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Патент USA US2403408

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2.403.408 '
PAE'TNT» or‘
Paul Stamberger, Dover, Del.
No Bra. Application January
11, _ 194s, '
Serial No. 472,022 ‘
This invention relates to the production of
thickened masses or ?lms from esters of long
chain fatty acids by a process of oxidation. Thev
masses or ?lms produced may be of sticky con
sistency or may have solidifying properties, or
may be solid, depending on the materials ‘and
treatment employed. '
The invention is especially adapted to effect
(or. 106-254) '
when hydrogen peroxide is brought in contact
with drying oils and similar products in the pres- '
ence of suitable catalysts, the solidi?cation of
the oil will take place within a very short time
even throughout a mass of considerablev thick
ness or‘ size, and that. when producing ?lms of
a few millimeters thickness, it is-not necessary to '
increase the surface of the oil to be oxidized to
the extent required for oxidation with oxygen or
persions or emulsions.
10 oxygen containing gas.
The present application is a continuation-in
Forlthe-r’process which is the subject of the
part of my copending application, Serial No.
present invention, it is essential that a non-gas;
465,636, ?led November 14, 1942. As is men
eous oxidizing agent, capable of being brought
tioned in said co-pending application, it is well"-~ ~ qhin solution, is used and that such agent decom
known that drying and semi-drying oils can be 15 poses without leaving a non-volatile residue. .
thickened and ultimately solidi?ed by oxidation. Thus hydrogen'peroxide and solutions of'hydro
- ing the oxidation of the esters in aqueous dis
This has frequently been done by blowing the ~
oil, usually at elevated temperature; with an
gen .peroxide may be employed. It is further an '
importantnfeature to use such amounts of the
oxygen containing gas, such as air, whereby the ' oxidizing agent that. an approximate saturation,
thickening and solidifying takes place. - Such 20 or complete‘saturation of the fatty acid esters
an oxidation is a relatively slow process which
can only be controlled with di?iculties and re
with the oxygen without decomposition of the
oil,v is attained, this being accompanied by a
spontaneous solidi?cation of the oil.
an oxidation reaction takes place on the inter
It is still further of importance that the oxi
face of the oil and the gas. The products of such 25 dation be carried out in the presence of catalysts,
quires considerable skill. It is ‘believed that such
an oxidation dissolve in the oil below such an
interface (which oil is still unchanged) and the
oxidation products thereby form a colloidal so
lution. This process continues until all the oil
is transformed into a mass containing a large
quantity of oxidized products. The velocity of
so that the oxidation may be effected at low
temperatures, even at room temperature, (that
is about 10°-40° C.) In this waysolid products
maybe formed even at room temperature. In
such a process the presence of catalysts acceler
ates the oxidation, and in addition, the nature
and quantity of catalysts otherwise in?uence the’ _
oxidation process. A product, the oxidation of
which is carried out to the extent above men
such a reaction may be increased by enlarging
the surface of the drying oil in contact with the
oxygen. This may be e?’ected either by spread
ing the oil into a thin ?lm Or by dispersing the 35 tioned, without decomposition of the fatty acid
oil in a medium, for example, by producing a dis
esters, has different and advantageous properties,
persion 0r emulsion of the oil in water with small
as compared with products obtained by a differ
dispersed particles. For this purpose the best
ent degree of oxidation.
particles are of one micron or less diameter.
In carrying out the process in the presence of
The present invention is based on the discov 40 catalysts, it is_ possible to in?uence the reaction
ery that esters of unsaturated fatty acids formed
to such an extent that a spontaneous and very
with polyvalent alcohols are oxidized remarkably
rapid solidi?cation of the fatty acid esters will
easily in the presence of hydrogen peroxide; and
take place; _In using hydrogen peroxide as the
further, on the observation that hydrogen p‘er
oxidizing‘ agent, various known metallic catalysts,
oxide itself is a very effective oxidizing agent for 45 consisting of heavy metals may be employed with
such unsaturated fatty acid esters, when the hy- _ de?nite advantage, since these catalysts are acti—
drogen peroxide is used in the presence of cat‘
vated by the hydrogen peroxide. ‘Such catalysts,
in fact, manifest far greater activity when used ’
According to the present invention such a pro!‘
with hydrogen peroxide, than when used with
ess is used to thicken and even to solidify natural 50 other-oxidizing-agents (for example, oxygen gas).
