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Патент USA US2412177

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Patented Dec. 3, 1946
r 2,412,171 '
Alexander Schwarcman, ,Bu?alo, N. vY., asaignor
to Spencer Kellogg ‘and Sons, ‘Inc., Buffalo,
N. 2., a corporation of New York
No Drawing. Application February 12, 1943,
Serial No. 475,852
12 claims. (on. zoo-404.8)
This invention relates
to drying oil manu- .
- lecture; and it comprises a method of preparing
drying oils having improved characteristics from
fatty oils, including drying and semi-drying veg
etable oils, and marine oils,,wherein a fatty oil,
such as linseed oil, is caused to react with a
minor amount of polyhydric alcohol, advantage
tacky for av considerably longer period. This is
a marked disadvantage for many vapplications,
since a film which remains tacky for any length '
of, time must be protected from dust, moisture, '
etc., during the drying period, or the coated sur
face will su?er permanently. Polymerized oil
‘films have therefore not been widely used in
ously glycerine, in a proportion from 1 to 7 per
many applications for which they are well '
cent-on the weight of the oil, forming an inter
suited, because other types of ?lmsdry much
.mediate ‘product having uncombined hydroxyl 10 more rapidly. This is a great advantage in
groups, and this intermediate is reacted with an
many industries, such as the automobile industry
and the furniture industry, where quick drying
amount of polybasic acid just su?icient to ester
is highly important. Quick drying is also very
ify the said uncombined hydroxyl groups, the
.polybasic acid also being used in the approximate
important in many other applications; such ‘as
proportion of ircm 1 to 7 per cent on'the weight ‘
lithography and printing, .Where slow drying of
of the oil; and it also comprises the improved
the ink causes spoilage, blotting, etc.
An object achieved by the present invention -'
drying oil obtainable as herein disclosed, this
new. oil having substantially the appearance and
is the production '01’ polymerized drying oils
many of the characteristics of untreated fatty ‘ which dry very rapidly to a dust-free, non-tacky
' oils, but being vcapable of polymerization in a 20 condition, often equalling in this respect other
very short time, of drying quickly to a tack
types of spraying lacquers. A further object
free?lm, and of forming especially waterproof: achieved by this invention is the provision of a
?lms upon drying; all as more fully hereinafter
polymerized oil which dries to an especially
set forth and as claimed.
waterproof ?lm. In accordance with a yet furMany of the known'drying oils, including-lin
ther object there is provided a modi?ed drying
seed oils, perllla oil, Shine-wood oil, oiticica oil:
oil product which is capable oi’ polymerizing
walnut oil, soya bean oil, sun?ower oil, poppy
much more rapidly with an accompanying elimi
seed-oil, etc., are used in their natural state 7
nation of adverse side reactions.
_ -
> .
as drying oils for the production of protective
These ‘objects and advantageous results are
or decorative coatings, preferably after ad 30 achieved in accordance‘ with this invention by
mixture of a minor amount of catalytic drier,
combining a fatty oil, such as a drying or semi
such as compounds of cobalt, lead, manganese,
drying vegetable oil or marine oil, with a minor
etc. It is also known that most of these oils
amount, ‘advantageously about 1 to "l. per cent
can be polymerized by heating to elevated tem
by weight, of a polyhydric alcohol, such as for »
peratures, which are usually of the order of 550°
example glycerine. The oil and glycerine are
to 600° F., and that the viscosity of the oils
agitated together at an elevated temperature,
is thereby increased, and certain other charac
usually between 400° and 500° F., :until reaction
teristics are modi?ed.
is complete and the free glycerine has disap- ,
peare'd. The time required for this operation
oils are widely used; This is often the case in 40 varies with the quantity of the materials treated,
For some purposes, the, raw or unpolymerized
general exterior and interior painting. The
polymerized oils, such as stand oil, are also widely
from'sev'eral minutes to one hour or more. The
time may 'be shortened ‘and the operation con
used in painting, usually after thinning or're
ducted more emc'iently by introducing‘ a small
ducing them with solvents to‘ the consistency
amount of catalyst. It is well known that lith-'
desired for brushing, spraying, or other methods 48 arse and various alkaline materials, as well- as
of application. It is well known that the poly
several of the alcoholates and soaps, are catalysts
merized oils have certain advantages over the
for reactions of this type, which is known ge
unpolymerized oils, in that they usually ?ow bet
nericallyas ‘alcoholysis.
