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2,410,635
Patented Nov. 5, 1946
2,410,635
HEAT STABLE COMPOSITIONS
John Kenneth Graver, Webster Groves, Mo, as
signor to Monsanto Chemical Company, St.
Louis, Mo, a corporation of Delaware
No Drawing. Application March 3, 1945,
Serial No. 580,935
11 Claims. (Cl. 106-316)
1
This invention relates to heat stable composi
tions and more particularly to heat stabilized
compositions composed of aryl sulfonamides and
aryl sulfones.
2
3 to 6 carbonv atoms; and an aryl sulfone of the
formula type
R
0
@“U
s
II
Aryl sulfonamides such as benzene sulfona
o
mides, toluene sulfonamides and their N-alkyl
in which R and R’ are residues selected from the
derivatives are known to be relatively unstable
under the in?uence of heat. This is true even
when the sulfonamides are substantially free
group consisting of hydrogen and methyl.
Among the aryl sulfonamides employed in the
from impurities. The aryl sulfona-mides have 10 preparation of the heat-stable compositions of
the present invention are the following: benzene
been found to possess the tendency of darkening
sulfonamide and ortho- and para-toluene sul
in color even upon standing at room temperature
fonamides, and the following N-alkyl deriva
and the phenomenon is greatly accelerated at
tives of these sulfonamides, such as the methyl,
temperatures above room temperature. When
the sulfonamides are exposed to heat stability 15 ethyl, propyl, isopropyl, butyl isobutyl, amyl, iso
amyl, hexyl, heptyl, octyl and ethylhexyl de
tests, the compounds turn dark and the decom
rivatives, and N-cycloalkyl derivatives such as
position appears to progress rapidly. Aryl sul
the cyclopropyl, cyclobutyl and cyclohexyl deriv
fonamides, which have thus undergone decom
atives. Mixtures of two or more of the afore
position, are greatly lessened in value and ren
described aryl sulfonamides may also be employed
dered useless for many purposes for which the
substances are normally used. This is particu
for the purpose of the present invention. More»
over, in the case of mixtures of the ortho- and
larly true when the sulfonamides are employed
para-isomers of the aryl sulfonamides such as
the ortho- and para-toluene sulfonamides, the
One of the objects of the present invention is 25 ortho- and para-isomers may be present in any
desired proportions.
to provide heat-stabilized compositions com
Among the aryl sulfones employed in the prep
posed of certain aryl sulfonamides and certain
aration of the heat stable compositions of the
aryl sulfones.
present invention are the following: diphenyl
A further object is to provide a process for heat
sulfone and the ortho- and para-isomers of di
stabilizing certain aryl sulfonamides.
tolyl sulfone. Mixtures of the ortho- and para
Further objects will become apparent from the
isomers of the aforedescribed sulfones may Vary
following description and examples.
over a wide range of proportions. Mixtures of
The composition of the present invention, gen
two or more of the aforedescribed sulfones, to
erally stated, comprises a blended mixture of at
gether with ortho- and para-isomers thereof, may
least one aryl sulfonamide of the formula type
as plasticizers or extenders for cellulose esters,
synthetic and protein coating compositions.
be employed.
SOZNELR’
R
40
in which R is a residue selected from the group
consisting of hydrogen and methyl and R’ is a
residue selected- from the group consisting of.
hydrogen, alkyl radicals having from 1 to 8 car- -
bon atoms and cyclo-alkyl radicals having from
‘
The heat stable compositions of the present in
vention are prepared by blending the aryl .sulfon
amides and the aryl sulfones in any desired man—
ner, as for example by adding the sulfones to the
sulfonamides and agitating the mixture until
uniform dispersion of the components is e?ected.
