as articles of commerce, and can be made by
thermal cracking of paraffinic hydrocarbons or by well-known Ziegler ethylene
chain growth technology. Individual olefins can be used as well as mixtures
of such olefins. ~xamples of olefins that can be used are 1-octene, 1-
. 20 nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-
pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene and mixtures of two
or more of such 1-olefins. Remotely branched 1-olefins such as 5-methyl-1-
heptene, 6-methyl-1-heptene, 6-methyl-1-octene, 7-methyl-1-octene, 6,7-
dimethyl-1-octene, 7,7-dimethyl-1-octene, 8-methyl-1-nonene, and iike 1-
olefins can also be used especially when used together with linear 1-olefins.
The more preferred olefins are linear alpha-olefin monomers containing about
8-14 carbon atoms. The most preferred 1-olefin monomers are 1-octene, 1-
decene, 1-dodecene and mixtures of any two or all three of these.
Minor amounts of up to about 50, and usually less than 25, mole % of
internal and/or vinylidene olefins can be present in the olefin monomers.
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The oligomerizable olefins used in the practice of this invention can
also be mixtures or combinations of olefins having an average in the range of
about 8 to about 20 carbon atoms per molecuie, such as mixtures of octenes,
decenes and dodecenes having an average carbon content per molecule
5 falling in this range.
Olefin Polymer with Penf~nt Ome~a-Hydroxyalkyl Groups
The olefin polymer having pendant omega-hydroxyalkyl groups can be
prepared in a two-stage operation. In the first stage a polymer having
hydrocarbyl-borohydrocarbyl groups depending from the backbone is formed.
0 This involves either homopolymerizing or copolymerizing a hydrocarbyl
borane monomer having an omega-alkenyl group (e.g., B-(5-hexen-1-yl)-9-
BBN, B-(7-octen-1-yl~-9-BBN, etc.) as described for example in U.S. Pat.
Nos. 4,734,472 and 4,~51,276. The polymerization is effected using a
suitable Ziegler-Natta catalyst system such as TiCI3AA/AlEt2CI (where "AA"
1~ means aluminum activated). Procedures for producing the
hydrocarbylborane monomers are also described in these two patents. When
forming the copolymers, the- hydrocarbyl borane having an omega-alkenyl
group is copolymerized with at least one straight chain 1-olefin, preferably a
straight chain 1-olefin having 3-10 (more preferably 3-6) carbon atoms or a
20 mixture of any two or more of these, most preferably propylene. The
copolymers formed in this first stage may contain from 0.1 to 99.9 mole % of
units derived from the hydrocarbyl borane monomer and from 99.9 to 0.1
mole % of units derived from the straight chain 1-olefin(s). Preferred
copolymers have from about 1 to about 15 mole % of units derived from the
25 hydrocarbyl borane monomer and from about 99 to about 85 mole % of units
derived from the straight chain 1-olefin(s).
In the second stage the hydrocarbylborane-substituted polymer formed
in the first stage is reacted with an inorganic base and a peroxide, preferably
sodium hydroxide and hydrogen peroxide, to form the olefin polymer having
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W O 97/21651 PCT~US96/19988
pendant omega-hydroxyalkyl groups. Once again U.S. Pat. Nos. 4,734,472
and 4,751,276 provide a detailed description of this synthesis procedure.
