U.S. patent number 3,793,203 [Application Number 05/152,303] was granted by the patent office on 1974-02-19 for lubricant comprising gem-structured organo compound.
This patent grant is currently assigned to Sun Oil Company of Pennsylvania. Invention is credited to Gary L. Driscoll, Marcus W. Haseltine, Jr..
United States Patent |
3,793,203 |
Driscoll , et al. |
February 19, 1974 |
LUBRICANT COMPRISING GEM-STRUCTURED ORGANO COMPOUND
Abstract
Polyolefins, paraffins and polar compounds containing a
gem-structured hydrocarbon "backbone" are useful as traction fluids
or as components of traction fluids. For example, compositions,
useful as additives to libricants (e.g., components of traction
fluids), are produced by oxonolysis of polyolefins, particularly of
polyisobutylene oligimers containing at least one pair of maximally
crowded geminal methyl groups. For example, ozonolysis of the novel
polyisobutylenes can produce oxygenated derivatives (ketones,
esters, acids, aldehydes, alcohols, etc.) which are useful as
components of traction fluids. Blends of the ketones or of mixtures
of the acids and ketones with a base oil (e.g., a paraffinic lube,
naphthenic lube, a hydrogenated naphthenic or paraffinic lube,
polyolefins or hydrogenated polyolefins) are especially useful as
traction fluids or as a lubricant for a friction drive or a limited
slip differential. Other polar compounds, useful as additives to
lubricants or other mineral oil products (e.g., rubber process
oils) can be obtained by conversion of polyisobutylene oligimers to
polar compounds containing such functional groups as amine, imine,
thioketone, amide, thioester, phosphate esters of the alcohols,
ether, oxime, acyl halide, acyl hydrazide, chloride, bromide and
maleic anhydride adducts. Salts of the carboxylic acids can also be
useful as lubricant additives. A tin complex can also be made which
has antiwear properties.
Inventors: |
Driscoll; Gary L. (Boothwyn,
PA), Haseltine, Jr.; Marcus W. (Brookhaven, PA) |
Assignee: |
Sun Oil Company of Pennsylvania
(Philadelphia, PA)
|
Family
ID: |
26841732 |
Appl.
No.: |
05/152,303 |
Filed: |
June 11, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
135295 |
Apr 19, 1971 |
|
|
|
|
144165 |
May 17, 1971 |
3715313 |
Feb 6, 1973 |
|
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Current U.S.
Class: |
508/463; 568/375;
568/400; 508/505; 508/583; 252/79; 554/221; 568/342; 568/361;
568/374; 554/1; 562/544; 568/356; 568/368 |
Current CPC
Class: |
C10L
1/308 (20130101); C10L 10/08 (20130101); C10M
171/002 (20130101); C10N 2050/04 (20130101); C10M
2205/026 (20130101); C10N 2040/17 (20200501); C10M
2205/04 (20130101); C10M 2205/028 (20130101); C10M
2227/083 (20130101); C10N 2040/16 (20130101) |
Current International
Class: |
C10M
171/00 (20060101); C10L 1/10 (20060101); C10L
1/30 (20060101); C10m 001/24 (); C10m 001/26 () |
Field of
Search: |
;252/55,56S,56R,56D,79 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Cannon; W.
Assistant Examiner: Cannon; W.
Attorney, Agent or Firm: Church, Esq.; G. L. Hess, Esq.; J.
E. Bisson, Esq.; B. A.
Parent Case Text
In our parent applications (of which this application is a
continuation-in-part) Ser. No. 135,295 and Ser. No. 144,165, now
U.S. Pat. No. 3,715,313, dated Feb. 6, 1973 filed Apr. 19, 1971 and
May 17, 1971, respectively, titled "Chemical Reaction Products of
Polyisobutylene" and "Traction Transmission Containing Lubricant
Comprising Gem-Structured Polar Compound," we disclose the
production of a large number of gem-structured polar compounds, all
of which can be useful in practice of the present invention.
Claims
The invention claimed is:
1. In a friction or tractive drive comprising at least two
relatively rotatable members in torque transmitting relationship,
the improvement wherein the tractive surfaces of said members have
disposed thereon a fluid tractant composition containing from 1.0
to 100 weight percent of at least one polar compound having the
structural formula: ##SPC34##
wherein n is an integer from 1 to 30, n' is an integer 0 or 1 and
R, R.sub.1 and R.sub.2 are independently selected from methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, isopentyl,
neopentyl, cyclohexyl, methylcyclohexyl, indanyl, hydrindanyl,
cyclohexylindanyl and cyclohexylhydrindanyl and where Y is selected
from; ##SPC35##
and wherein R.sub.3 and R.sub.8 are C.sub.1-7 alkyl, or saturated,
olefinic unsaturated or aromatic cyclic or alkyl-substituted cyclic
hydrocarbons; and R.sub.4 and R.sub.5 are hydrogen or R.sub.3 ; and
wherein each of R, R.sub.3, R.sub.4 and R.sub.8, when on the same
molecule, may be the same or different, the balance of said
composition comprising a hydrocarbon oil of lubricating viscosity
and an additive in lubrication improving amounts selected from the
group consisting of extreme pressure, antioxidant, antirust,
dispersant, anticopper corrosion and antifoam.
2. A drive according to claim 1 wherein y is ##SPC36##
a vapor phase chromatogram of said composition in the C.sub.15 to
C.sub.50 carbon number region shows nearly base line resolution and
is free of any significant envelope and peaks produced by
oxygenated hydrocarbons which do not correspond to said
formula.
3. A drive according to claim 2 and containing a hydrocarbon base
stock comprising from 15 to 100 volume percent of at least one
member from the group consisting of paraffinic oils, naphthenic
oils, olefin homopolymer oils, olefin copolymer oils and said oils
which have been at least partially hydrogenated.
4. Drive of claim 1 containing oil consisting essentially of at
least four structurally different members selected from at least
one of the groups (A) or (B) wherein (A) is a branched olefin
hydrocarbon having 16, 20, 24, 28, 32, 40, 44 or 48 carbon atoms
and (B) is a branched paraffinic hydrocarbon having 16, 20, 24, 28,
32, 40, 44 or 48 carbon atoms, said hydrocarbon having the formula:
##SPC37##
wherein n is an integer from 3 to 11 inclusive, and wherein Z is:
##SPC38##
when said hydrocarbon is a paraffin, and Z is: ##SPC39##
when said hydrocarbon is an olefin and wherein said oil contains
from 0.1 to 10 weight percent of a polar compound as defined in
claim 1.
5. A drive according to claim 1 wherein said polar compound has the
structural formula ##SPC40##
6. The drive as in claim 1 and wherein n is an integer of from 3 to
20.
7. A drive according to claim 5 and containing a hydrocarbon base
stock comprising from 15 to 100 volume percent of at least one
member from the group consisting of paraffinic oils, naphthenic
oils, olefin homopolymer oils, olefin copolymer oils and said oils
which have been at least partially hydrogenated.
8. A drive according to claim 1 wherein at least one of said polar
compounds has the formula ##SPC41##
wherein Z' is ##SPC42##
wherein n is 1 to 17.
9. A drive according to claim 8 and containing a hydrocarbon base
stock comprising from 15 to 100 volume percent of at least one
member from the group consisting of paraffinic oils, naphthenic
oils, olefin homopolymer oils, olefin copolymer oils and said oils
which have been at least partially hydrogenated.
10. The drive as defined in claim 8 and wherein when Z' is (f) or
(g), n is an integer from 2 to 16 and when Z' is (c), n is an
integer from 3 to 17.
11. A drive according to claim 5 wherein a vapor phase chromatogram
of said composition in the C.sub.15 to C.sub.50 carbon number
region shows nearly base line resolution and is free of any
significant envelope and peaks produced by oxygenated hydrocarbons
which do not correspond to said formula.
12. A drive according to claim 1 and containing a hydrocarbon base
stock comprising from 15 to 100 volume percent of at least one
member from the group consisting of paraffinic oils, naphthenic
oils, olefin homopolymer oils, olefin copolymer oils and said oils
which have been at least partially hydrogenated.
13. A drive according to claim 1 wherein Y is ##SPC43##
14. A drive according to claim 1 wherein Y is ##SPC44##
15. A drive according to claim 1 wherein Y is ##SPC45##
Description
SUMMARY OF THE INVENTION
Novel polyolefin oils consist essentially of "true isobutylene
oligimers." Such oligimers are gem-structured, have crowded geminal
methyl groups and are further described hereinafter. Substantially
pure olefins of a single carbon number can be obtained as
distillate fractions of such oils. The fractions or the oils are
useful as lubricants (as for traction drives) and can be converted,
by hydrogenation or other well known reactions, into gem-structured
paraffins or polar compounds, which are useful as lubricants or
components of blended lubricants.
More generally, novel polyolefin oils of monomers of the formula
##SPC1##
Wherein R is --CH.sub.3 and --C.sub.2 H.sub.5 and R.sub.1 is an
alkyl group of from one to 10 carbon atoms, have exceptionally high
viscosity indices and high coefficients of traction and consist
essentially of unisomerized, true oligimers, such as true
polyisobutylene oligimers (e.g., C.sub.16 H.sub.32, C.sub.20
H.sub.40, C.sub.24 H.sub.48 . . . C.sub.48 H.sub.96). The novel
oils are useful as electrical oils, as chemical intermediates or as
tractants (i.e., as traction fluids or as components of traction
fluids). The hydrogenated oils are novel and especially useful as
tractants, particularly when hydrogenated to a bromine number less
than 10 (more preferably, less than five). The unique character of
these novel oils, whether olefin and/or paraffin, can be proved by
a combination of gas chromatography and nuclear magnetic resonance
spectroscopy (NMR). These olefins, and the paraffins produced by
hydrogenation thereof, are characterized by "crowded" and
sterically hindered geminal methyl and isolated methylene groups.
The individual species in the range of C.sub.16 to C.sub.48 can be
separated from the whole oil by vapor phase chromatography. One
such novel polyolefin oil having an ASTM viscosity index greater
than 85, consists essentially of monoolefins of carbon numbers
C.sub.24, C.sub.28, C.sub.32, C.sub.36 and C.sub.40 and having
repeating isobutylene structures.
In general, improved traction fluids and components of traction
fluids can be obtained by putting a polar group on a gem-structured
hydrocarbon (such as the gem-structured polyisobutylenes),
preferably, the compound contains no aromatic or olefinic
unsaturation. The resulting polar molecular appears to be more
strongly attracted to metal surfaces (compared to the parent
hydrocarbon) and thus produces higher traction. That such traction
fluids exhibit high traction is unexpected since the literature
(see Rounds, J. Chem. & Eng. Vol. 5 (No. 4) Oct., 1960, and
included references) teaches that hydrocarbons containing polar
groups on one end reduce the static and dynamic friction of mineral
oils.
