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Патент USA US2117851

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2,117,851
Patented May 17, 1938
{ UNITED STATES PATENT
FFEQE
’
2,117,851
TREATMENT OF TERPENE ALCOHOL-ALKA
LI METAL BISULPHITE. REACTION PROD
UCTS
Henry J. Warmuth, Pen
sacola, Fla., assignors to Newport Industries,
Inc., Pensacola, Fla. , a corporation of Dela
. Robert C. Palmer and
ware
No Drawing. Application August 24, 1936,
Serial No. 97,658
6 Claims.
(Cl. 260-159)
I This invention relates to the treatment of re
action products obtained by reacting terpene ale
cohols with alkali metal bisulphites to convert
such reaction products into compounds having
I 5 good wetting and detergent properties.
More speci?cally this invention relates to the
pyrolysis of terpene alcohol-alkali metal bisul
phite reaction products to form new compounds
having good wetting and detergent properties.
action products of terpene alcohols and alkali
metal bisulphites.
A further object of this invention is to convert
terpene alcohol-alkali metal bisulphite reaction
products into new compounds having good wet
ting and detergent properties.
~
A further object of this invention is to pyrolize
terpene alcohol-alkali metal bisulphite reaction
products.
'
A further object of this invention is to prepare 10
It is known that unsaturated aliphatic or‘
cyclic terpene alcohols such as geraneol, linalool, wetting and detergent agents by pyrolysis of the
the terpineols and the like will react with alkali reaction products of a terpene alcohol and an al
metal bisulphites such as for example, sodium or kali metal bisulphite.
potassium acid sulphites. The reaction products
Other and further objects of this invention will
Ul obtained are water soluble and are believed to be become ‘apparent to those skilled in the art from 15
alkali metal salts of the sulphonic acids of the the following example and detailed description of
a preferred form of the invention.
terpene alcohols.
'
It is also known that there terpene alcohols
such as terpineols and the like possess strong
wetting and detergent properties but have very
'20
low solubility in water and must be reduced to a
colloidal state by means of soaps and the like to
utilize these properties. It might be expected
therefore that the water soluble reaction prod
me Or uctsof the terpene alcohols and alkali metal bi
sulphites would have even better wetting and
detergent properties than the terpene alcohols
themselves. However, such reaction products
possess practically none of these wetting and
' '30
detergent properties.
We have now found that the Water soluble re
action products of terpene alcohols and alkali
metal bisulphites readily undergo a fairly low
temperature pyrolysis to yield new products
35 which have excellent wetting and detergent prop
erties especially in the presence of strong acids.
The new products are reddish brown viscous
liquids, acidic in character, and can be neutral
ized with alkali metals to lemon yellow colored
40 compounds. The new products have a slight
terpene odor, nitrate readily, couple with diazo
tized amino compounds, react with solutions of
salts of the heavymetals, are quantitatively pre
cipitated by aluminum salts, and have good wet
45 ting and detergent qualities in the presence of
Preferred process of preparing terpene alcohol?
alkali metal bisulphite reaction products
20
It is known that terpene alcohols such as, for
example, alpha terpineol, will react with a dilute
solution of sodium bisulphite in water if a large
excess of the sodium bisulphite is used.
We prefer to prepare the reaction product, 25
however, with an excess of the terpene alcohol
present in the reaction mixture as follows: In
any type of vessel, either open or closed, are
charged 1500 parts of water, 100 parts of techni
cal grade sodium bisulphite and 150 parts of al
30
pha terpineol or a suitable mixture of solvents
containing 150 parts of alpha terpineol, and/or
other terpene alcohols. Steam distilled pine oil
containing 50 to 60% or more of tertiary terpene
alcohols is a suitable starting material.
35
The ingredients in the vessel are agitated at a
temperature of 40 to 45° C. until a clear solution
is obtained. Similar additional portions of re
actants are then added to the vessel and the
process is repeated. The process is repeated twice 40
more by the addition of two separate portions of
reacting ingredients. At the end of this time
there are approximately 1000 parts of reaction
product dissolved in 1500 parts of Water, plus un
reacted alpha terpineol and/or other terpene al
45
compounds in the presence of an alkali are some
cohols which are now in solution, plus a small
amount of unreacted sodium bisulphite and any
what poorer than in solutions having a pH value
impurities. The length of time of agitation for
below 5.v Nevertheless, the wetting properties of
each batch of added ingredients is about two
hours when a technical grade of sodium bisulphite 50
strong acids. The wetting qualities of these new
50 vthese new compounds even in the presence of an
alkali are much greater than the wetting proper
ties of the original terpene alcohol-alkali metal
bisulphite reaction products.
It is, then, an object of this invention to pre
55 pare wetting and detergent agents from the re
is used.