ter and spread to a uniform surface, which does‘
The product of this treatment is a homogeneous
not show brush marks.- Also, polymerization 60 ester of glycerol containing some free or uncom- ,
generally makes the ?lm produced from the oil
bined hydroxyl groups. To this product is added,
more water-proof, and eliminates a good deal
in substantially the stoichiometric‘al proportion
corresponding to the polyhydric alcohol intro
4. of the after-yellowing e?ect,- which is ,en
duced, a polybasic acid, and themixture is heated
countered with some‘ raw oils. Furthermore, I
when completely dried, either alone 'or in the 55 with agitation until esteri?catlon occurs. Any
, presence 01’ pigments, a polymerized oil ?lm is‘
of the various types of polycarboi'rylic acids may
generally harder. or more "thoroughly dry" than
be used for this purposeand especially advan
a raw oil ?lm.
tageous results are obtained when using maleic
acid or fumaric acid. Of ‘course the anhydrides
However, ?lms o! polymerized oils generally
of the foregoing acids are equally‘ suitable and
(dry more’ slowly than raw‘ oil ?lms, and remain
tained can be performed in the open at atmos
may be substituted for the respective acids with
pheric pressure. The operations can alsobe per
out I disadvantage. Phthalic acid and its anhy
formed under vacuum, and this is often advan
dride, when emplo ‘ed in this step or the process,
tageous, since it makes it posible to ‘obtain a
likewise results in materially improved product.
Advantageously the amount of polycarboxylic 5 lighter colored product. It is well known that the
presence of atmospheric oxygen during treat
acid employed corresponds approximately, to ‘that
vments at high temperatures generally has a tend
required for complete esteri?cation of the' poly;
hydric'alcohol added in the preceding step. In
ency to darken fatty oils, and, this is true in the
present case. Operating under vacuum, or in an
other words, the relative amounts of polyhydric
alcohol and acid employed are preferably propor 19 atmosphere of inert gas, prevents this.
tioned so as to substantially completely esterify
In a typical embodiment of this invention, 1900
pounds of linseed oil and 70 pounds of glycerine
all of the available alcoholic and carboxylic acid
groups introduced. ‘This result is conveniently
(3.7 per cent by weight) were mixed together with
0.6 pound of litharge, to serve as a catalyst. The
attained by continuing addition of the polycar
boxylic acid or its anhydride until a product of 15 ‘mixture was agitated while the temperature was
, low acid number results. The approximate rela
- , raised to 440° F., and this temperature was main
tive quantities of reagents required to complete
" tained until the free glycerine, which had origi
the reaction are equivalent to the stoichiometri
nally ?oated on the surface, disappeared. A sam
cal proportion of the alcohol and acid required
ple of the mixture taken at this stage was com
for complete esteri?cation. This, therefore, forms 20 pletely transparent and homogeneous. The heat
a good approximate index of optimum propor
ing required about forty minutes at the attained
tioning. ‘While the advantages of the present in
temperature in this instance.
vention are secured with some variation from op
The compound thus obtained, consisting prin- '
.timum procedure, it is, however, desirable in all
cipally of combinations of‘ giycerine with linseed
cases to approximate the final condition of low 25 oil acids with the glycerine present in excess, was
acid value desirable in drying oil of the present .
further agitated, and about ‘132 pounds of
class, namely, an acid number below 5 to 10.
In this part of the process, the temperature is
fumaric acid were added. The temperatureywas
brought up to 520° F., at which time there was a
advantageously raised somewhat above 500° F.
strong discharge of water, indicating that es
During the reaction, there is a substantial dis 30 teriilcation was taking place. After the water
charge of water vapor formed in the este'ri?ca
was completely discharged and the oil became
tion. When the reaction is complete, and the,
water has been eliminated, the product becomes
entirely ‘clear.
clear, the agitation was stopped.
At this stage, the product could be withdrawn
_ for use or sale, if desired.
