Note: Descriptions are shown in the official language in which they were submitted.
2152492
W094l15894 1 PCT/F~3/00560
A method to oligomerize C4 olefins together with linear alpha
olefins
The invention concerns a process in accordance with the
preamble of claim 1 for producing synthetic oils.
According to a process of the present kind, olefinic
hydrocarbons are polymerized in order to prepare oily
products whose number average molecular weights typically lie
in the range from 300 to 1200.
The invention also relates to copolymers in accordance with
the preamble of claim 17 useful as synthetic oils. A process
for preparing such copolymers is also disclosed.
In the petrochemical industry, a mixture of hydrocarbons
known as Raffinate II re~i n .s after the isolation of
1,3-butadiene and isobutylene from pyrolytic C4 fractions.
This kind of a mixture emanates, for instance, from the
production of polyisobutylene and, in particular, from the
production of methyl tert-butyl ether (MTBE) used as an
anti-knock in petrols. The Raffinate II contains, besides
n-butane and isobutane, large amounts of n-butenes. Thus, a
conventional Raffinate composition comprises some 30 to 55
by weight of 1-butene and 15 to 30 ~ by weight of 2-butenes
(i.e. cis- and trans-butene). In addition there are minor
amounts, typically less than about 3 ~ by weight, of iso-
butylene and some methanol, for instance less than about 3
by weight, in the Raffinate.
Normally large volumes of the Raffinate II are produced and
used in low value applications during processing of
polyisobutylene and MTBE. Here it has been suggested in the
prior art to use said Raffinate II and similar secondary raw
materials for preparing synthetic oils. Thus, EP Published
Patent Applications Nos. 0 337 737 and 0 367 386 teach a
process for preparing poly(n-butene) oils, which comprises
oligomerizing the olefinic C4 hydrocarbons of the Raffinate
II in a reaction carried out in the presence of an initiator,
WO94/15894 ~ 49~ PCT/F~3/00560
such as AlCl3 or alkylaluminium chlorides, and a coinitiator,
typically HCl. Because Raffinate II does not contain
isobutylene, or contains it in concentrations below 3 ~ by
weight, the produced oils are predominantly the copolymers of
1-butene with cis- and trans-2-butenes.
Although poly(n-butene) oils are not yet industrially
produced on a large scale, the}r broad application in
practice is expected because they can be produced from an
inexpensive secondary raw material, such as Raffinate II.
However, the viscosity of these oils is strongly dependent on
temperature, which today limits a broader utilization of the
poly(n-butene) oils in the field of engine lubricating oils
and for similar purposes.
The quality of lubricating oils is usually characterized by
the pour point and the viscosity index. The latter reflects
the temperature-dependency of the viscosity of the oil. In
the case of high-quality synthetic oils intended for use as
engine lubricating oils, it is generally required that the
value of the viscosity index be about 120 or higher. Such
values are obtained with conventional polyolefinic oils
produced by oligomerization of higher linear alpha-olefins
using Friedel-Crafts catalysts or Ziegler-Natta catalytic
systems. These oils are primarily produced by oligomerization
(i.e. trimerization to pentamerization) of l-octene or 1-
decene, giving oligomers with optimal properties from the
point of view of both viscosity index and pour point. In
comparison, it should be mentioned that the viscosity index
of poly(n-butene) based oils is below 75, which - although
too low for engine lubrication - still is sufficient for many
other applications.
The industrially produced oils from higher linear olefins
belong to the expensive oils on the market and therefore
their broader use is limited.
~ WO94/15894 215 2 ~ 9 2 PCT/~93/~0560
Thus, in summary, the conventional synthetic oils are too
expensive to be used on a larger scale, whereas the
properties of the much more inexpensive poly(n-butene) oils
do not meet the standards for engine lubricants.
One aim of the present invention is to eliminate the problems
related to the prior art in the field of synthetic
lubricating oils and to provide inexpensive new oils with
acceptable properties.
