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.PatentedNov.
1946
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‘
‘
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v ,,
UNITED STATES PATENT OFFI‘JE
‘TREATMENT OF POLYENE COMPOUNDS “
Anderson W. Ralston, Chicago, and Otto Turin
sky, Palatine, 111.,“ assignors to Armour and
Company, Chicago, 11]., a corporation of Illinois
No Drawing. Application January 22, 1942,.
‘
Serial N0. 427,834
6 Claims. (o1. 2s0_io5.6)
This invention relates to processes of treating '
change can be materially reduced by the use of '
polyene organic compounds and it. more speci?-'
high boiling organic solvents and strong alkalies.
.‘cally relates to the treatment'of unconjugated '
Other investigators have found that the alkali
polyene organic material, such asfats and fatty
process may be improved by conductingthe reac
acids having a plurality of double bonds with 5 tion in'aqueous solution at elevated temperatures
inorganic iodides of elements of the third, fourth
and pressures. However, any such process which
and ?fth groups of the periodic table of elements,
employs alkali has inherent disadvantages. In
whereby the unconjugated polyene materials are
order to conduct this process it is necessary that‘
converted to conjugated polyene products or to
the fats or fatty acids be converted ~to ‘soaps.
, products having improved drying or resinifying 10 These soaps must'then' be acidi?ed in orderto
jqualities.
Y
It has hitherto been recognized that the
obtain the transformed fatty acids. Where one
desires to conjugate an oil a number of steps are.
chemical properties of unsaturated organic comtherefore, necessary in orderto produce desired
pounds having a plurality of double bonds depend
results by these processes. It is necessary to ?rst
not only upon the degree of unsaturation but also 16 sappnify the fat and then to treat the soaps with
, upon the relative position ’of they unsaturated
strong caustic in order to bring about conjuga
bonds with respect to each other. If the un-. ‘' tion,_acidify the resulting soaps, purify the fatty ,
saturated bonds are conjugated then the organic
acids and ?nally r'eesterify them with‘glycerine.
compound has properties characteristic of un-
>
It would be extremely desirable. to develop a
saturated compounds, and in addition, has those 20 process whereby the unconjugated fatty acids or.
chemical properties characteristic of conjugated ,
fats could be treated directly without the neces
Systems.-
,
1 sity of saponi?cation or other chemical change.
The distinction ‘between conjugated - and un-
Such a process would be much easier to-conduct
conjugated systems is well illustrated by comparOn a commercial scale and would have :a number
ing the chemical behavior of linolenic acid and 25 of apparent advantages over the alkali processes
eleostearic acid. ‘ These acids are isomeric,
for bringing about this transformation. Even
straight chain fatty acids each containing three .
before the introduction ' of the alkali methods "
double bonds. It is believed that in‘linolenic acid
various investigators have sought to ?nd com
the double bonds are in the 9-10, 12-13 and
pounds which would produce the'desired isomeri
, 15-16 position while in eleostearic \acid they 30 zation directly. For example, the Schrieber
occupy the 9-10, 11--12 and 13-14 positions.
Patent No. 1,896,467 lists a number of compounds
Thus in eleostearic acid the double bonds are con- - including sulfuric acid, ferrous iodide, chlorine,
jugated. When linseed oil is used as a paint '
oxygen, etc., for this'purpose; butfnone: of these
vehicle the paint dries quite differently than itv
would if eleostearic acid were used.
compounds have proved effective or havecome
Eleostearic 35 into commercial use. .
acid is the chief fatty acid constituent present
,
in tung oil glycerides. Tung oil‘ “body-dries”
much
whereas
preferred
linseed oil
and“?lm-dries."
is believed to
Body-drying
result from
is
the fact that eleostearic acid is conjugated.
