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July 9, 1946.
2; ,35779
G. C. BAILEY
ì PROCESS FOR TREATMENT 0F'OLEFIN--CONTAINING~MIXTURES. 1
Filed octfso, 1941 `
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Patented July '9, 1946 y
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2,403,779
UNITED STATES Afiißxl‘fENi‘ OFFICE
PROCESS FOR TREATMENT 0F OLEFIN
` CONTAIîN‘ING IVIIXTURES '
Grant C. Bailey, Bartlesville, Okla., assignor to
Phillips Petroleum Company, V,a corporation .jof »
Delaware
Application october so, 1941, serial No. 41");,30’1l 4 Claims.
(Cl. ZBO-683.15)
l
yl-l-pentene, Z-methyl-2-pentene, 3-.methyl-2A
This invention relates to the catalytic polymer- l»
pentene and the like.
y
l ization of oleñns, and more particularly it re-Y
lates to the polymerization of selected Aoleiins
The rate at >which mono-ole?ins are polymer
contained in a 'hydrocarbon mixture. It further V ized is also to some extent a function of the mo
leculary weight of >said oleñns. In general," the
relates to the production of an optimum yield of f
superior lubricating oil
low-boiling olefins.
stock from a. mixture of *
'
The catalytic polymerization of olefins to com
pounds of higher molecular Weight is well known.
higher molecular Y»Weight oleñns polymerize `less
yrapidly than the lower molecular weight oleñns.
There‘are, however, exceptions to this general
ization, one of the most outstanding being ethyl
ene whichr is polymerized with diiliculty even> by
Charge stocks for such processes are preferably
mono-olefins, and include normally gaseus or liq
uid oleñns prepared by dehydrogenation of par
aluminum chloride catalyst.
,
,
’
.I
In’some polymerization proCSSSes'it has been
found that when a mixture of oleñns is to _be pol
afüns, dehydration of'alcohols, cracking or dehy
ymerized to form >lubricating oil stocks, high
drogenation of waxes or gas oils, etc. The ole
ñns may be used either singly or mixed with 15 yields of desirable products are rapidly obtained
by first removing substantially all of the tertiary
other oleñns or inert diluents. ' The reactions
base olei'ins and then polymerizing‘nontertiary
may be effected over a wide range of tempera
base cleñns in the presence of a suitable catalyst
ture, but usually in the range `of from "-30°1F.
to produce polymers suitable Afor use as lubricat
to 200° F. The active metal halides are preferred
as catalysts such as aluminum chloride, zirconi 20 ing «oil stock. The most desirable polymers suit
able for use as a lubricating cil stock are `pro
um chloride,`boron fluoride, and the like, used
duced from the polymerization of individual non
either alone or in combinationv with'various mod
vtertiary-base l-oleñns.
f
iñers such as are well known, including inorganic
. I have now found a satisfactory method of
materials such as sodium chloride and. organic
materials suchas ketones, etc.
25
,
Inpolymerization reactions, as briefly outlined
above, oils may be obtainedhaving widely vary
ing characteristics, depending markedly on both
the olefin charge and the properties and condi
tions of the polymerization system, In practice,
the charges used for the preparation of oils fre'
quently contain a wide variety of oleñn react
ants, even though one type may be 'in predomi
nance.
e
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Metal halides of the Friedel-Crafts type such
as boron ñuoride and aluminum chloride, gener
ally polymerizeoleñns at a rapid rate. For ex
.selectively 'polymerizing tertiary-base
olefins
which are present in a hydrocarbon mixture com
'prising
also
nontertiary-base
mono-olefins.
More specifically I have found a catalyst mate
rial that will polymerize tertiary-base oleñns,
-such 'as isobutene, without'promoting apprecia
ble polymerization of,> other types, of mono-olefins
‘such as >nontertiary-base mono-oleñns, that `may
bepresent in a hydrocarbon mixture. Such cat
alyst material comprises a tin tetrahalide, pref
erably in conjunction with a stabilizer, such as
will be discussed hereinafter. As a tin tetrahal
ide catalyst I include mixtures of tin4 tetrahal
ides, vsuch as a mixture of tin tetrachloride and
ample, when aluminum chloride is added to liq
uid isobutene at temperatures above about 0° F., ' tin"tetrabromide, and "also mixed tin tetrahal
the reaction proceeds with such rapidity that it ¿140 . ides, such astin tribromochloride, tin dibromodi
' vrchloride, tin bromotrichloride, and the like.
is difficult to maintain the temperature of the
One object» ofY this invention is >to selectively
reaction mixture at a constant value. Polymer
polymerize ole?lns.
.
ization reactions using phosphoric acid type cat
Another object of this invention is to polymer
> alysts usually proceed much more slowly. Still
ize only tertiary-base olefins »in awhydrocarbon
other catalysts such as those comprisingsilica
gel may require specific Yconditions of somewhat
higher temperature and pressures to ïpolymerize
~ oleñns atan appreciable rate.>
mixture containing tertiary-base oleflns and
nontertiary-baseV mono-oleñns.