Another aim is to provide novel olefinic copolymers which can
be used as lubricating oils or as part of synthetic oil
compositions.
Still a third aim is to provide processes for preparing the
novel oils and copolymers.
It has now unexpectedly been found that l-butene along with
the cis- and trans-2-butenes or their mixtures contained in
the Raffinate II can readily be copolymerized with higher
linear alpha-olefins in the presence of suitable initiators
to provide an oily product with high viscosity index and low
pour point. Thus, the invention is based on the idea of
polymerizing higher linear alpha-olefins in hydrocarbon
compositions containing essential amounts of olefinic C4
hydrocarbons, in particular compositions, which are comprised
of the residues of the pyrolytic C4 frac~ions, such as the
above-mentioned Raffinate II.
In particular the process in accordance with the invention is
characterized by what is stated in the characterizing part of
claim l.
The copolymers according to the invention are mainly
characterized by what is stated in the characterizing part of
claim l7.
WO94/15894 PCT ~ 3/00560
~ 2 ~9 2 4
The process for preparing copolymer useful as synthetic oils
is characterized by what is stated in the characterizing part
of claim 20.
r
Within the scope of the present application the term "to
polymerize" denotes the formation by chemical reactions of
large molecules built up by single monomers (or repeating
units) irrespective of the number of such monomers in the
product. Thus, for the purposes of this application
"polymerizing" also includes "oligomerizing", i.e. formation
of large molecules containing 2 to 10 monomers.
According to one preferred embodiment, synthetic oils are
prepared by polymerizing higher linear alpha-olefines (LAO)
in hydrocarbon compositions containing some 15 to 80 ~ by
weight of 1-butene, 5 to 50 ~ by weight of 2-butenes, and
about 10 ~ by weight or less of isobutylene. Preferably, the
olefinic hydrocarbon compositions contain about 25 to 70 ~ by
weight, in particular 30 to 60 ~ by weight of 1-butene and 10
to 40 ~ by weight, in particular 15 to 30 ~ by weight of 2-
butenes. In addition to these components the composition may
contain minor amounts of, for instance, n-butane, isobutane,
propane and other alkanes, isobutylene, methyl tert-butyl
ether and other etherification products, as well as various
other lower olefinic oligomers.
In particular, the olefinic hydrocarbon compositions comprise
mixtures of hydrocarbons remaining in a pyrolytic C4 fraction
after isolation of 1,3-butadiene and isobutylene. These kinds
of hydrocarbon mixtures may consist of Raffinate II which is
obtained from the production of methyl tert-butyl ether or
from the selective polymerization of isobutylene.
To the C4 hydrocarbon compositions there are added 1 to 99
by weight, preferably 5 to 90 ~ by weight and in particular
10 to 70 ~ by weight of higher LAO's. The amount of the added
LAO's is calculated on basis of the total amount of olefins
~ WO94/15894 21 S 2 4 9 2 PCT~93/~0560
in the composition after the addition. The added LAO's are
selected from the group comprising higher alpha-olefins
containing 6 to 24 carbon atoms, preferably the LAO's may be
selected from the group comprising higher linear alpha-
olefins containing 6 to 18 carbon atoms, and in particular
the LAO's are selected from the group comprising higher
linear alpha-olefins containing 8 to 16 carbon atoms.
Exemplifying LAO species are 1-octene, 1-decene, 1-dodecene,
1-tetradecene and 1-hexadecene.
The molecular weights of the produced copolymers depend on
the composition of the initial mixture, on the polymerization
temperature, and to some extent on the initiator system used.
Typically, the number average molecular weight, Mnl ranges
from 300 to 1200, preferably from about 350 to about 1000.
The polymerization is preferably carried out at -10 C to
+70 C. Without altering the composition of the reaction
mixture, the number average molecular weight of the
copolymers can be varied in the range from 300 to 1000 by
changing the temperature of the polymerization.
The initiator systems used for the polymerization are similar
to those previously employed for preparing poly(n-butenes).