'
‘
We have-now discovered a class of compounds '
which catalytically improve to a very marked
. unconjugated
degree the drying
systems.‘
or‘ resinifying
This improvementproperties inof
40 valves a change of the unconjugated unsaturated '
Therefore, it is highly desirable that ways be _
developed by means of which unconiugated
highly unsaturated'compounds can be converted
'10 Conjugated, unsaturated compounds and thus
gain the ~- advantages inherent in conjugated 45
systems.
system to a conjugated‘unsaturated system but'_
we cannot de?nitely state that all the improve
ment in drying properties is explained bythis
transformation.v The ‘substances which weuse '
. ‘The fact ‘that the relative position of double
bonds in an alkyl chain-can be changed 'byrtreat-
which shows that they function as truecatalysts.
The class of compounds we use can be generally
‘ ment with ‘strong ‘alkalies has been ‘known for
to bring about this transformation are used in _
relatively small amounts at elevated temperatures ‘
described as inorganic iodides of elements of the 4
some time.’ In Biochem. J. 31, 138 (1937') Moore 60 third, fourth and ?fth. groups of the periodic:
reported that‘treatment offats and fatty acids
. table of elements. Such iodides include iodides .
with alcoholic potassium hydroxide brings about -' ' ‘of phosphorus; tin, aluminum, antimony, and
a shift in the relative position of double bonds in .
arsenic, these being representative elements of
an alkyl group and that this shift is towards a.
the third, fourth and ?fth groups which form ,
conjugated con?guration. ,Recently Kass and 56 iodides. Iodides of aluminum have been found
Burr, J. Am.‘ Chem. Soc. 61, 3292' (1939; have
particularly desirable incur improved process.
shown that thethnenecessaryto bring about this
In practicing our process the unconiugated
2411.119
‘substance to be treated is admixed with small
. amounts of one or more of said iodides and then
the mixture is heated to produce a shifting of the
double bonds whereby a conjugated compound
is formed. In general we can treat any organic
' 4
. ' part by weight each of phosphorous iodide were
added eight minutes and sixteen minutes, respec
tively, ‘after. the addition of the ?rst portion.
Heating was discontinued and the ?ask was
cooled rapidly when the rate of increase in re
. fractive index dropped off materially. Thus the
polyene compounds which contains double bonds
in unconjugated relation. Of the natural oils,
linseed oil and soya fbean ‘oil are particularly
susceptible to this treatment, and castor oil and
?sh oil are also markedly improved by the treat 10
ment. Other oils, such as cottonseed oil, peanut '
total heating time in the presence of phosphorous
iodide was twenty-?ve minutes. The refractive
index of the original fatty acid mixture was
n2o=1.4663 which remained substantially con
stant until the phosphorous iodide was added.
The refractive index after treatment was
oil, corn oil and other oils not ordinarily regarded
as drying oils, can also be treated by this pro
cedure and their drying characteristics sub
stantially improved. Instead of treating the oils 15 The iodine value dropped from 135 to 105 dur
ing treatment and the diene value increased from
directly, we can hydrolyze the oils to obtain the
an initial value of 2 to a ?nal value of 34.3. These
natural mixtures of fatty acids and then sub
values
indicate that appreciable conjugation has
ject the mixture to the treatment for producing
conjugation. The conjugated mixtures thus pre- ‘ been brought about by means of this treatment.
Example 2
pared may suitably be reacted with a polyhydric 20
alcohol and a dibasic acid to form alkyd resins,
Sixteen parts by weight of linoleic acid which ’
or may be re-esteri?ed with glycerol or the higher
contained approximately 35% of oleic acid and
alcohols such as pentaerythritol or dlpentaeryth
0.016 part by weight of stannic iodide were mixed
ritol to form synthetic glycerides having im
together. A stream of nitrogen gas was passed
25
proved drying characteristics.
Particularly in connection with the oils which
are not normally classed as drying oils, such as
cottonseed 011, corn oil, peanut oil, soyabean oil,
etc., we find that especially good results can be
obtained by ?rst subjecting the acid mixture ‘obs
-tained from such an oil to fractional distillation
' and then/subjecting a relatively low boiling‘ vola
heating and cooling period. The test tube and
“its contents were heated in an air bath. After
three minutes the temperature was 200° C. The
30 heating was discontinued after 15 minutes. the
temperature havingattained a value of 345° C.
