Патент USA US2400521

May_21, 1946.
c. s. KUHN, JR
2,400,521
OLEFIN POLYMERIZATION.
Filed April 24, 1944
‘N m“a,i“
‘on
Arroim
2,400,521
Patented May 21, 1946
UNITED ‘STATES PATENT OFFICE
2.4.0.521
OLEIIN POLYIEIIIZATION
GarlS.Kuhn,Jr liallag'lexaadgnalgllymcane
Seem-Vacuum Oil Company,
IneorponteLNeIYoI-LEY, aveorporaiicn
of New York
Applica?lmhllilzl, 1944, WHO. 532,49.
15 claims. (CI- M15)
in the presence of a normal para?in hydrocarbon
_This invention relates, to the catalytic poly
merization of mono-ole?ns of four or more carbon
atoms and is a continuation-in-part of my co
pending application Serial Number 403,876, ?led
July 24, 1941. More speci?cally, the invention
is concerned with a particular type of polymeriza
tion of mono-ole?ns for the simultaneous pro
duction of an essentially saturated liquid hydro
carbon product and a highly unsaturated liquid
hydrocarbon product.
,
In the past mono-ole?ns have been polymerized
under both thermal and catalytic conditions. For
instance, in the catalytic operations, such cata
lysts as dilute sulfuric acid, various metallic
halides, etc., have been used. Usually the prod
ucts of such reactions have been ole?n polymers
which are linear dimers, trimers, etc., of the
original ole?n reactant. It also is known that
under suitable conditions, certain catalysts, such
as concentrated sulfuric acid and aluminum
chloride, can eifect a different type of polymer
ization of mono-ole?ns where there is obtained
a top reactant layer consisting essentially of sat
urated liquid hydrocarbons and a bottom reactant
layer which comprises terpene-like unsaturated
hydrocarbons in combination with the catalyst.
This latter type of polymerization apparently
involves a hydrogen exchange between the pri
mary polymerization products resulting in a satu
ration of one portion of the material at the ex
pense of the other. For’this reason the terms
solventathirdprimaryreactionistheoretically
possible, i. e., combination of the normal
with the ole?n by an aikylation reaction. Which
of these reactions is the predominant one depends
upon the reaction conditions used, and the reac
tion conditions necessary to favor a particular
reac?onwillintumv?-l’ywiththeparticular
ole?n utilized.
I have found that, in addition to the concen
tration of the'catalyst, the temperature and the
hydro?uoric acid to ole?n monomer ratio exert
an important effect in determining the nature
of the reaction. Since my inventioii'is concerned
15 with the formation of the ole?n polymers as a
primary reaction product, the essential conditions
will be considered from the standpoint of this
reaction. As mentioned above, a substantially
anhydroushydro?uoricacidisanessentialre
quirement. The ratio of hydro?uoric acid to
ole?n monomer must be high, at all times greater
than1to1andpreferably5orl0tolorhigher.
In a large scale operation, particularly on a con
tinuous basis. the preferred mode of operation is
to add the ole?n monomer to the catalyst-hydro
carbon mixture while agitating the mixture in
the manner utilized in the present day conven
tional alkyla?on
.
The effect of temperature varies widely with the
particularole?ntobereacted. Inthecaseofeth
ylene, increasing temperatures over the range of
from —l5° C. to +75“ 0. merely served to increase
the amount of ethyl ?uoride formed, and where
tion," and "conjunct polymerization” have been
the reaction rate of ethylene approached a‘ reason
it
applied
from the
to this
ordinary
complex
polymerization.
reaction to Therefore, “ able value, the ?uoride was the predominant prod
uct. Hydro?uoric acid alone seemed incapable of
the concentration of the acid must be suil'ieient
satisfactorily eifecting the polymerization of this
to give conjunct polymerization, and this lower
ole?n. With propylene, the effect of temperature
limit is about 90% acid. For the purposes of
on the nature of the reaction was very sharp.
de?ning my invention I shall consider anhydrous
40
In
raising the temperature from —5‘' C. to +10°
hydrogen ?uoride as hydro?uoric acid. Accord
C., the reaction changes sharply from one of pre
ingly, my catalyst is one consisting essentially
dominantly the formation of iso-propyl ?uoride,
of anhydrous hydro?uoric acid containing not
to
one of almost entirely polymerization. The
more than 10% of water by weight on the basis
exact temperature at which isopropyl ?uoride
of the hydrogen ?uoride content of the catalyst
although the titratable acidity of the catalyst in 45 formation, as an end product, is largely elimi
nated varies about plus or minus 5° C. from
the reaction zone may be considerably less than
+10‘ 0. with the hydro?uoric acid concentration
90% due to the presence of dissolved hydrocar
and acid-ole?n monomer ratio. On the other
bons and highly unsaturated polymer product,
hand, with ole?ns of 4 or more carbon atoms, I
which of course reduce the titratable acidity as 50 have not been able to observe any appreciable
well as water.
