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Patented Dec. 10, 1946
2,412,469 _
UNITED STATES PATENT OFFICE.
2,412,469‘
I
TRIETHYLENE GLYCOL mnnr'roa'rn
Leonard Nicholl, 'Nyack, and William P.'Bitler,
Haverstraw, N. Y., assignors to Kay-Fries
Chemicals, Inc., West Haverstraw, N. Y., a cor
poration of New York
-
No Drawing. Application November 16, 1943,
>
Serial No- 510,570
1 Claim. (Cl. 260-488)
,
' This invention relates to plasticizers for syn
‘2
-
the main condensation reaction and lower the
yield of heptyl heptoate. The water present in
0. thetic rubber, and to the compounds and meth
ods of. producing same.
the crude heptaldehyde is also required to be re
‘moved because it would hydrolyze the aluminum
_ In‘the utilization of the newly developed syn
thetic rubbers or elastomers, it has been found
. alkoxide catalysts, and thereby prevent the con
necessary to incorporate plasticizing agents
therewith in order to improve their workability
densation reaction from taking place, or it would
cause the yield of heptyl heptoate to be lowered
and wearing qualities. As there are a number
to a very considerable extent.
vof groups‘ of compounds utilized as synthetic
The several processes involved in the, prepara
rubbers, there are plasticizing problems inher 10 tion of the necessary reagents and the ‘carrying
ently different for each group of compounds.
out of the condensation reactions, will now be
_ The improvements of the present application
described:
are directed to the use of plasticizers particularly
Stripping of crude heptaldehyde
suited for work'with butadiene-acrylonitrile co
Crude heptaldehyde is stripped to remove acro- .
, polymers and comprising heptaldehyde products,
and, pen ticularly triethylene glycol diheptoate
lein and water in the following manner:
3,080 lbs. of crude heptaldehyde are loaded into
and diheptyl phthalate. These two novel com
a colunm still, together with v15 lbs. of tartaric
pounds maybe incorporated in synthetic rubbers
acid. The distillation is conducted with. a. liquid
oi the butadiene-acrylonitrile, and in amounts
varyingv from substantially 20 to 25% of the clas 20 temperature of 110° C. and a vapor temperature
of 80° C'., the distillation at the end being carried '
tomers'fjThese plasticizers have been found, on
out undeng. vacuum. of 180 mm. to 85
The
tests, to give a desirable “low temperature ?ex
ibility” to the elastomers under consideration.
distillant or still residue is cooled to room tem-,
a The plasticizers are themselves novel com
perature and drawn off into dry containers which
pounds which have not been described in the lit
25 are protected from ingress of moisture. The yield
erature so far as is now known. The two com
_ pounds are‘ derived from a series of reactions
x1 .
which are interdependent‘, and which comprise.
(1) condensation of heptaldehyde to heptyl hept
oate; (2) reaction of the heptyl heptoate pro 30
duced under (1) with triethylene glycol and
heptanol to form triethylene glycol diheptoate;
(3) recovery of excess heptanol and reaction of
same with phthalic anhydride to produce diheptyl
should be’ approximately 2860 lbs. of‘ stripped
crude heptaldehyde of 88% strength equivalent
to approximately 2500 lbs. of 100% heptaldehyde.
Preparation of catalysts I
As the aluminum .alkoxide catalyst, either-“alu
minum butoxide or aluminum heptoxide may be
used. These catalysts are prepared as follows:
Aluminum ‘butoaqide.—A thoroughly dried still
35 is loaded with a charge comprising 225 lbs. of
V butanol, 28.6 lbs. of aluminum, and 0.28 lbs. of
In the carrying out of the reactions indicated
. ,phthalate.
,
generally above, special results are obtained by
iodine. The still is provided with a moisture trap,
then the water, leaving ,the heptaldehyde and
‘ and the reaction has subsided, the still is heated
for one hour longer at 90 to 100° C. to complete
50 the reaction. This will give a solution of alu
and thecondenser column is open, to the air.