or modi?ed fatty oils or other natural or syn
It is an advantage of ‘the process that it can '
thetic esters containing unsaturated fatty acids,
and to produce therefrom solidi?able, sticky, or
be used in a very simple and effective manner
to carry out oxidation of dispersions and emul
_,=~s01id masses suitable respectively as film coat
sions of drying oils or materials containing dry
ings, adhesives, and the like. ‘It was found that 55 ing oil fatty acids, the oxidation being very effec
where it is desired to- secure relatively hard or
tive even in coarse dispersions with particle size
of 6 microns and larger. With hydrogen peroxide
the oxidation is completed in very short time and
a dispersion of solid products can easily be ob
tained. No ions are added or formed by the
solid products.
decomposition of hydrogenperoxide, and its use
Even in cases where the quantity of oxidizing‘
agent added is insuf?cient to yield products which
will display spontaneous solidi?cation, it may
nevertheless be of advantage to employ heat
bodied oils or esters or esters of fatty acids hav
has no adverse effect on the properties and sta
ing conjugated double bonds. In this event, addi
tional oxidation may, if desired, be effected by
The advantage of the process which is the 10 other oxidizing agents, such for instance, as
subject of the present invention may be demon
oxygen gas.
strated by the following experiment: 50 grams
In general, these starting materials, especially
bility of the emulsion.
of water, and 50 grams of an aqueous hydrogen _
heavily ‘heat bodied oils, require less oxidizing
peroxide solution of 30 volume per cent concen
agent for a given degree of change in consistency,
tration are placed in two separate ?asks. 20
thereby providing the advantage that smaller
grams of tung oil in which 0.3 gram of cobalt is
quantities of oxidizing agent may be used, with
dissolved are poured over each of these liquids
corresponding reduction in cost of materials.
forming a film of 10 millimeters thickness.
Moreover, the process ‘proceeds more rapidly
Within a few minutes a solid ?lm formation can
which‘ is of advantage, and products of improved
be observed in the ?ask containing hydrogen
properties are obtained from employment of
peroxide and in two hours time the entire oil
smaller’ quantities of oxidizing agent, since the,
?lm is transferred into a solid dry mass. The
less agent present, the less decomposition of the
reaction is accompanied by heat evolution but
oil or ester takes place. The quantity‘ of decom
no formation of oxygen gas could be observed.
In the other ?ask where the tune oil was placed
position products present, therefore, may be
observed after 30 minutes, and even after 24
hours the contents of the flask was only solid on
the surface, showing there a sticky,_soft mass.
in general may be used. I have found oxidation
catalysts known for use, with drying oils, as in
the manufacture of varnishes, lacquers and the
maintained very small.
over water only, ‘a ?lm formation could only be 25
As catalysts in the process, oxidation catalysts
This behavior of hydrogen peroxide is utilized
like, are particularly ,e?fective. For instance,
in the present invention for the production of 30 heavy metal soaps may be employed, such as
fast drying masses, solid dry masses, as well as
linoleates, resinates and naphthenates of cobalt,
manganese, lead, zinc, iron and copper. Salts
solid adhesives from esters of polyvalent alcohols
and unsaturated long chain fatty acids, or in
of such heavy metals with either organic or in
general from chemical compounds‘ containing 35 organic compoi' ds may be employed. It is ‘ad
such unsaturated long chain fatty acids. The ' vantageous to use combinations of catalysts.‘
best method found to carry out this invention
for transforming the fatty acid esters into prod
ucts having the improved properties, such as
thickened consistency, is to disperse the fatty
acid compounds in water by a process of emulsi
?cation and then bring the hydrogen peroxide
These can be added either to the oil before it is
dispersed or to the dispersion before or afterthe
in contact with the dispersed particles. Accord
acts quantitatively and gives up the free oxygen
addition of the hydrogen peroxide.
' The properties of the product can be controlled
over a wide range by varying the amount of hy
drogen peroxide which, as a matter of fact, re
to the drying oils or compounds containing un
viscous rapidly drying, for instance, solidifying 45 saturated fatty acids. The amount and nature
of the oxidation catalyst has also a marked effect
or a solid dry mass, or even an adhesive, will
remain after evaporation of the water or after
on the properties of the product formed.
ing to the extent of this oxidation process, a
coagulation of the dispersion.