formation of low boiling alkyl ?uorides down to
When an ole?n is admixed with essentially
low temperatures at which the reaction rate be
anhydrous hydrogen ?uoride at least two pre
comes slow. For example at a temperature of
dominant primary reactions are possible, i. e.,
—20° 0., polymerization is still the major reac
addition of hydrogen ?uoride to the double bond 55 tion. Polymerization represents the chief reac
“hydro - polymerization,” “dehydro - polymeriza
of the ole?n monomer to form volatile alkyl ?u
orides, and polymerization of the ole?n monomer
induced or accelerated by the catalytic effect of
the hydrogen ?uoride to the ole?n dimer, trimer,
tion for propylene as well as the ole?ns of 4 or
more carbon atoms through the ordinary as well
as the moderately elevated temperature levels up
to, say, 200' 0., although temperatures between
tetramer, etc. Where the reaction is carried out 60 about +10‘ and +30° C. are preferred for propyl
2,400,521
" 2
one, and about —20° and +60° C. are preferred
for ole?ns of 4 or more carbon atoms.
As mentioned previously, the acid to ole?n
monomer; ratio is an important factor in securing
the desired polymerization reaction. Since an
important object of my invention is to secure not
only a polymerization reaction, but to also're
cover the two types of product, i. e., the saturated
hydrocarbons and the highly unsaturated, ter
pene-like products soluble in the catalyst, the
relative proportions of acid to total hydrocarbons
in the reaction zone is important.
In the ab
sence of inert solvents an amount of acid of from
about 20% up to about 400% by'weight of the
ole?nic hydrocarbons may be utilized, or ex
pressed in another way from 25% to 500% by
weight of ole?ns ‘may be added to the hydro
to achieve substantial or nearly complete satura~
tion of the acid immiscible hydrocarbons varies
with the reaction conditions and the particular
ole?n monomer being processed. At normal room
temperature levels, total residence times of from
30 minutes to three hours are generally satis
. factory although these residence times are not
intended as limiting on the operation of my proc
ess. The residence time is correlatable with the
reaction temperature and the degree of satura
tion of the hydrocarbon layer products desired.
Referring to the drawing one possible form of
carrying out the process of my invention is dia
grammatically illustrated, which enables the con
tinuous production of the conjunct polymer prod
According to the form illustrated, the re
action is carried out in the presence of a normal
para?in hydrocarbon solvent.
To an emulsion of hydrofluoric acid and an
separable layers. Preferably the amount of ole
?ns added is from 331/3% to 200% by weight. 20 inert solvent such as normal butane, obtained in
?uoric acid withseparation possible into readily
the manner hereinafterdescribed, in a coil 1 in
Where inert solvents are utilized, the amount of
temperature control zone 2, an ole?n is intro
ole?n which may be added to the acid-hydrocar
duced through line 3 provided with a suitable
bon mixture will largely depend upon the relative
pump 4. The contact time of the ole?n charge
proportion of acid and inert hydrocarbon solvent,
and is normally within the range of from l62/3% v25 with the acid catalyst should be su?iciently long
within the temperature control zone 2 so that a
up to about 200% by weight of the amount of
substantial portion of the olefin reacts therein
acid, with amounts from 25% to 150% by weight
to form the ole?n dimers, trimers, etc. From coil
preferred. The difference in preferred ranges is
I, the ole?n polymer, solvent-catalyst mixture is
due to the fact that the inert solvent does not re
act to produce larger molecules (which as a result 30 led through lines 5 and ‘I to reactor 8 provided
with a suitable agitator '9, wherein the emulsion
of hydrogen exchange distribute themselves be
tween the acid and hydrocarbon phases) but re
is maintained for the‘ desired residence time to
permit the polymerization reactions to become
mains as a distinct hydrocarbon phase. Hence,
completed and allow hydrogen exchange to occur
assuming that'the amount of solvent is at least
as great as the amount'of acid, the minimum 35 ‘between the ole?n polymers as previously de
scribed Product mixture is continuously with-v
drawn from the reactor 8, and sent through line
ill to settling tank I5 wherein the emulsion is
allowed to stratify into an upper hydrocarbon
sirable to use relatively large amounts of inert 40 phase and a lower acid catalyst phase. From the
lower portion of the settling tank, catalyst phase
solvent, the maximum amount of ole?n which
is continuously withdrawn through line l6, and
may be added to the catalyst with satisfactory
separation after the reaction has been com
sent to fractionator l1, wherein the major por
tion of the hydro?uoric acid is distilled oif from
pleted, is reduced,
7'
The process may be carried out, in either the 45 the highly unsaturated terpene-like polymers con
tained therein. The hydro?uoric acid vapors
presence or absence of solvents, under conditions
similar to those utilized in carrying out alkyla
overhead from fractionator I‘! are then sent
through line 18 to condenser l9, collected in re
tion reactions, or the conditions used are what
might be termed “alkylation conditions” with re
ceiver 20, and returned through lines 2|, 22 and
spect to pressure, temperature (within the ranges 50 23 to reaction coil l. Line 23 is provided with
indicated), reaction system, mode of introduc
a suitable pump 24 to provide the necessary acid
tion of reactants and the like.