I
The contents of the vessel are then subjected
to steam distillation and the greater portion of
the excess terpineol and any other unreacted por
tions of the starting oil are recovered. When the 55
2,117,851
2 .
concentration of the reaction product becomes
from 55 to 60%, a precipitation of unreacted in
may vary from 26 parts to 56 parts; and the
organic material results. The distillation is then
stopped, the inorganic material ?ltered off and
but the amount of sodium bisulphate solution
formed should remain relatively constant.
the remaining reaction product in solution is ad
amount of water may be increased or decreased,
A variation . of several factors, such as the
justed by the addition of water to a concentra
tion of about 55% by weight. This gives a max
strength of acid, concentration of terpineol—sodi
um bisulphite reaction product, ?nal temperature
imum concentration of product which will not . of the reaction and rate of distillation will change
tend to crystallize at room temperature.
The 55% solution of terpene alcohol-sodium
bisulphite reaction products may then be used as
the starting material for the preparation of the
novel pyrolized compounds according to this in
vention.
Preparation of pyrol'ized terpineoZ-sodium bisul
phite reaction products
To 700 parts of terpineol-sodium bisulphite re
action products of about 55% concentration in
Water are added 180 parts of 77% sulphuric acid.
The mixture is heated gradually, preferably in a
closed system, and as the heat increases, water
is evolved as well as sulphur dioxide and a ter
the approximate quantities of some of the mate
rials produced by the reaction, but without great 10
1y changing the most important property of the
?nal product, viz., its wetting power.
7
The purpose of adding acid to the reaction
product of the terpene alcohol and alkali metal
bisulphite is to‘ convert the reaction product into 15
its acid form, since then the pyrolysis step pro
ceeds smoothly to the desired ?nal product. The
pyrolysis does not proceed so satisfactorily if a
free strong acid is present. Consequently, we use
only suf?cient sulphuric acid to form the acid 20
salt, viz. sodium bisulphate. We have found that
the acid salt is less soluble in the reaction mass
than the neutral sulphate and therefore its for
pene hydrocarbon oil. The reaction is controlled mation enables us to obtain a product more near
by measuring the amount of water distilled from ly free from inorganic salts. If other acids, such
the boiling mass. When 140 parts of water have as hydrochloric or phosphoric, were used in place
been distilled, the mixture in the still becomes of sulphuric acid, they should be used in amounts
only sufficient to produce the corresponding alkali
cloudyand separates into two layers. The top lay
er contains practically all of the organic matter, metal salts by combination with the alkali metal
some Water and sodium bisulphate. The bottom . of the reaction product. Preferably, no free 30
strong acid is present in the reaction mass, ‘but
layer consists principally of water and sodium bi
sulphate with practically no organic matter. By the scope of our invention does not exclude that
the time 250 parts of water have been distilled off, possibility.
The use of very dilute acids is not so practical,
a separation of these two layers should be made by
drawing off the lower layer. The top layer is since such use necessitates the evaporation of 35
subjected to further heating until 45 additional more water before it is possible to'reach the temé
perature at atmospheric pressure where the py
parts of water have been distilled and the tem
perature in the liquid is about, but does not exceed rolysis reaction proceeds moist readily. We’
therefore prefer to use a relatively concentrated
128° C.
mineral
acid in the acidi?cation step prior to‘ py~
A
second
separation
of
sodium
bisulphate
solu
40
40
tion is made at this point and the top layer set rolysis.
The
final
temperature
should
not
exceed
128°
aside for further processing.
C. Higher temperatures cause rapid destruc
It is preferred to make two separations of the
tion
of the product, converting it into water insol
water solution of sodium bisulphate because the
uble tar-like materials having little, if any, wet
45 amount of material to be separated reaches a
45
ting power.
'
maximum at the time 250 parts of water have been
The product of the above reaction may be neu
distilled off and thus a separation is made at this
tralized by any of the caustic alkalis or alkaline
point in order to remove the greatest volume at
earth metal hydroxides, but sodium or'ammonium
one time. If the separation is attempted in one
hydroxide is preferably used because the salts
step at the end of the reaction, it is found that produced have a greater solubility in water.
50
the control as evidenced by the amount of water
In order to produce approximately a 60% water
distilled off is no longer a guide of the progress of
solution of the sodium salt of the product, there
the reaction. Furthermore, in this event, the are added to 250 parts of the product obtained
?nal product is found to contain a larger amount
as described in the above example, 188 parts of 29‘
of sodium bisulphate and requires more alkali to
Bé. caustic soda solution (about 22% alkali)".
neutralize it, thus giving a poor quality product This yields a lemon yellow solution which can be
because of salt adulteration. At the end of the readily handled and which is readily soluble in’
reaction as speci?ed above there have been pro
water. By the Clarkson-Draves wetting speed
duced quantities of materials approximately as test, 0.35 part of this solution in 100 parts of
60 follows:
water will wet in 25 seconds or less, in the pres 60
ence of any strongly ionizable acid at 40° C. The
47 parts sulphur dioxide
amount of free acidity is relatively unimportant.
32 parts terpene hydrocarbon oil
260 parts sodium bisulphate solution of which Even 5% of free sulphuric acid does not impair
the efficiency of the wetting speed of the com
approximately
65
pound.