_
Another object of this invention is to produce
a lubricating oil base stock having superior qual.
In general, mono-oleiins having the tertiary 5.0 ities from low-boiling oleiins.
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'
base structure polymerize more rapidly than
Still another object of this invention is to pro
_other types of mono-olefins. By tertiary-base
vide a superior catalytic conversion system-for
oleñns I intend to include, in general, such'ole'
'the production ofV desired oils fromoleñns.
,
ñns which correspond to the formula `R2C=CRK2
A- further object of this invention is to purify
where each R is an alkyl group and each R’ is 55 an' olefin-containing mixture in such a manner
`hydrogen or any alkyl group. Such oleñns, up
that undesirable materials, such as tertiary-base
on hydrolysis in an acidic> medium, will general
ly yield a tertiary alcohol. Typical' low-boiling
tertiary-base
ole?ins
are
Z-methyl-propene»,
oleñns and/orv compounds >containing reactive
oxygen, sulfur, nitrogen, and the like, are re
moved.
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>Z-methyl-ll-loutene, Z-methyl-Z-butene, 2:-meth- L 60. f' Other objects and advantages of my invention
2,403,779
4
3
will be apparent from the accompanying disclo
of heat.
sure and discussion.
decreases with a concomitant separation of a light
`
amorphous precipitate, apparently a complex
Tin tetrahalides such as tin tetrachloride and
tin tetrabromide have been classed by other
workers in the art as active metal halide cat
alysts and as Friedel-Crafts type catalysts, along
with aluminum chloride, aluminum bromide,
boron iiuoride and the like. I have found, how
ever, that the tin tetrahalicles di’îer fundamental
However, the reaction rate gradually
stannous compound. The activity of the cat
alyst for such reactions can be increased and
maintained for a prolonged length of time by
the use of selected organic stabilizers.
Such sta
bilizers include nitro hydrocarbons, such as nitro
methane and nitrobenzene, and ketones having
ly from such catalysts in their polymerization 10 an alpha carbon atom to which is attached a
single hydrogen atom, such as methyl-isopropyl
characteristics; Aluminum chloride, aluminum
ketone, diisopropyl ketone, and isopropyl-phenyl
bromide, boron fluoride and the like readily poly
ketone. Other types of ketones, such as acetone,
merize nontertiary-base mono-oleñns such . as
acetophenone, benzophenone, and cyclohexanone,
propene, butene-l, butene-2, pentene-l, and the
like. Hereinafter, such catalysts will be termed 15 do not act as stabilizers for the reaction.
Relatively large proportions of such organic
metal halide catalysts which are active for the
stabilizers are necessary to influence the poly
polymerization of nontertiary-base oleñns. How
merization rate in a positive manner for a suit
ever, tin tetrahalides, such as tin tetrachloride
able period of time. For example, in the poly
and tin tetrabromide, do not polymerize such
compounds to any detectable extent under the 20 merization of isobutene ,at room temperature,
and atmospheric pressure using'tin tetrachloride
reaction conditions which form a part of my in
catalyst, it was >necessary to add 0.1 mole per
vention, but only polymerize tertiary-base ole
cent of nitrobenzene, based on the number of
iins, such as isobutene, as will be clearly shown
moles of tin tetrachloride in the systenrto ob
hereinafter. For example, I have found that Y
neither n-pentene-l, n-pentene-2, n-hexene-l, 25 tain appreciable stabilizing action; this was ef
Íective for only a short time. In contrast, the
nor n-octene-l can be polymerized in the pres
addition of 65 mole per cent of nitrobenzene on
ence of a tin tetrahalide at a temperature equal
the same basis not only accelerated ’the poly
to or below the boiling points of said compounds
merization but maintained the catalyst activity
at atmospheric pressure, although at the higher
temperatures halogenation reactions appeared to 30 at a constant value for a prolonged period oi
time.
'
take place. My invention is based, therefore,
Although it may be that the factors which
result in eventual decrease in activity when a
small amount of stabilizer is present will eventu
ally cause deactivation of catalyst even when a
upon the discovery that tin tetrahalides, per se,
are completely selective in their catalyzing action
for the polymerization of only tertiary-base ole
ñns under the reaction conditions which form a
larger amount of stabilizer is present, it is to be
appreciated that the actualfactors which affect
the system containing catalyst and stabilizer are
alyst will promote the polymerization of tertiary
not yet'completely known.