circulation. Make-up hydro?uoric acid is ad
Since the reaction gives o?’ a substantial
mitted, as necessary, to line 22 through line 25,
amount of heat, it is usually desirable to provide
provided with a control valve 26. The highly
suitable cooling means in order to maintain the 55 unsaturated polymer is removed from the bottom
temperature within the preferred limits. Usually
of the fractionator l1, and sent through line 30,
the reaction will be carried out so that the hy_
provided with a suitable pump 3|, to acid stripper
drogen ?uoride catalyst is in liquid phase, and,
32. In acid stripper 32, the ?nal traces of hy
therefore, in such cases su?icient pressure should
dro?uoric'acid are removed from the unsaturated
be provided to maintain the catalyst in liquid 60 polymer product by scrubbing the polymer with
amount of ole?ns necessarily added, where sol
vents are employed, is generally reduced by about
one-half to obtain satisfactory conditions of layer
separation. Similarly, especially where it is de
phase.
However, such procedure requires only
a hot inert gas such as nitrogen or methane in
su?icient pressure to maintain the inert solvent,
troduced through line 33. This includes not only
if any, and the hydrogen ?uoride in the liquid
hydro?uoric acid present as such, but also hydro
state. The ole?n is then passed through the well
gen ?uoride which may have added to double
agitated liquid at such a rate that it all reacts 65 bonds in the unsaturated polymer and is driven
to higher boiling hydrocarbons, wherefore no rise
oil by moderate heating. The overhead from the
in pressure results. Accordingly, relatively low
stripper 32 is sent to condenser 34 through line
pressures can be used.
35, and any condensable material, principally hy
,Since, in addition to the initial ole?n poly
dro?uoric acid, collected in receiver. 36, provided
merization, I desire to allow hydrogen exchange 70 with a suitable vent 31, and recovered from line
reactions to occur within the original polymer
38. Any hydrogen ?uoride escaping with the vent
products, further contacting of the reaction mix
gases may be recovered by any suitable means.
ture with the acid catalyst is desirable. The
The unsaturated polymer product is recovered
amount of residence time, of the hydrocarbon
{1mm
ghe bottom of the acid stripperthrough
products in contact with the catalyst, required 75 'ne, 3 .
2,400,521
a solvent is used, that it should not contain any
large amount of lsoparai?ns, especially the light
isopara?ins, isobutane and isopentane. Were
appreciable amounts of light isopara?ins present
with the hydrofluoric acid at the point of ole?n._
The hydrocarbon phase is withdrawn from the
top of settling tank 15, and sent'through line
45 to solvent stripper 46. Solvent vapors are
taken off overhead, sent to a suitable condenser
(not shown) through line 41, collected in a re
ceiver (not shown), and returned through line
48, provided with'a suitable pump 49, to line 23,
wherein the solvent is emulsi?ed with the hydro
monomer introduction, alkylation would set in as
a competing reaction. For this reason, as dis
cussed herein, inert solvents such as the normal
- para?in are use/d.
' ?uoric acid recycle returning through line 22,
In continuous operation, this
and returned to reaction coil l. A line 50 is pro 10 produces a distinction in the preferred mode of
operation over that utilized in the conventional
vided, connecting lines 48 and 1, and control
continuous alkylation process. Since the satu
valves 5| and 52 are provided in lines 50 and 48,
rated product formed from the ole?n polymers
respectively, so ‘that any desired portion of the
contains branched chain hydrocarbons (the na
recycle solvent may be returned only to reactor
> 8, rather than being emulsi?ed with the acid re 15 ture of which depends upon the particular ole?n
being processed) I prefer not to recirculate the
cycle and sent through reaction coil I. The bot
product mixture to the point of ole?n introduc
toms from the solvent stripper are Withdrawn
tion in order to avoid alkylation of isoparaf?nic
through line 55, and sent to heating coil 56 in
polymer products. One way of accomplishing
a suitable heater 51, wherein they are preheated
to a temperature which will decompose the ?uo 20 this is shown in the drawing, wherein the in
itial ole?n addition is to product-free acid, and
rides. Although the major portion of the hydro
the additional contacting at the longer residence
?uoric acid dissolved in the hydrocarbon layer
time is effected in a separate reactor. This does
and most of the readily decomposable organic
not mean that all or part of the product mixture
?uorides, which may be formed in small amounts
in the reaction, are removed from the hydrocar 25 could not be recirculated and the ole?n intro
duced into the product-acid emulsion, since any
bons as hydro?uoric acid in the solvent stripper
alkylation that occurs does no harm, but merely
and returned to the reaction zone, some hydro
increases the amount of heavier saturated hydro
?uoric acid or hydrofluoric acid forming com
carbons formed. Also, the isoparamns initially
pounds remain in the saturated hydrocarbon
product. These ?uorine compounds are removed 30 formed are largely those of six or more carbon
atoms (depending upon the ole?n and the extent
by passing the preheated material from coil 56
of polymerization).