If water dispersions of the unsaturated fatty
acid compounds are to be produced, it is impor
The application of hydrogen peroxide as an
oxidizing agent, preferably in a concentrated 50 tant to carry out the process in such a manner
that the stability is not impaired during or after
solution, allows the reaction to be carried out
the reaction. To produce stable dispersions or
in the emulsi?ed state of the oil or similar prod
emulsions it is advisable to use emulsifying agents
ucts at room temperature.
which will keep the dispersion in- a stable un
As above mentioned, products of different con
sistency may be secured by appropriate selection 55 changed state after the oxidation process is com
of materials and regulation of the treatment.
pleted. For this purpose, the dispersing agents
As a guide in this connection, it is mentioned
should be of a type such that if the formation of
that solid and sometimes even quite hard prod
ucts are secured either (a) when employing heat
bodied or blown esters of fatty acids having more 60
than one double bond, for instance, heat bodied
linoleic acid esters, heat bodied or blown oils, or
(b) when employing fatty oils or esters. having
conjugated double bonds, whether or not the
acidic oxidizing or decomposition products takes
place, the consequent change of the pH of the
dispersion will not a?'ect the stability of- the dis
Agents of the type mentioned just aboveare
disclosed in my copending application 455,607,
?led August 21, 1942. In general, such agents
materials of this group are heat bodied or blown. 65 belong to that class of materials‘ which are non
ionic or are cation active substances, as brought
Examples of the latter class are tuna oil; oiticica
out more fully in said copending application. 1
oil and dehydrated 'castor oil.
These agents can be added bef0re,:_during or
Considerable advantage is‘ obtained from the
employment of heat bodied oils having more
than one double bond.‘ Such heat bodying may ‘
be achieved in any of various different ways, as
by heating at ele ‘ ted temperature in the pres
ence or absence of agents tending to promote
heat bodying.
Blown oils or esters, secured for '
after the emulsion is made, separately or in
combination with each other. Em'uisi'fying agents
belonging to the. class of non-ionic substantial‘;
are, for example, esterszof long chain fatty acids
such as nonaethylen'glycolmonooleate', higher fat
ty alcohols such as dodecylalcohol, condensation
instance by blowing air therethrough at elevated '75 products
temperature, will“ also attain satisfactory, body
of polyethylenoxides. Emuisitying. sta
bilizing and dispersing agents belonging to the
hydrogen peroxide in which event a drier product
class of cation active substances are, for ex
ample, so called invert soaps, in which, contrary .
may be secured.
To modify the products obtained-natural or ’
synthetic resinsfsuch as rosins or gums, can be
to anionic soaps, the long chain is attached to a
dissolved in the material to be oxidized, for in
stance in a fatty oil or in mixed esters of unsatu?
rated fatty acids with polybasic, acids, such as‘ _v
decylammonium bromide or cetylipiridinium
phthalic or imaleic acids. Furthermore, phenolic
bromide and similar substances. '
resin modi?ed oils and the like can also be used.
It is furthermore desirable to work under con
Inorganic pigments, dyes and ?llers can be dis
ditions which permit no unreacted oxygen gas 10
persed in the oil before emulsi?cation or oxida- ‘
to escame from the reaction vessel, due to too
tion. The dispersion of inorganic pigments prior ._
rapid decomposition of the hydrogen peroxide.
’ to emulsification or oxidation has'particular ad
If the decomposition takes place too rapidly or
vantages, especially when employing ?nely di
suddenly, it tends to be accompanied by gas
evolution which may be so rapid as to take place 15 vided pigments such as zinc oxide and precipi
positive group such as a quaternary ammonium
group, or a pyridinium group, for example,'duo
on the surface of the dispersion before thorough
admixture with the total qu'antityof materialto
be oxidized. This may cause unwanted foaming
and may also adversely in?uence the economy
of the process.
Diiiiculties of this type may be avoided by op
erating under superatmospheric pressure which
tated whiting. Bythe' dispersion of such pig
ments, drier and stronger products, such as ?hns,
may be secured.
‘Esters of the above mentioned substances with
20 tetrahydric alcohols, such as pentaerythritol have
de?nite advantages, i. e. they give‘harder an
will serve not only to prevent escape of oxygen
but also to decrease foaming, and in this case
more water resistant products. -
; >
Solutions of the products to'be subjected to the
oxidation process or emulsions of such solutions
the pH need not be retained within any special 25 can also be used.