Reference is made, in particular, to the above-mentioned
European Published Patent Applications Nos. 0 337 737 and
0 367 386, the disclosures of which are herewith
incorporated by reference.
Thus, the initiator system may be based on AlCl3. However,
the copolymerization does not proceed solely with AlCl3 and,
according to one preferred embodiment, AlC13 is therefore
added in an ethyl chloride solution or as a liquid complex
formed from AlCl3, toluene or an equivalent aromatic solvent,
and hydrogen chloride. The advantage of these forms of AlCl3
consists in easy dosing of the initiator into the reaction
system and also in the fact that AlCl3 does not need any
WO94/15894 ~ 1~ æ 4 9 2 PCT ~ 3/00560
additional coinitiator if added in this form. Since the
aluminium trichloride liquid complex is not soluble in
Raffinate II, vigorous stirring of the reaction medium is
required to avoid deposition of the catalyst system on the
bottom of the reaction vessel.
According to another preferred e~bodiment, an alkylaluminium
chloride of the general formula~ R,AlCl or RAlCl~ is employed
as an initiator and an anhydrous hydrogen halide as a poly-
merization coinitiator. In the above general formulas R
stands for a lower alkyl having l to 6 carbon atoms.
Preferably alkylaluminium dichloride compounds of the general
formula RAlCl~ are used and, in particular, the compounds are
selected from the group comprising methylaluminium
dichloride, ethylaluminium dichloride, propylaluminium
dichloride and butylaluminium dichloride. The hydrogen
halides may comprise hydrogen chloride or hydrogen fluoride,
hydrogen chloride being preferred.
Gradual addition of the initiator into the reaction mixture
will assist in governing the rate of copolymerization by
providing practically isothermal reaction control of the
strongly exothermic copolymerization. In this way it is
possible to ensure that a product of even quality will be
obtained.
In the case of an initiator system comprising an initiator
and a coinitiator, it is preferred to add the coinitiator at
the beginning of polymerization. If anhydrous hydrogen
chloride is used, the total amount of initially added
coinitiator ranges from O.l ~ by weight to 0.3 ~ by weight.
The coinitiator can be added dissolved in the reaction
mixture. Alkylaluminium dichloride can be then added in small
portions, preferably in an inert solvent, and thus an almost '
isothermal course of polymerization can be secured at the
required temperature. At an inverse addition order of
components, there is a danger that the exothermal reaction
= ~ == =
WO94/15894 21 S 2 ~ ~ 2 PCT/F~3/00560
cannot be controlled and proceeds extremely fast. In such a
case, an undesirable overheating of the reaction mixture may
take place.
The initiator and the coinitiator are consumed by the
polymerization reaction. At polymerization temperatures below
-10 C, the relative consumption of the initiator increases
and high conversions are hardly attained. Therefore, as
mentioned above, the reaction is preferably carried out at
temperatures above -10 C. Typically, the initiator
consumption (calculated on basis of the obtained product)
amounts to 0.3 - 0.7 ~ by weight at temperatures in the
preferred range from -10 C to +70 C at olefin conversion
rates in excess of 90 ~.
According to one particularly preferred embodiment of the
invention, to an olefinic hydrocarbon composition, which
contains n-butenes in a total concentration of at least 30
by weight, there are added alpha-olefins containing 6 to 18
carbon atoms in the molecule. The alpha-olefins are reacted
with the butenes of the hydrocarbon composition in the
presence of an initiator system comprising a solution of
AlCl3 in ethyl chloride or a liquid complex formed from AlCl3,
toluene and HC1 to provide oils with viscosity indeces from
100 to 150 and pour points from +5 C to -65 C, the molar
ratio of alpha-olefins to n-butenes being in the range from
1:1 to 1:5.