The refractive index'of the original fatty vacid
tile fraction so obtained and containing a higher
proportion of the polyene acids, to the catalytic '
treatment described above.
,
over the surfaceof the mixture both during the
-
mixture was n2o=1.4672 and the refractive index
after treatment was 1l2o=1.4733. The iodine value
35 of the original fatty acid mixture was 144 which
dropped to 117 after treatment. The diene value
Another procedure includes ?rst subjecting the
acids obtained through hydrolysis of natural oils -
to solvent extraction whereby there is produced
a portion which contains unsaturated acids in
greater proportion than in the original acid mix
of the original mixture was 2 and attained a value
of 24.3 as‘ a result‘ of the treatment. These
values indicate that appreciable conjugation has
40 been brought about by means of this treatment.
Example 3
,
ture, and then subjecting this portion to cata
lytic treatment as before described or, additional
Three-hundred and thirty-nine parts by weigh
bene?ts may be obtained by ?rst fractionally dis
of refined soybean oil was weighed into' a reac
tilling the acid mixture, treating the fraction so
45 tion vessel. The vessel was equipped with a mo
obtained by solvent extraction, and then cata
tor stirrer to give e?icient agitation. A stream
lytically treating the resulting product using the
‘of nitrogen gas was passed over the surface both
herein disclosed inorganic iodides as the catalyst.
during the heating and cooling period. The mix
Though our improved process finds its greatest
ture was continuously stirred and heated to'a
advantage in connection with those oils or natural
temperature of 265° C. Phosphorous iodide was
. mixtures of fatty‘acids which are classed as un 50 then added in approximately 0.1 part by weight
conjugated oils or acids, the process can also
be used to advantage in connection with oils and '
quantities throughout the heating-period. The
total heating time in the presence of the cata
acids normally classed as conjugated but con-_
lyst was 2 hours and 20 minutes. The tempera
taining appreciable amounts of unconjugated
ture was allowed to increase gradually to 300°
. compounds. Dehydrated castor-oil is one of 55
C. - The total :amount of phosphorous iodide
7 those products normally considered conjugated,
added was 2.2 parts by weight. The refractive
but it does contain amounts of unccnjugated com
index of the original oil was nzo=1.4'753 which
. pounds'and it is markedly improved by the cata
remained constant until thevphosphorous iodide
lytic treatment described herein.
a
We shall now give examples of specific ways 60 - was added.- The refractive index after treatment
was nzo=1.4‘797. The iodine value dropped from
I of practicing our process.
Example 1
133 to 109_ during treatment and the-diene value
increased from an initial value of 1.5 to a ?nal
value of 10.0. When spread on glass the above
‘ Seven-hundred and ?fty-seven parts by weight
of ‘linoleic acid which contains approximately 65 treated. oil dried giving a ?lm which appeared
~ “frosted,” a characteristic of those oils in which
40% of oleic acid was weighed into a suitable re-'
there occur unsaturated conjugated systems.
A
stream
of
nitrogen
gas
was,
action vessel.
These data indicate that appreciable conjugation
bubbled through the mixture both during the
heating and cooling period, as presently described, , has been brought about by means of this treat
'to serve as a means of agitation and to supply 70
'
' Example 4 ‘
an inert atmosphere. The mixture was heated
ment.
to 255° C. and one part by weight of phosphorous
iodide added. The temperature was held between .
255° C. and 260° C. throughout the remainder of I '
‘
‘
a
‘
,
~
=
Three-hundred and seventeenv parts by weight '
of linoleic acid containing 30% of oleic acid was
the heating period. Two more portions of 0.5 75 heated .to 260° C. with continuous stirring under
- 2,411,118
an atmosphere of nitrogen. When the tempera
ture reached 260° C., 0.15vpart by weight of alu
of the refractive index was
minum triiodide‘was added and the reaction mix
acids were rapidly cooled inan atmosphere of
ture was maintained at 260° C. for 35 minutes
nitrogen.’ The following analytical data shows. 7
after which time 0.1 part by weight of aluminum
that appreciable conjugation‘ has been brought
triiodide was added and the mixture heated for
' about by this procedure.
seven minutes. Then an additional 0.01 part
by weight of aluminum triiodide was added. The ‘
total heating time was 42 minutes, and the tem
perature ranged during this period from 260' C. 10
to 270° C. The addition of the catalyst brought
about a rapid rise in refractive index, and the
heating was discontinued when the rate increase
fatty acids cooled rapidly.