On the other hand, instead of ‘employing super
In all examples the ‘hydrogen peroxide used for
oxidation was of 30% concentration by volume.
atmospheric pressure, too rapid decomposition of
the hydrogen peroxide can be avoided if the pH
value of the dispersion be adjusted within certain 30
limits mentioned below prior to addition of the
oxidizing agent. Thus, I have found that if the .
pH value of the dispersion is properly adjusted,
the oxidation may be caused to take place at a
higher, or at least at no lower, rate than the
rate of decomposition of the hydrogen peroxide.
400 parts of a dehydrated castor oil was mixed
with a solution of driers, as naphthanates, so the
oil contained 0.3% Pb, 0.03% 00., and 0.02% Zn.
To emulsify the oil the following emulsifying
agents were added: 2 parts of a polyethylene- .
It was found that for the above purpose the
oxide condensation product with castor oil, (a
limits are between pH l0iand pH 4. It was fur
satisfactory product .of this type being marketed
ther found that especially good results were ob
by the-General Dyestu? Corporation under the '
tained when the pH of the dispersion to which 40 trade name of Emulphor ELA), which is a non
the hydrogen peroxide is added is kept about
8.5. ,If the pH is more on the alkaline side, too
rapid decomposition of the hydrogen peroxide
will take place and unreacted oxygen gas will
ionic product made by condensation of polyethyl
enoxide‘with an alcohol; ,1 part of cetyl dimethyi
benzyl ammonium chloride (which is marketed‘
by the Rohm & Haas Company'under the‘ trade
escape, causing considerable foaming. If, on the 45 name of Triton K-60) , which is a cationic active
other hand, the pH is far on the acidic side, for
soap, consisting of a quaternary substituted am
example, below 4, the action of the hydrogen
product. 200 parts of water whiehiwas
peroxide is slowed down to such an extent that
mixed up with 0.5 part of an aralkyl polyether the oxidation of the dispersed particles is negli
condensation product, which is a non
gible, even after several days. It should be un 50 alcohol
ionic emulsifying agent (a satisfactory product
derstood that the optimum hydrogen ion concen
of this type being marketed by the Rohm 8r Haas
tration will vary within the above
, Company under the trade name of Triton NE),
ing to the rate of combination of the drying oil
and 1 part of triethanolamine was stirred in the
or ester with oiwgen.
The mixture was allowed to‘pass through a ‘
It is also possible to reduce the amount of 55 so-called colloid mill. The resulting mass was
a dispersion of oil in water having rather high
oxidizing agent used with the dispersion'of the
oil by oxidizing the oil previous to the dispersion
consistency. ,The pHlof this dispersion‘was 8.7.
process, or by heat-bodying the oil. Such a proc
To oxidize the product, 60 parts of a hydrogen
ess can be carried out by blowing the oil with
of 30 volume percent active
oxygen containing gases and/or heating the oil 60 hydrogen peroxide content was mixed in slowly.
at elevated temperature.
The above process can also be carried out by
passing oxygen or an oxygen containing gas
The hydrogen peroxide was a stabilized commer- '
cial product, the pH of which was 6. Slight foam- -
ing-wasobserved during the addition of the hy
through the dispersion containing a suitable liquid
oxidizing agent such as hydrogen peroxide, in the 65 drogen peroxide and some heating effect. The
pH of the mix after the total quantity of the H202
presence of .an oxidation catalyst. ’ Such a process
can be advantageously carried out by applying '
was mixed in was 6.5. '24 hours later all the H202 .
was combined with the oil and no surplus could
the gas under pressure which is greater than at
detected; The‘pH of such a mixrwas 4.7.
mospheric. The oxygen containing gas and the
drying by evaporation of -the'water,_a solid
liquid oxidizing agent, such as a solution of‘ hy 70 After
but soft ?lm remained which became hard and '
drogen peroxide in water, can be introduced
solid ‘by drying on the air (in'a similar manner
simultaneously. The dispersion itself can also be
as drying oils behave when exposed to the oxi
kept under the same pressure as the oxidizing
dizing action of the air). By elevated tempera
\gas. Supplemental treatment with oxygen gas
- ture, this process took only 10 minutes. The tem- may be adopted subsequent to the treatment with
perature-was 110° C. The ‘dispersion remained -
- ~
2,408,408 I
An aqueous dispersion or the oil containing the
unchanged tor several months. After two, weeks
driers was then made up 0! the following parts
(by weight) :
100 parts with maleic anhydride chemically
treated linseed oil (containing the metal
the pH was found to be 4.1.
