Note: Descriptions are shown in the official language in which they were submitted.
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FLUID ~l~lul~ES OF METHYLIDENE- OR METHYL-SU~3Sll~u
LINEAR HYDROCARBONS AND DERIVATIVES THEREOF
Technical Field
This invention relates generally to diene oligomers and
more specifically to linear ~,~-diene oligomers which have
reactive vinylidene groups along the backbone of the
5 oligomer chain and which are useful as lubricants and
lubricant additives.
Backqround
Synthetic hydrocarbon lubricants are known in the art.
For example, polyalphaolefins (PAO~s) are made by
oligomerizing C6 to C20 ~-olefins~ These oligomer fluids are
usually hydrogenated to improve their stability to oxida-
tion. The residual internal double bond in each molecule
can also be functionalized to form, for example, al~yl
phenols, carboxylic acids and esters, alcohols, mercapta~s,
aldehydes, and sulfonates. However, the hindered nature of
the double bond can make functionalization difficult,
especially with higher oligomers. Also, because only one
double bond is available, the ability to form multifunc-
tional molecules is limited.
U.S. Pat. No. 5,306,856 granted April 26, 1994 to
Streck et al. describes a method of manufacturing
methylidene-group-containing ~,~-unsaturated oligomers from
~,~-diolefins in the presence of organoaluminum compounds as
catalysts. The reaction is performed at 150~-350~C. The
products of the reaction are identified by the formula:
_ ' _, R~
where R and R' eac~ independently represent hydrogen or an
alkyl, aryl, aralkyl or cycloalkyl group; x is l or a number
between 3 and 25; y = x or x + 2; n is a number between 1
and 99; and
SUBSTITUTE St~EET ~Rl ~LE 26)
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~ Ck = (x+4)(n+2)-(n+1)
is the expression for the sum of the C-atoms in the chain.
The Invention
We have found that substantially straight chain, low
molecular weight synthetic fluids can be prepared by
oligomerizing ~,~-dienes using an aluminum alkyl catalyst.
These oligomers possess a series of vinylidene groups along
the backbone of the oligomer chain which are readily
available to react so as to permit the easy formation of
derivatives of the oligomers.
This invention provides, inter alia, fluid mixtures of
specified hydrocarbons meeting an array of structural
criteria which, whether end-capped or not, and whether
hydrogenated or not, have desirable lubricating properties
such as suitably low pour points and/or low NOACK volatility
and/or very high viscosity index and thus can be used as
base oils or as components in formulating lubricants.
In one embodiment of the invention there is provided a
hydrogenated saturated synthetic lubricant which has
excellent lubricant properties, including low NOACK
volatility and a very high viscosity index, said lubricant
consisting essentially of a mixture of hydrocarbons of
particular chemical structures described hereinafter.
In accordance with an embodiment of this invention
there is provided a process for preparing a substantially
linear oligomer of a ~,m-diene which has vinylidene groups
along and directly attached to the oligomer chain. The
process comprises reacting an ~,~-diene in the presence of
an organo-aluminum catalyst so as to form said oligomer.
Pursuant to one preferred embodiment of this invention
there is provided a novel fluid mixture of vinylidene hydro-
carbons having linear backbones and methylidene group(s)
depending therefrom, sald mixture consisting essentially of
hydrocarbons having the formula
SUBSTITUTE SHEET (RULE 26)
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R1 - [_-Il_R2_]x [-9-R3-~y ~-C-R~-]s - C - R5 (I)
CH2 CH2 CH~ CH2
wherein
R1. and R5 are omega-alkenyl groups having,
independently, n or n+2 carbon atoms, and where n is
the m;niml~ number of linear carbon atoms in each said
alkenyl group and is at least 6;
R2 is an alkylene group that has a length of n carbon
atoms and which may contain one or more hydrocarbyl
substituents depending therefrom, but which preferably
is an unsubstituted polymethylene group having n carbon
atoms;
R3 is an alkylene group that has a length of n+2 carbon
atoms and which may contain one or more hydrocarbyl
substituents depending therefrom, but which preferably
is an unsubstituted polymethylene group having n+2
carbon atoms;
R4 is an alkylene group that has a length of n-2 carbon
atoms and which may contain one or more hydrocarbyl
substituents depending therefrom, but which preferably
is an unsubstituted polymethylene group having n-2
carbon atomsi and
x, y, and z are, independently, integers from 0 to
about 100. This mixture is further characterized in
that:
a) the groups depicted within brackets in formula (I) are
disposed within the individual molecules such that
substantially all molecules of formula (I) in which the
sum of x, y and z is 3 or more contain at least two
different groups depicted within brackets in that
formula; and
b) this mixture of hydrocarbons has a pour point of -10~C
or below, and a viscosity index of 150 or above.