The quantity of aryl sulfone to be blended with
aryl sulfonamides to provide the heat stable com
positions of the present invention may range from
1 to 15% by Weight of the composition. The de
2,410,635
sired range is 5 to 15%. When substantially pure
g. of diphenyl sulfone. The mixture was heated
aryl sulfonamides are employed, the amount of
to 153° C. and agitated until a uniform blend of
sulfone required to provide a heat stable com
the components was obtained.
position may range in some‘ instances from 1 to
E sample II
10%. When impure sulfonamides are employed, 5
the amount of sulfone required for the purpose IS
A mixture of 65 parts Nqsopropylbenzene Sui
hkely to be @n the range of 5 to 15%- In generel»
fonamide, 25 parts of N-isopropyl- p-toluene sul
no substantial improvement of the heat stability
fonamide and 10 parts of a mixture of orthm
of the composition is e?eeted when the amount ’ and para-ditolyl sulfone was heated to 50° C. and
of sulfone present in the composition is increased 10 agitated to provide a uniform blend of the com_
above about 15%. The sulfones employed in the
ponenta
Preparation of_ the n°Ve1_ cempesltlons of the
Compositions prepared as described in the fore
present invention are solids at room. tempergoing examples as Well as others prepared ac_
ajture' It 15 one of the features of ‘thls _1I_1Ven'
cording to the procedure in those examples, to
tion that these sulfones impart heat-stability to 15 gather with Specimens of the corresponding aryl
the Sulfonamldes _descnbed herelP when the em‘
sulfonamides containing substantially no aryl sul
fones are present in the compositions of the presfones were tested for heat stability and the speci
ent invention in amounts insu?icient to give rise
mens were thereafter Compared with known color
to ineompetlbmty m plague comeesltloes in Whmh
standards. The heat stability test was performed
the composltlons of the present Invention may be 20 by inserting the respective compositions and sul
used‘ :I’Pe sulfene center‘? of ehe heat Stable
fonamides into 13 mm. diameter test tubes and
compositions of the present invention may be proimmersing the test tubes for one hour in an agi_
‘need durmg the formetlfm °f the aryl summ'
tated oil bath maintained at 205° c. The tem
amide by a suitable selection of operating condiperature was selected because it provides a Drab
tions, which under normal circumstances are 25 ?cal Safety factor above any temperature to
usually controlled to avoid the formation of sulwhich the composition is likely to be exposed in
fones.
-
. .
-
‘
-
molding operations where the compositions are
. The.heat stable commiems of the pltesent
used as plasticizers or softening agents for cel
invention possess substantially the properties or
lulose esters synthetic resins and protein coat_
characteristics of the aryl sulfonamides them- 30 mg Compositions The time S e1 ecte d for the test
silgest’ gltlifiigx?ggogf tgséttgg 50511130213328
provides a practical safety factor in excess of the
g
the I: ult of ex Os r to otelgl em-
time during which the composition is likely to
beer gwhgll the heat gtabieucom sitions:
of the extent of decomposition developed in the
53s‘ e
tginpo Snail fro groom tenfaelite re to 20%‘, C
an
of thee res’ent inven? n r
be subjected to such temperatures. A measure
m 10 dies 18$ 35 composition when subjected to the heat test is
ticizersp for example c)fora ceeltleu‘gseyeesters p‘the
.
provided according to the practice in this art by
. .
color com arison with known color stan ard .
amount of aryl sulfones present in the plasticized
The c 01 orpst an dards employed for compgrisoi
ester as the result of their existence in the heat
were those known as the Gardner 6 0101, Standards
stable compositions of the present invention are 40 These standards were employed in conjunctiori
‘far less than’ the quantity. of my} Sulfones re."
vwith‘ a comparator of the Hellige type in the
(wired wi‘?ect any appreclame degree of mesh"
manner known to those skilled in the art The
012mg actlon .On the ester‘
.
.
color is reported in terms of the Gardner number
The following examples will serve to illustrate
m
.
.
of the respective standards used for the com_
D.
_
.
.
2211;561:1222;goTggzglggglggispggieiiDiem/2351:5532; 45 parison. By these standards the compositions
'
'
. r
.
.