.
' ‘
through line 58 to scrubber 59, wherein the liquid
For the purpose of further illustrating the in
is countercurrently scrubbed with an aqueous al
vention, the following examples are given; how
kali solution. The scrubbing solution is removed
from the bottom of the scrubber through line 60, 35 ever, it is to be understood that the invention
is not to be limited by the speci?c details there
and recirculated through line 61 by means of '
of as there may be variations therefrom without
pump 62. The‘scrubbing solution may be with
departing from the scope of the invention.
drawn in part continuously, or from time to time,
and fresh scrubbing medium supplied to line 61
Example 1
through line 63, provided with a suitable control 40
168-parts
by
weight
of normal butene were
valve 64. The scrubbed hydrocarbon liquid is re
added over a period of about four hours to 300
moved overheadqthrough line 10, and sent to frac
parts by weight of essentially anhydrous hy
tionating column ‘H to be separated into the de
drogen fluoride, and while maintained in the
sired fractions. The overhead vapors in line 12
are sent to a condenser 13, and the liquid con
liquid phase, were subjected to continuous and
vigorous agitation. A noticeable temperature
densate recovered in receiver ‘I4, provided with a
rise occurred during the addition of the ole?n
suitable vent 15 for noncondensable gases. A
which necessitated cooling the mixture to main
portion of the condensate in receiver 14 is re
tain an average temperature of about 25°_ C.
cycled through line '56, provided with a pump
11, to the upper portion of the column as re?ux 50 After completing the addition of ole?n,- agitation
and the remainder withdrawn through valved line
o
This material consists of substantially sate
urated hydrocarbons boiling in the gasoline range.
Vapors withdrawn from near the center of the
column through line 80, condensed in condenser
8 I, and collected in receiver 82, are largely kero
sene boiling range saturated hydrocarbons and
are drawn off for recovery through valved line 83.
A portion of this kerosene boiling material may
was discontinued, and the two liquid phases, i. e.,
the saturated hydrocarbon phase and the unsat
urated hydrocarbon-hydro?uoric acid phase. al
lowed to separate. The two phases were then
' separately recovered and the saturated liquid
hydrocarbon phase fractionated to obtain the
gasoline-range material. The weight ratio of the
product in the .upper layer to that in the lower
layer was 1.23. 40.3% by weight of the total
be returned to the column through line 84, by 60 product from the saturated hydrocarbon layer
means of pump 85, as re?ux.
The material com
ing off the bottom of column through line 86 is
a, heavy predominantly saturated hydrocarbon
distilled in the range 40° to 220°_C., and was com
posed principally of saturated hydrocarbons as
shown below by the physical properties and
bromine numbers of the various fractions:
material and can be further fractionated under
vacuum if necessary to produce a valuable lubri 65
cating oil material.
‘
'
Many modi?cations of the process illustrated
will be readily apparent to those skilled in the
art. For example vacuum stripping of the hy
‘ N!)20 I 1120/4 l 620 I Br. No.
B. pt., °C.
40-140 ________________________ __
l. 3911
l4()—l8U_._._
1.4110
180-220 _ _ _ . _ . . . _ _ . . _ _ . . _ _
_ _ _ . _
l
0. 689
103. 4
0. (‘I
0.730
100.5
2.1
0. 754
102. 3
4.
l
‘ dro?uoric acid from the unsaturated polymer
may be substituted for the step of scrubbing withv
The hydro?uoric acid phase was distilled to‘
separate the hydrogen ?uoride from the unsatu
rated hydrocarbons associated with it. Prac
process resemble what might be called "alkyla
tion conditions,” it is of importance that where 75 tically all of the hydrogen ?uoride was recovered
an inert gas.
_
Inasmuch as the conditions utilized in my
4
2,400,621
from the mixture by heating to about 100° C.
The remaining product was composed principally
physical properties and bromine numbers of the
various fractions, 1. e.:
of high boiling unsaturated hydrocarbons having
‘physical and chemical properties similar to ter-
B_pt,,°c_
ND“
dZ?/l
m
MN“
pene hydrodcarbons of the cyclo-dioleflnic series. 5
‘1x136....................... ._
0.703
steam and had the following properties: bromine
--------------- --
0. 730
98.9
11).;
number, 130; NDZO, 1.4760; (120/4, 0.860; b. pt.
About 18% of this product was distillable with
180-220"""""""""""" '"
0'760
102's
29‘1
gipgcs?lyto -144 C. at a pressure of 19 mm. 10
'
Example 2
66_8 parts by weight of nomal butene were
07.3
4.3
The product from the hydro?uoric acid phase
gave 19.8% of material distilling in the range of
70°-144° C. (at 19 mm. of mercury). The prop
erties of this
were as follows: bromine
added over a period of about four hours’ and
number, 212; ND , 1-4716; 112°”, 0.858.
twenty minutes tof an agitated gliiigllre 05 6146 15
gzgitbgf X55028; 1132215326 $.28 prod‘?gg 3181.2;
I Example 5
398 parts by weight of propylene were added '
recovered as in Example 1. 52.0% by weight
0V?!‘ 8‘ Del-19d of about two hours to .9‘ vigorously
of the total product from the hydrocarbon layer
ilggtliagggtggfggg gégg?gggigig?gfg‘;:égg;
composed principallypf saturated hydrocarbons
23:52:61" ‘21:80520g;‘it;ig?zeogeig‘éeig‘gaiispgdi?