Suitable olefin polymers having pendant omega-hydroxyalkyl groups
comprise poly(1-alken-m-ol) polymers in which the 1-alken-~-ol units contain
~ ~ 6 to about 12 carbon atoms each, and poly(1-alkene-co-1-alken-m-ol)
polymers in which the alkene units contain 3 to about 10 carbon atoms each
and the 1-alken-~-ol units contain 6 to about 12 carbon atoms each. The
homopolymers are typified by poly(1-hexen-6-ol) and poly(1-octen-8-ol). The
copolymers include poly(1-butene-co-1-alken-m-ol) polymers, such as poly(1-
butene-co-1-hexen-6-ol) and poly(1-butene-co-1-octen-8-ol); poly(1-pentene-
co-1-alken-~-ol) polymers, such as poly(1-pentene-co-1-hexen-6-ol) and
poly(1-pentene-co-1-hepten-7-ol); and poly(1-hexene-co-1-alken-~-ol)
polymers, such as poly(1-hexene-co-1-hexen-6-ol) and poly(1-hexene-co-1-
decen-10-ol). Particularly preferred olefin polymers having pendant omega-
15 hydroxyalkyl groups are poly(propylene-co-1-alken-~-ol) polymers, such as
poly(propylene-co-1-hexen-6-ol), poly(propylene-co-1-hepten-7-ol),
poly(propylene-co-1-octen-8-ol), poly(propylene-co-1-nonen-9-ol), and
poly(propylene-co-1 -decen-1 0-ol). These propylene-derived copolymers
when suitably prepared have crystallinity and brush-like molecular structures
with the hydroxyl groups at the ends of flexible side chains. Note in this
connection, T. C. Chung, Polymer News, 1993, Volume 18, pages 38-43 and
Chemtech, 1g91, Volume 21, pages 496-499. Thus they are capable of
forming highly active catalytic complexes according to this invention.
Poly(propylene-co-1-hexen-6-ol) is a particularly preferred hydroxyalkyl olefin
polymer for use in the practice of this invention.
Cataiyst Systems or Complexes with Organomagnesium Halide
In the embodiment of this invention in which organomagnesium halide
is employed in forming the catalyst system or complex, the olefin polymer
having pendant omega-hydroxyalkyl groups is first reacted with an
organomagnesium compound, preferably an organomagnesium halide,
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commonly known as a Grignard reagent. The olefin polymer is preferably
treated in a particulate or finely-divided state while suspended in an
anhydrous inert medium such as paraffinic, cycloparaffinic or aromatic
hydrocarbon, and under an inert atmosphere. The treatment is normally
5 conducted at ordinary room temperatures. Reaction periods of up to 8 hours
or more at room temperature can be used.
Suitable hydrocarbylmagnesium halides include alkylmagnesium
chlorides and bromides, such as ethylmagnesium chloride, propylmagnesiun
chloride, butylmagnesium chloride, butylmagnesium bromide,
10 isobutylmagnesium chloride, pentylmagnesium chloride, heptylmagnesium
bromide, octylmagnesium chloride, and the like. Cycloalkyl and aryl Grignard
reagents such as phenylmagnesium chloride can also be used.
Alkylmagnesium chlorides are preferred. Grignard reagents are often
regarded as containing a complex of RMgX or a complex of R2Mg and MgX2
15 in equilibrium with R2Mg and MgX2. Thus the terms organomagnesium halide
and the terms of like import (e.g., hydrocarbylmagnesium halide,
alkylmagnesium halide, etc.) are intended to encompass the materials
commonly known as Grignard reagents, whatever their precise chemical
structure or configuration may be.
2Q Opon completion of the above treatment with the Grignard reagent, the
particulate or powdery product is separated and recovered from the liquid
phase by filtration or other suitable solids-liquid physical separation technique
such as centrifugation or decantation, and washed with an anhydrous,
oxygen-free inert diluent such as hexane. Then the product is re-suspended
2~ in an anhydrous, oxygen-free inert liquid, such as a paraffinic or
cycloparaffinic hydrocarbon, preferably a low boiling hydrocarbon such as
hexane, and treated with boron trihaiide, preferably by bubbling boron
trifluoride through the suspension at ordinary room temperature and
atmospheric pressure for a suitable period of time, e.g., up to 5 or 6 hours or
30 more. The resultant product can be separated from the liquid phase, if
:
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desired, by filtration or other suitable solids-liquid physical separation
technique such as centrifugation or decantation, and washed with anhydrous,
oxygen-free inert diluent such as hexane. The product can be dried under
vacuum at room temperature or slightly elevated temperature (e.g., up to
5 65~C) and stored under anhydrous oxygen-free conditions such as under a
vacuum or under a dry inert gas such as nitrogen or argon. Alternatively the
product may be kept in an anhydrous, inert liquid such as a paraffinic or
cycloparaffinic hydrocarbon (e.g., hydrogenated alpha-olefin oligomer) which
can be used as a medium in which the oligomerization reaction is to be
1 o conducted.