Those molecules as depicted in formula (I) in which the sum
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of x, y and z is 3 or more that do not contain at least two
different groups depicted within brackets in formula (I)
contain the depicted groups containing R2, but do not contain
the depicted groups containing R3 or R4.
Another preferred embodiment of this invention provides
novel fluid m~ixtures of end-capped vinylidene hydrocarbons,
said mixture consisting essentially of hydrocarbons having
the formula:
R - [-C-R~-]X [-f-R3-]y [-C-R~-]z - C - R' (II)
CH~ CH2 CH2 CH2
wherein
R and R' are, independently, aliphatic hydrocarbon
groups each having from 12 to about 40 carbon atoms and
one olefinic double bond, mostly as a methylidene
group; and R2, R3, R4, x, y, and z are as defined above
with reference to formula (I).
This mixture is further characterized in that:
a) the groups depicted within brackets in formula (II) are
disposed within the individual molecules such that
substantially
all molecules of formula (II) in which the sum of x, y
and z is 3 or more contain at least two different
groups depicted within brackets in that formula; and
b) this mixture of hydrocarbons has a pour point of -10~C
or below, and a viscosity index of 150 or above.
Those molecules as depicted in formula (II) in which the sum
of x, y and z is 3 or more that do not contain at least two
different groups depicted within brackets in formula (II)
contain the depicted groups containing R2, but do not contain
the depicted groups containing R3 or R4.
Another feature of the above-described fluid mixtures
o~ vinylidene hydrocarbons of formulas (I) and (II) is that
they can contain up to about 2 mol percent (preferably no
more than about 1 mol percent) of olefinically unsaturated
hydrocarbon molecules in the same molecular weight range as
the molecules of formulas (I) and (II) but in which the
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linear backbone itself contains internal olefinic
unsaturation, and for each such internal double bond there
is one less dependant methylidene group in the molecule.
The amount of such internal double bond-containing molecules
in the fluid product mixture is primarily a function of
reaction temperature used in producing the mixture. For
example, when the product is formed at temperatures in the
range of about 120 to about 130~C the product will typically
contain up to about 1 mole percent of such internal double
bonded molecules. But at temperatures above about 140~C the
extent of internal double bond formation can increase
dramatically. Thus at about 140~C, products having at least
12 mol percent of internal double bonded molecules are
typically formed. In situations wherein the product is to
be used without prior hydrogenation as a lubricant or
lubricant additive for high temperature service in the
presence of air, the amount of internal double bond-contain-
ing species in the vinylidene hydrocarbon product should be
no more than about 2 mol percent, as substantially greater
amounts can lead to oxidative instability and possible chain
scission.
A further preferred embodiment of this invention
comprises a novel fluid mixture of hydrocarbons having
linear backbones and methyl group(s) depending therefrom,
said mixture consisting essentially of hydrocarbons having
the formula
R6 - [-Cl-R2-]x [-C-R3-]y [-C-R~-]~ - C - R7
CH3 CH3 CH3 CH3
wherein
R6 and R7 are alkyl groups having, independently, n or
n+2 carbon atoms, and where n is the minimum number of
linear carbon atoms in each said alkyl group and is at
least 6; and R2, R3, R4, x, y, and z are as defined
above with reference to formula (I).
This mixture being further characterized in that:
a) the groups depicted within brackets in formula (III)
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are disposed within the individual molecules such that
substantially all molecules of formula (III) in which
the sum of x, y and z is 3 or more contain at least two
different groups depicted within brackets in that
formula; and
b) this mixture of hydrocarbons has a pour point of -10~C
or below, a NOACK volatility of 9 or below, and a
viscosity index of 150 or above.
Those molecules as depicted in formula (III) in which the
sum of x, y and z is 3 or more that do not contain at least
two different groups depicted within brackets in formula
(III) contain the depicted groups containing R2, but do not
contain the depicted groups containing R3 or R4.