‘
-
20
After
treatment
1.4668 ..... __
Iodine value_. ________________________ _.
‘ Dione value
.
1.4734.
145 ________ __
101.
1.5.-
26.6.
Action with stannic chloride __________ ._ Very- slight.. Gelled.
/
.
v25
.
1.5-
"
‘
511811‘?
a
21.2.
'
'
'
‘
.was prepared as follows:'- Eight parts by weight
of- iodine ‘and 7- parts by ‘weight ofaluminum
turnings
carbon disul?de‘
were mixed
andwith
the 30‘
mixture
parts by‘weight
re?uxed for
of
about ‘20 minutes. After this time the color .of- ~
the iodine had completely'disappeared indicate
ing the formation of aluminum triiodide. Since
an excess ‘of aluminum wasjemployed, the .re
tallic
mainder
aluminum.
was unreacted
The catalytic
and was
mixture
presentwasthen
as me-_ ~
These results indicate that appreciable con-‘
jugation has been brought about by this treat
ment.
1.4m.
1N1.
1
Example
.
Fourteen-hundred parts by ‘weight of extracted . '
soy bean oilwere treated'with ,a catalyst which
.
Before
treatment
Refractive index (me) _______________ ---._
1.4068 ..... --
146 ‘
_
‘
-
-
After
treatment
Refractive index (up) __________ ___ _____ __
Action with stannic chloride. ‘
The following data shows changes resulting‘
from this treatment:
Before
treatment
Iodine value-.Dione value
of refractive index was markedly lower. ‘After
42 minutes, heating was discontinued and the 15
,
lower.
When the ‘heating was discontinued,‘ the fatty
added to the soy been .011‘ and this mixturewas .
30. then heated to 170° under an atmosphere of
‘
Example 5
nitrogen andwith sumcient stirring until the
Three-hundred and seventeen ‘parts by weight
. refractive index of. the oil showed no further in
- of the linoleic-oleic acidmixture described in the
This required a total time of 48 mm.
utes. There was a. marked ‘increase in‘the‘re
0188.56.
preceding‘example was heated to 260° C. with
- continuous stirring in an atmosphere of “nitro
fractive index of the oil at the’ time the item?
perature reached a value of 130° C. It required
gen. The catalyst in this case was antimony tri
lodide which was added in‘ three portions, that is,
0.1 part by weight was added when the tempera
' an additional 20 minutes heating time to raise
the temperature to 170° C., and the mixture was
ture attained 260° C., an additional 0.2 part‘by ‘ then heated for an additional 20 minutes ‘at this
weight was added 20 minutes later, and a final 40 temperature.- After this heating ‘period, the re-’
0.1 part by weight was added-50 minutes after
action mixture was cooled under an ‘atmosphere
the ?rst addition.’ The reaction temperature
of nitrogen. The constants of the .oil before‘ and
varied from 260° C. to 270° C. The addition of
the'catalyst brought about rapid rise in refrac- ‘
'tive index, and the heating was discontinued
when this rate of ‘rise in refractive index was
markedly lower. The total'heating time in this
case was 60 minutes, after which time the fatty
acids were rapidly cooled in an atmosphere of
nitrogen.
.
after treatment were as'follows:
Before treatment
Refractive index (on) . . .
Iodine value. _.
_
Diene value_-_.
_
I
After treatment
1.4836. ‘
101.6. '
0
1 5
. Drying behavior ______ __
-
'
hours.
Slightl
tac :froeted
iilmgimhgurs.
.
Immediate ‘rubbery
The following examination of the sample be- , 60 Reaction of stannic Non-ge1ling_ _ ;_ _
chloride.
gel.