. . “
prior to subjection to the heat test range in color
merely as illustrative and not as limiting the
mvennon'
Emm Z 1
'
p e
To 95 g. of benzene sulfonamide was added 5
' No.
from G_1 to G40 Moreover the color may vary
within this range depending upon the impurities
50 present.
The following table shows the results
of the tests:
I
Composition or substance
Eat-gig‘;
Heat stability
((ilai'd?i;
0001‘5
1
2
3
Benzene sulfonamide ________________ __
Benzene snlfonamide; diphenyl sulfone
N-isopropylbenzene sulfonamide _____ __
.
é N-isgpropylbenzene sulfonamide;diphenyl sulfone
_.-_.
7 _.___do___
8
9
10
11
_____do
8
G-5
Very good.
1o
G-2
Do.
~
_ ._ _ _ _
. _ _ _ _ _ _ __
N-butylbenzene sulfonamide _____________________________________________________ ._
N-butylbenzene sulfonami'de; dipbeiiyl suli'one.-.
____ __
__
p-Toluene sulionamide ________________ __
l2
p-Toluene sulfonamide; diphenyl sulfone.
,N-methy1-p~toluene sulionamide ....... __
___
l4
N-methyl-p-toluene sulfoiiamide; dipheiiyl sulfone
N-ethyl-p-toluene sulfonainide; diplienyl sulfone__
N-isopropyl-p-toluene sulfonamide ___________________ _.
lg N-isgpropyl-p-toluene sulfonamide;diphenylsuli'one-..
0
15
G-2
0
1O
G-l8
G-lO
gall-(.1
00
.
Do.
Do.
Good.
_
0
10
6-10
Good.
0
(3-15
Poor.
10
(3-10
Good.
____ ..
Poor.
0
(3-15
Poor.
l2
G-12
Fair.
0
G~l8
Very poor.
13
______ __'_ _____________________________________ __
G~15
Very poor.
Good.
.
Very poor.
__
N-ethyl-p-toluene sulfonami'denr ____________ __
l6
17
._-__
G-l5
6-?
G-l8
Ll,
______________________________________________________ .-
13
15
0
8
0
0 __________________________________________ _-
6 _-___do.__
Rating
.
'
(6-185)
Geog.
—
0.
20
N~cyclohexyl benzene sulfonamide ___________________ _.
.
0
G-l4
Poor.
21
N-cyclohexyl benzene sulionamide; diphenyl sulfone _________________________________ _.
_
l0
G-lO
Good.
70% N -isopropylbeiizeiie sulfonamide; 30% N -isopropyl—o- and p-toluene sulionamides _______ _.
0
6-12
Fair.
0
12
G~16
(3-8
Poor.
Good.
22
23
‘ ‘
70% N -isopropylbenzene sulfonamide; 30% N—isopropyl-o- and p-toluene sulfonamides; mixture of the o- and p-ditolyl sulfones.
24 70%are
N-isogiggiyylbetizene
sulfoiiamide; 30% N-isopropyl toluene sulfonamlde
containing 80%
8D
0!‘ OlSOlIlEl'S.
~
25 701%, N-isoprop(ylbenzene sulfonamide; 30% N-isopropyl toluene sulfonamide containing 80%
‘
para and 20% ortho isomers; mixture of o- and p-ditolyl sulfones.
8
G-8
Good.
. _
.
2,410,635
5
.
7
‘It is observed from the foregoing data that the
compositions of the present invention are re
markably stable to heat under conditions to
which they are likely to be exposed in use as
plasticizers and softening agents for cellulose
esters, synthetic resins and protein coating com
6
4. A heat-stabilized composition comprising
N-isopropyl benzene sulfonamide and from 5 to
15% of diphenyl sulfone.
5. A heat stabilized composition comprising
N-isopropyl benzene sulfonamide, N-isopropyl p
toluene sulfonamide and from 1 to 15% of a
mixture of diphenyl sulfone and ortho- and para
positions. The sulfonamides alone on the other
isomers of di-tolyl sulfone.
hand were all poor in stability at the temperature
6. A heat stabilized composition comprising
and for the time of the test.