According to another particularly preferred embodiment of the
invention, to an olefinic hydrocarbon composition, which
contains n-butenes in a total concentration of at least 30
by weight, there are added alpha-olefins containing 8 to 16
carbon atoms in the molecule. The alpha-olefins are reacted
with the butenes of the hydrocarbon composition in the
presence of an initiator system comprising an alkylalumium
dichloride together with hydrogen chloride to provide an oil
with viscosity index from 100 to 140 and pour points from
W094/15894 ~ 2~S 2 ~9 2 PCT/F~3/00560 ~
0 C to -65 C, the molar ratio of alpha-olefins to n-butenes
being in the range from l:1 to 1:5.
The copolymers according to the invention essentially consist t
of repeating units of n-butene, cis-; and trans-2-butenes and
higher linear alpha-olefins with 6 to 18 carbon atoms. The
polydispersity of these copolymer~s defined as the ratio MW/Mn
is lower than 1.4.
As mentioned above, the invention also concerns a process for
producing a copolymer product useful as a synthetic oil or
part thereof. The process may be summarized as comprising the
steps of
- mixing higher linear alpha-olefins having 6 to 18
carbon atoms with a C4 hydrocarbon composition derived
from the production of methyl tert-butyl ether or from
the selective polymerization of isobutylene and
containing at least 15 ~ by weight of 1-butene and at
least 5 ~ by weight of 2-butenes to form a reaction
mixture,
- adding an initiator system to the reaction mixture,
- keeping the temperature of the reaction mixture in the
range from -10 C to +70 C,
- allowing the higher linear alpha-olefins to react with
the 1-butenes and 2-butenes to form a reaction product,
and
- separating volatile components and any initiator system
residues to form a oily product consisting essentially
of copolymers having a number average molecular weight
in the range from 300 to 1200.
The oily products of the invention are characterized by
having higher viscosity index than have the poly(n-butene)
oils as such. Also the pour point is improved by the
copolymerization of n-butenes with higher linear alpha-
-olefins. The pour point of the present oils is lower than
that of poly(n-butene) oils and it is, in fact, even lower
~1~2~92
~ W094/15894 ~ PCT ~ 3/00560
that the pour points of oligomers of higher linear alpha-
-olefins of comparable molecular weights.
According to a preferred embodiment of the present invention,
the hydrocarbon composition should contain only trace
amounts, if any, of methanol, since the methanol may
interfere with the polymerization reaction by consuming the
initiator and causing inhibition of the polymerization.
Therefore, if Raffinate II obtained from the production of
methyl tert-butyl ether is used, which sometime may contain
up to a couple of per cent per weight of methanol, the
residual methanol is removed or its concentration lowered to
below 3000 ppm before the polymerization reaction.
The viscosity index of the copolymerisate depends on the
content and the kind of the higher linear alpha-olefins used
and tends to increase with increasing content and length of
the linear alpha-olefin. Pour point of the obtained copolymer
also depends on the higher linear alpha-olefin used and
increases with increasing length of the copolymer molecule
and with increasing molar content of n-butenes.
After polymerization, the reaction mixture is processed by
methods known per se. According to a preferred embodiment, it
is washed, in particular, with an about 5 ~ aqueous solution
of soda and then with water. Alternatively, sorption clay is
added to the mixture in an amount of approx. 0,5 to 10 ~, in
particular about 2 ~, calculated on basis of the initial
content of olefins, to remove the catalyst. The low-boiling
portions are distilled off by heating to at least 140 oc at
13 Pa. A colourless or slightly yellowish oil is obtained
with a kinematic viscosity in the range from 4 to 15 cSt at
+100 C and in the range from 27 to 160 cSt at +40 C. The
obtained copolymers are characterized by a relatively narrow
distribution of molecular weight corresponding to a
polydispersity defined as the ratio MW/Mn lower than 1.4.
W094/1589~ 2 4 ~ ~ PCT ~ 3/00560
The invention provides considerable benefits. A particularly
important advantage of the present process resides in the
fact that the copolymerization of n-butenes can be carried
out in Raffinate II, which is a cheap-secondary raw material
normally discarded, without having to isolate and purify the
n-butenes.