For example, compounds which are useful as traction fluids or as
components of traction fluids or other lubricants can be
represented by the following structural formula: ##SPC2##
wherein n is an integer from 1-30, n' is 0 or 1, R, R.sub.1 and
R.sub.2 are one or a combination of the following radicals: methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, isopentyl,
neopentyl, cyclohexyl, methylcyclohexyl, indanyl, hydrindanyl,
cyclohexylindanyl, cyclohexyl hydrindanyl; and where Y would be any
of the following functional groups: ketone, carboxylic acid, acid
salts, ether, alcohol, ester, acyl halide, acyl hydrazide,
mercaptan, epoxy, thioester, thiolester, thioether, phosphate
(including coesters), phosphite (including coesters), sulfate,
sulfite, sulfonate, halide, oxime, imine, amide, amine or maleic
anhydride adduct. More than one functional group can be present in
a given molecule (e.g., imine and amine). Also, the indanyl
compounds and/or their cyclohexyl moieties, may be C.sub.1-6 lower
alkyl-substituted, as for example, with a methyl group. Tin
complexes, as hereinafter described, are also polar compounds
within the scope of this invention.
In the above described polar compounds, the following structural
formulae represent the various indicated functional groups:
##SPC3##
wherein X is chlorine, bromine iodine and one or more of the
hydrogens of the corresponding hydrocarbon is replaced by halogen.
##SPC4##
where n" is an integer from 1 to 12,
Amine includes ##SPC5##
and any radical which can be obtained by reduction of the amide (as
with hydrogen in the presence of Raney Nickel in a solvent, e.g.,
ethanol).
In the above structures, R.sub.3 and R.sub.8 can be an alkyl group
having one to seven carbon atoms or a cyclic or alkyl-substituted
cyclic hydrocarbon radical which can be saturated, olefinic or
aromatic (and preferably saturated), and includes (but is not
limited to) the radicals described hereinabove as R, R.sub.1 and
R.sub.2. R.sub.4, R.sub.5 and R.sub.7 are hydrogen or any of the
radicals or groups described for R.sub.3 and R.sub.8. R.sub.6 is
methyl or hydrogen. R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7,
when on the same molecule, can be the same radical or different
radicals.
A preferred class of polar compounds coming within the
above-described structural formula is obtained from the "true"
polyisobutylene oligimers, or the other vinylidene polymers,
described more fully hereinafter, by such chemical reactions as
those of the examples herein or by conventional organic reactions
used to make polar derivatives of olefins. With the polyisobutylene
oligimers, these polar compounds can be described by the formula
##SPC6##
where n, n' and Y are as previously described.
Such polar compounds are particularly useful as tractants when
added in major (e.g., 50-90 volume percent) quantities or minimum
effective amounts (e.g., 1 percent, more preferably 3 percent, and
typically at least 6 percent) to such base oils as paraffinic lubes
(preferably solvent refined and/or dewaxed), naphthenic lubes
(preferably naphthenic acid free), polyolefin fluids and synthetic
(e.g., see U.S. Pat. No. 3,287,259) naphthenic lubes. All of the
above-referred to base oils can be partially or fully hydrogenated
to improved chemical and/or thermal stability and to permit longer
periods of high traction under use conditions. Particularly useful
lubricants comprise such a hydrogenated base oil which contains
less than 5 weight percent of gel aromatic compounds and less than
10 weight percent of olefins and which also contains from 0.520
percent of a gem-structured polar compound, preferably,
corresponding to the above formula.
In one embodiment, the present invention involves lubricant
compositions comprising chemical compounds which can be produced by
the action of various chemical reagents on the polyolefins or
polyolefin oils. Similar reactions can be performed on other
gem-substituted olefins to obtain the polar component of the
present invention. Such compounds are useful as lubricant
additives, particularly lubricants for tractive drives, friction
drives and limited slip differentials.
One typical toric traction transmission is that described in Hewko
et al., "Tractive Capacity and Efficiency of Rolling Contacts,"
Proceedings of the Symposium on Rolling Contact Phenomena, Elsevier
Amsterdam, 1962, pp. 159-161.
Circulation of the lubricant throughout the drive unit can be
accomplished by spray lubrication or by splash effect. In a further
embodiment, the lubricant is applied in mist or aerosol form. For
mist lubrication, the lubricant can contain, to improve
reclassification and/or reduce stray mist, an effective amount
(e.g., 0.01-2 weight percent polymer) of a polymeric additive
selected from one or a mixture of acrylic, methacrylic, olefin
(e.g., isobutylene) and styrene (e.g., .alpha.-methylstyrene)
polymers having a viscosity average molecular weight in the range
of 10,000-2,000,000 (preferably 100,000 to 500,000). Such additives
are described in the prior art. Of the above noted polar additives
the more preferred are the polyolefins and the polar polyolefins
(e.g., poly(methyl methacrylate)).
For example, one embodiment of the invention is a traction drive
comprising at least two relatively rotatable members in torque
transmitting relationship, the tractive surfaces of said members
having disposed thereon a tractant composition containing at least
one weight percent, preferably, at least 5 percent of an
oxygen-containing chemical compound of a branched olefin
hydrocarbon having 12 to 120 carbon atoms (more preferably 20-80),
said olefin hydrocarbon having the formula: ##SPC7##
wherein n is an integer from 0 to 29 inclusive (more preferably
2-10), and wherein Z is: ##SPC8## pg,12
For example, such a compound is produced when said olefin is split
at the double bond to produce two fragments, each said fragment
having a carboxyl group at the site of the original attachment.
Other compounds can be produced by further reaction of one of said
fragments, said reaction involving either further fragmentation
(e.g., decarboxylation), further oxidation, or both.
Ozonolysis of the olefin is one means of producing said
compositions. Various novel compounds and compositions can be
produced depending upon the nature of the olefin. For example, when
Z is (A), such compounds can be produced by at least one of the
following reactions: ##SPC9##
or when Z is (B), said compounds can be produced by the reaction:
##SPC10##
or when Z is (C) such compounds can be produced by at least one of
the reactions: ##SPC11##
or when Z is (D) such compounds can be produced by the reaction:
##SPC12##
or when Z is (E) said compound is produced by at least one of the
reactions: ##SPC13##
One class of preferred oxygen containing compounds in the present
invention contain at least 11 carbon atoms (more preferred at least
15) and have the structural formula ##SPC14##
where n is an integer from 0 to 29 inclusive and wherein Z' is
##SPC15##
Typically, compositions can be obtained which contain 85-99 weight
percent of one or a mixture of such oxygen-containing compounds
having a polyisobutylene backbone.
Epoxides can be made from any of the above-described olefins by
reaction of the olefin with 30-95 percent (e.g., 90 percent)
hydrogen peroxide preferably in the presence of MoO.sub.3
catalyst.
The substituted polybutene components of the present invention are
usually liquids and have good solubility in petroleum oils.
Therefore, these derivatives can be especially useful as lubricant
additives or as additives to other oils, or petroleum products
(such as rubber process oils, hydraulic fluids, fuels,
refrigeration oils, textile machinery lubricants, coolant for a
nuclear reactor, paints, etc.). By choice of the molecular weight
(or viscosity) of the polyolefin starting material, the derivatives
can be "tailored" to a desired viscosity or molecular weight.
An important requirement of a traction fluid for use in such an
automotive transmission system is that it not only have good
traction properties, but also be a good lubricant for the
differential gear and differential ball, and a good lubricant for
the rollers and races. Although such a traction fluid could also be
used as the hydraulic fluid in the toric unit, if a hydraulic fluid
of low traction (e.g., high VI) is used, it is preferred that the
hydraulic fluid contain an indicator means, such as a distinctive
dye, so that leakage of the hydraulic fluid into the main body of
the drive unit can be detected by inspection of the main body of
traction fluid, such as by a dip-stick arrangement.
To prevent loss of fluid by vaporization and to insure against
introduction of contaminants into the fluid, the transmission
system should be fully enclosed and well sealed. With the more
volatile fluids, the seals and system should be capable of
withstanding pressure exerted by the vaporized portion of the fluid
at operating temperatures.
DESCRIPTION OF THE DRAWING
The accompanying drawing is typical of a vapor phase chromatogram,
in the C.sub.16 -C.sub.32 region, of a novel polyisobutene oil of
the present invention, and, by nearly baseline resolution (the
broken line is the base line), indicates the very minor content
therein of cracked, isomerized or other non-isobutene oligimer
species. The vapor phase chromatogram of the same oil after
hydrogenation will also be similar to that of the figure with
respect to the virtual base line resolution.
Each peak in the drawing is produced by a unique hydrocarbon
species (e.g., C.sub.20), characterized by maximally "crowded" and
sterically hindered geminal methyl and isolated methylene
groups.
Vapor phase chromatograms of commercially available polybutene oils
show that such oils do not consist essentially of true oligimers of
isobutene but contain appreciable amounts of virtually all of the
carbon number species which could be present within the carbon
number range of the oil. For example, a commercially available
polybutene oil produced distinct VPC peaks within the C.sub.16
-C.sub.29 range which could be identified as C.sub.16, C.sub.17,
C.sub.19, C.sub.20, C.sub.23, etc. This oil also had far from base
line resolution (i.e., an "envelope"), thus, indicating the
presence of many isomeric forms of the other possible carbon number
species (e.g., C.sub.18, C.sub.22, C.sub.26).
The novel polyisobutylene and hydrogenated polyisobutylene oils of
the present invention have a higher viscosity index (usually at
least 10 percent higher) than oils of the same viscosity at
210.degree.F prepared from polyisobutylene by prior art techniques.
Although the present invention includes oils consisting essentially
of isobutene oligimers in the C.sub.12 -C.sub.48 carbon number
range, the more preferred polyisobutene oils described herein, have
a viscosity index in the range of 90-130 (typically at least 95)
and consist essentially of true polyisobutene oligimers in the
20-40 carbon number range. As used herein viscosity index (unless
specified as "ASTM") refers to Viscosity Temperature Function
Viscosity Index (VTF-VI) as determined by the technique of W. A.
Wright as set forth in ASTM Bulletin No. 215, 84, (1956). This
value is similar to that obtained by ASTM D 2270 which is reported
herein as ASTM-9.
FURTHER DESCRIPTION
The proper selection must be made of solvent and catalyst in order
to produce oligimers of the olefin starting material with a minimum
of the disproportionation and isomerization that are found in oils
of the prior art processes. The solvent serves as a polar solvent
to solvate the intermediate carbonium ions formed during the
reaction, and to complex the catalyst to give a catalytically
active species which remains in the solvent phase. The nitromethane
and nitroethane also dissolves appreciable amounts of monomer but
little of the oils. This last property is believed to be partly
responsible for the narrow molecular weight distribution obtained
in the product when using these preferred solvents, which results
in a more favorable product distribution. Suitable solvents for
meeting the requirements for this purpose have been found to be
nitromethane, nitroethane, nitropropane, nitrobenzene, benzene,
lower alkyl benzenes and mixtures thereof. Suitable lower alkyl
benzenes include toluene, the xylenes and ethyl benzene. Of these
nitro compounds are preferred (with nitroethane being the
especially preferred solvent). Reasonable yields of polyisobutylene
oils having KV.sub.210 =1.5-20 and VTF-VI=95-115 can be
prepared.
The preferred process for the preparation of these fluids involves
the use of substantially anhydrous stannic chloride as catalysts
and nitromethane (or nitroethane) as solvent. However, small
amounts of water can act as reaction promotors.
The catalyst used in the preferred process (for making oils having
an average molecular weight up to about 1,000) is stannic chloride.