base olefins sufficiently faster than the polymeri
When producing products within the conven
zation of other oleflns that a selective polymeriza 40
tional lubricating oil range it is desirable that
tion vmay be accomplished. Furthermore, I have
such products have‘viscosities ranging from about
found that tin tetrahalide catalysts do not appear
100 seconds at 160° F. to about 2Go seconds Say
to promote copolymerization reactions between
bolt viscosity at 210° F. although oils above
tertiary-base oleñns and other mono-oleíins, so
and/or below this range may be useful for spe
that tin tetrahalide catalysts may be used to de
part of my invention, and not upon determining
conditions at which a known polymerization cat
cial purposes.
crease the content of tertiary-base olefins in a
The molecular weights of these
desired products are normally greater than about
300 and less than 800, and generally they are less
than 500, although products somewhat either side
Vmixture without concomitantly decreasing the
content of other mono-oleñns. It is a character
istic of catalysts such as aluminum chloride,
of these-limits may at times be found desirable.
boron fluoride, zirconium tetrachloride and >the
The primary product of my process is a simple
like, that in the polymerization of oleiins the
olefin polymer, having one double bond pe'r‘mole
reaction is promoted by the presence of the cor
cule, and for use as a> component of lubricating
responding hydrogen halide or a compound that
oil it is generally desirable to increase its sta
produces hydrogen halide under the conditions
of the reaction, such as water or tertiary butyl 55 bility toward oxidation, as by nondestructive hy
drogenation. The hydrogenated or unhydrogen
chloride. Other types of modifiers, such as or
ganic nitro compounds, ketones, ethers, and the
like, have little or no apparent effect and in some
cases may even have a tendency to lower the
reaction rate. I have found that tin tetrahalides,
particularly tin tetrachloride and' tinl tetrabro
mide, when used as catalysts in olefin polymeriza
tion reactions show unique response to added
so
ated produ-ct _may be used as a lubricating oil as
such, or may be blended with various other stocks
to produce a composite lubricating oil. In some
instances my process may be operated to produce
oleñnic products from the tertiary-base olefin
polymerization
and/or
the
nontertiary-base
mono-olefin polymerization of somewhat lower
molecular weight than that suitable for direct
modiñers. As an illustration, when a tin tetra
halide comprises the catalytic material for facili 65 use as lubricating oil, and such olefinic products
may be employed to alkylate aromatic hydrocar
tating the polymerization of olefins, the presence
of hydrogen halide actually inhibits said reaction.
bons, such as benzene, or toluene, or their deriv
atives,~to form hydrocarbons of suitable molecu
This is in direct contrast to the action exhibited
lar weight and viscosity characteristics having
by the presence of a hydrogen halide in the pres
ence of an aluminum chloride type of catalyst 70 also enhanced solvent characteristics and the
like. Oleñnic products suitable for such addi
for a similar charge stock. Also, when passing
isobutene for example, in intimate contact with
tional treatment are included, along with prod
a tin tetrahalide, such as tin tetrachloride at
ucts suitable for direct use as lubricants, in the
atmospheric pressure and room temperature, said
broader consideration of my invention, and are
isobutene is rapidly polymerized with @Volutlon 75 to be included in the term lubricating oil stocks.
2,403,179
According to» thisinvention. a mixture con
fins.. . îI'he catalystand stabilizer,v are-so» chosen
tainingtertiary-base-and nontertiary-base mono-êy
that: theyV canbe satisfactorilyïremoyecl from vthe
reactionjmixture `Without interfering Awithisub
oleñnssis treated with a tin. tetrahalide, such' as
tin tetrachloride or 'tin tetrabromide, preferably
in admixture with, a stabilizer, as is described
herein, at a temperature in a' >range of about 30
sequent usage of any other desirable compu
nentzof the reactionmixture. Usually Y,both cata
lyst and` stabilizer'.> are removed kby extraction
to v212° F. and at a'pressure at which said olefin
mixture is'v inthe> liquid state. Tin tetrachloride
methods. >based 4on their own physicaland/ox:
chemical, properties,l as will -he readily" appre
and tin> tetrabromide are» very soluble in hydro
ciated by one’skilled in theV art..
. carbons and-_under the conditions oftreatment 1.0
the system is homogeneous and thevr reaction'
takes place inv a single liquid phase.V Thereac
tion is exothermicr and suitablemeans ofagi'ta
`
,
.
' Whena mixtureto be' treated. according to my
invention containsr hydrocarbons having ai com
paratively wide range of molecular weightsizfor
example from' 3 »tof16 carbon. atom'sxper‘molecule,
it is evident-that after a treatment .withïa tin
tetrahalide there may be van appreciable ramount
tion and’cooling shouldbe >provided- for optimum
results. By this treatment substantially only
vtertiary-base> joleñns. are selectively converted to
polymers, Vthe lowest. boiling ofrwhich'isr :diiso
butene having a boiling point of about- 215A to
2210" F. ¿ By conducting the.` polymerization' at
of tertiary-base `‘oleiin- polymers> withinl >this
means known to the art.. Before a separation
tially olefin and'some-parañ‘i-n hydrocarbpnsïhav;
step, ‘such as distillation, it may bey desirable to
remove tin halide catalyst,> such as` by extracting
with cold water followed by filtration *using- an
jected to polymerization conditions „to form
molecular weight. range., Such a situation-may
be undesirable and' .often should? be gavoided‘.