Yet another preferred embodiment of this invention is
a novel fluid mixture of hydrocarbons having linear
backbones and methyl group(s) depending therefrom, said
mixture consisting essentially of hydrocarbons having the
formula
R - ~-C-R2-]X ~-C-R3-]y ~-C-R~-]z - C - R~
l l l l (IV)
CH3 CH3 CH3 CH3
wherein
R and R' are alkyl groups having, independently, 12 to
about 40 carbon atoms; and R2, R3, R4, x, y, and z are
as defined above with reference to formula (I).
This mixture is further characterized in that:
a) the groups depicted within brackets in formula (IV) are
disposed within the individual molecules such that
substantially all molecules of formula (IV) in which
the sum of x, y and z is 3 or more contain at least two
different groups depicted within brackets in that
formula; and
b) this mixture of hydrocarbons has a pour point of -10~C
or below, and a viscosity index of 150 or above.
Those molecules as depicted in formula (IV) in which the sum
of x, y and z is 3 or more that do not contain at least two
different groups depicted within brackets in formula (IV)
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contain the depicted groups containing R2, but do not contain
the depicted groups containing R3 or R4.
Another feature of the above-described fluid mixtures
of methyl-branched hydrocarbons of formulas (III) and (IV)
is that they may contain up to about 2 mol percent of one or
more saturated hydrocarbon molecules formed by hydrogenation
of the internally unsaturated hydrocarbon molecules referred
_ to above in connection with formulas (I) and (II).
Additional preferred embodiments of this invention are
fluid mixtures in accordance with the respective formulas
(I), (II), (III) and (IV) above wherein the sum of x, y and
z in substantially all molecules of formula (I), (II), (III)
or (IV) (as the case may be) is no higher than about 100,
more preferably no higher than about 10, and most preferably
no higher than about 6.
Non-limiting examples of ~,~-dienes for use in the
above process of the invention, are ~,~-dienes containing
from 8 to 30 carbon atoms in the chain. They can be
substituted elsewhere than at the double bonds by alkyl,
cycloalkyl, aryl or aralkyl groups having from 1 to 30
carbon atoms, but preferably are substantially linear,
unsubstituted ~,~-dienes. Specific ~,~-dienes include 1,7-
octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,
1,11-dodecadiene, 1,12-trideca-diene, 1,13-tetradecadiene,
1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadeca-
diene, 1,17-octadecadiene, 1,l8-nonadecadiene/ and 1,19-
eicosadiene including mixtures thereof. By choosing
different dienes, the spacing between the vinylidene groups
can be selected to provide oligomers whose properties are
tailored to specific applications. It is to be noted tha~
when a single ~,~-diene hydrocarbon is used in the
oligomerization, n in the above formulas is an integer that
is two less than the number of linear carbon atoms in the
diene. For example, if 1,7-octadiene is oligomerized, n is
6, whereas in products derived from 1,9-decadiene, n is 8.
Products of this type wherein n is in the range of 6 to 18
are preferred.
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Suitable aluminum alkyl compounds for use as catalysts
preferably contain two or three alkyl groups, each having
from 1 to about 20 carbon atoms. Non-limiting examples of
aluminum alkyls include trimethylaluminum, triethylaluminum,
tri-n-propylaluminum, tri-n-butylaluminum, triisobutyl-
aluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-
decylaluminum, tri-n-dodecylaluminum, and diisobutylaluminum
hydride. The catalysts are used in effective amounts to
oligomerize the ~,~-diene. Preferably, mole ratios of
catalyst to diene of from about 1:1,000 to 1:10 are used
with mole ratios of from about 1:20 to 1:100 being
preferred.
The reaction can be carried out neat or in the presence
of an inert dry organic solvent. Non-limiting examples of
suitable solvents or diluents include linear and cyclic
aliphatic hydrocarbons containing from about 5 to 20 carbon
atoms, such as pentane, isopentane, hexane, cyclohexane,
heptane, octane, decane, and hexadecane, and aromatic
solvents having from about 6 to 20 carbon atoms such as
benzene, toluene, xylene, ethylbenzene, and cumene
mesitylene.
The reaction temperatures are chosen to provide
oligomerization in a reasonable time without causing side
reactions such as isomerization of the vinylidene groups or
the formation of excessive amounts (i.e., more than about 2
mol percent) of deep internal olefins and, preferably, range
from about 50~ to 140~C. More preferably the temperature
ranges from 100~ to 140~C and most preferably from 120~ to
125~C. As noted above, at temperatures above 140~C the
mechanism of internal olefin formation becomes significant.