400 parts of a dehydrated castor oil as above
were blown with air at 180° C. for 3 hours. The
2.5 parts a polyeth'yleneoxide condensation prod
dryers were added as 0.3% Pb, 0.03% Co and
uct with oleyl alcohol (as above) (preliminarily
0.03% Zn (calculated on the oil) and the term
dissolved in the oil)
perature was reduced to 120° C. and the blowing 10 1 part an .alkyl'dimethyl benzyl ammonium chlo
with air continued for 1 more hour. To disperse
ride, a quaternary ammonium salt (as above)
the mix the temperature was reduced to 60°_ Cg
and 2 parts of a polyethyleneoxide condensation
product with castor oil, (as above) 1 part of cetyl
45 parts of water (in which 0.4 part of trieth
anolamlne was dissolved)
Ten parts of hydrogen peroxide were added to
dimethyl benzyl ammonium chloride, (as above.) 15
the dispersion. After standing for twenty-four
and ‘A part of nonaethyleneglycolmonooleate
hours, apparently no surplus of hydrogen per
were used. The water used for emulsiiication
oxide remained, and at this time a liquid product
was 230 parts with 0.5 part of hydroxiethylethyl
was secured upon evaporation of water. from a
endiamixie dissolved. 'Ihe emulsi?oation was car
. ‘
ried out in the usual manner. The emulsion had 20 test sample. 7
wFive additional parts of hydrogen peroxide‘ were
a pH of 8.2. For oxidation to a solid oil, only 16
' added,’ which apparently were not absorbed by
parts of H202 solution (as above) were neces
the oil, since a. surplus was present even. after
sary. The pH after addition of the H20: was 7.1.
forty-eight hours standing. A ?lm produced from
After 24 hours standing, this reduced to 6.8.
this dispersion remained liquid after evaporation
The residue was a solid ?lm having similar prop
G25 of the water, but upon further
in air, the
erties as the ?lm obtained in Example 1.
?lm solidi?ed very rapidly, showing wrinkle for
mation. The pH of the
rsion was 4.7.
Although surplus hydrogen peromde was pres
A phenolic resin modi?ed varnish made in the
ent, liquid ?lms were stilhproduced irom'test
usual manner, by cooking a gallons of China-wood 30 samples made even after the dispersion had stood‘
oil, 16 gallons of linseed oil and 100 lbs. oi! a para
for sixty days.
tertiary alizyl phenol formaldehyde condensation
Similar liquid products and
were obtained
product type resin, said type also referred to in
by the same general procedure when
the literature as “pure phenolic resin," (a suitable 35 other oils, including maleic =.‘
de mood
product being marketed by the Stroock 8; Wltten
soya bean oils, sardine ,oil, and alkali
ed lin
berg Corporation under the trade name oi.’ Aro
seed oil.
tene ‘700) was used. Briers were added which
All of the oils justimentionedias well as the
were calculated on the fatty oil constituents of
the oil. The ultimate quantity of driers were 40
0.3% lead, 0.02% cobalt and 0.05% manganese.
For emulsifying, for every 100 parts of the var
nish 2 parts of a polyethyleneoxide condensation
product with castor oil, (as above,) 0.3 port of a
polyethylene oxide condensation product with 45
oleyl alcohol (a non-ionic emulsifying agent of
this type being marketed by General Dyestuil’
maleic anhydride modi?ed linseed oil indicated
that oxidation took place by treatment with .
hydrogen peroxide, this being indicated by disap
pearance of hydrogen peroxide and also by pro
duction of decomposition products of acidic na
ture. With all oi these oils liquid products were
The eiliect oi incre
the quantities of driers
Corporation under the trade name of Emulphor
is indicated bythis example.
ON) and 0.5 part of triethanolamine‘ were dis
Here a batch of a maleic anhydrlde modi?ed
solved in the varnish itself. 50 parts water were 50
linseed oil was also employed, being mixed'witli'
used, in which 1 part of cetyl dimethyl henzyl
driers as naphthanates, giving 1.0% lead, 0.1%
ammonium chloride, (as above.) and 0.2 part of
cobalt, and‘ 0.1% manganese on the basis of the
an alkyl dimethyl benzyl ammonium chloride, a
quaternary ammonium salt. '(a- suitable product
.being marketed by the General Dyestu'f!v Corpora
tion under the trade name of zep'hiran) were dis
solved. All the other ingrediéntsere identical
dation 100 parts of thew? % dispersion were slow
ly mixed with 16 partner 30 volume percent hy
droeen peroxide'solutio‘n. Alter the reaction was
hatches. the batches thereafter being intermixed.