108 parts is sodium bisulphate and
From the above description itshould be under
152 parts is Water
stood that this invention provides a method for
250 parts of the desired ?nal product contain
the production of novel pyrolized products by
ing approximately
acidifying and heating a terpene alcohol-alkali
63
parts
of
sodium
bisulphate
but
practically
70
no water
250 parts of water which has been distilled off
during the reaction.
The sulphur dioxide produced may vary from
30 parts to 94 parts; the terpene hydrocarbon oil
metal bisulphite reaction product. Duringr'this'
heat treatment, sulphur dioxide, a-terpene hy
drocarbon oil, ‘sodium bisulphate solution, the
novel pyrolized product and water are obtained.
The pyrolized product can be used as such as
a wetting agent or detergent or can be con 75
2,117,851
3
verted into a caustic alkali metal or an alkaline
3. The process of preparing wetting agents
earth metal salt, which are also water soluble
which comprises preparing a mixture of an aque
ous solution of a terpineol-alkali metal bisul~
phite reaction product and suf?cient acid to com
bine with the alkali metal of said reaction prod
and form excellent wetting agents or detergent
material. Both the pyrolized product and its wa
ter soluble alkali metal and alkaline earth metal
salts are also good emulsifying and dispersing
agents. For instance, a 60% concentration of the
pyrolized product, or of any of its water soluble
salts, in aqueous solution, enables the formation
10, vof clear solutions with ordinarily water immisci
ble liquids, such as vegetable oils, fatty acids,
petroleum hydrocarbons, esters, ketones, terpene
hydrocarbons, alcohols, natural resins, and the
like.
The clear solutions so formed, upon dilu
15 tion with water, become stable emulsions or dis
persions which may have a wide variety of uses.
The pyrolized product and its salts may, there
fore, be used to advantage as emulsifying agents
for water insoluble wetting agents like steam dis
20 tilled pine oil, or terpineol, particularly so since
it is possible to make both acid and alkaline emul
sions that have stable characteristics. A large
variety of other uses may be mentioned, includ
ing the use of the pyrolized product and its salts
25 in the manufacture of lubricants, polishes, insec
ticides, emulsi?ed coating compositions, clean
ing and scouring compositions, waterproo?ng
emulsions, and many others.
We are aware that numerous details of the
'30 process may be varied through a wide range
uct, heating said mixture to distill oil water from
said mixture until the mixture separates into two
layers, drawing oil the lower layer, subjecting the
top layer to a further heat treatment to distill
oif more water therefrom, permitting the mixture 10
to separate again into two layers and recovering
the top layer, the heating and distillation steps
being carried out at a temperature not over 128°
C.
4. The process of preparing wetting and de 15
tergent materials which comprises heating a mix
ture of 700 parts of a terpineol-sodium bisulphite
reaction compound of about 55% concentration
‘in water and the equivalent of about 180 parts of
77% sulphuric acid, allowing sulphur dioxide, 20
a terpene hydrocarbon oil and water to be dis
tilled from the mixture until the mixture sepa
rates into two layers, drawing off the bottom lay
er, further heating the top layer to distill off more
water therefrom, allowing the mixture to- sepa 25
rate again into two layers and recovering the top
layer containing the wetting and detergent mate
rial, the heating and distillation steps being car
ried out at a temperature not over 128° C.
5. The process of making wetting and deter
without departing from the principles of this in
gent material which comprises heating together
vention, and we, therefore, do not purpose limit
’700 parts of a 55% aqueous solution of a ter
ing the patent granted hereon otherwise than
necessitated by the prior art.
We claim as our invention:
1. The process of preparing wetting agents
from terpene alcohol-alkali metal bisulphite re
30
pineol-sodium bisulphite reaction product and
the equivalent of 180 parts of 77% sulphuric acid,
distilling off 250 parts of water from the mixture
at atmospheric pressure until the mixture sepa
rates into two layers, drawing off the lower layer,
action products which comprises heating the acid
further heating the upper layer at atmospheric
forms of said products at a temperature of not
over 128° C. to distill oil‘ water therefrom until
the mixture separates into two layers, and recov
pressure to distill off 45 additional parts of wa
ter therefrom, again allowing the mixture to sep 40
arate into two layers, and recovering the layer
containing the pyrolized terpineol-sodium bisul
ering the top layer.
2. The process of converting a terpene alcohol
alkali metal bisulphite reaction product into a
.45 wetting agent which comprises heating an aque
ous solution of said reaction product at a tem
perature of not over 128° C. in the presence of
suf?cient acid to combine with the alkali metal
of said reaction product to distill off water from
.50 the reacting mixture until the mixture separates
into two layers, and recovering the top layer.
phite reaction product.
6. The process according to claim 5 in which
the pyrolized product is reacted with an alkali
hydroxide selected from the class consisting of
alkali metal and alkaline earth metal hydroxides
to produce a lemon yellow colored solution which
is soluble in water;
ROBERT C. PALMER.
HENRY J. WARMUTH.
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