-
A further advantage of the invention consists in producing
high quality synthetic oils with viscosity indeces on the
same level as those of expensive synthetic oils prepared from
pure higher linear alpha-olefins.
The oils produced by copolymerization of n-butenes with
higher linear alpha-olefins according to this invention can
be used for a number of different applications. In
particular, because of their very convenient values of
viscosity index and pour point, they can be employed as high-
quality engine lubricating oils in applications where the
viscosity changes with temperature should be as small as
possible. The low polydispersity of their molecular weights
is important as it indicates that the oil viscosity will not
change too much during long-term mechanical stress. The
obtained properties are similar to these of multigrade oils
with long-term service lives.
Another important feature of the present oils consists in the
fact that they do not release any carbonization residue after
heating to high temperature or combustion. This is why their
expected use is as lubricating oils for two-stroke combustion
engines, as oils useful in metallurgy for rolling and drawing
of metallic materials, as oils for transformers, electrical
insulations and cables, as oils for energy transfer in
cooling and heating systems, and as oils for many other
similar applications. The oils are non-toxic and can be
utilized as additives in plastics and rubbers.
In the following, the invention will be further Px~mined in
WO94/15894 21 S 2 ~ 9 2 PCT/F~3/00560
detail with the aid of working examples illustrating the
copolymerization of n-butenes with higher linear alpha-
olefins in a Raffinate II. It should, however, be understood
that the scope of the invention is not limited to these
examples. In particular it should be noted that other
hydrocarbon compositions containing essential amounts of
olefinic C4 hydrocarbons can be used for the purposes of the
present invention.
Eguipment and materials
The copolymerizations were carried out in a glass reactor
with a volume of 150 ml or, alternatively, in a stainless
steel reactor with a volume of 1000 ml. Both reactors were
equipped with a magnetic stirrer, valve for charging and
dosing the initiator and with outside cooling. The
temperature of the reaction mixture was monitored with a
thermocouple connected to a recorder. The polymerization
course was controlled by gradual dosing of the initiator so
as to keep the temperature of the reaction mixture in the
region of +3 C around the required temperature.
For the purpose of preparing the oils, a hydrocarbon
composition (Raffinate II) comprising the residue of a C4
fraction from the production of MTBE was used. It was washed
three times with water in order to remove methanol and dried
in the liquid state over KOH in a pressure vessel.
The hydrocarbon composition refined in this way had the
following composition: 49.2 ~ 1-butene, 15.1 ~ trans-
-2-butene, 9.7 ~ cis-2-butene, 2.2 ~ isobutylene, 15.6 ~
n-butane, 7.2 ~ isobutane and 0.6 ~ propane. The methanol
content was always less than 3000 ppm and the content of
methyl tert-butyl ether was less than 0.2 ~. The linear
alpha-olefins were of commercial purity and contained more
than 99 ~ by weight l-olefin.
W094/15894, 21~ ~9 2 PCT ~ 3/00560 ~
12
Molecular weights Mn and Mw and polydispersity MW/Mn of the
products were evaluated by GPC and VPo.
Example 1
Copolymerization of n-butenes was carried out in a mixture of
hydrocarbons known as Raffinate II which had been separated
from the C4 fraction in the production of MTBE . To this
mixture 30 mol ~ of l-decene was added, the amount of l
decene added being calculated on basis of amounts of olefins
in the new mixture formed. The copolymerization was performed
at a mean temperature of +20 C by gradual addition of small
amounts of a lO ~ AlCl3 solution in ethyl chloride in such a
way that the reaction mixture was not overheated by more than
3 C. The polymerization was stopped after 40 min by addition
of alcohol, the reaction mixture was washed with a 5 ~
solution of soda and then with water. The hydrocarbon layer
was separated, mixed with filtration clay and filtered under
pressure. Volatile fraction was removed by heating the
reaction mixture up to 120 C at 13 Pa. The colourless oil
obtained had a number average molecular weight Mn = 810 and a
viscosity index of 107. The consumption of AlCl3 related to
the final product was 0.6 ~ by weight at an olefin conversion
rate of 97 ~ by weight
Example 2
Copolymerization of n-butenes with l-dodecene was carried out
in Raffinate II in an analogous way as in Example l. The
copolymer prepared with 30 mol.~ l-dodecene at polymerization
temperature +20 C had a molecular weight Mn of 850, a
viscosity index of 122 and a pour point of -43 C. The
consumption of AlCl3 was 0.7 ~ by weight at a conversion rate
of 95 ~ .