The stronger Lewis acid catalysts such as aluminum chloride,
aluminum bromide, titanium tetrachloride and antimony
pentachloride, do not cause any appreciable polymerization of the
monomers in nitromethane. Boron trifluoride in nitromethane gives
an oil product from isobutene having a viscosity index of about 75.
Stannic chloride does not catalyze the polymerization of these
monomers satisfactorily in such solvents as ether, water, dioxane,
acetic acid, acetone, acetonitrile, acetic anhydride, diethylene
glycol monoethyl ether, chloroform, methyl acetate,
dimethoxyethane, N-methyl-pryrolidione, and
hexamethylphosphormaide.
This system is operated at low pressure near ambient temperature,
gives high ratios of product to catalyst consumed, is highly
selective for isobutylene while tolerating a wide variety of feed
compositions, is easily controlled to give the desired products,
and is well suited for continuous recycle operation.
Product isolation involves simple phase separation. The product
distribution is suffciently narrow that simple vacuum topping is
required so no heavy by-products are formed. By-product dimer,
trimer and tetramer have some commercial uses and are also readily
cracked to isobutylene for recycle.
The most important reaction variables are the temperature and the
rate of feed relative to the amount of catalyst present (which
determines the reaction rate).
In general the temperature can be varied from -30.degree.C to
+100.degree.C with from -30.degree.C to 50.degree.C being the
preferred range 0.degree.C to 35.degree.C being an especially
preferred range. Electrical oils are generally obtained at lower
temperatures than those used in obtaining tractants. The volume of
oil prepared is generally at least equal to the volume of solvent
for a given run but the ratio of volume of oil prepared to volume
of solvent present may easily exceed 10:1. When carrying out the
process in a continuous operation by continuously removing the
reaction medium and separating the product from the catalyst and
solvent; the ratio of solvent to product generally is maintained at
from 2:1 to 1:2.
The catalyst may be used in an amount equal from 0.1 to 40 volume
percent of the solvent present, and preferably from 1 to 20 volume
percent of the solvent present.
The concentration of the free monomer in the reaction medium is
relatively small and can be controlled by the pressure maintained
at given temperature for gaseous feeds, and by rate of addition for
liquid olefin feeds, thus, controlling the molecular weight of the
product. Generally pressures of from about 1 to 275 psi absolute
have been found most suitable with from 10 to 100 psia being the
preferred range.
The feed stock can vary from 5 to 100 percent vinylidene monomer
(e.g., isobutylene), the remainder being any inert hydrocarbons.
The presence of hydrocarbon non-vinylidene compounds is not
detrimental since the vinylidene monomers as defined herein are
selectively polymerized by the catalyst system. For instance, the
efficiency of isobutene removal from mixtures of isobutene and
other butenes and/or butanes depends on the particular process but
is relatively insensitive to small amounts of impurities such as
air, water, organo-sulfur or organo-nitrogen compounds.
Distillation to produce different oil compositions can give varying
results depending on the vacuum, the apparatus, the distillation
rate and the composition of the reaction product which is
distilled. Under some conditions, considerable (>15%) trimer can
be left when the oil is topped to 80.degree.C, under other
conditions little (<10%) of the trimer or tetramer will remain.
More typically one-third of the tetramer remains in the oil, and
two-thirds of the tetramer and nearly all of the trimer are
removed. In addition, distillation is inherently limited by the
thermal stability of the oil. At temperatures (of the overhead
distillate) from 175.degree. to 225.degree.C, cracking of the oil
can become so severe that the pressure starts to increase (usually
the pressure is less than 1.0 mm Hg.
Vapor phase chromatograph (VPC) scans give good information on the
relative amounts of dimer, trimer, etc., up to about C.sub.48.
The oils produced by the process may have a number average
molecular weight of from 224 to about 2,000. The preferred product
contains principally the tetramer to decamer range. The tetramer in
the present case consists predominantly of a major and a minor
component. In the case of isobutene the hydrogenated major tetramer
component has the structure: ##SPC16##
and the minor component has the structure: ##SPC17##
This latter type of structure predominates above the tetramer
(i.e., at pentamer and above). The repeating unit for components of
the pentamer and higher oligimers is indicated by the brackets in
the formulae. The higher olefins such as 2-methylbutene-1 produce
the corresponding regular structures when oligimerized in
accordance with the previously described process conditions.
"Vinylidene" monomers suitable for preparing novel, "unisomerized"
oligimer oils, by the process described herein, have the formula:
##SPC18##
wherein --R is --CH.sub.3 or C.sub.2 H.sub.5 and R.sup.1 is an
alkyl group of from 1 to 10 carbon atoms.
These oligimers are useful in the "as produced" unsaturated forms
as electrical oils. When the oils are to be used as traction fluids
they may be hydrogenated using a conventional hydrogenation
catalyst such as Raney nickel, platinum, palladium or rhodium to
improve the oxidative stability thereof. However, the olefinic oils
are relatively stable and do not require further treatment in order
for them to be suitable for use as traction fluids. For most uses
such as traction fluid the higher molecular weight product may be
left with the tetramer to decamer range material, but the dimers
and trimers should be separated therefrom along with the monomer.
This is readily accomplished by distillation.
The oils as produced by the present process find particular
advantage in their use as traction fluids (particularly in blends
with saturated cyclic compounds) due to their high coefficients of
traction and excellent viscosity-temperature properties. The
requirements of a traction fluid are discussed in the U.S. Pat.
Nos. 2,549,377; 3,440,894 and 3,411,369. Compounds described in the
present application can be incorporated, as additives, to such
prior art traction fluids. Exemplary tractive devices in which the
traction fluids of the present invention find use are disclosed in
U.S. Pat. Nos. 1,867,553; 2,871,714; 3,006,206 and 3,184,990.
Additionally these oils find use in caulks and as reactants,
electrical oils, etc.
ILLUSTRATIVE EXAMPLES
Example 1
A three-necked, one-liter, round-bottomed flask was equipped with a
mechanical stirrer, a gas inlet tube (which also serves for
intermittent product removal), and a reflux condenser containing a
thermometer which dipped into the liquid layer and was capped with
a gas exit tube leading through a mercury bubbler to the
atmosphere. Nitromethane (200 ml.) and stannic chloride (5 ml. =
11.15 g.) were added to the flask and the isobutylene flow started.
The reaction was maintained at 3+1.degree.C with an ice bath. The
rate of isobutylene addition as 7.2 g/min. which resulted in 8.5
ml/min. of product (density about 0.85) formation. At 20 minute
intervals, the isobutylene feed and the stirrer were stopped and
the layers permitted to separate. The top oil layer (170 ml.) was
removed and the nitromethane (bottom) layer was returned to the
reactor with 5 ml. (3 percent of product volume) fresh nitromethane
added to compensate for solubility losses. After four 20-minute
runs, the reaction was stopped. The catalyst in the nitromethane
layer was readily killed with water with some production of HCl
fumes. No difficulty with an exotherm was encountered when killing
the catalyst. The combined oil layers (665 ml. including 20 ml.
nitromethane) were washed with water, with 5 percent sodium
hydroxide solution, and twice more with water. A solvent such as
pentane or hetane can be added to facilitate handling.
Although the oil of this example contains all of the novel
polyisobutylene oligimers in the series C.sub.16 -C.sub.20 . . .
C.sub.48.sup.+, fractional vacuum distillation can be used to
obtain a fraction relatively pure in a given oligimer (e.g.,
C.sub.16).
In the reaction of this example, small amounts of water in the
catalyst and/or feed material can act as a reaction promoter. If
extremely pure materials are used in the process, a small amount of
water can be added to initiate or hasten the reaction. A lower
alcohol (e.g., methanol) or acid (e.g., acetic acid) can also be
used as such a promoter. Generally, the reaction rate can be
increased (over anhydrous) by addition of 0.1-1.5 moles H.sub.2 O
per mole of SnCl.sub.4.
Polyolefin products, such as that of this example, can contain
residual tin and chlorine (e.g., 250-5,000 ppm Cl). As is discussed
in more detail hereinafter, these elements, particularly the tin,
can be present as a metal-organic compound which imparts EP
(extreme pressure lubricant) properties to the product. However, if
one desires, the chlorine (e.g., 2,000 ppm) can be removed from the
product by heating the product with calcium oxide (lime) followed
by filtration. Mild catalytic hydrogen treatment (e.g., 200 psi of
H.sub.2, 200.degree.C, Harshaw NI-0104P catalyst) can also be used
to reduce the tin and chlorine content to very low levels (e.g., Cl
from 2,000 ppm to 6 ppm).
The process of the present example can also be used to convert
butadiene to trans-1,4- and 1,2-polybutadienes. This is surprising
since prior art cationic catalyst systems convert butadiene to
cyclized polymers.
1-Decene can also be polymerized with the catalyst system of the
present example if AlCl.sub.3 is substituted for SnCl.sub.4,
particularly to get high yields of a low viscosity oil. Oxygenated
derivatives of these poly 1-decenes can be obtained by ozonolysis
in a similar manner to the process of the next example.
Example 2
Polyisobutylene oil from Example 1 (260 ml., 221.4 g.) and
anhydrous methanol (800 ml.) were placed in a three-necked,
2-liter, round-bottomed flask equipped with a gas inlet tube, a
mechanical stirrer and a reflux condenser. The flask was maintained
at about 0.degree.C by means of an ice bath while an oxygen-ozone
stream (5.2 millimoles O.sub.3 per minute) was passed through for
150 minutes. After this time the product was given a "hydrolytic
work-up," that is distilled water (300 ml.) was added and the
mixture heated to reflux for 90 minutes. The oil layer was diluted
with pentane (500 ml.) and successively extracted with about 250
ml. of water (twice); 5 percent ferrous sulfate solution; 5 percent
sodium carbonate solution; water; 5 percent sodium carbonate
solution; and water (twice).
The combined sodium carbonate and water extracts were acidified
with concentrated hydrochloric acid and extracted with ether. After
drying, the ether was removed to recover 8 g. (3.6 percent) of an
acidic fraction.
The main pentane layer was dried over calcium chlride and the
pentane removed on a steam bath to recover 194 g. (87.6 percent by
weight) of a neutral fraction. The infrared spectral analysis of
this material showed that it contained mainly carbonyl (aldehyde or
ketone) functionality with smaller amounts of hydroxyl
functionality. Analysis by gas-liquid chromatography showed that
the composition of the product was essentially a repeating pattern
of three major components in a given molecular weight range. It is
possible that other components were not separated using 6-foot
silicone oil columns and 6-foot polyethylene glycol columns.
Several minor components were also detected. Very little unreacted
oil was present. This product will be referred to sometimes
hereinafter as "PIB-ketone" or "PIB-ketone, hydrolytic
work-up."
Example 3
The neutral product (PIB-ketone) of Example 2 was tested for its
traction using a Roxana Four-Ball tester sold by Roxana Machine
Works, St. Louis, Mo. It showed a traction higher than the original
polyisobutylene (about 85 g. of torque versus about 72 g.
initially) and higher than for commercially available polybutenes
(about 66 g. of torque). This indicates that the product is useful
as a traction fluid or as a component of a traction fluid.
Example 4
The PIB-ketone of Example 2 was distilled under vacuum and
separated into several fractions. One of these fractions was
collected over the range of 80.degree.C to 110.degree.C at 0.8 mm.