This can be accomplished in mostl instancesfby
about room temperature, only a small. propor 20 separating such a mixture into >fractions` >of
tion of isobuteneY polymer will consist of dimer..l
narrower boiling range and treating‘feachffrac
The remaining nontertiary-base mono-oleñns
tion separately.Y However, in'k specific- . »casess
maybe- separated fromjthe reaction mixture by
special techniques may produce thenesiredî re- l
distillation, absorption methods, or any Aother
sul't. For example, a mixture contai-ningessen
ing 6 to `16 carbon> atoms per moleculefwas sub
products Yin the viscosity range oi'VV lubricating
oils. The mixture comprisedfprimarily straight
chain mono-ol‘eñns but contained> su-,mci'ent ter
tiary-base Yolefins, di'olefms, bXygenw-containing
compounds, and Vthe/like that polymerization
usingy zirconium tetrachloride: plus "hydrogen
chloride promoter produced an oil having- van
adsorptive clay filter aid,i especially when the
catalyst is tin tetrachloride.
In some cases tin
tetrahalide may be separated and' purified in
such a manner that-itA may be recycled Vto treat
additional mixtures ‘containing oleñn hydro
carbons.
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Besides promoting the removal of tertiary
unsatisfactorily low viscosity index.
` 1_
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`
base mono-oleñns from mixtures containing such
oleñns, I have.' alsov found that tin tetrahalides
tetrachloride together withf'd-iisopropylketone at
can be used to separate di'olefins,` reactive or
a temperature of- about 175 to 210°'Fiy and sufñ‘
’ When the? mixture-was first Vtreated'y with tin
ganic oxygen-containing compounds, reactive
cient pressure to Yallow liquid phase'y operation,
organic sulfur compounds, and the like from 40 the- polymers produced were almost’enïtirely'be
mixtures containing such ycompounds and non
low `thel molecular weight' range of lubricating
tertiary-base `mono-ole?lns without appreciably
aiîecting the nontertiary-base` mono-oleñns.
Such a separation isaccomplished by converting
dioleñns, reactive- organic oxygen-containing
oils. Also, the ¿tin tetrachloride reacted with
undesirable compounds to form a precipitate.
The reaction mixture was cooled, filtered and- the
catalyst removed by the extraction with cold
water. The purified eñluent which stillu «con
compounds and reactive organic` sulfurV com
pounds intol higher molecular 4weight compounds
in the presence of a
tained a small amount of diisopropyffketone was
tetrahali'cle catalyst,
subjected to polymerization condi-tionsusi-ng zir
these compounds oftenv being insoluble. in the
conium tetrachloride in the presence of hy"
unreacted hydrocarbon material'.
'
y
50
drogen chloride. The product in the lubricating
When the material that is being- treated' by a
oil range from» this polymerization possessed a
tin tetrahal-ide isv essentially a hydrocarbon
high viscosity index. The tertiary-base, oleñn
mixture containing tertiary-base olefins and non
polymers in the charge to the zirconium tetra
tertiary-base mono-olefinsv and no appreciable
chloride polymerization step had only'l a slight
amount of dioleñn's andwhen the-tertiary-base 55 tendency to polymerize further to luìn'i‘cat'i'ngJ oil
olefin content of said mixture is- substantially
range product. Such polymer" was Í therefore
pure isobutene, polymerization at room tempera
easily separated from higher boiling" material by
ture and sum-cient pressurev to result in a liquid
fractional distillation.
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Y
phase will produce an appreciable proportion of
Ideally, all tertiary-base Aoleflns> in av mixture
polymer in the viscosity range of lubricating oil'. 60 treated with a, tinV tetrahalide are polymerized
On separation of this oil from the remainder of
and Äall nontertiary-base mono-ol'efirisy are- un
the mixture, such as by fractionation, an oil frac
changed. Actually', such complete conversion -of
tion is- obtained having> a relatively high viscosity
tertiary-base oleñns is often impracticable and
index, higher than the viscosity index of a frac
unnecessary. The deleterious effect of the
tionk of similar Viscosity obtained by polymerizing 65 presence of tertiary-base olefins inthe subse‘-,
substantially pure isobutene using aluminum
chloride catalyst.