21524~2
WO94/15894 PCT/F~3/00560
13
Example 3
Copolymerization of n-butenes present in Raffinate II was
carried out with the addition of 30 mol.~ l-tetradecene
analogously as in Example 1. The molecular weight Mn of the
oil obtained at a polymerization temperature of +20 C was
810, whereas the polydispersity MW/Mn was 1.3 and the
viscosity index was 141.
Example 4
Copolymerization of n-butenes was carried out in the residue
of a C4 fraction (Raffinate II) with the addition of 30 mol.~
1-hexadecene (the added amount related to the total amount of
olefins in the same way as in Example 1). The
copolymerization was conducted at +20 C, the conversion
rate, as calculated on basis of the olefins present in the
mixture, being 92 ~. The prepared oil had a number average
molecular weight Mn Of 910, a polydispersity MW/Mn of 1.1, a
viscosity index of 148 and a pour point of -3 C. The
consumption of AlCl3 was 0.65 ~ by weight at a 92
conversion rate.
Example 5
Copolymerization of n-butenes present in the residue of a C4
fraction was carried out with the addition of 30 ~ by weight
of 1-hexadecene at +20 C under initiation with a liquid
complex of AlCl3, toluene and anhydrous HCl. The liquid
complex was prepared by introducing gaseous HCl into a
suspension of 5.0 g AlCl3 in 6.0 ml toluene at 0 C until all
AlCl3 was transferred into the solution. A conversion rate of
94 ~ was attained by gradual dosing of the initiator into the
reaction mixture for 30 min.
The obtained oil had a molecular weight Mn of 700, a poly-
dispersity MW/Mn of 1.31, a viscosity index of 130 and a pour
WO94/15894 PCT/F~3/00560 ~
215~ 14
point of -15 C. The consumption of AlCl3 related to the
product was 0.6 ~ by weight.
Example 6
,~
Copolymerization of n-butenes was~carried out in the residue
of a C4 fraction with 50 ~ by weight of 1-decene at +70 C
under initiation with a liquid AlCl3 complex prepared
according to Example 5. The polymerization was stopped after
30 min by addition of alcohol at a 93.5 ~ conversion rate.
The oily product had a molecular weight Mn = 560, a viscosity
index of 117 and a pour point of -38 C.
Example 7
Copolymerization of n-butenes was carried out in Raffinate II
by the addition of 30 ~ by weight of 1-dodecene related to
the total content of olefins in the resulting mixture using a
liquid AlCl3 complex prepared according to the disclosure of
Example 5 as an initiator. The copolymerization proceeded at
-10 C during 50 min under gradual dosing of the initiator up
to a conversion rate of 85 ~ related to the total content of
olefins. The obtained copolymer had a molecular weight Mn of
860, a viscosity index of 105 and a pour point of -31 C. The
consumption of AlCl3 related to the product was 0.83 ~ by
weight.
Example 8
Copolymerization of n-butene in Raffinate II was carried out
with linear alpha-olefins C6 to C~6 added into the reaction
mixture in an amount of 37 ~ by weight related to the total
amount of olefins in the new resulting mixture. The poly-
merizations were carried out at +20 C under initiation with
an AlCl3 solution in ethyl chloride. The consumption of AlCl3
related to the product ranged from 0.45 to 0.75 ~ by weight.