Hg pressure. This fraction contained relatively few components. The
individual components were isolated by gas-liquid chromatography
and characterized by means of infrared, mass and nuclear magnetic
resonance spectral data. The predominant component was
##SPC19##
4,4,6,6,8,8-hexamethyl-2-nonanone. The two lesser components were
identified as ##SPC20##
1,1,3,3,5,5,7,7-octamethyl-1-octanol and ##SPC21##
2,2,6,6,8,8-hexamethyl-4-nonanone.
The structural formulae of higher boiling fractions correspond to
the above structures with an additional appropriate number (e.g.,
up to a total carbon number of at least about 49 for the ketones
and at least about 50 for the alcohols) of ##SPC22##
units inserted after the first t-butyl group. The "PIB-ketone" is
therefore a mixture containing predominantly ketones (at least
about 75 mole percent).
Example 5
The neutral product (50 g.) of Example 2 was dissolved in 200 ml.
of diethyl ether and reacted with an excess of lithium aluminum
hydride (8.0 g.) for 4 hours at reflux. The excess hydride was
decomposed by reaction with ethyl acetate and 200 ml. of 15 percent
hydrochloric acid was added cautiously. The ether layer was
extracted twice with 250 ml. of water, dried over calcium chloride
and the ether removed on a steam bath. The oily product (48 g., 96
percent by weight) was characterized as an alcohol by its infrared
spectrum. No carbonyl absorption remained. Its gas-liquid
chromatogram showed a repetition of two major peaks, the components
having the same molecular weight no longer being separated by this
column (6 feet of silicone rubber).
The alcohols which contain a large non-polar portion and a very
polar alcohol portion are referred to sometimes hereinafter as
"PIB-alcohol" and are useful as solvents and especially as
components of traction fluids and as components in solvents for
polymers such as polystyrene and polymethylmethacrylate. They are
also useful as intermediates in the preparation of the
corresponding acetate esters.
Example 6
The alcohols of Example 5 (20 g.) were mixed with an excess (30
ml.) of acetic anhydride and heated on a steam bath for one hour.
Excess water (100 ml.) was added to decompose the excess acetic
anhydride. The mixture was heated for an additional hour. Ether
(100 ml.) was added and the ether layer separated. The ether layer
was extracted twice with approximately 100 ml. portions of water
and then dried over calcium chloride. After the ether was removed,
an infrared spectrum was obtained on the remaining 20 g. (100
percent by weight) of oil. The infrared spectrum showed the
presence of carbonyl groups (ester) and the substantial absence of
hydroxyl groups (alcohol). This ester was useful as a traction
fluid, both alone and in blends (as with hydrogenated polyolefin
oils or hydrogenated paraffinic or naphthenic lubes or with
snythetic naphthenes or adamantanes). The ester is also useful as a
component of a gear lube, especially a lubricant for a limited slip
differential. Typically blended fluids or lubes can contain in the
range of 1 to 95 percent of such an ester and 99-5 percent of one
or a mixture of oils of the paraffinic, naphthenic or polyolefin
classes (such oils can be partially or fully hydrogenated).
Example 7
A solution was prepared in a two-liter flask by mixing
hydroxylamine hydrochloride (100 g.), water (600 ml.), 10 percent
sodium hydroxide solution (400 ml.), and ethanol (400 ml.). This
mixture was stirred while the neutral ketone product (40 ml., 34
g.) prepared according to Example 2 was added. The resulting
mixture was heated and stirred at 80.degree.C for 30 minutes. The
entire mixture was diluted with 1,000 ml. water and extracted with
500 ml. ethyl ether. The ether layer was extracted twice more with
500 ml. portions of water. The ether layer was dried over calcium
chlroide and the ether removed on a steam bath. The resulting oil
28 g. (82.4 percent by weight) was found by infrared spectroscopy
to contain oxime functions and substantially no unreacted carbonyl
functionality. This oxime is soluble in paraffinic and naphthenic
petroleum oils and is useful as a traction component or as a
viscosity stabilizer for oil-extended unvulcanized rubber
stock.
Example 8
A three-liter, round-bottomed flask was equipped with a gas inlet
tube, a mechanical stirrer and a reflux condenser. This was charged
with acetic acid (1,500 ml.) and polyisobutylene oil (500 ml.)
prepared according to Example 1. An oxygen-ozone stream (5 liters
per minute, 5.3 millimoles ozone per minute) was passed through the
mixture for 240 minutes. The temperature was maintained in the
range of 25.degree. to 50.degree.C by means of a water bath. The
reaction mixture was initially two phases, but became homogeneous
near the end of the reaction time.
The crude mixture was then given an "oxidative work-up," that is,
it was heated to 90.degree. to 100.degree.C and 30 percent hydrogen
peroxide solution (500 ml.) was added cautiously over a period of
50 minutes. The mixture was then refluxed (about 110.degree.C) for
6 hours. Ether (1,000 ml.) and water (150 ml.) were added and the
layers separated after stirring. The ether layer was washed twice
with water and twice with 0.2 percent ferrous sulfate solution (500
ml. each). The ether layer was next washed with 10 percent sodium
carbonate solution (500 ml.) and twice with water (1,000 ml. each
time). Since the sodium salt of the acid is much more soluble in
water than in sodium carbonate solution, most of the separation
occurs in the two water washes. The remaining ether layer was dried
over calcium chloride and the ether removed on a steam bath to give
the neutral ketonic fraction. Gas-liquid chromatography and
infrared spectroscopy indicated that the product was similar to the
product of Example 2, but more complex and showing indications of
significant isomerizations. This neutral fraction amounted to 232
g. (55.0 percent by weight) and is hereinafter sometimes referred
to as "PIB-ketone, oxidative work-up."
The sodium carbonate extract and the two following water extracts
were combined and made acidic by cautious addition of excess
hydrochloric acid and extracted with diethyl ether (500 ml.). The
ether layer was dried over calcium chloride and the ether removed
on a steam bath. The resulting liquid acid fraction weighed 134 g.
(32.3 percent by weight) and is hereinafter referred to sometimes
as "PIB-acid." The infrared spectrum showed the absorbance bands
characteristic of carboxylic acid functions.
Ten percent PIB-ketone in a hydrogenated solvent-refined paraffinic
oil yields a torque transmission of 67 grams compared to 58 grams
for the hydrogenated oil containing no additives. The "PIB-ketone,
oxidative work-up" produces similar results.
Any of the polar compounds described herein perform as a traction
improving additive in any petroleum oil (paraffinic or naphthenic),
including oils produced by hydrocracking, or any compatible
synthetic fluid (silicones, ester oils, polyolefins, fluorinated
fluids).
The polar compounds can be used as extreme pressure additives
and/or wear additives. The polar end of the molecule is apparently
strongly attracted to the metal surface, resulting in less wear of
the surface due to the protective action of the gem-structured
"backbone."
Example 9
The sodium salt of the acidic fraction can be readily obtained by
proceeding according to Example 8 to the first water extraction
following the 10 percent sodium carbonate extraction. When these
two extracts were mixed, a phase separated. This can be diluted
with diethyl ether and the phase separated. Drying over calcium
chloride and removal of the ether on a steam bath results in a
viscous liquid product which has an infrared spectrum consistent
with a sodium carboxylate.
This product is useful as a detergent, as a surface active agent,
and as a solubilizing agent. At least 20 percent diethyl ether can
be dissolved in water containing a few percent of this salt.
The sodium salt can also be prepared directly from the acid and a
suitable base under nearly anhydrous conditions. Salts of other
metals, e.g., lithium, calcium, magnesium, barium, zinc and cobalt,
can also be prepared in a similar manner. Such salts are useful in
compounding greases, hydraulic oils, lube oils, etc. Such salts
(e.g. Na.sup.+) can be used to increase the viscosity and/or reduce
acidity of lubricants, especially lubricants for traction or
friction drives.
Example 10
The acidic fraction prepared according to Example 8 (25 ml., 22.6
g.), methanol (200 ml.), and 96 percent sulfuric acid (30 ml.) were
placed in a 500 ml. round-bottomed flask and refluxed for 6 hours.
Water (200 ml.) and diethyl ether (200 ml.) were added and the
layers separated. The ether layer was successively extracted with
water, 10 percent sodium carbonate, and water using 200 ml. each
time. The ether layer was dried over calcium chloride and the ether
removed on a steam bath. The resulting neutral ester product
weighed 18 g. (80 percent by weight) and is sometimes referred to
hereinafter as "PIB-ester." Gas-liquid chromatography showed the
repeating pattern to be three major components at each general
molecular weight level. The repetitions were characterized by the
four-carbon ##SPC23##
unit. Infrared analysis showed the absorbance expected for ester
functionality and the absence of acid functionality.
The ester was useful as a traction fluid and as a component of
blended traction fluids. Particularly useful blended base stock
comprises 1 to 99 percent of the ester and from 99 to 1 percent of
at least one naphthene or paraffin having an SUS viscosity at
100.degree.F in the range of 25-25,000.
Example 11
An acid (1 g.) prepared according to Example 8 was mixed with
thionyl chloride (1 ml.) and carefully warmed on a steam bath until
the bubbling subsided. It was then heated and a nitrogen flow
maintained while the thionyl chloride evaporated. Finally, a water
aspirator-produced vacuum was applied to the solution which was
maintained at 80.degree.-90.degree.C for 5 minutes. An infrared
spectrum on the oil product (which had a sharp odor) showed
absorbance characteristics of acyl halides.
Example 12
The acyl halide product of Example 11 was poured into methanol (25
ml.). Water (50 ml.) and diethyl ether (50 mol.) were added and the
layers separated. The ether layer was extracted (once with 5
percent sodium carbonate [50 ml.] and twice with water [100 ml.
each]). The ether layer was dried over calcium chloride and the
ether removed on a steam bath. The resulting oily product was shown
by gas-liquid chromatography and infrared spectroscopy to be
identical with the PIB-ester of Example 10.
Example 13
An acid (50 g.) prepared according to Example 8 and excess (20 g.)
of 85 percent hydrazine hydrate (the remaining 15 percent being
water) were mixed in a 250 ml. Erlenmeyer flask with magnetic
stirring. The mixture immediately became warm. The temperature was
then raised by external heating to 125.degree.C and excess
hydrazine fumed off in a well-ventilated hood. The temperature was
maintained at 125.degree.C for 2 hours then raised to 185.degree.
to 210.degree.C for a further 2 hours. An infrared spectrum of the
very viscous material showed that it was substantially converted to
the acyl hydrazide derivative. The product was dissolved in diethyl
ether (400 ml.) and extracted twice with water (500 ml. each time).
Many of these extractions resulted in serious emulsion
difficulties. Such emulsions were broken with concentrated sodium
chloride solution, but separation times of one to two days were
still occasionally required. The ether layer was dried over calcium
chloride and the ether removed on a steam bath.
The product was very viscous and light orange in color. An infrared
spectrum was again determined and showed somewhat sharper bands.