If all of the hydroxyl groups of the pendant omega-hydroxyalkyl groups
of the initial olefin polymer participate in the reaction with the
organomagnesium halide, and if all of the resultant -O-Mg-X groups
participate in the reaction with the boron trihalide, the complex of this
15 invention as formed will typically have a magnesium:boron:haiide:oxygen
atom ratio of 1:1:4:1, respectively. It will be appreciated however that not allof the hydroxyl groups need participate in either of the reactions, that not allof the groups that are reacted with the organomagnesium halide need react
with the boron trihalide, and that the boron trihalide can react with some or all
20 of the hydroxyl groups that have not reacted with the organomagnesium
halide. Consequently as long as the polymer contains at least one and
preferably a plurality of pendant groups containing a moiety composed of one
atom of magnesium, one atom of boron, four atoms of halide and one atom of
oxygen -- a moiety which for convenience may be depicted as
25 -O-Mg-X-BX3- -- such polymer constitutes a composition of this invention.
Preferably at least 50%, and more preferably substantially all (i.e., at least
90%) of the initial hydroxyl groups on the polymer will have been converted
into such moieties.
A few illustrative complexes of this invention are tabulated below with
30 reference to the reactants used for producing them:
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WO 97/21651 PCT/US96/19988
P(Jly~Cf 12~f~pnt t~J~ t 3E2r~g~nt BX~
poly(propylene-co- l-hexen-6~1) BuMgC1 BF3
poly~p~opylene-co-1-hexen-6~1) AmMgC1 BC13
poly(propylene-co-l-hepten-7-ol) BuMgC1 BF3
poly(propylene-co-l-octen-8~1) iso-PrMgC1 B~3
poly(propylene-co-1-nonen-9~1) BuMgCI BC13
poly(propylene-co-l~ecen-10 ol) iso-~uMgCI BF3
poly(1-butene-co-1-hexen-6-ol) BuMgBr BF3
poly(l-~ co-l-octen-8~1) is~AmMgCI BC13
poly(1-o~,t~ co-1-penten-5~1) iso-BuMgBr BF3
Oligomerization Reaction
In conducting the oligomerization process of this invention,
oligomerization is effected by contacting the monomer(s) with a catalytic
amount of the catalyst system. Typical catalytic amounts fall in the range of
20 about 0.~% to about 30% of the weight of the monomer to be oligomerized.
Preferably the catalyst system is used in the range of about 1% to about 15%
of the weight of the 1-olefin monomer with about 5% to about 10% being
most preferred when using catalyst formed without use of organomagnesium
halide component, for example formed from olef n polymer with pendant
25 omega-hydroxyalkyl groups and boron trihalide. Oligomerization
temperatures are typically in the range of about 0 to about 80~C, and
preferably are in the range of about 20 to about 60~C. Thus in conducting the
oligomerization reactions of this invention at least a substantial portion of
each individual reaction (e.g., at least for one-half of the total reaction period)
30 the oligomerization reaction is performed at one or more temperatures in the
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1 1
foregoing ranges. To ensure intimate contact between the liquid oligomer
and heterogeneous catalyst system, the reaction mixture can be agitated
during the reaction, or the liquid phase can be passed through a bed of the
catalyst system. Reaction times will vary depending on the type of product
5 desired and reaction conditions used. Generally speaking reaction times will
fall in the range of about 0.25 to about 3 hours. However, departures from
this range are permissible whenever deemed necessary or desirable, and are
within the scope of this invention.
Conventional protic catalyst promoters are not required, but can be
used if desired. Among promoters that can be used are water, carboxylic
acids, mineral acids, alcohols, phenols, carboxylic acid esters and
anhydrides, ketones, aldehydes, hydroxy ketones, hydroxy aldehydes,
alcohol alkoxylates, and mixtures of any two or more of the foregoing. If and
when used, the amount of such promoter is typically from about û.001 to
15 about 0.04 moles per mole of 1-olefin monomer(s). The promoter can be
mixed with the olefin feed or the promoter can be charged separately to the
reactor, either entirely at the outset or portionwise as the oligomerization
proceeds.