Temperatures of 120~ to 125~C. maximize the formation of the
desired vinylidene products (90~+) at reasonable reaction
times. Reaction pressures preferably range from atmospheric
to about 1,000 psig. The oligomers have number average
molecular weights Mn ranging from about 150 to 3,000 and,
preferably, from about 250 to 1,800.
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g
"End-capping" of the vinyl groups at the end of the
oligomer chain is accomplished by adding C6 to C30 alpha mono-
olefins to the reaction. A vinylidene is formed at the
reaction site but the new ends of the polymer are saturated
and unreactive. Under relatively mild conditions, the
vinylidene groups along the chain do not react. Some of the
added alpha-olefins react with themselves to form vinylidene
compounds.
Non-limiting examples of alpha-olefins which can be
used for end-capping include 1-butene, 1-pentene, 1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
and 1-octadecene, including mixtures thereof. Preferably,
amounts of from about 0.05 to 5 moles of alpha-ole~in per
mole of ~,~-diene are used.
The vinylidene hydrocarbon mixtures of formula (I)
above, exemplified by oligomerization of 1,9-decadiene,
comprise the following dimer, trimers, tetramers and
pentamers (as well as higher oligomers): 9-methenyl-1,19-
eicosadiene; 9,18-di-methenyl-1,29-triacontadiene; 9,20-
dimethenyl-1,29-triaconta-diene; 11,18-dimethenyl-1,29-
triacontadiene;9,18,27-tri-methenyl-1,39-tetracontanadiene;
9,20,27-trimethenyl-1,39-tetracontanadiene; 9,20,29-
trimethenyl-1,39-tetracontanadiene; 11,18,27-trimethenyl-
1,39-tetracontanadiene; 9,18,27,36-tetra-methenyl-1,49-
pentacontanadiene; 9,18,27,38-tetramethenyl-
1,49-pentacontanadiene;9,18,29,36-tetramethenyl-1,49-penta-
contanadiene; 9,18,29,38-tetramethenyl-1,49-pentacontana-
diene; 9,20,27,36-tetramethenyl-1,49-pentacontanadiene;
9,20,27,38-tetramethenyl-1,49-pentacontanadiene;9,20,29,36-
tetramethenyl-1,49-pentacontanadiene; 11,18,27,36-tetra-
methenyl-1,49-pentacontanadiene; 11,18,29,36-tetramethenyl-
1,49-penta-contanadiene; or 11,20,27,36-tetramethenyl-1,49-
pentacontana-diene.
Hydrogenation of the above product mixture yields a
mixture as depicted in formula (III) above, that includes
the following C20, C30, C40, C50 (and higher molecular weight)
methyl-branched hydrocarbons: 9-methyl-1,19-eicosane; 9,18-
SUBSTITUTE SHI--ET (RULE 26)
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dimethyl-1,29-triacontane; 9,20-dimethyl-1,29-triacontane;
11,18-dimethyl-1,29-triacontane; 9,18,27-trimethyl-1,39-
tetra-contane;9,20,27-trimethyl-1,39-tetracontane;9,20,29-
tri-methyl-1,39-tetracontane;11,18,27-trimethyl-1,39-tetra-
5 contane; 9,18,27,36-tetramethyl-1,49-pentacontane;
9,18,27,38-tetramethyl-1,49-pentacontane; 9,18,29,36-
tetramethyl-1,49-pentacontane; 9,18,29,38-tetramethyl-1,49-
pentacontane; 9,20,27,36-tetramethyl-1,49-pentacontane;
9,20,27,38-tetra-methyl-1,49-pentacontane; 9,20,29,36-
tetramethyl-1,49-pentacontane;11,18,27,36-tetramethyl-1,49-
pentacontane; 11,18,29,36-tetramethyl-1,49-pentacontane; or
1l~2o~27~36-tetramethy~ 49-pentacontane.
The endcapping reaction is illustrated below using 1-
dodecene as the alpha-olefin. Mixtures of alpha-olefins can
also be used.
Rl - [-Il-R2-~x [-C-R3-]y [-C-R~-]~ - C - R5 2 C = C - C10
CH~ CH2 CH~ CH2
.
Cq - [-C-R~-]X [-C-R3-]y [-C-R~-], - C - C~
CH2 CH2 CH2 CH2
where Rl, R2, R3, R4, R5, x, y and z are as defined in
connection with formula (I) above, and Cq is a C10 or Cl2
hydrocarbyl group.
The oligomers can be hydrogenated by conventional
methods. Supported nickel catalysts are especially useful.