122E275?£3212:galzlilglicgggézgesrgleg .and bromme
from the hydrocarbon layer distilled in the range
distilled in tie range of 40° to 220° C., and was 20
’ '
o
B‘pt" C‘
Y
Mm
‘1M
‘520
40-140 ________________________ __
1.4042
0.717
108.1
4.4
140-180 ....................... _.
1.4185
0.743
105.8
4.8
180-220 ....................... .. 1.4310
0.104
109.0
4.9
Br‘No'
.
_
of 40° to 220° C., and was composed principally of
saturated hydrocarbons as shown by the physical
25 properties and bromine numbers of the various
fractlons' 1' e':
RptqOQ
ND.0
The product from the hydro?uoric acid phase 30 40440 ........................ _. 1. 3941
oil
was having
steam-distilled,
the following
yieldingproperties:
11.8% of abromine
yellow
igg; """""""""" "
-
(120,.
m
BLNIL
0.094
09.5
3.0
89%
'
185-3
'
'
number, 193; N 2°, 1.4770; 1120/4, 0.849.
D
Z 3
_
“mp e
The experiment given in Example 1 Was re
peated in the presence of a 5:1 mol ratio of
Two such experiments gave 176.5 parts by
30 weight of hydrocarbon from the hydro?uoric
phase, which was then vacuum-distilled to yield
15.6 parts by weight of distillate and 161 parts by
weight of residue. The vacuum-distillation resi
normal butane to normal butene by adding 149
parts by weight of normal butene to a vigorously
due so obtained was then dissolved in 409 parts
agitated mixture of 777 parts by weight of normal 40 by weight of cyclohexane and hydrogenated over
butane and 300 parts by weight of hydrogen
active nickel at 164° C. and 2375 pounds per
?uoride. The products were recovered as in Ex
square inch hydrogen pressue to yield a viscous
ample 1. , 149 parts by weight of normal butene
yellow oil. The properties of the original vac
yielded 103 parts by weight of saturated product
uum-distillation residue and the hydrogenated
45
and 39 parts by weight of unsaturated hydrocar
material are given below for comparison:
bon product, or the ratio of 2.64 to 1. 56.4% by
weight of the total product from the hydrocar
N13"
‘ 1111/4
Br. No.
bon layer distilled in the range 40° to 220° C.,
and was composed principally of saturated hy
Vacuum distillation residue_.._ l. 5122 0.888
222
drocarbons as shown by the physicalproperties 50 Hydrogenated
V. D. residue... 1. 4934 0.900
05
and bromine numbers of the various fractions,
1. e.:
The hydrogenated vacuum-distillation residue
amyc
din/4
1120
1.4018
0. 710
91.5
0.5
140-180 ________________________ _. 1.4152
0.735
91.5
8.0
180420 _______________________
0.772
99.0
12.0
40440 ________________________
| ND!"
1.4200
Br. No.
had an apparent molecular weight of 351 and a
55 viscosity of 3333.3 Saybolt Universal units at
100°F.
Example 6
The experiment given in Example 1 was re
The product from the hydrofluoric acid phase 60 peated at a temperature of —18° C. controlled to
gave 48.8% of material distilling in the range of
70°-l44° C. (at 19 mm. of mercury). The prop
erties of this distillate were as follows: bromine
number, 189; ND”, 1.4802; 1120/4, 0.855.
Example 4
149 parts by weight of isobutene were added
over a period of three and one-half hours to a
vigorously agitated mixture of 777 parts by weight
of normal butane and 300 parts by weight of hy
drogen ?uoride. The products were recovered as
plus or minus 2° C. In this case, the weight ratio
of the product in the upper layer to that in the
lower (hydrogen fluoride) layer was 4.69 as com
pared with the value of 1.23 obtained at a tem
65 perature of 25° C. in the absence of any solvent.
No discernible amount of lower boiling alkyl ?u
orides were formed, indicating that polymeriza
tion was still the ‘predominant reaction.- In con
trast to the result obtained in Example 1 at a
70 higher temperature, only 14.5% by weight of the
total product from the hydrocarbon layer distilled
in the range 40° to ‘200° C., indicating that lower
temperatures favor the formation of larger
range 40° to 220° C., and was composed princi~
amounts of the heavier hydrocarbons. This dis
pally of saturated hydrocarbons as shown by the 75 tillate was composed principally of saturated hy
in Example 1. 55.0% by weight of the total prod
uct from the hydrocarbon layer distilled in the
5
2,400,521
drocarbons as shown by the physical properties
have failed to do so and because of this failure
and bromine numbers of the i'ractions:
have received little attention.