The material was especially characterized by absorbances near 3.1M
and 6.1M, typical of acyl hydrazides. This hydrazide was different
from others because it was liquid, rather than solid, and was
soluble in pentane, white mineral oil, and other hydrocarbons, but
insoluble in water. This is to be contrasted with the hydrazide
from oleic acid, which is solid and unsoluble in oil. Adipyl
dihydrazide, acetyl hydrazide and benzoyl hydrazide are also solids
which are soluble in water but insoluble in hydrocarbons. The
hydrazide of this example is especially useful as a traction
component, or as a viscosity stabilizer in oil-extended
uncompounded synthetic rubbers because of these solubility
properties. It is also useful as an emulsifying agent and as an
antiozonant in rubber.
Example 14
The acid (10 g.) prepared in Example 8 was dissolved in methanol
(50 ml.) containing added water (1 mol.). Sodium borohydride (3 g.)
was added in small portions over one hour. Ether (100 ml.) and
water (100 ml.) were added and the layers separated. The ether
layer was extracted twice more with water (100 ml. each) and the
ether layer discarded. The combined water layers were cautiously
acidified with concentrated hydrochloric acid and ether (100 ml.)
was added. The layers were separated. The ether layer was extended
with water (100 ml.), dried over calcium chloride and the ether
removed. The resulting acid was converted to its corresponding
ester by the procedures of Examples 11 and 12. Gas-liquid
chromatography showed that the middle component of the three major
components described in Example 8 was considerably enhanced.
Since it is well known that sodium borohydride will not reduce
carboxylic acids under these conditions but will reduce esters,
ketones and aldehydes, it is reasonable to conclude that the center
and largest component represents the original acidic component and
the other peaks represent other carbonyl components not separated
due to the previously mentioned strong solubilizing power of the
sodium salt of the carboxylic acid.
Example 15
The neutral ketone (10 g.) prepared according to Example 2 was
slowly added to 85 percent aqueous acetic acid (100 ml.) containing
chromic acid (2 g.) heated on a steam bath to around 90.degree.C.
This was left for 2 hours with occasional shaking. Then water (200
ml.) and ether (200 ml.) were added. The ether layer was extracted
with water, 10 percent hydrochloric acid, 10 percent sodium
hydroxide solution and twice with water. It was then passed over a
3 foot .times. 1 inch column of chromatographic grade alumina. The
ether used for this elution was removed to leave a product of a
dissolved salt of chromium (III). Gas-liquid chromatographic
analysis showed that the resulting product was a substantially
purified form of the indicated ketone: ##SPC24##
The paramagnetic complex, europium (III)
2,2,6,6-tetramethylheptanedionate [tris(dipivalomethanato)-europium
(III)], reffered to hereinafter as Eu(DPM).sub.3), can be used as
an NMR shift reagent and, thus, provides a means of characterizing
oxygenated compounds, such as those of Example 4 and Example 15.
Eu(DPM).sub.3 can be used to produce selective proton resonance
shifts which accentuate chemical shift differences between geminal
methyl and between isolated methylene groups, as in the highly
branched alcohols and ketones.
Example 16
The reaction product of Example 1 contains substantial amounts of
tin and chlorine. More probably, the tin and chlorine are
chemically combined, in a highly soluble and compatible form, with
one or more isobutylene oligimers. In any event, the recovered
polyisobutylene oil can also contain such tin and chlorine. Such a
novel tin and/or chlorine containing polyisobutylene oil has
improved antiwear properties (e.g., a 4-ball tester "wear-scar" in
the order of 0.4 to 0.6 mm. compared to about 0.75 mm. for a
solvent refined paraffinic lube of comparable viscosity). Chemical
derivatives (such as those of the preceeding Examples 2 to 6 and
10) can also exhibit improved antiwear properties, which can be
caused in whole or in part by inclusion of such tin and chlorine
or, perhaps, the improved antiwear properties may be, in whole or
in part, an inherent property of said derivative.
An antiwear additive (e.g., for incorporation in conventional
naphthenic distillate oils, hydrorefined oils, hydrocracked oils,
white oils, solvent refined paraffinic oils or mixtures of two or
more such oils) can be obtained from such reaction products (or tin
and chlorine containing oils) by such means as extraction with a
solvent (preferably acetone) for the presumed organo tin-chlorine
complex. Preferred solvents comprise acetone, ethanol, methanol,
methyl ethyl-ketone, dimethyl formamide, furfural, nitromethane,
nitroethane, and the like; that is, solvents which will not
dissolve the oil but will dissolve the more polar complex. Readily
detectable antiwear protection is provided by such additives at
concentration levels which impart 100 parts of tin per million
parts of oil, with a typical range being 50 ppm. to 10 weight
percent of tin.
Therefore, one aspect of the present invention is novel lubricating
oil additives comprising the tin-containing products of the
polymerization of isobutylene using stannic chloride catalyst, such
polymerizations being carried out between -80.degree.C and
100.degree.C at a pressure from 0-250 psia. These additives can
contain from 0.005 to 50 weight percent tin.
These compositions can also be used as additives to fuels (e.g.,
diesel oil, gasoline and jet fuel) to prevent wear.
A one-liter round bottom three-necked flask equipped with a
mechanical stirrer and a thermometer was charged with nitroethane
(200 ml.) and stannic chloride (5 ml. = 11.2 g.). The temperature
was maintained at 30.degree.C with an external ice bath while
isobutylene was bubbled in for 1 hour. After this time the stirring
was stopped and the upper oil layer (530 ml.) was separated from
the lower nitroethane layer (160 ml.). After water washing and
drying over calcium chloride, the oil layer was distilled to get a
fraction boiling up to 82.degree.C at 2 mm. Hg (which was
discarded), a fraction boiling from 82.degree.C at 2 mm. Hg to
175.degree.C at 1 mm. Hg,KV.sub.210.sub..degree.F =18.14 cSt.
In the same equipment, except that the flask had a volume fo 500
ml., the charge was nitromethane (200 ml.) and stannic chloride (20
ml. = 44.6 g.). The temperature was maintained at 15.degree.C for
21 minutes at the same rate of isobutylene addition used before.
The upper layer was washed with water and dried over calcium
chloride. It was then distilled to remove distillate boiling up to
80.degree.C at 1 mm. Hg pressure. The remaining oil residue
(KV.sub.210.sub..degree.F = 46.74 cSt) was saved for wear
testing.
In the same equipment, the charge was nitromethane (200 ml.),
pentane (200 ml.), stannic chloride (20 ml. = 44.6 g.) and water
(150 microliters). The temperature was maintained at-10.degree.C
for one hour at the same rate of isobutylene feed. The mixture was
allowed to stir for an additional 30 minutes. The oil product was
washed and dried over calcium chloride. The pentane was removed
under aspirator vacuum and the product distilled to a boiling point
of 80.degree.C at 1 mm. Hg, the small amount of the distillate
being discarded. The bottoms (KV.sub.210.sub..degree.F about 420
cs) yield was about 500 ml. It contained 4.5 percent tin and 2.5
percent chlorine after filtration through distomatious earth at
80.degree. to 100.degree.C. This oil (100 ml.) was extracted three
times with acetone (25 ml. each time). The extracts were combined
and the acetone was removed by heating to 90.degree.C under a
stream of nitrogen. The extracted oil, about 90 ml., and the
extract, 10 ml. had similar viscosities. The initial oil had 4.6
percent tin; the extracted oil had 1 percent tin; and the extract
33 percent tin. This oil and the extract, as with the other
tin-containing products referred to above, can be added to
lubricants to impart antiwear properties thereto.
Example 17
A polyisobutylene oil (33 g., about 1 mole) prepared according to
Example 1 was dissolved in carbon tetrachloride (150 ml.) and
bromine was added dropwise to the stirred solution. White fumes
could be seen above the reactor. These fumes tested very acidic on
moist indicator paper. The fumes, caused by the presence of
hydrogen bromide, indicate that a substitution reaction was
occuring as well as the expected addition reaction. Bromine
addition was continued until the color of unreacted bromine
persisted for several minutes of warming. The total amount of
bromine added was about 40 grams or 21/2 times the theoretical
amount needed for the addition reaction. The CCl.sub.4 layer was
extracted twice with water, once with sodium bisulfite solution (to
remove the excess bromine) and twice more with water. The CCl.sub.4
was removed by heating on a steam bath to leave a light brown oil,
sometimes referred to hereinafter as "PIB-bromide." Its infrared
spectrum showed CH, CC and CBr functionality. The oil was a source
of active halogen and was found to be useful as an anti-weld
component of cutting oils. The yield was 60 grams of isolated
product oil. The chloride can also be prepared by a similar
reaction of the olefin with chlorine and is useful as an EP
additive, particularly in lubrication of a traction or friction
drive. PIB-bromide (or individual bromated polybutenes) can be
reacted with diamines or other polyamines (e.g., at reflux in
dimethyl formamide solvent) to form an imine-amine, those of the
following structure being especially good traction fluid
components: ##SPC25##
Preferably n is 2-10 (e.g., 2) and n' is 1-20 (e.g., 3). A
preferred polar tractant is
5,5,7,7,9-hexamethyl-4-azadecylamine.
Example 18
Polyisobutylene oil (330 g., about 1 mole) prepared according to
Example 1 was mixed with maleic anhydride (100 g., about 1 mole)
and heated to 225.degree.C (attained over a period of about 1.5
hours) in a stirred flask equipped with a reflux condenser. The
reaction could be followed by infrared spectroscopy. Over a period
of time, the absorbance due to the double bonds in the oil
disappeared. At the same time, the absorbances due to maleic
anhydride diminished and new bands appeared. These still indicated
an anhydride functionality. After 6 hours, the reaction was stopped
and allowed to cool and stand overnight. The mixture developed some
solid content during this time. Pentane (500 ml.) was added and the
mixture cooled in ice to case additional precipitation. The solids
were filtered from the mixture on a porous glass filter using a
small amount of cold pentane to wash the solids. The white solid
weighed 23 g. when dry and had an infrared spectrum which showed it
to be unreacted maleic anhydride. The pentane was removed on a
steam bath to give a very viscous, sticky oil. The yield was 400 g.
The infrared spectrum of the derivatized oil showed a little
remaining maleic anhydride, with a large amount of other anhydride,
probably polyisobutylene succinic anhydride. This viscous oil was
useful as a detergent, as an antiwear agent and as an intermediate
in the production of a "hydrazide" derivative.
Example 19
The product of Example 24 (42 g., about 0.1 mole) was stirred and
85 percent hydrazine hydrate (11.8 g., about 0.2 mole) was added.
The temperature of the mixture rose to about 80.degree.C during the
addition. The resulting mixture was stirred for 1 hour, then heated
to 150.degree.C while nitrogen was passed through the mixture for 2
hours. This removed the excess hydrazine and converted the portion
present as a salt into hydrazine. The resulting mixture was
dissolved in ether and extracted with water to remove hydrazine and
its salts. The ether was removed to leave a very viscous, sticky,
yellow-brown oil (33 g. or 70 percent of theory). The infrared
spectrum of this material was similar to the infrared spectrum of
other acyl hydrazides. It is useful as a component of a traction
fluid.
Example 20
Polyisobutylene oil, produced as in Example 1, was fractionally
distilled, at atmospheric pressure, to obtain a product which
contained at least 80 weight percent of the C.sub.16 isobutylene
oligimer (i.e., "tetraisobutylene"). This predominantly C.sub.16
fraction boiled in the range of 190.degree. to 245.degree.C and
over 90 volume percent boiled at 240.degree.C. Analysis by vapor
phase chromatography showed that this predominantly C.sub.16
fraction contained less that 10 weight percent C.sub.12 oligimer
and less than 10 weight percent of the C.sub.20 and higher
oligimers.