First batch
50 parts of oil (containiliz the driers) ‘
‘ not with caster cilia above)
' Alter combining
dispersion. the piI-ot
- linseed oil was employed in this example. said oil 70 -~ _'1'en parts of j
beinseasnialeic anhydrideymodmed linseed oil.
To the batch naphth‘enate driers were added, in
quantities giving metal content on the‘ basis of the
on as follows: 0.24%‘ lead, 0.048% cobalt, and
,. ' ,
2 parts a polyethyleneoxide condensation prod
were. noticeable:
- .
, .
- completed, the pH of the dispersion was 7.5.
85!; parts water‘ 1,
After evaporation ofthe water at room tempera 65 0.2 port triethauoishiiile
ture a solid, strong elastic
‘Mi Part cetyl dim‘ghw“
A batch '0! a. chemically treated alkali re?ne
55 pose ‘the ingredients were prepared in two
with those used in the previous?";._é_$%mples. The
parts are calculated on the varnish content or
the dispersion. After the emulsiiflcationpmc- '
ess. the pH of the dispersion was- 82. For oxi
A dispersion was then produced, for which pur- ,
(u ‘
woman toforni'the
7.7.‘ v'
some normal oi
hydrogen peroxide remained in the dilperlion._
The P3 ‘ml’ WI addition was 0.86. ‘A tut tam-g
ple produced. a product of liquid consistency after
evaporation of the water.
Company under the trade name ‘of Aerosol
A further ten parts of hydrogen peroxide were
added and at this time considerable heating was
noticeable. Moreover, excess hydrogen peroxide
1750 parts of a 1% aqueous casein solution
A .test sample from the above dispersion indi- _
cated that the product did not dry as rapidly -
apparently remained in the dispersion, and the
‘as the oil which was not dispersed.
pH was reduced to 4.55.
Some hydrogen peroxide was then added to a '
Samples tested at this time also indicated a
?lm of liquid consistency after evaporation of the
portion of the foregoing dispersion, and during
water, although the ?lrnédried very rapidly to a 10 addition of the hydrogen peroxide coagulation
took place, the coagulum being a solid mass.
solid ?lm in the air.
' '
After standing for thirty days. the‘ pH was, This portion contained only an anion active'stabi
lizing agent.
found to be 3.9. with excess hydrogen peroxide
Another'portion of. the foregoing dispersion
still present. At this time also the dispersion
yielded a, liquid product which dried very rapidly 15 was then taken and employed as a batch for
additional treatment. vTo improve the stability
upon evaporation of the water. No wrinkle for
of the dispersion there was added ?ve parts of.
mation was noticeable.
water on the basis of 100 parts of the batch now >
being used, in which water there were dissolved
A batch of 100 parts of a dehydrated castor oil
non-ionic stabilizing agents, i. e., one part of
was milled on a paint mill with‘ thirty-one parts 20 a polyethyleneoxide condensation product with
of zinc oxide. Driers, as naphthanates, were
castor oil and- 0.5 part of a polyethylene oxide‘
then added, giving 0.07% lead, 0.03% cobalt and
condensation product with oleyl alcohol (both as
0.03% zinc.
above). Twentyparts of hydrogen peroxide ‘were
A dispersion was then produced, the constit
then slowly added and immediately after this
uents being prepared in two batches which were 25 addition some foaming could be observed al
subsequently combined:
though heating was not noticed.
First batch
130 parts of the above mixture of oil, zinc oxide
continued for some time. while the mixture stood
at room temperature. The dispersion contained
uct with castor oil (as above)
large quantities of unchangedhydrogen perox
and driers
2 parts a polyethyleneoxide condensation prod
The foaming '
ide. The product secured afte'r evaporation of
the water ‘was a sticky solid which lost‘ its sticki
ness in about two hours.
1 part cetyl dimethyl benzyl ammonium chloride
The reaction of the dispersion was acidic, the
(as above)
1 part Emulphor ON
thereof being 4.8 after standing for 48 hours.