B. pt., '0.
ND’
-
an
120
....---. ................ .- 1.4011
0.121
111.0
0.85
‘1230* ___________________ -- 1. 4019
0.150
101.0
0.12
-
The terpene-like unsaturated hydrocarbons
form a valuable product having many potential
_ Br. No.
uses, primarily as a raw material for the manu
facture of other products. Thus, for example,
this product may be steam-distilled to yield a
_ suitable fraction that may serve as a turpentine
The total top layer product (before fractionation)
contained 2.5 percent by weight of combined
substitute, or other solvent-type material, or the
product or fractions thereof may be hydrogen
ated; ‘as, for example, the non-steam-distillable
residue (or vacuum-distillation residue which
?uorine, the majority or which was liberated as
hydrogen ?uoride during the distillation step. .
may be considered as an equivalent) may be hy
Example 7
drogenated to form material boiling in the lubri
The experiment in Example 3, in which a 5:1 15 eating oil range. Further, hydrocarbons of this
mol ratio of normal butane to normal butene
product may be dehydrogenated to aromatics, or,
was employed, was repeated at a temperature of
54° C. The products were recovered as in Ex
still further, they may be reacted with a suitable
resinfying agent to form desirable resins.
ample 3, yielding 47 parts by weight of unsatu
Therefore, it is particularly interesting to ob
rated hydrocarbons from the hydro?uoric acid 20 serve that an inert solvent in the reaction has
layer and 113 parts by weight of substantially
an e?ect on the terpene-like product as well as
saturated hydrocarbons boiling above normal
on the saturated hydrocarbon product. In order
butane from the hydrocarbon layer. 70.9 percent
to show the e?ect of an insert solvent, the re
by weight of the total product from the hydro
sults of several runs using different amounts of
carbon layer distilled in range 40° to 220° C. and
solvent with the same ole?n, n-butene, are given
below. All runs were made at about25° C. with
a constant mol ratio of hydrogen ?uoride to total
had the following properties:
B. pt., °0.
Np»
all‘
:20
99.0
Br. No.
...................... _- 1.3948
0700
302301.. ____________________ __ 1.4108
0.728
94.1
1.68
180-220______________________ -- Lms
0.751
10 0
3.01
1. 25
n-butene of 5:1.
~
30
M01 ratio of n-butane to n-butene
5. 04
l. 00
0. 91
No
mbutane
Even at this relatively high temperature there
was no ‘evidence of reaction of the normal butane 35
with the ole?n. The weight of total products
recovered (160 parts by weight) was equivalent
Product in upper layer:
Wt. ratio to product in
to the weight of normal butenes added within
the limits of accuracy'oi the experiment. Fur
thermore, substantially all or the normal butane 40
(770 parts by weight) was recovered unchanged.
Careful fractionation of the gasoline boiling range
material from the hydrocarbon layer revealed
no plateaus in the region of the octanes and
'
lower layer..._. ......... --
2. 64
l. 67
l. 46
l. 23
to 220° C _______________ ._
Product in lower layer:
56. 4
'
45. 9
44. 6
40. 3
144° Q. at 19 mm____'_.._____.
Properties of vacuum distillate:
48.8 ,;23.7_
Wt. percent Distilling up
Wt. percent'distillingupto
Refractive index N1)"I .... __ l. 4802
Density. sin/t. _-__ _________ .- 0. 855
Spec1?c dispersion 620- - -__ 138. l
1. 4729
0. 863
119. 4
21.3
new
11.7
1. 4640
0. 835
119. 7
l. 4760
0. 860
104. 8
Therefore, it will be seen very clearly from the.
therefore furnished no evidence for alkylation 45
‘above data that larger quantities of gasoline;
of normal butane with normal butene.
,
boiling saturated hydrocarbons and‘ larger quan
In comparing this experiment with that given
tities
of vacuum-distillate terpene-like hydrocar
in Example 3, which was conducted at 25° C., it
bons are obtained when an inert solvent (n
will be seen that the higher temperature favored
a lower ratio of saturated hydrocarbon product 60 butane) is used, and that the increase in quan
to unsaturated hydrocarbon product (2.40 at 54°
as compared with 2.64 at 54° C.), and a higher
percentage of gasoline boiling range material in
the saturated hydrocarbon product (70.9% at
tity e?these products is larger, the larger the
amount of ‘inert solvent used.‘ Accordingly, by
using suitably large ratios of inert solvent to
ole?n the greater part of the products will be
composed of comparatively low molecular weight
54° as compared with 56.4% at 25° C.). A simi 55 hydrocarbons.
\
lar e?ect or temperature has been noted for the
The effect of solvent is further illustrated in
propylene polymerization reaction where the ex
the examples and speci?cation in my copending
periments were conducted in the absence of a
application Serial Number 532,489 ?led April 24,
paramn hydrocarbon solvent as disclosed in ex
1944, referred to above.
amples included in my copending application
Serial Number 532,489, ?led April 24, 1944, where
in the conjunct polymerization of propylene is
claimed.