Y
-
Removal of tertiary-base, Aoleñns from .a mix
ture containing them is readily accomplished ‘
whenftheboiling range ofthe mixtureis so
narrow that the boiling rangev of the .polymers
produced by treatment- with a tin tetrahalide is
above the boiling range of said mixture. . In such
cases fractional distillation serves; to separate
polymeric material from vunreacted ,mono-ole-î
quent polymerization of nontertiary-'b‘ase mono
oleiins is Aroughly proportional tothe concentra
tion of the tertiary-base oleñns-softhat in some
cases essentially complete frenio'valj lis necessary,
while in others economic considerationsfmay'per
mit as much as» several! per cent of theremain-Í
ing olelinicf material toïbe tertiary-base oleñns;
VWhen it is- stated that vol'eiinic material is freed
o_f its content of- tertiary-base 'oleñnsg 'such‘fac
tors should be taken into consideration.
"
‘ ‘
2,403,779
7
.
It -is preferred that the conversion of tertiary
base oleiins- according to my invention be carried
out inthe liquid phase, and while higherv pres
8
.
be added to the polymerization zone with the tin
halide through conduit 49, or separately through
sures may-be used where an additional advan
tageous effect resu1ts,» generally a pressure suñì
conduit 39 controlled by a valve 40. vThe poly
merization is preferably carried out under condi
tions suitable to produce low-boiling polymers,
cient to maintain an initial liquid phase will be
found sufficient. With low-boiling oleñns it may
such as aresuitable for use as motor fuel or as
motor fuel stocks, or such as to produce polymers
be desirable to include a high-boiling inert dil
uent to aid in forming and maintaining a liquid
suitable for use as lubricating oil stocks, as pre
phase under relatively low pressures. Generally
paraiiins and cycloparafiins are best suited for
such-use.
The reaction time for polymerizing tertiary
zone I2 vwill consist of suitable polymerization
viously discussed herein.
The polymerization
units together with heaters, coolers, catalyst
chambers, and the like known to the art.
When the hydrocarbonmixture to be treated
according to my invention contains tertiary-base
base oleñns in the presence of a tin tetrahalide
varies over a wide range depending to a great 15 and nontertiary-base mono-oleiins within a wide
range of molecular weights it may be desirable to
extent upon the amount of'tin tetrahalide cata
pass such a mixture through. conduit I3 con
lyst employed in the polymerization step and on
trolled by valve I4 to a separating meansV I5 from
the temperature. For example, when the cata
which a selected fractionof narrow boiling range
lyst comprises 10 to 20 weight per cent of the re
actant material, a reaction time within the range 20 or narrow molecular weight range is removed
through conduit I6 controlled by a valve I1 and
of thirty to fifty minutes at room temperature
passed tothe polymerization zone I2. Material
and under sufficient pressure to result in liquid
removed through conduit 20 controlled by Valve
2I may be further separated into other narrow
the vamount - of catalyst is only about 2 to 5| 25 boiling range fraction and each fraction sub
jected to individual polymerization conditions
weight per cent of the reactant material, a re
which are optimum for polymerization of sub
action time as high as six hours is not uncom
stantially only tertiary-base oleiins in the pres
mon for producing desirable results. The reac
ence of a tin tetrahalide. Often, however, it will
tion time is lowered by an increase in the tem
perature employed for the polymerization step. 30 be unnecessary to separate such a mixture into
several fractions when desirable results can be
A tin tetrahalide employed as a catalyst in my
obtained by treatment of such a mixture in a
process is preferably soluble under the reaction
single zone under conditions suitable for the
conditions and when a tin tetrahalide catalyst
polymerization of tertiary-base oleñns contained
isV employed which is normally solid within the
temperature range disclosed herein for operat
therein.
The eiliuent from the polymerization zone I2
ing my process, usually a suilìcient amount of it
containing unr'eacted> nontertiary-base mono-ole
can be dissolved in the material being treated
ñns passes through pipe 22 and valve 23 to
to promote the reaction.
phase conditions will produce desirable results.
However, under the same conditions except that
separating means 24.- In separating means 24 un
The> reaction temperature for conducting the
conversion in the presence of a tin halide may be 40 reacted non-tertiary-base ole?lns are separated
from polymers produced in unit I2. These poly
chosen within a rather wide range. Higher tem
mers may be removed with or without separa
perature promote a -rapid polymerization but gention into various fractions, through suitable
erally lresult in a, product of lower molecular
means represented by a conduit 25 controlled by
weight. A suitable temperature for any particu
lar case may readily be determined by trial, by 45 valves 26 and 11. When these polymers, -or a
one skilled in the art, in the light of the present
fraction thereof, are suitable for use as a lubri
disclosure, and will generally be found in the
eating oil stock, such material may be passed
from conduit `25 through conduit 10 controlled
range between about 0 and about 240° F, A pre
by a valve 28 for blending with a lubricating oil
ferred range is between 30 and 200° F.
AThe use of tin tetrahalides for the separation 50 stock produced i'n a subsequent part of the proc
of oleñns in the manner described is not limited
ess, as will be described. However, when the
charge stock to my process contains some diole
to any specific embodiment because it is evident
ñns, reactive oxygen-containing compounds, re
that the details of such a process will depend
active sulfur compounds and/ or other gum form
upon,y among other things, the nature of the
charge stock and the use that is to be made of 55 ing material as well as tertiary-base olefins, other
the Ȗnal products.