35 pHAfter
about ?vev days‘the pH'was reduced to
about 3.75am! at this time the‘ dispersion co
Second batch
agulated, giving a coherent solid mass.
60 parts water
1 part an aralkyl polyether alcohol condensation
1. A process in accordance with claim,9 in,
product (as above)
4O which-the pH value of the dispersion during the- .
After mixture of the two batches and forming
‘oxidation is‘about 8.5.
' .
the dispersion therewith, one part triethanola
2. A process in accordance with cla'imf9 in
mine was added to the dispersion. This, disper
which the emulsion being oxidized also. contains
sion was of the water-in-oil type which was 45. an inorganic pigment, which. has been incorpo
converted to the oil-in-water type by the addi
rated into the ester prior to the preparation of
tion of seventy parts of water in which four parts
theaqueous emulsion.
of morpholine and two parts of a polyethylene
3. A‘ process in accordance with claim 9 in
oxide condensation product with oleyl alcohol (as ‘ . which the emulsion’ being oxidized also, contains
above) were dissolved. The pH of the disper 50 zinc oxide, which has bee'nincorporated into the
sion was 8.9.
ester prior to the preparation of the aqueous '
Ten parts of hydrogen peroxide were then
added, and a test sample indicated a relatively
_4. A process in accordance with claim :9 in. .
hard solid, with a dry surface, after evaporation
which the ester sele'ctedfor emulsi?cation and '
of the water.
Similar procedure was followed but without
incorporating zinc oxide in the oil. This yielded
a solid product which product, however, was
5. A process in accordance with claim 9 in ‘
which the ester'selected for emulsi?cation and .
oxidation comprises an ester formed with a tetra- -
rather soft and had a somewhat sticky surface. .
‘7-. A process in'accordance'with claim 11,in_
65 which said ester is a bodied drying fatty oil.
8. A process in'accordance with claim 9’in.
which the ester selected for the emulsiflcation.
and oxidation comprises an ester of a fatty acid
Following this initial stage of heating, the batch
hours at 100“ C. Thereafter an aqueous emulsion
was prepared as follows:
3 parts triethanolamine
3.3 parts of dioctyl ester of sodium sulfo-suc- ‘
cinic acid (a suitable product of this kind
ing fatty oil.‘ .
of oil was then subjected to air blowing for two
330 parts of the blown linseed oil
6. A process in accordance with claim 9 in
oxidation comprises a partially polymerized dry
to 350° C. until it became quite viscous and until
a ?lm (containing 0.3% lead and 0.15% cobalt)
hydric alcohol. '
which the ester selected for emulsi?cati'on and’ ~
A batch of linseed oil was heated at from 300
yielded a solid ?lm in two hours at room tem
oxidation comprises a drying fatty ‘oil.
having conjugated double bonds in the fatty acid ' I
9. A process for producing stable aqueous oil-‘
in-water emulsions of thickened esters, which
process comprises emulsifying in water by the
aid ofan emulsifying agent a polyhydric alcohol
being marketed by the American Cyanamid 75 ester of a'polyunsaturated long chain fatty'acid,
to form an oil-in-water emulsion and subjecting
the emulsi?ed particles to oxidation with hydro
gen peroxide in the presence of a drier, the
emulsion, during oxidation, having a pH value
between about 4 and 10, and the oxidation being
continued until the ester is appreciably thick
10..A process for producing stable aqueous oil
between about 4 and 10, and the oxidation being
continued until the ester is appreciably thick
11. A process for producing stable aqueous oil
in-water emulsions of thickened esters, which
process comprises emulsifying in water by the
aid of an emulsifying agent‘a polymerized poly
hydric alcohol ester of a'polyunsaturated long
chain fatty acid, to form an oil-in-water emul
i'n-water emulsions ‘of .thickened. esters, which 10 ,sion, and subjecting the emulsi?ed particles to
process comprises emulsifying in water by the aid
oxidation with hydrogen peroxide in the presence
of an emulsifying agent a polyhydric alcohol
of a drier, the emulsion, during oxidation, hav
ester or a polyunsaturated long chain fatty acid,
ing a pH value between about 4 ‘and v1!}, and the
to form an oil-in-water emulsion and subjecting
oxidation being continued until the ester is appre
the emulsi?ed particles to oxidation with hydro 15 ciably thickened.
gen peroxide in the'presence of a drier, the emul
sion, during oxidation, being maintained-under
super-‘atmospheric pressure, having a pH‘. value
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