For example, nickel on a Kieselguhr support gives good
results. Batch or continuous processes can be used. For
example, the catalyst can be added to the oligomer liquid
and stirred under hydrogen pressure or the oligomer liquid
can be passed through a fixed bed of the supported catalyst
under hydrogen pressure. Hydrogen pressures of about 100 to
1,000 psig at temperatures of about 150~C to 300~C are
especially use~ul.
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The vinylidene groups along the oligomer chain of the
unhydrogenated oligomer can also be ~eacted to form useful
derivatives. For example, the groups can either be coupled
with another oligomer molecule, cross-coupled with other
olefins, ~uch as vinylidenes, to form branched polyolefins
and/or reacted with various compounds such as acrylic acid,
maleic anhydride succinic anhydride, phenols, halogen,
hydrogen halides, or hydrogen sulfide to add functional
groups along the polymer chain. Also, non-end-capped
oligomers can be recovered from the oligomerization reaction
and the different reactivities of the vinylidene and vinyl
groups used to sequentially react the vinylidene group and
the vinyl groups with different reagents to form multi-
functional compounds or two oligomer molecules can be
coupled through the vinylidene group to form tetra-alpha-
olefins.
The invention is further illustrated by, but is not
= intended to be limited to, the following examples.
Example 1
A mixture of 99.8 g of 1,7-octadiene and 4.6 g of tri-
n-octyl aluminum (TNOA) was prepared. The mixture was then
stirred and heated to 115~C, maintained near that temper-
ature for 52 hours, and cooled. The pressure was ambient,
and the vapor space was free of air and moisture. The
reaction mass was sampled after 0, 21, 45, and 93 hours from
the beginning of the run. At the end of the reaction, 52.0
g of hexane were added to the "gel" as a diluent. Then,
54.6 g of 25~ caustic were added to "kill" the TNOA. The
aqueous layer was separated from the organic layer in a
separatory funnel.
Time (hours) o 21 45 93
wt. ~ octadiene100.0 91.2 66.6 10.4
mol ~ alpha 100.0 97.0 88.3 16.0
mol ~ vinylidene0.0 3.0 11.7 78.8
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Examples 2-7
A series of oligomerizations of 1,9-decadiene were
conducted as in Example 1 using tri-n-octylaluminum as the
catalyst with the catalyst loadings, reaction times and
temperatures listed in Table 1 below. Increasing the temper-
ature greatly enhanced the conversion o~ monomer. NMR
analyses showed that the products are almost exclusively
vinylidenes.
SUBSTITUTE SH EET (RU~E 26)
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--13--
o
~ :, 0 za ~ za
V ~- ~ N N ~- N ~ N ~-
a ~- ~ O ... .. .. O ... ..
tll C U Z ~I N_I 111 U~ 0 N 0
.~ _
V~ ~ ~I N U~ N
Q) ~
E o
.,1 ~ 0 0 ~ O~ N O~ ~r
E-l -- ~ I' N ~ D N tt1 N
~ U u~ o o 1~
V o ul O O O O O r~ U) o
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H m
_i a) ~
o o o o o
1~ v a) _~ N N ~~ ~~ ~ ~) ~.D
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a .c
115 ~ 01 0 0 ~ I ~I N
u ~a ~
v .~ ~ ~ ~ v
v ~ r ~ r o - ~ -
v~ o o ~ o o o
~ r - c - ~ r~
U v 1~ V t~ ~It LJ r~ V 1~
N N r~ D r ~:
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Example 8
1,9-Decadiene (1122.6 grams) was oligomerized using 95
grams of tri-n-octyl aluminum catalyst. The temperature
ranged from about 105~C to 118~C and the total reaction time
was 64.2 hours. The analysis of the product is shown below.
Wt ~ Mole
decadiene 40.3 vinyl 74.3
C20 30.0 vinylidene 23.7
C30 15.7 tri-substituted 0.0
other lights 0.9 internal 2.0
C40 7.4
Cso 3.4
C60 1.3
other heavies 1.1
The product was fractionated by distillation and a mostly
decadiene trimer (C30) fraction was hydrogenated. The
synthetic fluid had a very low NOACK volatility and a very
high viscosity index. Table II shows its properties
compared to a commercial hydrogenated 4 cSt 1-decene PAO.