The results are given in Table I.
2l52~92
WO 94/15894 PCT/F193/00~60
Table 1 Characteri~tics of copolymers of n-butenes in
Raffinate II with various 1-olefins (about 37 % by
weight 1-olefin, 20 C)
l-olefin Conversion Molecular Kinematic Viscosity Pour
96 weight viscosity index point
Mn Mw [cSt] C
100
C4 83.3 620 740 156.0 12.9 66
C6 92.5 690 820 155.1 13.8 82
C8 - 750 840 147.6 13.7 87
89.4 680 800 131.3 12.8 88
ClO 94.0 660 810 98.5 10.9 94
Cl~ 93.8 760 910 109.0 12.2 102 -38
C~4 96.4 680 860 64.9 9.3 122 -33
Cl6 95.4 680 860 56.5 8.6 127 -16
Polymerization conditions: initiator - aluminium chloride
in ethyl chloride,
polymerization temperature +20
C
The content of 1-olefins (C4-C~6) relates to the olefins
present in the Raffinate II only
Example 9
Copolymerization of n-butenes was carried out in a mixture of
C4 hydrocarbons (Raffinate II) obtained from the production
of MTBE. To this mixture 37 ~ by weight of 1-decene was
added, the added amount being calculated on basis of the
total amount of olefins in the new mixture formed. Before the
polymerization, 0.3 ~ by weight of gaseous hydrogen chloride
was introduced into the reaction mixture. The
copolymerization was performed at a mean temperature of +20
C by gradual addition of small amounts of a 10-~ EtAlCl~
solution in heptane in such a way that the reaction mixture
W094/15894 2~5 2 49 2 PCT/F~3/00560
16
was not overheated by more than 3 C. The polymerization was
stopped after 40 min by adding alcohol, the reaction mixture
was washed with a 5 ~ solution of soda and then with water.
The hydrocarbon layer was separated, mixed with filtration
clay and filtered under pressure. Volatile fraction was
removed by heating the reaction mixture up to 120 C at 13
Pa. The colour-less oil obtained had a number average
molecular weight Mn of 640 and a viscosity index of 97. The
consumption of EtAlCl2 related to the final product was 0.5
by weight at a 92 ~ conversion rate of the olefins.
Example 10
Copolymerization of n-butenes with 1-dodecene was carried out
in Raffinate II in an analogous way as in Example 9. The
copolymer prepared with 37 ~ by weight of 1-dodecene at a
polymerisation temperature of +20 C had a molecular weight
Mn of 111 and a pour point of -38 C. The consumption of
EtAlCl2 was 0.7 ~ by weight at a conversion rate of 93 ~.
Example 11
Copolymerization of n-butenes present in Raffinate II was
carried out with the addition of 37 ~ by weight of
1-tetradecene analogously as in Example 9. The oil obtained
at a polymerization temperature of +20 C had a molecular
weight Mn of 630, a polydispersity MWrn of 1.2, a viscosity
index of 109 and a pour point of -33 C.
Example 12
Copolymerization of n-butenes was carried out in a residue o~
a C4 fraction (Raffinate II) with the addition of 37 ~ by
weight of l-hexadecene related to the total amount of olefins '
in the same way as in Example 9 at +20 C. The prepared oil
had a number average molecular weight Mw of 820, a poly-
dispersity MW/Mn of 1.25, a viscosity index of 110 and pour
21~2~92
WO94/15894 PCTn~93/00560
17
point of -16C. The consumption of EtAlCl~ was 0.65 ~ by
weight at a conversion rate of 91 ~. Anhydrous hydrogen
chloride was added at the beginning into the initial reaction
mixture in the amount of 0.25 ~ by weight.
Example 13
Copolymerization of n-butenes present in a residue of a C4
fraction was carried out with the addition of 13 ~ by weight
of l-hexadecene at +20 C under initiation with anhydrous HCl
and EtAlCl2. A 89 ~ conversion rated was attained by gradual
dosing of the initiator into the reaction mixture for 30 min.