The total top layer product (before fractiona
tion) contained only 0.0756 percent by weight of
Many modi?cations of _my invention will "be -
apparent to those'skilled in the art, and there
fore only such limitations should be imposed as
_ are indicated in the appended claims.
I claim:
.‘I
1. A process for the polymerization of an ole?n
combined ?uorine as compared with 2.5 percent
of more than 3 carbon atoms which comprises
found in the product from Example 6.
adding from about 16% to about 500 parts by
Since the reaction product in the acid layer is
weight of the ole?n to about 100 parts of essen
composed of a very substantial portion of ter
pene-like hydrocarbons, it can be appreciated 70 tially anhydrous hydro?uoric acid as a catalytic
agent at a temperature less than 200° C. at a
readily that e?icient recovery of such fraction is
rate such that the relative proportion by weight
necessary for any practical operation. Accord
of ole?n monomer in the reaction mixture is less
ingly, from the above examples, it can be seen
than that of the hydro?uoric acid, agitating the
that my process permits e?lcient recovery of all
the reaction product, whereas prior art processes 75 resulting mixture for a period of time su?icient to
6
2,400,521
allow the saturation of a major proportion of the
acid catalyst immiscible polymer products to oc
cur, separating the acid immiscible hydrocarbon
phase containing saturated hydrocarbons from
the acid catalyst phase containing highly un
saturated hydrocarbon polymers, and separately
recovering the hydrocarbons from each of said
phases.
‘
2. The process of claim 1 in which the ole?n
is a butene.
material and a highly unsaturated hydrocarbon
material, separating the reaction mixture into an
acid phase and a hydrocarbon phase, recovering
the hydrocarbon products from each of said
phases.
10. In a process for the polymerization of ole
?ns of more than three carbon atoms to produce
saturated hydrocarbons and terpene-like unsatu
rated hydrocarbons the steps of (1) vintroducing
10 the ole?n monomer into a liquid mixture of nor
_
3. The process of claim 1 in which the reaction
is carried out'at a temperature between —20° C.
mal para?in hydrocarbon and hydro?uoric acid
maintained at a temperature of less than 200°
C. at a rate such that the amount of ole?n mon
4. The process for the‘conjunct polymerization
omer by weight at anytime is less than one
of an ole?n of more than 3 carbon atoms to pro 16 tenth the amount of hydro?uoric acid, (2) trans
duce saturated hydrocarbon polymers and ter
ferring the mixture of primary polymerization
pene-like unsaturated hydrocarbons which com
products and acid catalyst to a reaction zone
prises contacting the monoole?n with a catalyst
wherein the mixture is agitated and maintained
consisting essentially of hydro?uoric acid of
at a temperature of less than 200° C. and allowing
about 90 to 100 percent concentration, correlat 20 further contacting of the acid catalyst and ole?n
ing the amount of hydro?uoric acid, the reac
including primary polymerization products to
tion temperature and time to effect polymeriza
' occur during a residence time su?icient to allow
tion of the ole?n as the principal reaction of the
. substantial saturation of acid immiscible ole?n
process and allow hydrogen exchange between the ,
polymers, (3) withdrawing reaction mixture con
ole?n polymers to occur to form saturated hydro 25 taining hydro?uoric acid and hydrocarbons in
carbon material and a highly unsaturated hydro
cluding ole?n reaction products and any unre
carbon material, separating the reaction mixture
acted ole?n monomer from said reaction zone,
into an acid phase and a hydrocarbon phase, re- _
(4) passing the mixture so withdrawn to a sepa
covering saturated hydrocarbon products having
ration zone for separation into a lower acid phase
more carbon atoms than the olefin from the hy 30 and an upper hydrocarbon phase, (5) withdraw
and +60° C.
y
drocarbon phase, and recovering terpene-like un
saturated hydrocarbons from the acid phase.
5. The process of claim 4 in which the ole?n
is contacted with the acid in the presence of a
normal para?in hydrocarbon at a temperature of
from -20° to +60° C.
'
v
6. The process of claim 4 in which the mono
ole?n is added to the acid at a rate such that the
weight ratio of acid to ole?n monomer is main
tained at a value of at least 10 to 1.
7. A process for the polymerization of an ole?n
of more than 3 carbon atoms which comprises
ing the acid phase and vaporizing hydro?uoric
acid from the terpene-like unsaturated hydro
carbons therein, (6) condensing and returning
at least part of the hydro?uoric acid to the point
of said ole?n introduction, and (7) withdrawing
the hydrocarbon phase and recovering predomi
nantly saturated C5 plus hydrocarbon products
therefrom.