In one embodiment of the oligomerization process of this invention the
1-olefin or mixture of 1-olefins, boron trihalide, and polymer having pendant
omega-hydroxyalkyl groups can be charged to the reactor in any suitable
sequence. Preferably, however, the boron trihalide is introduced directly into
a heterogeneous mixture of the 1-olefin and the solid polymer having pendant
omega-hydroxyalkyl groups. In another embodiment, the catalyst complex or
2~ system formed from polymer having pendant omega-hydroxyalkyl groups,
organomagnesium halide and boron trihalide is contacted with the 1-olefin or
mixture of 1-olefins. As noted above, boron trifluoride is the preferred boron
trihalide for use in forming the catalyst system.
The oligomerization reaction is typically conducted at about
atmospheric pressure, but super-atmospheric pressures can be used, if
-- .
~ CA 02239182 1998-0~-29
- 12 ~ Pa
desired. Normally it is unnecessary to exceed pressures of about(100 psig)
If it is desired to monitor the progress of the reaction, sampes of the
oligomerization mixtures can be taken at suitable periods during the course of
the reaction and subjected to gas chromatographic (GC) analysis. The
reaction can be conducted in a single stirred reactor or in a series of reactors.
Alternatively, the reactor may contain a bed of the catalyst through which the
liquid phase is continuously passed or circulated in a closed loop.
To terminate the oligomerization reaction, the reaction mixture is
simply separated from the heterogeneous catalyst for further processing such
0 as distillation and/or hydrogenation. Unreacted olefin can be recovered and
recycled.
As indicated above, because a heterogeneous catalyst is used in the
process, the alpha-olefin oligomers can be in a series of two or more
separate oligomerization reactions wherein the same solid polymer
component of the catalyst is used over and over again. Thus in one of its
embodiments this invention provides a process which comprises:
a) conducting a first or initial reaction of a series of separate
oligomerization reactions by contacting at least one
oligomerizable 1-olefin having in the range of about 8 to about
20, preferably about 8 to about 14, and most preferably about 8
to about 12 carbon atoms per molecule with a catalyst system
formed from (i) a solid olefin polymer having a linear backbone
and a plurality of pendant omega-hydroxyalkyl groups, and (ii) a
boron trihalide, and, optionally, (iii) an organomagnesium
halide, whereby the oligomerization results in a reaction mixture
comprising a liquid alpha-olefin oligomer phase and a solids
phase comprising solid olefin polymer catalyst residue;
b) separating the liquid phase and said solids phase from each
other; and
A.~ D~D SHE
IP~3JEP
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13
c) conducting another such reaction by contacting at least one
oligomerizable 1-olefin having in the range of about 8 to about
20, preferably about 8 to about 14, and most preferably about 8
to about 12 carbon atoms per molecule with a catalyst system
formed from (i) the separated solids phase from the preceding
reaction and (ii) when the separated solids phase includes
solids formed from olefin polymer having pendant omega-
hydroxyalkyl groups and boron trihalide, a fresh charge of boron
trihalide, and when the separated solids phase includes solids
formed from olefin polymer having pendant hydroxyalkyl groups
and organomagnesium halide and boron trihalide, an optional
fresh charge of boron trihalide.
Thus a series of 5, 10, 15 or more successive separate oligomerization
reactions can be performed in which after the end of each reaction the liquid
phase and the solids phase are separated from each other, and the solids
phase is reused as the catalyst or suppiemented with a fresh charge of boron
trihalide (preferably boron trifluoride) to form catalyst. In either case, such
catalyst is used with a fresh charge of an oligomerizable 1-olefin in
conducting the next oligomerization reaction of that series of reactions. The
1-olefin can of course be varied from one run to the next.
Solvents or reaction diluents such as suitable parafFinic or naphthenic
oils or paraffinic, cycloparaffinic or aromatic hydrocarbons such as hexane,
heptane, octane, decane, cyclohexane, toluene, xylene, etc., can be
employed if desired. Excess unreacted olefin can also serve as a diluent.
2~ Whenever deemed necessary or desirable, the oligomer can be recovered
from the liquid phase in which it is formed by conventional procedures such
as distillation.