While the compositions of the present inven 10 N~isopropyl benzene sulfonamide, N-isopropyl p
toluene sulfonamide and from 5 to 15% of a,
tion have been described and illustrated in the
mixture of diphenyl sulfone and ortho- and para»
foregoing speci?cations and examples, it is to be
observed that the present invention is not to be
isomers of di-tolyl sulfone.
-
'7. A heat -stabilized composition comprising
construed as being limited in respect to any par
N-isopropyl
benzene sulfonamide, N-isopropyl p
15
ticular substances, proportions, conditions or
toluene sulfonamide, N-isopropyl o-toluene sul
combinations except as de?ned in the claims.
fonamide and from 1 to 15% of a mixture of
I claim:
'
l. A heat-stabilized composition comprising at
least one aryl sulfonamide of theformula type
diphenyl sulfone, o-di-tolyl sulfone and p-di»
tolyl sulfone.
8. A heat-stabilized composition comprising
20
N-isopropyl benzene sulfonamide, N-isopropyl p
toluene sulfonamide, N-isopropyl o-toluene sul- '
fonamide and from 5 to 15% of a mixture of
R
diphenyl sulfone, o-di-tolyl sulfone and p-di
in which R is a radical selected from the group
25 tolyl sulfone.
9. A heat-stabilized composition comprising
consisting of hydrogen and methyl, and R’ is a
70% of N-isopropyl benzene sulfonamide, 30%
radical selected from the group consisting of hy
of ortho- and para-isomers of N-isopropyl tolu
drogen, alkyl radicals having from 1 to 8 carbon
ene sulfonamide and from 1 to 15% of a mixture
atoms and cycloalkyl radicals having from 3 to 6 30 of diphenyl sulfone, o-di-tolyl sulfone and p-di
carbon atoms; and from 1 to 15%, by weight of
tolyl sulfone.
the composition, of at least one aryl sulfone of
10. A heat-stabilized composition comprising
70% of N-isopropyl benzene sulfonamide, 30%
of ortho- and para-isomers of N-isopropyl tolu
the formula type
R
RI
0
@“U
s
35 ene sulfonamide and from 5 to 15% of a mixture
of diphenyl sulfone, o-di-tolyl sulfone and p-di
tolyl sulfone.
H
o
11. A process for preparing a heat-stable com
in which R and R’ are radicals selected from the
group consisting of hydrogen and methyl.
position comprising mixing at least one ‘aryl sul
2. A heat-stabilized composition comprising 40 fonamide of the formula type
at least one aryl sulfonamide of the formula type
SOzNELR’
R
R
45
in which R represents a radical selected from the
group consisting of hydrogen and methyl, and R’
in which R is a radical selected from the group
represents a radical selected from the group con
consisting of hydrogen and methyl, and R’ is a
radical selected from the group consisting of 50 sisting of hydrogen, alkyl radicals having from 1
to 8 carbon atoms and cycloalkyl radicals having
hydrogen, alkyl radicals having from 1 to 8 car
from 3 to 6 carbon atoms; with from 1 to 15%
bon atoms and cycloalkyl radicals having from 3
to 6 carbon atoms; and from 5 to 15%, by weight . of at least one aryl sulfone of the formula type
of the composition, of at least one aryl sulfone
R
c")
R’
of the formula type
55
@SU
11
o
.in which R and R’ represent radicals selected
from the group consisting of hydrogen and meth
in which R and R’ are radicals selected from the 60 yl; heating and agitating the mixture until a
homogeneous solution is formed and subsequently
group consisting of hydrogen and methyl.
allowing the mixture to cool.
3. A heat-stabilized composition comprising
N-isopropyl benzene sulfonamide and from 1 to
15% of diphenyl sulfone.
JOHN KENNETH ' CRAVER.
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