.
fore treatment and after treatment show that
appreciable conjugation has been brought about '
by, this process.
These analytical corfstants and observations
Before
treatment
.
After
treatment
_
‘ show ‘that appreciable conjugation has been
65 brought about in this soy bean oil by this treat
ment.
Refractive index (mo) _________________ -.
Iodine value __________________________ _.
Diene value ____ _.'. ______ __'__
_
Action with stannic chloride‘ __________ ..
‘
‘
‘
Example 8 ‘
)
1.4729.
14
.5_.
117.
_
Slight ..... __
14.6.
Gelled.
The catalyst employed was aluminum triiodide '
60 which was prepared in a manner‘ similar to that
described under the previous example; The
El'rample 6
‘ Three-hundred and two parts by weight of the
linoleic-oleic' acid mixture described in the pre
ceding example was heated‘to 260° C. with con
tinuous stirring. under an atmosphere of nitro
gen. When the temperature attained 260° C.,
0.2 part by weight of arsenic. triiodide was added
only difference in the catalyst used in this ex
as
ample and in‘ the‘. previous example was that
16 parts 'by‘weight of iodine wereemployed inf
stead of 8- parts by weight as, in the former ex
ample. The‘catalyst mixture was added'to 1400
. parts by‘ weightiof raw linseed oil and the heat
ing was conducted as described in the foregoing
example. The oil showed a marked increase in
and the heating continued for 35 minutes, after 70 ‘refractive index when the temperature reached
which time 0.03 part by weight of arsenic tri
125° C. It required 52- minutes to heat the oil
iodide was added. The total heating time under
these conditions was 40 minutes and the tem
perature varied from 260° C. to ‘270° C. The
‘ to 160° C. and the refractive index became con
stant 36 minutes laterwith the temperature
rising slowly to 180° v(2. ,‘jThe reaction mixture
heating was discontinued when the rate of rise 75 was then cooled under an‘atmosphere of nitrogen
'_ _2,411,11s
dioxide, as ‘we have found that this practice '“
yields aproduct of a desired character having
‘ and the following analytical constants recorded:
.
'
_
Before treatment ,
improved color and drying characteristics.
,
‘After treatment.
However, our invention may be practiced without
this feature.
‘
We can operate at various times and temper-I.
one
we ___________ ._
.
............ --
.
-
-
.
V
Reaction
Non-gelling-.-" immediaterubberygel.
of , stannie
gtyntggg alter
.
'
______ ._
Drying behavior
' ‘
‘chloride.
,
‘
tacky‘ frosted
?glmziter
15 hours.
-
v
atures. One of the characteristics of our inven
I
Sli ht]
-
tion is that conjugation is imparted quite rapid
.
ly, and this is a. de?nite commercial advantage.
10 Our oils and fatty acids can be ‘heatedfor longer
,
periods of time, if, for example, it is desired
to impart bodied characteristics to the-oil ratherv
than conclude the heat treatment after conjuga
tion alone has been imparted to the oil or fatty
I acid., That is to say, conjugated, unsaturated
fatty acids and glycerides thicken when heated
'
Example 9
‘ The catalyst was prepared “by shaking; to
gether 1.2 parts by weight of iodine, 1' part by
weight‘ of phosphorus and 10 parts by weight of
carbon disulflde. This .was added to 195 parts
- by weight of extracted soy bean oil and the‘ mix
ture was heated in an atmosphere of nitrogen
I for somewhat longer periods of time than we have
indicated in our examples.. Therefore, we can,
of course, impart conjugation to the unsaturated '
with su?lcient stirring. At the end of 15 min
utes the temperature rose to 150° at which time 20' compound during a relatively short period and
the refractive index of the oil showed appre
continue the heating for a longer period of time,
' ciable ‘increase. The temperature was permitted
up to two or three hours, if we wish to “body”
to rise slowly and after an additional 68 minutes,
the oil or fatty acid. “Such thickened oils have
it had reached 178° C. at which time the refrac
much higher viscosity than the simple conjugated
tive index showed no further increase. The 25 ?uid oils, and this may be the result of polymer
reaction mixture was then cooled in an atmos
ization of '- the conjugated material present. -
phere of nitrogen. The following analytical
constants and observations were obtained upon
Therefore, we do not wish our invention to be
the initial andthe. starting'materials. '
V30
Before treatment
‘Refractive index (nit). __
j Iodine value __________ __
l
102.