My invention will now be illustrated in connec
high-boiling material will be produced besides
that from tertiary-base olefins. When this is the
case, a mixture containing such higher boiling
material is removed from separator 24 through
tion with the accompanying drawing which shows
diagrammatically one arrangement of apparatus
by lwhich my invention may be practiced.
60 conduit 25 and valve 2B and at least a part or all
may be discharged from the process through
A hydrocarbon mixture containing both ter
valve 11 or passed through conduit 'I2 controlled
tiary-base and nontertiary-base mono-olei'lns is
by valve 13 to separating means 14. In separat
introduced to the system through conduit I0 con
ing means 14 desirable polymers produced from
trolled by a valve II to polymerization unit I2,
whereiny the mixture is treated with a tin tetra 65 tertiary-base oleñns may be removed through
conduit 21 controlled by valve 'I8 and passed to
halide catalyst, preferably -tin tetrachloride or
conduit 10 for blending as herein described. Un
ti'ritetrabromide, which acts as a catalyst for the
desirable high-boilingv material can be removed
selective polymerization of tertiary-base oleñns.
Such a catalyst may be conveniently admitted to
from separating means 14 through conduit 'I5
polymerization Zone I2 with the incoming feed 70 controlled by valve 16. High-boiling material re
moved through valve 11 may be Vtreated in such a
stock or; separately through conduit 49, controlled
by a valve 50. A stabilizer for said catalyst se
manner as appears desirable. For example, ter-Y
tiary-base oleiin polymers so removed may be
lected from the group consisting of nitro hydro
passed to a catalytic alkylation step to react with
carbons- and ketones having an alpha carbon atom
to which is- attached. a single'hydrogen atom may 75 paraiîlin` hydrocarbons for the production of
2,403,779 '
10
highly -branchedhigher boiling paraffin hydro
tion suitable for allubricating oil` stock Ymay vbe
carbons of superior antiknock quality, and suit
Y passe-dl from-conduit '41 through conduit 5I Vcon
able as constituents of motor fuel. Various alkyl
ation catalysts such ashydrofluoric acid, sulfuric ,
acid,. aluminum chloride, silica> alumina, .and the
like may be' employed in Vsuch a step.
l
A material containing Vvnontertiary-base mono
oleflns and substantially free of tertiary-base ole
ñns,.as herein discussed, is passedfromseparat
ing means 24 `through a conduit 3| controlledv by 10
a valve 29 to apolymerizationunit 33 wherein la
polymerization is ‘eñ‘ected to form vpolymers suit
able for >use as a lubricating oil stock.
The ole
trolled' by a valve 48 toa hydrogenator 54 where
in/»a major part of the polymer- fractionl is non
destmctívely yhydrogenated .in the presence >of a
suitable hydrogenation catalyst and. in the pres
ence ¿of hydrogen added lthrough >conduit. 55 con
trolled bya valve 56. A resulting saturated 'hy
drocabon material is passed through conduit 51
controlled by a valve 58 to?separating means 6|.
lll-saturated` `hydrocarbon* material suitable for
use as» a lubricating oil stock may be recovered
fromv 4separating v,means'tl through conduit 62
i'lns polymerized in unit 33 may be supplemented
controlled byy valve :63 and> anyj vundesired mate
by nontertiary-base mono-oleñhs added to the 15 rial maybe discharged from the system through
system through a conduit 30 controlled by a valve
aconduitiß‘d cont-rolled'by- a valve 65.
'
_
32 passing to conduit 3|, `and in some instances
When the polymerization in unit |2 Vis such> a
olei'lns so added mayconstitute the sole source
to produce polymers suitable for use as lubricat
of olelinic material charged to this step. Poly
' ingpoîlestoclc, such polymers ymay be blended with
merization in unit 33 is carried. out in the pres
polymers: producedinunit 33 to forma compos-.I
ence offacatalyst active for the polymerization
ite product of the ,two :types ofY polymerization.
of nontertiary-base olefLns, such as aluminum
When.-r arpolymer fraction fromunit |2 is recov
chloride, zirconium chloride, boron fluoride or
ered without. additional treatment, a polymer
other halides of aluminum, ‘zirconium and boron
fraction passing throughconduit 10 and valve 28
associated with a hydrogen halide which maybe 25 Ymay Vbe'passed Ythrough valve 1| to conduit 41
addedïthrough a conduit 31 controlled by a valve
and ¿the `composite lubricating oil stock recov
38. However, it is to be understood that such
ered vthrough valve 53,. When it is desired to
catalysts are not to be considered as equivalents
subject polymer passing'through conduit .10 to
to one another, either in regardrto polymeriza
subsequent hydrogenation, such polymermay be
tion conditions >or characteristics of ' products 30 removed from conduit 1|!4 through a conduit 66
formed.. The polymerization conditions are such
that al1-,optimum yield o-f rpolymers*suitable for
>5| and hydrogenator 54 for further treatment
use as .a lubricating oil kstock are produced as
as previously discussed.
controlled by a valvev 61Y andpassed` to conduit
previously has been discussed, and the unit 33 -will
, .Y
A
~
It 'is to be appreciated that the drawing just
lcomprise suitable catalyst chambers, âheaters,
described is diagrammatic ' only.
coolers, pumps, and the vlike as Vmay be supplied
pieces of equipment illustrated and discussed are`
for any particular case by, one skilledrin the art.