the use of aluminum alkoxides as catalysts. By
The reaction mixture is heated, while stirring,
the use of the processes herein and using dry
aluminum alkoxides as catalysts,‘ it has been 40 until the reaction becomes vigorous and re?ux
ing takes place. 'If necessary, the reaction'may
found possible to treat crude heptaldehyde
be controlled bycooling the still. vWhen the ‘re
_ (oenanthal),‘containing 175 to 90% of heptalde
action has been brought under control, an addi
hyde,‘.when the crude aldehyde, which normally
tional 230 lbs. of butanol is added, as rapidly as
contains higher organic acids, acrolein and water,
is freed from acrolein and water. The crude 45 possible, while still controlling the reaction with
cooling water. After all the butanol has been
heptaldehyde, which is usually derived from cas
added, which will take approximately one hour,
tor oil, is distilled to remove the acrolein, and
the higher organic acids as a residue. By this
treatment, and with this discovery, the prepara
tion of a pure heptaldehyde as a starting ma
-- terial for the condensation is not required. It
is to be noted that in order to obtain maximum
minum butoxide in an excess of butanol.‘ '
‘Aluminum heptorida-Into-a thoroughly dryv ‘
still there is loaded a charge comprising 715 lbs.
yields from the pure heptaldehyde that the aero
heptanol, 28.6 lbs. of aluminum, and 45oz. of
lein must be removed or it wil1 interfere with 65 iodine. The still is closed, the condenser being ‘
2,412,469
3
4
left open, and provided with a moisture trap.
Preparation of trieihulene ulycol diheptoate
The reaction mixture is re?uxed at 160° C. (col-
(B. P. ca. 250-255° C. at 2 mm.)
umn temperature) for 11/2 hours, with good agi
tation. At the end of the reaction time, the re-
In the preparation of this compound there is
action mixture is allowed to cool to room tem- 5 a straight ester exchange, 8-8 Opposed to a new
perature.
In addition to the specific aluminum alkoxides
reaction between heptyl heptoate (or butyi hep
toate and heptyl heptoate) and triethylene
disclosed, it has also been found that other alu818001, with Sodium ethoxide being used as 8
minum alkoxldes and other alcohols will work.
catalyst- There are two methods of carrying out
‘Thus, aluminum ethoxide in an excess of ethanol 10 this reaction depending on whether heptyl hep
gives desirable results as a catalytic mixture.
toate is used, or the mixture of butyl heptoate
Condensation of stripped, crude hepialdehyde
:53 1.225% gsgfl’gggz These Separate reactmns
- Using aluminum butomide as a catalyst-2860
Using a mixture of butt/l heptoate and heptyl
lbs. of stripped. crude heptaldehyde are added 15 heptoate.—-Into a thoroughly dry- Still there is
to the aluminum butoxide catalyst. The mixture
charged 768 lbs. of triethylene glycol and 370
is well agitated over a period of one hour, and
lbs. of sodium ethoxide in anhydrous ethyl alco
hol solution (containing 6.5% sodium). The
the temperature is maintained at 26-30“ C., by
the use of cooling water on the still jacket, and
reaction mixture is heated to 100° C. and the
by controlling the rate of addition of the crude 20 alcohol liberated is distilled oil‘ to a liquid tem
heptaldehyde to the still. When the heptaldeperature of 110° C. To remove the residual alco
hyde has been completely added, the reaction is
hol a vacuum of 35 mm. may be pulled on the
continued for another four hours at the same
still. To the dealcoholized reaction mixture there
temperature. The reaction mixture is then fracis charged a mixture of 1560 lbs. of heptyl hep
tionated according to the following schedule:
25 toate and 615 lbs. of butyl heptoate. The tem
iweight 0mm), 3,240 g_]
perature of the reaction mixture is raised to 132
135° C. under a vacuum of 60-65 mm. Butanol
mm
Fm‘ te‘ucilp,
-
vm
teglépn
distllls over at a still-head vapor temperature of
Pm" ‘git-13111
Remarks
60-65° C. The liquid temperature will have-tube
-
55_ 50
raised to 145°-l55° C. in order to remove the re
5H0
61-82
30 sidual butanol. Thereafter the vacuum is in
creased slowly to 10 mm., and the temperature
of the reaction mixture reduced to 125-130“ C.
a’a’i‘i's Bum“
91 Int. cut.
gfjlga
58
MHGO
20-3
17
354 Heptanol.
The heptanol set free in the reaction will start
600 Butylheptoabe_ 35 p to distill over at a vapor temperature at approx
1,530 Hepmheptom.
imately 78-79" C. The vacuum distillation of
55o Residue.
heptanol is continued while gradually raising the
liquid temperature to a ?nal value of approxi
The reaction should be carried out within the
mately 220° C- After Tem°va1 of the heptaml
temperatures stated, as it has been found that, 40 the reaction mixture is allowed to cool, and is
’ at higher temperatures, such as 40° C., the yield
then washed with it to 1A of its volume of 1—5%
is cut by approximately 10%. The total time of
sulphuric acid and at a temperature of 60—'70°
reaction should approximate five hours, although
C» until it is neutral 01‘ Only Slightly acid- The
it may be extended to fourteen hours, or more,
washed oilis permanganate treated in‘dilute acid '
providing the temperature limits are not ex- 45 solution, using 1% of the weight of the reaction 1
ceeded. A second condensation can be run in
mixture of permanganate 1n 9' 2% 50111151011
the same still, merely requiring the draining o?