Example 21
Twenty-two hundred and sixty ml. of winter strained lard oil were
blended with 400 ml. of tetraisobutylene (prepared as in Example
20) in a 5-liter kettle equipped with a vibromixer. The mixture was
heated to 250.degree.F and the vibromixer operated at maximum
speed. Sulfur (239 g.) was added and the temperature of the mixture
raised to 375.degree.F for 2 hours. The mixture was then cooled to
200.degree.F and air was bubbled through the mixture by means of a
glass tube at a moderate rate (below that at which splashing and
agitation take place) for 1 hour. The resulting sulfurized oil was
analyzed and found to contain 8.23 percent sulfur. A 10 gram
portion of the sulfurized oil was dissolved in 100 g. of a
commercially available solvent refined paraffinic lube having a
viscosity at 210.degree.F of 40.45 SUS, and ASTM viscosity index of
104 and containing 12 percent aromatics (by ASTM D2007). The oil
solution remained clear with no separation after being tested at
36.degree.F overnight and for 1 week at room temperature.
Example 22
Winter strained lard oil (2550 ml.) was blended with 450 ml. of 80+
percent pure triisobutylene (prepared by a distillation similar to
that used in Example 20 but at a lower temperature), in a 5-liter
kettle equipped with a vibromixer. The mixture was heated to
250.degree.F and the vibromixer operated at maximum speed. These
conditions were maintained while 266 g. of sulfur were added over a
period of 30 minutes. The temperature was raised to 375.degree.F
for 2 hours. The mixture was then cooled to 200.degree.F for 1 hour
and air was bubbled through the mixture by means of a glass tube at
a moderate rate below that at which splashing takes place. The
resulting sulfurized oil was analyzed and found to contain 8.6
percent sulfur as based on the total composition. A ten gram
portion of the sulfurized oil was dissolved in 100 g. of the
solvent refined paraffinic oil described in Example 27. The oil
solution remained clear with no separation after being tested at
36.degree.F overnight and for 1 week at room temperature.
Example 23
A useful lubricant for a controlled-slip differential, and which is
also useful for lubrication of a traction drive transmission,
comprises a blend of the following (all hydrogenations are to at
least 98 percent saturation):
KV210.degree.F. KV100.degree.F. Volume % Component (c.s.) (c.s.)
__________________________________________________________________________
7.0 Hydrogenated Cosden SH06 11.04 124 Polybutene 28.0 Hydrogenated
Cosden SH15 33.5 744 Polybutene 31.6 Hydrogenated Poly
.alpha.-Methyl 23.0 2463 Styrene 21.0 Hydrogenated Poly
.alpha.-Methyl 4.65 39.6 Styrene 7.4 Anglamol 93 (E.P. Additive)
3.0 Amoco 9000 (Dispersant) 1.0 Ultraphos 11, (Low Static Modifier)
1.0 Synthetic Sulfurized Oil of Example 21 or 22
__________________________________________________________________________
The Ultraphos 11 additive is a surface-active, organic phosphate
ester of a linear aliphatic, ethoxylated alcohol. The hydrogenated
poly(alphamethyl styrene) is primarily in the hydrindan form. A
useful fluid can also be formulated wherein the corresponding indan
is substituted for some or all of the hydrindan. The dicyclohexyl
alkane polymer forms are present as minor constituents of the
hydrogenated poly(alphamethyl styrene). Operable fluids can be made
using up to 100 percent of such "dumbbell" polymers.
Other hydrocarbons which can be present in such traction fluids (in
addition to the previously mentioned oils, e.g., hydrogenated
paraffinic or naphthenic lubes) can be made by interaction (as by
alkylation) of isobutylene or polyisobutylene with napthene
hydrocarbons (such as adamantanes, hydrindanes or cyclohexane).
Such isobutylene interaction products with adamantanes are
described in Example 24.
Example 24
Ethylaluminum sesquichloride (ml. of 25 vol. percent solution) was
added to a mixture of dimethyladamantane (50 ml.) and
t-butylchloride (1 ml.). The mixture was maintained at
0.degree.-5.degree.C. while isobutylene (45 g.) was added as a gas.
The reaction was killed with 5 ml. of water, extracted with water
and distilled under vacuum. The distillation vessel was kept at
280.degree.C. to crack any high boiling product. The overhead was
at about 170.degree.C. About half of the oil was cracked in this
manner, the rest distilled without cracking. About 30 ml. of oil
was obtained. It had KV.sub.210 of 4.40 cs. and VTF-VI of 26. A
similar run at -30.degree.C. gave about 20 ml. (nearly all cracked)
having KV.sub.210 of 4.22 cs. and VTF-VI of 62. Infrared
spectroscopic analysis indicated that the adamantane moiety was
present in the product oil. This oil is useful as a traction fluid
or as a component of a traction fluid. The structure of one of the
more important components of such a fluid is the following:
##SPC26##
where n is an integer from 1 to about 20 and R' is ##SPC27##
or one of the olefinic terminal groups previously referred to under
the heading "Summary of the Invention."
The adamantane compounds containing such olefinic terminal groups
can be converted to polar compounds (as by the reaction of the
examples) containing any of the previously described functional
groups.
Example 25
3Cyclohexyl-1,1,3-trimethyl indan can be used as a traction fluid
base stock component. The structural formula of this compound is
(I). ##SPC28##
This compound was prepared in a 1 liter steel, rocker bomb which
was charged with solid .alpha.-methylstyrene, 100 g. indan dimer
(3-phenyl-1,1,3-trimethylindan), and 2 g. 5% rhodium-on-carbon
catalyst (Englehart Industries). The bomb was charged with 1,700
psig. hydrogen and heated to 100.degree.C. The pressure dropped to
400 psig. after 1.5 hours. The bomb was cooled and the contents
mixed with pentane. The pentane solution was passed through a
silica gel column (2 ft. .times. 2 in.) and eluted with more
pentane. The first two fractions (9 g. total) were the fully
hydrogenated hydrindan derivative. The next 5 fractions contained
80 g. of the above compound I. About 10 g. of unreacted starting
material was recovered by further elution. The structure of I was
determined by a combination of infrared analysis, NMR spectoscopy,
and mass spectrometry. The purity by VPC analysis was .apprxeq.80%.
The oil had a KV.sub.210.sub..degree.F. of 3.24 cs.; a
KV.sub.100.sub..degree.F. of 25.17 cs. and VTF-VI of-139 The
3-cyclohexyl-1,1,3-trimethylindan was tested for traction using the
Rexana Four Ball Tester. The torque value for this sample was 68 g.
The corresponding value for the fully hydrogenated material
(hydrindan derivative) was 70 g. The unhydrogenated sample has a
torque value of 59 g. The precision of a single value in this test
is .+-.1-2 grams.
Example 26
1,1,3-Trimethyl-3-(2,2-dimethyl propyl) hexahydroindan can be used
as a component of hydrocarbon base stock for use in compounding a
lubricant for a traction or friction drive. This compound was
readily prepared by hydrogenation of the corresponding indan. This
compound is especially remarkable because of its low viscosity
compared to the corresponding compound in the .alpha.-methyl
styrene dimer series (KV.sub.210 about one-half as much) and its
viscosity index which is much higher than the parent compound. The
fully saturated and the aromatic version have about the same
traction properties.
1,1,3-Trimethyl-3-(2,2-dimethylpropyl) indan (80 ml.) prepared as
previously described in Example 25 was placed in a 300 ml. rocker
bomb with 2 g. 5% rhodium-on-carbon. The bomb was charged to 1,500
psig. with hydrogen and heated to 200.degree.C. After 6 hours the
bomb was cooled and the oil removed and filtered. The crude product
had a KV.sub.210.sub..degree.F. of 1.86 cs.; a
KV.sub.100.sub..degree.F. of 5.91 cs. and VTF-VI of 108. Since
there appeared to be a small amount of volatile material present
(probably caused by cracking during the hydrogenation), the sample
was topped to 60.degree. at 0.2 mm. Hg pressure. Only about 2-5 ml.
of distillate was collected. The viscosity properties were
KV.sub.210.sub..degree.F. of 1.91 cs.; a KV.sub.100.sub..degree.F.
of 6.46 cs. and VTF-VI of 85. The sample contained at least 60%
cis-trans isomers of the structural formula II. ##SPC29##
The compound was tested for traction using the Roxana Four Ball
Tester, modified to show torque measurements. The torque for this
sample was 65 g. The corresponding torque for unhydrogenated
.alpha.-methylstyrene dimer is 59 g. The precision of the test is
about .+-.1-2 g.
Example 27
400 ml. nitromethane and 300 ml. distilled isobutylene trimer were
placed in a one-liter flask and heated to 85.degree.C. 6 ml. of
SnCl.sub.4 were added. Then 75 ml. of .alpha.-methylstyrene were
added dropwise over 35 minutes. The temperature quickly rose to
95.degree.C. and was kept there. After the addition was complete,
the mixture was stirred at 95.degree.C. for an additional 10
minutes, then cooled to room temperature. The upper oil layer was
separated and washed twice with water, the water layers being
discarded. The oil layer was dried over CaCl.sub.2 and distilled,
and the 80 ml. of product that boiled from 60.degree.-100.degree.C.
at 0.5 mm. Hg. pressure was retained. The major component (about
t60 vol. %) was identified as III by a combination of infrared,
NMR, and mass spectroscopy. It had a KV.sub.210.sub..degree.F. of
1.65 cs.; a KV.sub.100.sub..degree.F. of 5.69 cs. and a VTF-VI of
-2. ##SPC30##
The same compound could be made using diisobutylene.
The compound, 1,1,3-trimethyl-3-(2,2-dimethylpropyl) indan, can be
used as a component of a hydrocarbon traction fluid base stock
(e.g., that of Example 23).
This compound was prepared as described below. Although fairly pure
isobutylene trimer was charged, the major product was apparently
derived from isobutylene dimer. The following equilibrium is
probably involved: ##SPC31##
Stannic chloride in nitromethane under certain conditions will
rapidly polymerize some olefins, but not isobutylene oligomers
(indeed, not most olefins, including polar olefins, such as
methylmethacrylate). Styrene, .alpha.-methylstyrene, isoprene,
butadiene, isobutylene, 2-methylbutene-1, are olefins that can be
polymerized. If the .alpha.-methylstyrene cation can be generated
in the presence of a large excess of the other olefin, addition
should be the predominant reaction. Running the reaction under
conditions known to give the indan dimer with .alpha.-methylstyrene
produces substituted indans. The compound of this example has a
remarkably low viscosity and high viscosity index compared to the
corresponding .alpha.-methylstyrene dimer derivatives.
The compound was tested for traction using the Roxana Four Ball
Tester. The torque for this sample was 63 g.
Table III presents Roxana Four Ball Torque data for a number of
polar compounds previously described herein.