TA~3LE II
Visc. (cSt) Visc. (cSt) Pour Pt. NOACK VI
~ 100~C ~ 40~C (~C) (wt. ~)
Ex. 8 3.6 12.3 -18 7.4 195
PAO 3.9 16.8 <-65 13.0 129
Example 9 illustrates another embodiment of the
invention in which the ~,~-diene oligomer is reacted with a
molar excess of a vinylidene olefin using a BF3 catalyst
which is activated by a proton source such as H2O or an
alcohol. The vinylidene olefin preferably contains from
about 8 to 60 carbon atoms and is a dimer of an ~-olefin
having from about 4 to 30 carbon atoms. More preferably the
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vinylidene olefin has from about 12 to 40 carbon atoms and
is reacted in amounts of from about 0.1 to 20 moles per mole
of ~,~-diene oligomer.
Example 9
A C20,30 decadiene oligomer fraction (C20 1.9 mole, C30 1.0
mole) was reacted with excess (27.5 mole) Cl6 vinylidene (C8
dimer) using a BF3-MeOH catalyst (O.896 BF3 and 0.13 wt.
MeOH). The conversion was 71 wt. after 56 minutes. Of all
the remaining material, 99 wt. ~ was Cl6 tri-substituted
olefin. A:Eter the unreacted Cl6 and by-product C3236 were
distilled away a very linear medium viscosity product
resulted. The properties of the unhydrogenated product
compared with a 10 cSt l-decene PAO product are shown in
Table III below.
TABLE III
Vis. (cSt) Visc. (cSt) Pour Pt. VI
@ 100~C ~ -40~C (~C)
PAO 9.6 32650 -53 137
Ex. 911.6 36490 -48 147
Exam~le 10
A mixture of 98.1 grams of 1,7-octadiene and 515.2
20 grams of l-decene were reacted in the presence of 49.2 grams
of tri-n-octyl aluminum catalyst. The temperature ranged
from about 113 to 118~C and the reaction was continued for
a total of 144.6 hours. The conversion of diene was 76.7
wt. ~. The product distribution was as shown below:
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Wt.
Octadiene 3.3
C10 28.4
Cl6 1.9
Cl8 16. 3
C20 30.4
Theoretical
Other lights 0.9
C242628 13.4
C32, 34, 36 3.8
Other heavies 1.1
Exam~les 11-18
The variety and range of physical properties possessed
by unhydrogenated fluid mixtures of vinylidene hydrocarbons
of this invention are illustrated by the data in Tables IV
and V. The tables identify the diene subjected to
oligomerization ("Cl0" is 1,9-decadiene and "C8" is 1,7-
octadiene) and where end-capping was used, the 1-olefin em-
ployed as the end-capping agent was 1-decene ("C10"). In
Tables IV and V, "nd" means not determined.
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TABLE IV
ExampIe 11 12 13 14
Diene C10 Cl0 C10 C8
1-Ole~in none none none none
Dimer, wt~ 52.3 0.7 0 4.6
Trimer, wt~ 46.4 92.8 59.3 89.0
Tetramer, wt~ 1.3 6.5 38.8 6.3
Pentamer, wt~ 0 0.1 1.9 0
Visc., cSt ~ 100~C 2.15 3.29 4.06 2.06
Visc., cSt ~ 40~C 6.09 10.9 14.6 5.94
Visc., cSt ~ -25~C nd nd nd 79.4*
Pour point, ~C -36 -27 -27 -51
VI 187 191 196 165
* Vicosity at -40~C was 225 cSt
SUBSTITUTE SHE T (RULE 26)
CA 02222038 l997-ll-24
W 096/37580 PCTrUS96/07578
- 18 -
T~iBLE V
Example 15 16 17 18
Diene C8 C8 C8 C8
1-Olefin none none Cl0 C10
Dimer, wt~ 0.1 0.1 3.1 0
Trimer, wt~ 24.7 8.0 92.9 25.4
Tetramer, wt~ 68.9 41.0 4.0 50.2
Pentamer, wt~ 5.2 50.7 0 24.4
Visc., cSt ~ 100~C 3.25 26.7 2.84 5.7
Visc., cSt ~ 40~C 11.2 172 9.27 24.3
Visc., cSt ~ -25~C nd nd nd nd
Pour point, ~C -42 -36 -18 -27
VI 172 192 169 189
The fluid mixtures of this invention may be produced by
other procedures such as by synthesis and blending together
of individual compounds or by use of suitable thermal
cracking procedures. However, use of low temperature (100~
to 130~C and most preferably 120~ to 125~C) oligomerization
of ~,~-dienes is the preferred method presently known.
SUBSTITUTE SH EET tRULF 26)