The eiliuent of unit 33 passes througha con
duit34 controlled by a valve 35 to separating
mea-ns36 vand when the material passing through
conduit 34 consists substantially only of hydro
The various
conventional in nature, ‘and in any application `
of my invention there will be associated with the
individual units shown various pumps, heaters,
coolers, reflux accumulators, heat exchangers,
fractionating columns, temperature indicating
carbons, the fractions recovered from the mate
rial may> be separated by simple fractional dis'
and control devices and the like known in the art
and which may be suitably supplied for anyfpar
tillation and one or more fractionating columns
ticular case by one .skilled in the art following
as'may be readily ascertained ‘by one skilled in 45 the teachings of the reaction conditions and ma
fthe art. In some instances when a mobile poly
terial flows disclosed and discussed herein.
merization catalyst is used in unit 33, separating
My invention will be further illustrated by the
means36 may also Vinclude suitable equipment for
following specific examples, which show various
removal of the catalyst and >any impurities con
advantages of the invention but which are not
tained in the material> passing through conduit
necessarily to be construed as hunting the'inven
34 as may be suited .to the particular material
tion.
being treated. Unreacted oleñns and/or .low
boiling polymers may be removed from separat
~
Y
EXAMPLE
I
~ f
,
~
Y
Isobutene was passed in contact with approxi
mately 100 parts by weight of tin tetrachloride at
a valve 42 and returned for further reaction >in 55 roomtemperature and atmospheric pressure at`
unit 33 by conduits 3U and 3|. Undesired low
the rate of about 25 vparts by weight per hour.
boiling material, which may include paranins,
The isobutene was bubbled through the body of>
is discharged from the system through a conduit
the tin tetrachloride which was present as a
43 controlled by a valve 44. Heavy hydrocarbons,
liquid and constantly agitated with a suitable
tar and/or sludgemaybe discharged from the 60 stirring device. Polymerization began immedi
system through a conduit 45 controlled by a valve
ately. At said addition rate only a small amount
46. One or morefpolymer fractions »containing
of isobutene passed through the system uncon
polymers suitable for use as lubricating oil stock
verted. The tin tetrachloride catalyst was slowly
are recovered from separating means A36 through
deactivated, so' that 'after' two hours a major por
one or more conduitsk illustrated by conduit 41 65 tion'of the isobutene ~was passing through un
and may be discharged from the system through
converted,
'
ing means 36 `through a conduit 4| ' controlled by
valves 52 and 53.
_f
p
.
As previously discussed it isgenerally desirable
F.
The run was repeated ata temperature of 140°
Under such conditions the corresponding ex
to subject such polymers to further treatment
tent of deactivation occurred in about a half hour,
which may include alkylation with aromatic hy 70 showing the marked 4eiîect of reaction tempera
drocarbons, >saturation with hydrogen by non
ture on deactivation rate.
destructive hydrogenation, or the like. Such
EXAMPLE II
further treatment will be illustratedby nonde
structive hydrogenation and whensuch treat
The run cited in Example I conducted at room
ment is desired, anypart or all of a polymer frac 75 temperature was repeated. When the activity of
2,403,779
11
12
the catalyst had decreased considerably, ’0.1 mol
merized With al catalyst consisting of aluminum
per cent oaf nitrobenzene Was added. The cata
lytic activity was increased only for a short time.
Sixty-live mol per cent of nitrobenzene Was then
liquid phase at. 86„to„95‘îVv F. The ’catalyst was
rapidly deactivated With the formation of a dark
added. During an eight hour reaction period,
the catalytic activity did not decrease notice
ably. The stabilizing effect of nitrobenzene was
thus evident.
.
.
_ EXAMPLE III
chloride plus hydrogen ’ chloride promoter in
colored insoluble residue. , The resulting polymer
fraction in the lubricating voil viscosity range
possessed viscosity indexgvalues of 10 to 35. ’t
Another portionof this stockwas treated with
10 per cent -by weight ,of aV tin Ytetrachloride
10 nitrobenzene mixture vat 140° F; for -aftwo hour
` The run cited in Example I conducted at room
period.` The unreactedoleñn-parañin constitu
temperature WasV repeated using as catalyst tin
tetrachloride plus 50 mol per cent of diisopropyl
ketone. Isobutene was bubbled into the catalyst
entswere separatedby distillation; .It was found
that about 20 per cent ofthe total oleñn content
mixture for 22 hours.
of the charge Was removed in this treatment. _ The
15 remaining olefin-paraffin mixture in the'.,122 to
The reactionV rate de
creased only slightly throughout the entire reac
167? F. boiling range was treated with aluminum
tion period.
chloride plus hydrogen chloride promoterin liquid
'
.