Upon completion of this treatment a slight excess
of the used catalyst and replenishment with
of 50% sodium bisulphite Solution 18 added to
‘fresh catalyst,
decolorize the reaction mixture. The aqueous
Using aluminum heptoxide as a. catalyst-This 5o layer is separated from the oily layer and washed
reaction is conducted under substantially the
with Water until free from any soluble mansan
same conditions and limitations as applied to
the use of aluminum butoxide.
ese salt. The treated oil is further treated with
The stripped,
1/2% Nuchar (decolorizmg carbm)» blown dry,
' crude heptaldehyde (2860 lbs.) is added to the
and ?ltered
aluminum heptoxide catalyst and the mixture 55 Using hept1/lhept°at¢-_A charge 01 12301b$~
well stirred. The reaction mixture is maintained
triethyene glycol and 570 “35- sodium ethoxide
at 26-30" C. by cooling the still, and by control- ling the rate of addition of the heptaldehyde.
When all the heptaldehyde has been added, the
reaction is continued, at the same temperature, 60
for a time period of four hours. The reaction
mixture is then fractionated according to the
following data:
in absolute alcohol solution (containing 6.5% so
dium) are loaded into a thoroughly dry still
The reaction mixture is heated to 100° C., and
ethanol distilled o?f to a liquid temperature of
110° C. A ?nal vacuum of 35 mm. is usually
required to be pulled on the still in order to get
the last traces oi alcohol over. To the dealco
[Weight oi batch 340 g.)
Wt. oi
Wt. low
traction
mm
1s. 7
boll
.
Wt ‘
‘55
4.5
12.0 ___
33.2
Remarks
13.7 .................. -. ‘Impurities in crude heptaldehyde.
55
7.5
219
Wt.
heptyl
heptanol heptome
.__. ____ __
3.0
219.0
12.0
Heptanol.
Int. cut.
Heptyl heptoete.
End cut heptyl heptoaie.
Residue.
“I
2,412,469
'
6
holized reaction mixture in the still, there is
added 2785 lbs. of heptyl heptoate. The tem- ‘
perature of the ‘reaction mixture is raised to 100°
C. and a vacuum of 35 mm. is pulled. A small
amount of ethanol may be drawn off through the
column at a liquid temperature of 120° C. and a
vapor temperature of 78° C. Thereafter the
distillation is continued to a ?nal liquid tem-.
perature oiapproximately 220° C. to recover the
liberated heptanol. The residual reaction mix 10
ture is then washed, permanganate treated, car
bon treated, and blown dry in same manner as
(540%) sodium carbonate solution, until slightly
alkaline. The mixture is then permanganate
treated with {a of its weight of potassium per
manganate, in a 2% solution, under slightly acid
conditions. Manganese dioxide is precipitated
out, and vis dissolved in a slight excess of 35% so
dium bisulphite solution. . The washed water
layer is separated, and the reacted mixture'asain
washed with water, until ‘free from soluble mari-v
ganese salt. The washed product is then treated,
with decolorizlng carbon, blown dry, and ?ltered.
The compounds, triethylene glycol diheptoate
and diheptyl phthalate are novel and useful and
are prepared from an originally crude product,
15 namely, heptaldehyde, which is stripped to re
In this process phthalic anhydride is esteri?ed ~ move water and acrolein, both of which com
with heptanol in the following manner. Into a
pounds‘ have a. deleterious e?ect on the condensa
indicated immediately above.