In order to demonstrate the beneficial results achievable by the
practice of this invention, an extended series of batch-type oligomerizations
of 1-octene was carried out using a preferred catalyst system of this
'. ~ 3~ r~,~
CA 02239182 1998-0~-29
invention, namely a system formed from poly(propylene-co-1-hexen-6 ol)
("PP-~H"), boron trifluoride and, in some cases, a hydrocarbon-soluble
alkylmagnesium chloride. A typical procedure for producing PP-OH involves:
a) forming B-(5-hexen-1 -yl)-9-borobicyclo[3.3. 1 ]nonane ("hexenyl-
9-BBN"),
b) copolymerizing the hexenyl-9-BBN with propylene to form
poly(propylene-co-1-hexen-6-yl-9-BBN), and
c) oxidizing this boron-containing polyolefin polymer to PP-OH by
use of sodium hydroxide and hydrogen peroxide.
10 Although full details for conducting such procedures, including the
preparation of hexenyl-9-BBN, are published in patents and technical
journals, illustrative procedures are given below. It is to be noted that the
copolymerization descri~ ~ in Example 2 below is performed using a new
continuous process thc ~es superior results as compared to prior batch-
15 type polymerizations. Synthesis details and oligomerization procedures andresults are illustrated by the following examples.
EXAMPLE 1
Preparation of Hexenyl-9-BBN
A dry 2-liter flask is equipped with a magnetic stirring bar and a
20 connecting tube leading to a nitrogen source. The flask is thoroughly flushedwith nitrogen before the injection inlet is capped with a rubber serum stopple.
A slight positive pressure of nitrogen is rnaintained in the flask thereafter.
The flask is charged via syringe with 190 ~ (1.6 mole) of 1 ,5-hexadiene. To
~ nl
the stirred diene solution is then added (via syringe) 800 ~t: of a 0.5 molar 9-
25 BBN-THF solution. The reaction is effected with constant stirring at room
temperature. After a period of three hours, excess 1,5-hexadiene and THF
solvent are stripped by distillation at reduced pressure. Pure hexenyl-9-BBN
is obtained at 130~C andL~0,~nf. 9).
1-33 kPa
T.~- 5~ S r~ ~~
i CA 02239l82 l998-0~-29
EXAMPLE 2
Copolymerization of Propylene and Hexenyl-9-BBN in a Continuous Re~ction
~n~
In a typical operation, 15.477 9 of hexenyl-9-BBN and 200 ~ of
hexane are placed in an argon filled Parr stirred pressure reactor and sealed.
5 Then 12 9 of propylene are added under N2 pressure. A slurry of 1.027 9 of
TiCI3 and 4.705 9 of AlEt2CI in 80 ~ of toluene are then added under N2
pressure to catalyze the copolymerization. Additional propylene is added at
30-minute intervals with 10, 8, 6 and 5 9 of propylene added, respectively.
After the last monomer charge, the reaction is run for an additional hour
before terrninating the reaction by injection of 100~ of isopropyl alcohol.
The reaction mixture is stirred for an additional 1/2 hour before venting the
excess pressure and flushing the polymeric product with additional isopropyl
alcohol. Some typical results for copolymerization of propylene and hexenyl-
9-BBN using this continuous polymerization procedure are summarized in
Table 1. The process produces copolymer with narrow compositional
distribution and higher yield of borane monomer than previously reported
procedures.