`
'
'EXAMPLE IV
phase at`86 to 95° F. , Only a small'proportion of
. The run in Example I conducted at room tem
dark-colored sludgeV ÍWas formed Aduring poly
merization. Theresulting polymer fractions'in
- Y
perature was repeated using as catalyst tin tetra
chloride plus Y50 mol per cent nitromethane.
The reaction was continued for eighteen hours.
The activity of the catalyst vdid not noticeably
the lubricating oil viscosity range, which were
equivalent in volume to those produced `in the
preceding experiment.' possessed viscosity index
values of 40 to 65.r The tin tetrachloride treat
increased to a maximum of 104° F. during the 25 ment thus removed from the olefin-containing
decrease duringA` this period. The temperature
experiment.
charge stock materials which adversely affected
the activity of the aluminum chloride catalyst
and also materials which produced low viscosity
About 24 per cent ofthe resultant
polymer was in the viscosity range of lubricating
oil. The characteristics of two fractions are
given in Table I.
index polymers.
, .
30
Table I
Viscosity
n
zag-21150.
-
v Fraction
s ____
______
Viscosit Y
index
..
.
.
Iniview of many possible modifications of the
process that will be obvious to those skilled in the
art, the invention should not be limited unduly
by the foregoing speciñcation and examples, but
it should be understood to ber extensivein scope
35 and equivalents, Within the limits of the appended
_________________ __
39.8
93
9 ____________________________________ __
60. 6
85
claims, Without departing from Vthespirit of the
disclosure and teachings.
I claim:
EXAMPLE V
„
'
.
‘
t
‘
1. In a process for the selective polymerization
The -run cited in Example I conducted at room 40 oftertiary-base oleflns which are associated with
nontertiary-base oleñns, the improvement which
comprises subjecting a liquid hydrocarbon mix
lowing materials: carbon tetrachloride, tertiary
ture which contains such oleñns to the polymer
butyl chloride, hydrogen chloride, water. None
ofY these promoted the polymerization of iso
izing actíon'of a tin tetrahalide associated with a
45 ketone in which there is an alpha carbon which
butene, and they may actually have hastened the
has a single hydrogen to polymerize only tertiary
deactivation of the catalyst.
.
base oleñns, and recovering from said polymeriza
temperature Was repeated adding each of the fol
EXAMPLE VI
tion a hydrocarbon mixture which contains unre
Tin tetrachloride and liquid propene were
acted nontertiary-base oleflns and is substantially
sealed in a glass tube in a Volume ratio of ,1:15. 50 free Yfrom tertiary-base olefins.A ~ » '
After standing four days at room temperature, no
polymer Was formed.
2.v In a process for the selective polymerization
of tertiary-base oleñns which are associated with
EXAMPLE VII
nontertiary-base oleñns, the improvement which
comprises subjecting a liquid` hydrocarbon mix
The run cited in Example I conducted at room 55
temperature Was repeated using tin tetrachloride
plus pentene-l. No polymervvas produced. This
run was repeated adding each of the following
ture which contains vsuch oleñns to the polymer
izing action of a tin tetrahalide associated with
diisopropyl ketone vto polymerize only tertiary
base oleiins, and recovering from said polymeriza
compounds: carbon tetrachloride, tertiary butyl
tion a hydrocarbon mixture which contains unre
chloride, water, nitromethane, and diisopropyl 60 acted nontertiary-base oleñns and is substantially
ketone. YNo polymer Was obtained from any of
free from tertiary-base oleñns.
these runs.
Y
'
Y
EXAMPLE VIII
The oleñn li-methylpentene-Z was not poly
`
-
«
’ 3. A process for the polymerization of tertiary
base oleñns > whichY comprises -subjecting such
oleñns to the polymerizingaction of a tin tetra
merized at room temperature using tin tetra 65 halide associated with a ketone in which there is
chloride catalyst either alone or with stabilizersv
an alpha carbon atom to whichV is attached a single
such as employed in Example VII.
hydrogen atom.
v
~
`
EXAMPLE IX-
.
.
An oleiin-containing charge stock boiling be
tween 122 and 167° F., obtained from thermal
conversion of low-boiling hydrocarbons, was poly
~ 4. A process according to claim 3 wherein said
70 tin tetrahalide is tin tetrachloride and said ketone
is diisopropyl ketone.
‘
`
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`
‘
GRANT C. BAILEY.
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