Table IV presents the structural formulae of a number of cyclic
polar compounds which are useful as components of lubricants for a
traction transmission or a friction drive. These components are
especially useful when present in the range of about 0.5 to 10
weight percent in a base lubricant comprising at least one fully or
partially hydrogenated oil selected from polymers of styrene (or of
substituted styrene, such as .alpha.-methylstyrene), polyolefins,
naphthenic and paraffinic lubes. Such polar compounds can also be
used in such lubricants which also contain from 0.1 to 95 percent
of the gem-structured polar compounds previously referred to
herein. Sebacate esters (such as dioctyl sebacate or dibutyl
sebacate) can be used as polar components (in the 0.5 to 10 weight
percent range) of lubricants (as those referred to above) for a
traction or friction drive. For example, up to about 7 volume
percent of such esters can cause a significant increase in the
traction coefficient of the blend of hydrocarbon base oils
disclosed in Example 23 hereof, or in the entire lubricant
composition disclosed in Example 23.
The ozone treatment described in Example 2 can also be used to
improve the initial and aged (with copper ASTM D1923-B) power
factors of hydrorefined mineral oils, used as electrical
hydrorefined naphthenic oils having a SUS viscosity in the range of
40-20,000 SUS at 100.degree.F. For Example, a 2000 SUS (at
100.degree.F) hydrorefined (625.degree.F, 1000 psig of 100 percent
H.sub.2, 0.3 LHSV, sulfided Ni, Mo oxides on Al.sub.2 O.sub.3)
naphthenic distillate was contacted with 0.5 weight percent ozone
to produce a dark colored oil which, after 96 percent H.sub.2
SO.sub.4 treatment, washing, neutralizing and adsorbent contacting
(to remove the dark products). produced a good cable oil.
Methods for analysis of the branched olefin and paraffin oils
described herein (as in Example 1) can be found in J. Poly. Sci,
part A-1, volume 9, pp. 717-745 (March 1971).
Example 28
Nitromethane (200 ml.) and SnCl.sub.4 (5 ml.) are stirred in a
three-necked, round-bottomed flask (500 ml.) equipped with a gas
inlet tube, mechanicall stirrer, reflux condenser, external bath
and thermometer, while isobutene is passed into the mixture kept at
36 C. The isobutene is feed to the flask at a rate sufficient to
maintain no flow on the outlet side after air has been swept from
the flask. After 26 minutes the isobutene flow is stopped and the
contents of the flask transferred to a separatory funnel.
Conversion of the isobutene is quantative. After allowing 5 minutes
for phase separation, the nitromethane layer (202 ml.)is drained
from the bottom of the funnel. The oil layer (235 ml.) is washed
twice with saturated aqueous sodium chloride solution, once with 5
percent aqueous sodium chloride solution and twice more with
saturated aqueous sodium chloride solution. The oil layer is then
dried over anhydrous calcium chloride and placed in a vacuum
istillation apparatus. It is distilled to remove all material
boiling below 80.degree. at 0.5 mmHg. The remaining oil fraction
(100 ml.) has the following properties: * KV.sub.210.sub..degree.F
=4.25 cs, KV.sub.100.sub..degree.F =22.42 cs. VTF-VI = 98 ASTM-VI =
104. The distillate (100 ml.) was approximately (by VPC) 49 percent
trimer and 49 percent tetramer. Any dimer would have been lost to
the trap (10 ml.). The loss on batch drying is about 30 ml.
* as used herein KV stands for Kinematic Viscosity as determined by
ASTM D 445
Example 29
Example 28 was repeated except that the oil was distilled,
collecting as the oil fraction the portion boiling from 80.degree.
to 200.degree.C. This had the following properties:
KV.sub.210.sub..degree.F = 3.23 cs, KV.sub.100.sub..degree.F =
14.09 cs, VTF-VI = 105, ASTM-VI = 104. This illustrates that the
high viscosity index of the product is not due to a wide blending
range of product molecular weight.
Example 30
A polymerization is carried out as in Example 28 except that the
reaction temperature is maintained at 25.degree.C. Again, 235 ml.
of product is obtained in 26 min. The distillation gives 33 ml. of
low boiling distillate (40 percent trimer, 57 percent tetramer) and
188 ml. remaining oil. This oil is percolated through about 12 in.
of a column packed with activated alumina. The resulting oil is
completely clear and has the following properties:
KV.sub.210.sub..degree.F = 13.56 cs, KV.sub.100.sub..degree.F =
145.2 cs, VTF-VI = 96, ASTM-VI = 96.
Any of the polyolefin oils of the present invention can be
partially or fully hydrogenated by known methods (e.g., palladium
on charcoal catalysts, 2,500 psi hydrogen, at 274.degree.C) to
improve their stability. The polyolefin oils or hydrogenated oils
can be fractionally distilled under vacuum at from 40.degree. to
250.degree.C. Distillate fractions covering the complete boiling
range can be taken as feed stocks from which individual hydrocarbon
species (olefins or paraffins) can be recovered.
The major branched hydrocarbon species of the distillate fractions
can be separated and isolated into chromatographic fractions of
reasonably high purity by linear temperature programmed and
isothermal gas chromatography. In most cases, chromatographic
fractions representative of a single molecular species of each
carbon number can be obtained using silicone rubber columns under
isothermal conditions ranging from 210.degree. to 280.degree.C. In
certain instances fractions consisting of hydrocarbons having
several different carbon numbers have been prepared using such
columns. These concentrates can then be rechromatographed over
analytical columns and pure chromatographic fractions of single
carbon number species collected.
Example 31
A polyisobutylene oil was prepared by thoroughly vacuum cracking
commercial polyisobutylene (having a number average molecular
weight of 23,000) in a stirred, round bottom flask at about
375.degree.C and 1 mm. Hg. The product was taken overhead
continuously with essentially no reflux or fractionation. The
distillate products and traps were combined and redistilled at
100.degree.C at 0.3 mm. Hg and the more volatile distillate
fractions discarded. The remaining less volatile, thermally cracked
polyisobutylene "bottoms" fraction, which represented about 35 to
40 percent of the total charge, can be used as an olefin oil to
make polar compounds, as in the reactions of Examples 2, 5 to 19,
21 and 22. Fractions, as by non-distructive distillation, of such
bottoms can also be used to make such polar compounds.
Example 32
The "thermally cracked" polyisobutylene oil of Example 29 was
hydrogenated in a 1 liter stainless steel hydrogenation reactor at
2,500 psi hydrogen and 274.degree.C for 6 hours. The catalyst was
0.5 percent palladium on 4 to 8 mesh coconut charcoal.
A gas chromatogram of the hydrogenated, thermally cracked
polyisobutylene contains a series of peaks which represent a
homologous series of two different basic classes of branched
hydrocarbons. One class is symmetrical, has an odd number of carbon
atoms, and is terminated with two isopropyl groups. The second
species is non-symmetrical, consists of an even number of carbon
atoms, and is terminated with an isopropyl group and a tertiary
butyl group. The incremental increase of carbon number for each
series is due to an additional C.sub.4, isobutylene, unit in the
hydrocarbon chain. No significant amounts of the odd carbon
numbered species which are terminated with two tertiary butyl
groups were found to be present in these nonvolatile fractions. In
the C.sub.11 to C.sub.40 range, the concentrations of the C.sub.11
and C.sub.2 species were much lower relative to the concentration
of higher carbon numbered species, probably due to the loss of a
portion of these hydrocarbons to the volatile fractions. The purity
and molecular weight data obtained for each collected hydrocarbon
species, C.sub.11 to C.sub.40, are given in Table I. The purity of
these fraction varied from 96.7 to 99.sup.+ percent and the
calculated molecular weight of each carbon number species was in
good agreement with the experimental molecular weight value
obtained using vapor pressure osmometry.
The identity of these branched hydrocarbons, as determined by MNR
spectroscopy, are indicated by the structural assignments shown in
J. Poly. Sci, part A-1, Volume 9, pp. 717 to 745 (March, 1971). The
observed resonance positions in CCl.sub.4 and assignments for the
methylene and methyl protons of this series of hydrocarbons are
summarized in the above paper. Methyl and methylene protons of the
same type and having the same degree of steric hinderance and
"crowding" were found to have essentially the same chemical shifts
in CCl.sub.4 for each individual hydrocarbon species regardless of
carbon number. Differentiation and assignment of a number of the
maximally "crowded" methylene and maximally "crowded" geminal
dimethyl groups in these compounds was possible from 100-MHz
spectra obtained using C.sub.6 D.sub.6 solvent. The observed proton
resonance positions for these groups in C.sub.6 D.sub.6 and their
assignment in the C.sub.19 to C.sub.40 hydrocarbon species are
summarized in the above paper.
Table II gives the refractive indices determined at 25.degree.C for
the C.sub.11 to C.sub.40 hydrocarbon species. These values are
compared with the calculated values obtained for these compounds
using the Greenshields and Rossini method. The difference in
refractive indices, .DELTA.RI, (calculated minus experimental) was
found to increase with increasing carbon number. Included also in
this table are density values which were obtained from the
calculated molal volumes (25.degree.C) of these hydrocarbon species
and two experimental density values which were determined for the
C.sub.35 and C.sub.36 species. Positive deviations between
calculated and observed density values were found for the C.sub.35
and C.sub.36 hydrocarbon species.
Substantially pure olefin species can be obtained and characterized
in a similar manner from the unhydrogenated polyisobutylene
oils.
The novel branched paraffin and olein hydrocarbon species are
characterized by "crowded" and sterically hindered methyl and
methylene groups. This crowding effect, although somewhat less
pronounced in the lower carbon number species, becomes
significantly greater with an increase in the carbon chain. The
introduction of methylenes between two internal geminal methyl
groups or between an internal geminal methyl and a t-butyl group
(.alpha. to each group) causes significant bending of the
hydrocarbon chain. This bending results in much greater "crowding"
and steric hinderance of the various protons which in turn restrict
free rotation of the individual methylene and geminal methyl
groups. Resulting anisotropy changes cause a downfield chemical
shift of their proton resonance signals.
The lower limit of this downfield shift in branched paraffins
(CCl.sub.4 solutions) is 66 Hz (1.10 ppm) for internal geminal
methyls and 85 Hz (1.42 ppm) for isolated methylenes. This occurs
in the polymer, polyisobutylene, where the repeating isobutylene
unit provides maximum "crowding" of both the geminal methyl and the
isolated methylene groups. The lower carbon number, C.sub.11,
C.sub.12 and C.sub.15, branched hydrocarbon species have no
maximally "crowded" geminal methyl groups.
The C.sub.16 hydrocarbon species is characterized by having both
"crowded" and maximally "crowded" geminal methyl groups. This is
the first molecular species in this series of compounds which has
maximum "crowding" of a geminal methyl group. A geminal methyl
group has maximum "crowding" when it is (1) adjacent, .alpha., to
two isolated methylene groups and (2) beta, .beta., to two
quanternary carbon atoms. This "crowding" is comparable to the
maximum "crowding" of geminal methyls of high molecular weight
(e.g., 200,000+) polyisobutylene. The resonance signal for the
maximally "crowded" geminal methyl, like the resonance signal for
the maximally "crowded" geminal methyls of polyisobutylene, is
shifted downfield and appears at 65-66 Hz (1.08-1.10 ppm). The two
isolated methylenes in this molecule (referred to as the terminal
isolated methylenes in the longer carbon chain species) are both
adjacent to a maximally "crowded" geminal methyl group and are,
therefore, more sterically hindered and "crowded" than the isolated
methylenes of the C.sub.12 and C.sub.15 species. This increased
methyl "crowding" causes a 5 Hz downfield shift of the methylene
resonance to 80 Hz (1.33 ppm), where one single resonance peak is
observed for both isolated terminal methylene groups. These
methylene groups are defined as "crowded" methylenes and are found
in all of the higher carbon nubmer species (C.sub.16 and
above).