Table 1
20 Ru~ l~io. Mol 9G Hexcnyl-9- Mol % Hexenyl-9-BBN Rcaction Yield, %
BBN in Fecd in Copolyrncr Time, hr
3.S 3 62
2 10 4.2 5 75
3 13 5.0 3 65
25 4 13 7.f~ 5 72
,; _ . _
: CA 02239l82 l998-0~-29
16
E~CAMPLE 3
Oxidation of PropylenelHexenyl-9-BBN Copolymer
Propylene/hexenyl-9-BBN copolymer and 700,~ of THF are placed in
a 2-liter round bottom flask equipped with septum and stirrer. To the
5 resultant non-homogenous slurry is added dropwise a solution of 19 9 of
nll
NaOH in 100 ~ of degassed water. The flask is then cooled to 0~C before
slowiy adding 87.6 9 of degassed 30% H2O2 soiution via a double tipped
needle. The reaction mixture is allowed to slowly come to room temperature
before heating up to 55~C for 6 hours. The PP-OH polymer, poly(propylene-
10 co-1-hexen-6-ol), is then precipitated in water, squeeze dried, and placed in a
ml
slurry 500 ~ of methanol. After 3 hours of vigorous stirring, approximately
rr- I
75 r~ of MeOH is distilled off under N2 to remove boric acid-methanol
azeotrope. The poly~~- is again precipitated in water, squeeze dried,
washed with acetone, .ld dried under high vacuum at 45~C. Typical
properties of the PP-OH polymer fommed in this manner and of polypropylene
homopolymer made by the same polymerization method (Run No. 5) are
summarized in Table 2. The PP-OH polymers of Run Nos. 6 and 7 of Table 2
were produced from the hexenyl-9-BBN polymers of Run Nos. 1 and 3 of
Table 1 respectively. Molecular weights were determined by intrinsic
20 viscosity as measured in a conelplate viscometer at 1 35~C in decalin
solution .
Table 2
Run No. Mol% OH in Melting Heat of Ft~sion. Intrinsic Mu, ~lmol
Polymer Pt ~C J/g Viscosity
none 163 62.5 2.07 230.000
6 3.5 161 54.1 1.78 183,000
7 5.0 158 44.6 1.71 174,000
AM~NO~O Sl lE{~
h~ -~JF p
._
t CA 02239l82 l998-0~-29
Without desiring to be bound by theoretical considerations, the data in Table
2 indicate that the crystallinities, shown by melting point and heat of fusion, of
the PP-OH polymers are not much different from that of the polypropylene
homopolymer, which is therefore attributed to a tapered structure of the PP-
OH poiymer. Also, the functional groups on the side chains are concentrated
at the end of the polymer chain indicating that the polypropylene units are in
consecutive sequence to form crystalline phases.
EXAMPLE 4
Oligomeri~tion of 1-Octene with PP-OH/Boron Trifluoride Catalyst
0 A series of 15 consecutive oligomerization reactions was conducted in
which the same 0.7 gram sample of poly(propylene-co-1-hexen-6-ol) was
recovered by filtration after each run and reused in the next run, a procedure
that was repeated ove -nd over again throughout the entire series. In each
ml
run the PP-OH copoly - and 20 r~ of 1-octene were charged to an air-free
flask and at the start of each run BF3 was bubbled into the fresh mixture for
10 minutes while stirring the mixture. The slurry was then maintained under
the selected reaction conditions for the desired reaction time. After each run
the oligomer-containing reaction product was filtered to separate the PP-OH
copolymer from the liquid oligomer-containing phase. The recovered PP-OH
n~l
and a new 20 ~ portion of 1-octene were charged to the flask for the next
run. Table 3 summarizes the conditions used and the results obtained.
Table 4 summarizes analytical data concerning the composition of some of
the oligomers formed in these runs.