'
.
~
I
ciable improvement in diene value is‘secured and
.
1&0.’
'
Dry after 70 hours.
_
Reaction with stannic
chloride.
._
h
'
temperature. At the temperature‘ stated con-_
.jugation is imparted rapidly. Lower. tempera
,
Non-gelling".-. Rubbery gel in 5 min.
‘
>
These analytical constants and observations
show that the oil has been appreciably con
jugated by this treatment.
40
exceed the volatllization temperature of the ma
terial-undergoing treatment, nor should it be so
» been catalytically treated in the above described
processes, can be esteri?ed to form esters, and
can be used in the arts wherever the'use of con
jugated unsaturated fatty acid esters is desir- ,
.
tures can be used but with a relatively slower
reaction rate. For example, we can operate at
temperatures below 100° C. and under certain
conditions this. has been found to be advan- I
, tageous.v Obviously, the temperature should not ;
'
'In all instances the fatty acids which have
able.
the oil or fatty acid is to be heated until appre
that heat is to be discontinued before this prod
uct is bodied more than is‘ desired.
Similar considerations apply with respect to
..35
1.4811.
Diane value ___________ _. ' 1.6
Drying behavior. ...'....
After treatment
limited to any particular time of heating. Those
skilled in the art will understand different oils
may'require different heating periods and that
' I high as to decompose the oil or fatty acid. ‘ But
within these operative vlimits suitable ,tempera- tures can‘ be chosen.
-
In the foregoing examples wherein iodine and »
phosphorus or '~ aluminum. or other element of
Having‘ thus described our invention, what we
claim as new and desire to secure by Letters
the third, fourth and fifth‘ groups are brought 50 Patent is:
pound chosen f-rom the group consisting of ‘un
oil or fatty acid, it is desirable to have a slight
conjugated polyene fats and fatty acids which
comprises heating said polyene compound in the
excess of the metal element present. However,
as the foregoing examples show, an excess of
the metal is not essential.
_ '
'
-
1. The process of conjugating a polyene com
together and the resulting product added to the
55 presence of an inorganic iodide chosen from the
The oil or other polyene compound,‘ ‘ after
treatment in‘ accordance with our process, need
not'be separatedfrom the catalyst for most uses;
group consisting of iodides of elements of the
third, fourth and fifth groups of the periodic j '
system, and discontinuing said heating after sub- '
stantial conjugation of said polyene compound
to which the treated oil.is to be put. However,
the catalyst can be separated from the treated 60 has been effected, but before the thus conju- . ’
_
material by the application of conventional
gated polyene compound becomes substantially
caustic re?ning processes.
heat bodied.
* '
The amount of catalyst required is‘ small. The Q
'
2. The process as ‘in claim 1 ‘wherein the iodide _
is phosphorous iodide.
amounts given in the foregoing examples have
beenfound to give good results but still lesser 65 3. The'process as in claim 1 wherein the iodide
quantities maybe employed. More than ‘the _.
is aluminum iodide.
quantities stated can, of course, be used but this
4. The process as in claim 1 wherein the polyene '
compound is soy bean oil.
5. The process as in claim 1 wherein the polyene “
_ is wasteful and serves no useful purpose.
If
'
'
desired the catalyst may be removed from the
.
'final oil by any of the usual refining methods, 70 compound is linseed oil. ,
6.‘ The process as in claim 1 wherein the polyene '
but in general we prefernot to remove it since
compound is heated at a temperature of about '
its presence is usually not harmful“
During the heating and cooling it is of special
ANDERSON w.,rtA1sTon.' q
advantage to maintain the reaction mixture in
o'rro ronmsxr.
an inert atmosphere such as nitrogen or carbon 75
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