The C.sub.19 hydrocarbon species is the only other compound in this
series which has a single maximally "crowded" geminal methyl group.
This molecular species, which is symmetrical about the maximally
"crowded" geminal methyl group, has two isolated methylenes, having
exactly the same molecular environment. These groups are,
therefore, magnetically equivalent. The NMR spectrum of the
C.sub.19 species in both CCl.sub.4 and C.sub.6 D.sub.6 solvents
show a single proton resonance peak for these "crowded" methylenes.
All of the odd carbon numbered species in this series are
characterized by this molecular symmetry and have terminal isolated
"crowded" methylene groups which are identical. The unsymmetrical
C.sub.20 hydrocarbon species is the first species of this
hydrocarbon series which has a maximally "crowded" methylene group.
An isolated methylene group has maximum "crowding" when it is
adjacent to, or between, two maximally "crowded" geminal methyl
groups such as in polyisobutylene.
The subsequent higher carbon numbered novel hydrocarbons (C.sub.23
to C.sub.40) have an increasing number of maximally "crowded"
geminal methyl and maximally crowded methylene groups, and consist
of two basic species (1) and odd carbon numbered species terminated
with two isopropyl groups and symmetrical about either a maximally
"crowded " geminal methyl group or a maximally "crowded " methylene
groups and (2) an even carbon numbered species terminated with both
an isopropyl and t-butyl group and without a center of symmetry.
The C.sub.23 and C.sub.24 species are illustrated below where A
refers to maximally "crowded" geminal methyl groups and B
corresponds to maximally "crowded" methylene groups. ##SPC32##
Integrated intensities of the observed resonance for each carbon
number species were consistent for the theoretical number of
maximally "crowded" methylenes and maximally "crowded" geminal
methyls predicted for each assigned structure. The number of
maximally "crowded" methylene groups is always one less than the
number of maximally "crowded" geminal methyl groups. Further
details of the characterization of compounds containing side groups
can be found in the J. Poly. Sci. paper.
TABLE I ______________________________________ Purity and Molecular
Weight Data for Collected Fractions
______________________________________ Molecular Weight
______________________________________ Carbon Relative No. Purity,
%.sup.a Calculated Observed.sup.b Error, %
______________________________________ 11 99+ 156.3 161 +3.0 12
97.5 170.3 177 +3.9 15 99+ 212.4 214 +0.7 16 99+ 226.4 219 -2.8 19
99+ 268.5 271 +0.9 20 99.0 282.5 275 -2.7 23 96.7 324.6 322 -0.8 24
96.9 338.6 344 +1.4 27 99+ 380.7 377 -1.0 28 99+ 394.7 397 +0.6 31
98.8 436.8 426 -2.5 32 98.7 450.8 444 -1.5 35 97.3 492.9 490 -0.6
36 99+ 507.0 513 +1.2 39 99+ 549.0 544 -0.9 40 99+ 563.1 570 +1.2
______________________________________ a Capillary gas
chromatography. b Vapor pressure osmometry.
TABLE II
__________________________________________________________________________
Physical Property Data
__________________________________________________________________________
Refractive Index RI
__________________________________________________________________________
Calculated.sup.b Carbon Calculated.sup.a Observed .DELTA.RI Density
No. (25.degree.C) (25.degree.C) (Calc.-obs.) (25.degree.), g/cc
__________________________________________________________________________
11 1.4143 1.4165 -0.0022 0.7375 12 1.4254 1.4257 -0.0003 0.7561 15
1.4380 1.4380 -- 0.7816 16 1.4460 1.4441 +0.0019 0.7942 19 1.4533
1.4530 +0.0003 0.8092 20 1.4592 1.4564 +0.0028 0.8185 23 1.4636
1.4615 +0.0021 0.8282 24 1.4684 1.4648 +0.0036 0.8355 27 1.4713
1.4679 +0.0034 0.8419 28 1.4753 1.4704 +0.0049 0.8479 31 1.4772
1.4725 +0.0047 0.8525 32 1.4805 1.4750 +0.0055 0.8575 35 1.4818
1.4768 +0.0050 0.8607.sup.c 36 1.4849 1.4780 +0.0069 0.8651.sup.d
39 1.4856 1.4798 +0.0058 0.8674 40 1.4881 1.4815 +0.0066 0.8712
__________________________________________________________________________
a See Greenshields and Rossini b From calculated value of molal
volume at 25.degree.C c Observed value = 0.8584 g/cc. d Observed
value = 0.8631 g/cc.
TABLE III
__________________________________________________________________________
ROXANA 4-BALL TESTING Traction Running (grams of VTF Sample
Designation Time torque) KV.sub.210 KV.sub.100 VI Scar
__________________________________________________________________________
1. PIB (Starting material) 73.3 4.49 24.14 101 Med. 1/2 min 72.8 1
min 73.9 2. PIB-Ketone (Batch I) 83.2 3.97 21.14 88 Med. (Oxidative
Work-Up) 1/2 min 82.5 1 min 84.0 3. PIB-Ketone (Batch I) 84.4 (See
No. 2) Med. (Oxidative Work-Up) 1/2 min 83.0 1 min 85.8 4.
PIB-Ketone (Batch I) 83.8 (See No. 2) Med. (Oxidative Work-Up) 1/2
min 82.5 1 min 85.2 11/2 min 85.9 2 min 86.9 5. PIB-Ketone (Batch
2) 75.9 Med. (Oxidative Work-Up) 1/2 min 73.9 1 min 77.8 11/2 min
82.8 2 min 85.5 6. PIB-Ketone (Batch 2) 74.0 Med. (Oxidative
Work-Up) 1/2 min 71.4 1 min 76.5 11/2 min 80.5 2 min 82.3 7.
PIB-Ketone (Batch 2) 77.5 Med. (Oxidative Work-Up) 1/2 min 71.5 1
min 83.5 11/2 min 85.5 2 min 89.2 8. PIB-Ketone (Hydrolytic 72.6
Med. Work-Up) 1/2 min 71.9 1 min 73.4 9. PIB-Ketone (Hydrolytic
71.3 Slight Work-Up) 1/2 min 70.9 1 min 71.7 11/2 min 72.3 2 min
73.5 10. PIB-Ketone (Hydrolytic 74.6 Very Work-Up) Composite 1/2
min 74.5 Slight 1 min 74.7 11/2 min 75.2 2 min 75.4 11. PIB-Ketone
(Hydrolytic 74.2 Very Work-Up) (Metal Catalyst) 1/2 min 74.2 Slight
1 min 74.1 11/2 min 74.9 2 min 75.4 12. PIB-Ketone (Hydrolytic 71.9
Slight Work-Up) (High Temp.) 1/2 min 71.5 1 min 72.2 11/2 min 73.0
2 min 74.3 13. L-10-Ketone (Hydrolytic 63.0 6.86 57.8 67 Med.
Work-Up)(Indopol Poly- 1/2 min 63.0 butene) 1 min 62.9 14.
L-10-Ketone 70.8 Large 1/2 min 67.6 1 min 73.9 11/2 min 77.9 2 min
78.5 21/2 min 79.9 15. L-10-Ketone 72.1 (See No. 14) Large 1/2 min
68.7 1 min 75.5 11/2 min 76.3 2 min 77.5 16. PIB-(Ketone/Acid) 75%
75.5 Med. (25% - PIB) 1/2 min 74.8 1 min 76.2 17. PIB-Acid 74.0
17.51 377.9 25 Slight 1/2 min 73.9 1 min 74.2 18. PIB-Alcohol (75%)
70.8 Very (25% - PIB) 1/2 min 69.9 Slight 1 min 71.8 19. PIB-Ester
81.4 Ex- 1/2 min 80.6 tremely 1 min 82.2 Slight 20. PIB-Ester + 10%
K0880* 71.7 Very 1/2 min 71.9 Slight 1 min 71.6 21. PIB-Br 69.1
Very 1/2 min 69.1 Large 1 min 69.1 22. 40 PIB-Ketone
__________________________________________________________________________
77.2 60 Polybutene 1/2 min 76.5 1 min 78.0 23. No. 22 + 12% K0880
68.5 Slight 1/2 min 68.6 1 min 68.4 24. 10 PIB-Ketone
__________________________________________________________________________
66.6 Large 90 H.P.O.** 1/2 min 65.5 Scar 1 min 67.7 H.P.O.** 57.9
3.99 20.51 96 Large 1/2 min 57.7 1 min 58.2 Polybutene 67.5 3.34
16.36 82 Med. 1/2 min 67.7 1 min 67.2 PAMVCH *** 75.4 6.83 97.87
-72 Med. 1/2 min 74.7 1 min 76.2 11/2 min 75.9 2 min 76.2
__________________________________________________________________________
* K0880 is a typical commercial additive package for use in
conventional automotive automatic transmission fluids of the "Ford"
type. The package comprises additives for EP, antioxidant,
antirust, dispersant, anticopper corrosion and antifoam. **
Hydrogenated paraffinic oil *** PAMVCH = a hydrogenated dimerizate
of .alpha.-methylstyrene, mainly the hydrindan form. "Med." is an
abbreviation for N.B. All percentages in the above table are by
volume ##SPC33##
CROSS REFERENCE TO RELATED APPLICATIONS
In commonly owned copending application Ser. No. 52,301, filed July
6, 1970, of Gary L. Driscoll, Irl N. Duling and David S. Gates,
novel polyolefin and hydrogenated polyolefin oils are described
which are useful as traction fluids, or as components of traction
fluids. In particular, said application discloses oils consisting
essentially of isobutene oligimers in the C.sub.12 -C.sub.48 carbon
number range. The novel polyolefin oils or the individual olefins
therein are also disclosed as being useful as chemical
intermediates to prepare novel polar components (such as alcohols,
acids, esters, ketones, thioketones, amides, amines, thioesters,
phosphate esters of the alcohols and thioesters). The ketones, and
other non-acidic ozonolysis products are disclosed as being useful
as traction fluids or as components of traction fluids. Said
application also contains a declaration that such derivatives, and
their use as traction fluids or as antiwear additives in lubricants
are the invention of Gary L. Driscoll and Marcus W. Haseltine, Jr.,
the present applicants.
Said application further declares that the processes for
preparation of said ozonolysis products are the invention of Gary
L. Driscoll. One such process, disclosed in said application,
involves mixing the polyolefin oil with about 3 volumes of acetic
acid or methanol and adding ozone thereto. The reaction can be
effected in the range of -80.degree.-100.degree.C. (preferably
0.degree.-80.degree.C.). The amount of ozone can be about one
molecule of ozone per each double bond in the oil. After reaction
of the double bond with the ozone, an excess of water or hydrogen
peroxide is added to hydrolyze the ozonolysis products. About 1
volume of water per volume of oil is sufficient to produce a
mixture comprising acids and ketones.
* * * * *