v~ 13'-2 S~._C~
! ~--~/~p
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18
Table ~
Run No. ~ rti~n Reaction Time, Product Yield, Co,~ , %
Temp., ~C hr. g
1 7.28 50.9
2 20 1 7.31 S1.1
3 20 1 7.51 52.S
4 20 ~ 7.40 51.7
1 7.14 49.9
6 20 1 7 59 53 0
7 20 1 7.32 51.1
8 20 1 7.28 S0.9
9 20 1 7.38 51.6
1.S 9.60 67.1
11 20 1 7.24 50.6
12 40 1 9.98 69.8
13 60 1 13.3S 93.3
14 60 0.5 6.91 48.3
lS 20 1.5 10.40 72.7
ZO
Table 4
Run No. I~imer, % Truner, % Te~amcr, % reu~-l.,., %
7.8 56.9 18.9 16.4
4 8.1 58.6 17.8 14.5
1'' 14.5 73.7 9.S 2.3
13 33.4 59.8 6.8 trace
14 35.4 64.0 0.6 --
lS 5.8 66.0 17.1 11.1
_
CA 0 2 2 3 9 1 8 2 1 9 9 8 0 ~ 2 9
EXAMP~E 5
Pre~aration of Catalyst Complex from PP-OH. Gri~nard Rea~ent and Boron
Trifluoride
Poly(propylene-co-1-hexen-6-ol (PP-OH polymer)) containing 3 mole
5 % of hexenol groups, prepared as in Example 3, is ground to a fine powder
and vacuum dried for two hours. In a dry nitrogen atmosphere, the dried PP
OH polymer (6 grams) is suspended in 40,~ of anhydrous, oxygen-free
hexane, and then 50 mmol of butylmagnesium chloride is introduced into the
slurry. The mixture is kept at room temperature for five hours. The resultant
10 complex (PP-OH-Mg-CI) is in the form of powdery solids, and is separated
from the liquid phase by filtration through a glass frit and washed three times
with anhydrous, oxygen-free hexane. The PP-O-Mg-CI powder is then
resuspended in 40 ~ of dry, oxygen-free hexane, and while continuously
stirring the mixture, boron trifluoride is introduced at atmospheric pressure
~5 c~r ~ th~ee-h~ur pe~i~. T. he !;~it~ are again seqaratç~ by filtration using a
glass frit and washed three times with anhydrous, oxygen-free hexane. The
washed powdery product, PP-O-Mg-CI-BF3 complex, is dried under vacuum
for several hours. A sample of a complex formed from the PP-OH, Grignard
reagent and BF3 in this manner was subjected to structure characterization~0 and was found to have an Mg:B:F atom ratio of 1:1:3.
EXAMPLE 6
Oligomeri7~tion of 1-Octene with C~talyst Complex from PP-OH. Grignard
Reagent ~nd Roron Trifluoride ~ C~lyst
A series of 12 consecutive oligomerization reactions was conducted in
25 which the same 1 gram sample of PP-O-Mg-CI-BF3 complex produced as in
Example 5 was recovered by filtration after each run in a dry box and reused
in the next run, a procedure that was repeated over and over again
rn I
throughout the entire series. In each run powdery soJid complex and 10 r,~
of fresh 1-octene were charged to an air-free 50 ~ flask and the mixture
30 was heated up to 60~C for the desired reaction time. After each run the
IENDED SHE~;,
IP~AIEP
CA 02239182 1998-05-29
W O 97/21651 PCT~US96/19988
oligomer-containing reaction product was filtered to separate the catalyst
complex from the liquid oligomer-containing phase for use in the next run.
The separated liquid phase was distilled under vacuum to remove unreacted
1-octene monomer. Elemental analysis of the recovered catalyst after the
5 last run of the series showed that almost no change in BF3 concentration in
the catalyst occurred after 12 reaction cycles. Table 5 summarizes the
conditions used and the results obtained in these 12 runs. Table 6
summarizes analytical data concerning the composition of some of the
oligomers formed in these runs.
Table 5
Run No. Re~ion R~eno~ Ti~, Product Yield, Col~vc.~on,
Temp., ~C hr. g
1 60 2 1.62 22.7
2 60 2 1.84 Z5.7
3 60 2 1.74 24.3
4 60 2 1.78 24.9
3 2.45 34.2
6 60 4 3.04 42.5
7 60 2 1.72 24.1
8 60 2 1.85 25.8
9 60 2 1.74 24.3
2 1.80 25.1
11 60 3 2.29 32.0
12 60 4 3.10 43.3
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21
Table 6
~un No. D~ner, % Tr~ner, % Teo~mer, % P~u~uue~, %
3 55.5 42.5 2.0 none
8 58.3 40.7 1.0 none
0 The entire disciosure of each and every U.S. patent and each and
every technical publication referred to in any portion of this specification is
incorporated herein by reference for all purposes.
This invention is susceptible to considerable variation in its practice.
Therefore the foregoing description is not intended to limit, and shouid not be
construed as limiting, the invention to the particular exemplifications
presented hereinabove. Rather, what is intended to be covered is as set
forth in the ensuing claims and the equivalents thereof permitted as a matter
of law.