The obtained oil had a molecular weight Mn of 680, a
polydispersity MW/Mn Of 1.15, a viscosity index of 83 and a
pour point of -45 C. The consumption of EtAlCl2 related to
the product was 0.6 ~ by weight.
Exa~ple 14
Copolymerization of n-butenes was carried out in a C4
fraction residue with 50 ~ by weight of 1-decene at +70 C
under initiation with HCl and EtAlC12 . The polymerization
was stopped after 30 min by the addition of alcohol at a
conversion rate of 93.5 ~ by weight. The oily product had a
molecular weight Mn of 560, a viscosity index of 119 and a
pour point of -63 C.
Example 15
Copolymerization of n-butenes was carried out in Raffinate II
with the addition of 30 ~ by weight of 1-octene related to
the total content of olefins in the resulting mixture using
EtAlCl2 as an initiator. The copolymerization proceeded at
-10 C during 50 min under gradual dosing of the initiator up
to a conversion of 85 ~ by weight related to the total
content of olefins. The obtained copolymer had a molecular
weight Mn of 860, a viscosity index of 105 and a pour point
W094/1~894 2 ~ 5 2 ~ 9 2 PCT/F~3/00560
18
of -21 C. The consumption of EtAlCl2 related to the product
was 0.83 ~ by weight. Anhydrous hydrogen chloride was added
at the beginning into the reaction mixture in an amount of
0.35 ~ by weight.
~J:
Example 16
Copolymerization of n-butene in Raffinate II was carried out
by adding linear alpha-olefins C6 to Cl6 into the reaction
mixture in an amount of 37 ~ by weight related to the total
olefins in the new resulting mixture. The polymerizations
were carried out at +40 C under initiation with a solution
of EtAlCl2 and HCl as coinitiator. The consumption of EtAlCl~
related to the product ranged from 0.40 to 0.70 ~ by weight.
The results are given in Table 2.
Example 17
Copolymerization of n-butenes present in Raffinate II was
carried out with the addition of lO ~ by weight of 1-octene
and 10 ~ by weight of 1-decene at +20 C under initiation
with anhydrous HCl and methyl aluminium dichloride MeAlCl2.
The polymerization was stopped at a coversion rate of 93 ~ by
weight. The consumption of MeAlCl2 related to the product was
0.65 ~ by weight, the number average molecular weight (Mn) of
the oily product was 610, the viscosity index 95 and the pour
point -55 C.
Example 18
Copolymerization of a n-butenes mixture in the Raffinate II
was carried out with 50 ~ by weight of l-decene under
initiation with HCl and butyl aluminium dichloride BuAlCl2 at
+50 C.
The isolated polymer had a molecular weight Mn of 550, a
viscosity index of 108 and a pour point of -51 C. The
WO 9411S894 21 S 2 4 9 2 PCT/~93100560
consumption of BuAlCl~ was 10.73 ~ by weight at a conversion
rate of olefins of 92 ~ by weight.
Table 2 Characteristics of copolymers of n-butenes in
Raffinate II with various 1-olefins (about 37 % by
weight 1-olefin, 40 C)
1-Olefin Conversion Molecular Kinematic Viscosity Pour
weight viscosity index point
Mn Mw [cSt] C
100
C4 89.9 560 690 68.4 7.9 74
C6 90.9 490 610 40.3 5.8 78
C8 95.2 520 620 45.8 6.7 98
C~0100.0 570 720 48.6 7.0 99
C~283.2 500 680 25.1 4.7 107 -61
Cl492.1 530 700 26.3 5.0 115 -41
C~690.8 660 820 56.6 8.1 111 -23
Polymerization conditions: initiator system: ethyl-
aluminium dichloride,
polymerization temperature +40
C
aContent of 1-olefins (C4-CI6) relates to the olefins present
in the Raffinate II only