Preparation of diheptyl phthalate
still there is charged 3380 lbs. of hepta'nol, 2160
lbs. oi’ phthalic anhydride and 27.7 lbs. of con- '
centrated sulphuric acid. The reaction mixture
' tion reactions here involved. Ordinarily, in mak
ing a series of condensations, heptanol will not be
available to make the aluminum heptoxide cat
is raised to a temperature of 125-130" 0., when
alyst. However, heptanol is produced in, the
water should begin to distill over, at normal pres
triethylene glycol diheptoate reaction. Conse
sure. The reaction mixture is maintained at
' quently butanol must be‘ used for the ?rst con
substantially constant temperature, and a vac
' densation (Equation 2) and the heptanoli'ormed
uum, up to25 mm., is applied, in order to main 25 inthis reaction may be used to make the desired
tain the distillation. Any heptanol distilled over
catalyst. When butanol is used, a mixture 01'
butyl‘ heptoate and heptyl heptoate is formed,
I with the water is separated and returned to the
reaction mixture, so that the amount of heptanol
insteadvoi the plain heptyl heptoate, which is
iormediwhenheptanol alone is used to make the
in the reaction mixture is maintained substan
tially constant. This is continued until the re 30 catalyst. Where the mixed heptoates are used,
action is completed and no more water dis
there .is produced a mixture 01' heptanol and
tilled over. The completion of the reaction is
butanol, which as shown above, are'readily sep
tested so that one cc. of the reaction mixture is
aratedand recovered by fractionation.
equivalent to approximately 3 cc. of N/10 NaOH.
The reactions involved in the above described
When the reaction mixture has dropped to a 35 processes may be graphically illustrated by the
following‘ equations:
temperature of 60-7 0° 0., it is washed with dilute
Condensation of heptaldehudc
With aluminum heptoxide as catalystr
iii-heptoxide in '
(1) 2CHs(CH|)|CHO
(Heptaldehydc)
.
'
_
1
'
-—+
CHiwHmC O O CH|(CH;);OH| Y
excess of heptanol
(Heptyi heptoate)
Al-butoxide in
--—o
(Heptaldehyde)
excess oi butanol
OHI(CHI)ICOOOHI(CHI)2Q_HI + CHatOHzhCOOCHKOHrhCH: + EOCHKCHshCH:
(Butyl heptoa'te)
. (Hept'yl heptoate)
/ (Heptanoi)~
Preparation of Triethylenéfplycol diheptoate by
an. ,
ester ‘ exchange
With heptyl heptoate:
I
HOCH!
' (a) zoniwnmcooemwmtom +
(Hep'tyl heptoate)
'
'
CH1
0
35; -_.
8H,
8g; + aomwemcmoa I
8H,
(heptanol)
HO OH:
CHKCHghCOOCH:
(Trlethylene
‘with
7
butyl heptoate:
‘
Trieth lene
glycol)
col
(
.
HO-CH1
CHs(OH|)5COOCHs
H:
H:
(4) zomwmncoocniwmhom Q
(Butyl heptoate)
.
$2’
'
vi‘H,
———o
I
AH:
HO-JJH;
T1’! 111
.
( zigtwbm
$3. + mniwncionion I
(I)
{EH1
cmd'irmicooéHr
T ?l
( diimbkge'iml ‘ i
(Butanol)
2,412,409
-
7
.
8
With mixed butyl heptoate and heptyl heptoate:
’
HOCH:
CHKGMICOOCH:
Hg
H:
(5) cmwmncoocmwmncn,
J)
(Heptyl Iheptoate)
H:
> +
cmwmhcoocmwmhcm
(B
uty p
m mm
H!
H. -__.
‘12K + cmwnmcmoa
(g
)
'
éHg
43H;
no HI,’
cmwnmcooom
(Trlethylene
(Triethylehe glycol I
'
glycol)
(autism;
V
+ crmcnmcmon I
(Heptmol)
/
'
diheptotte)
Preparation 0;‘ diheptyl phthalate
(a)
0-0 "
/0
ciocmwmncn,
0 + 2OHx(CHr)|(_CH|OH) -—-—-r
0
(Heptanol
0:0
Phthsli
aghydrldg)
from Equation 2)
+ H20 I
%
(Water)
0-0 CH1(CH1)|CHQ
( Dih 9p t y1 ph t h 81m)
stripped to remove interfering components and
It will now be appreciated that there
has been provided novel plasticizers for synthetic
reactions carried out in the presence 01' non-in
elastomers, and particularly derivatives of buterfering residues.
tadiene-acrylonitrile type in which desirable 30 What is claimed is:
"low temperature ?exibility” is imparted to the
Triethylene glycol diheptoate.
elastomers. It will also be appreciated that there
has been provided novel method of preparing
the plasticizers in which a crude product is
'
'
LEONARD
NICHOLL.
WILHAMRBI'I‘IER.
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