11. A process for the production of para?inic
hydrocarbons from ole?ns of more than three
carbon atoms which comprises‘ adding about 16%
to about 500 parts by weight of the ole?n to about
adding from about 33% to about 200 parts by
weight of the ole?n to about 100 parts by weight
100 parts of essentially anhydrous hydro?uoric
-20° C. to about 60° C. at a rate suchthat the
relative proportion of ole?n monomer by weight
in the reaction mixture is less than that of the
tion mixture is less than that of the'hydro?uoric
acid to effect polymerization of the ole?ns, agi
tating the resulting mixture for a period of time
acid as a catalytic agent at a temperature less
of essentially anhydrous hydro?uoric acid as a 46 than 200° C. at a rate such that the relative pro
catalytic agent at a temperature of from about
portion by weight of ole?n monomer in the reac
hydro?uoric acid, agitating the resulting mixture 60 su?'icient to allow saturation of a major propor
-for a period of time su?icient to allow the satura
tion of a major proportion of the acid catalyst
tion of the polymer products to occur to form
of more than 3 carbon atoms which comprises
dro?uoric acid as a catalytic agent in admixture
adding from about 16% to about 200 parts of
the ole?n by weight to 100 parts by weight of
essentially anhydrous hydro?uoric acid in admix
ture with at least as much normal paraffin hy
with at least as much normal para?in by weight
as hydro?uoric acid at a temperature less than
200° C. at a rate such that the relative propor
acid immiscible para?inic hydrocarbons there
immiscible polymer products to occur, separating I from, separating and recovering the para?lnic
the acid immiscible hydrocarbon phase contain
hydrocarbon products from ‘the acid catalyst.
ing saturated hydrocarbons from the acid cata 65
12. The processes of claim 11 in which the ole
lyst phase containing highly unsaturated hydro
?n is a butene.
carbon polymers, and separately recovering the
13. A process for the production of para?inic
hydrocarbons from each of said phases.
hydrocarbons from ole?ns of more than three
8. The process of claim '7 in which the ole?n
carbon atoms which comprises adding from about
is a butene.
60 162/3 to about 200 parts by'weight of the ole?n
9. A process for the polymerization of an ole?n
to about 100 parts of essentially anhydrous hy
drocarbon as acid at a temperature of from about
—20° C. to about +60° C. at a rate such that
the ratio of acid to ole?n monomer is at least
tion by weight of ole?n monomer in the reaction
mixture is less than that of the hydro?uoric
acid, agitating the resulting mixture for a period
of time su?icient to allow the saturation of a sub
5 to 1, allowing the hydrocarbons to remain in 70 stantial portion of the polymer products to occur
contact with the acid catalyst for a residence
to form acid immiscible paraf?nic hydrocarbons
time su?icient to effect polymerization of the ole
therefrom, separating and recovering para?inic
?n as the principal reaction of the process and
hydrocarbon products from the acid catalyst.
allow hydrogen exchange between the primary
14. A process for the conjunct polymerization
polymers to occur to form saturated hydrocarbon
of mono-ole?ns of more than three carbon atoms
2,400,521
7
to a reaction zone wherein the mixture is agitated
and maintained at a temperature between about
-20° C. and +60° C. and allowing further con
tacting of the acid catalyst and butene, including
to produce saturated hydrocarbon polymers and
terpene-like unsaturated hydrocarbons which
comprises contacting the mono-ole?n in admix
ture with an inert solvent for saturated hydro
carbons with a catalyst consisting essentially of
hydro?uoric acid of about 90 to 100% concen
primary polymerization products, to occur during
a residence time su?icient to allow substantial
saturation of acid immiscible ole?n polymers,
tration at a temperature less than 200° 0., sepa
(3) withdrawing reaction mixture containing‘
hydro?uoric acid and hydrocarbons including the
covering the hydrocarbon phase containing the
saturated hydrocarbon polymers, vaporizing the 10 ole?n reaction products and any unreacted ole?n
rating the reaction mixture into two phases, re
monomer from said reaction zone, (4) passing the
mixture so withdrawn to a separation zone for
separation into a lower acid phase and an upper
hydro?uoric acid from the catalyst phase and re
covering the terpene-like unsaturated hydrocar
bons remaining after removal of the hydro?uoric
acid.
-
15. In a process for the polymerization of bu
tene to produce therefrom saturated hydrocar
bons and terpene-like unsaturated hydrocarbons
15
hydrocarbon phase, (5) withdrawing the acid
phase and vaporizing the hydro?uoric acid from
the terpene-like unsaturated hydrocarbons there
in, (6) condensing and returning at least a part
of the hydro?uoric acid to the point of said bu
the steps of (1) introducinglbutene monomer into
tene introduction, (7) withdrawing the hydrocar
a mixture of a normal para?ln hydrocarbon of
less than 5 carbon atoms and liquid hydro?uoric 20 bon phase and separating and recovering pre
dominantly saturated C5+ hydrocarbons there
acid maintained at a temperature between about
from, and (8) recycling the normal para?ln hy
-20° C. and +60° C. at a rate such that the
drocarbons of less than ?ve carbon atoms sepa
' amount of butene monomer by weight at any
rated from the hydrocarbon products in step '7
time is less than one-tenth the amount of hydro
?uoric acid, (2) transferring the mixture of pri 25 to step 1.
CARL S. KUTHN, JR.
mary polymerization products and acid catalyst