However, in this in
At this stage, there is obtained an ‘improved ?” stance, the temperature was brought up to 590°
drying oil having very low acid number and ex- . F., and maintained at that point for about forty
veellent drying properties. The material may be
minutes. At that time, a polymerized oil having
sold and used as such, but is advantageously poly
a viscosity of Z-6 on the Gardner-Holdt'scale
merized before use. , Polymerization may be ef
- fected by the manufacturer, or as a separate proc
ess' conducted by the purchaser. It is generally
most economical to polymerize immediately, since
all that is required for this purpose is to raise the
temperature to the bodying range, which is usu-v
ally somewhat above the reaction temperature, 45
‘and to maintain it for a very short time.
. of the advantages of this product is that it poly
merizes so much more rapidly than the oils used
was obtained.
After cooling, the oil was tested, and found
to have an acid number between 2 and 3. A sam
ple of the oil was subjected to a drying test and
found to lose its tackiness in about two hours
and to form an extremely waterproof ?lm.
In another embodiment 01' this invention 1500
pounds of soya bean oil were heated to about 300°
F., 45 pounds of glycerine (3 per cent by weight)
were added while stirring, and the temperature 5
as starting materials. This is highly advan
tageous, since the loss of oilduring polymeriza 50 was brought up to 430° F. and held for one half
hour. The temperature was then raised to480°
tion and the development of acidity are usually
and held there for another half hour until the
functions of the time required for polymerization.
In hodying ordinary linseed oil, a time on the
oil was entirely clear and no more‘ vapor was es- ‘
caping. ‘The oil was then cooled down to about
to bring the oil up to a viscosity of 2-6 on the 55 300° F., and 85 pounds of i'umaric acid were
added. The temperature was brought up slowly
Gardner-Holdt scale. - During this treatment
to 520° F. and after there was no more discharge
there is a'ssubstantial loss of oil,- and the acidity
of water, indicating that the esteri?cation oi the
may increase to 8 or 10 per cent. In contrast,
added acid and the newly formed glyceride ‘was
the same body may be obtained in an oil treated
0 completed, the temperature was brought up to
as described hereinabove, by heating for consid
about 560° F. At .this temperature any remaining
erably less than one hour—often in 30 to 40 min
- . orderv of five hours or more is generally required
traces of the acid were combined, giving a prod: ‘
utes. Under these conditions, the loss of oil dur
ing polymerization is negligible, and the acidity ‘ not of very low acid value. '- During the two stages,
- namely, the combination with glycerine and the
does not increase beyond 1 or 2 per cent.
Further advantages of the product are that cs?steri?cation with acid, a current of inert gas
(such as nitrogen orcarbon'ic acid) was passed
after polymerization, it will dry to .a dust-free ?lm‘
through the oil or into the space above the oil,
in four hours or less, as compared with v48 hours
or more for the ordinary polymerized linseed oil.
Furthermore? when dry, it forms a ?lm of greatly
to eliminate oxidation and darkening.
At this stage the oil was somewhat heavier than
increased resistance to moisture, or “waterproof 70v the original oil and could be used as such, but
ness.” In this-respect,‘ the improved'oil of this
the heating was continued at560° F. and the con
sistency increased very rapidly to 2-6, reaching '
invention more closely resemblesu China-wood oil
than the polymerized linseed oil available hereto
. this viscosity in about one-third the time required
- to polymerize the original oil to this extent. By
The process by whichthis improved 011 is 0b 75 the same procedure, exceptionally good resultsv
we're obtained with marine oils, such as men
haden oil.
Similar operations were also conducted under
- decreased addition of acid will result in a product 1
of lower acid number. It will be apparent that
the quantity of polycarboxylic acid ‘necessary to
vacuum with similar results, except that a some
complete the reaction may be readily determined
what lighter colored product was obtained. Also.
from the acid testing of successive test samples.
various other‘ oils of the type previously men
In accordance with anotherembodiment 10,000
tioned were treated in a similarmanner with
pounds of linseed oil were heated to about 300° 1'‘.
similar results. ‘As noted, exceptional results
were obtained in the treatment of marine oils,
marine oils are generally used only in admixture '
and 520 pounds of penta-erythritol were added
slowly by stirring, while the temperature was
brought up to about 450° F. -Heating and mixing
were continued until the polyhydric alcohol had
been completely absorbed into the oily mass,
leaving a homogeneous transparent composition.
A't'the end'oi this time 748 ‘pounds of maleic an
hydride were slowly added while,.the temperature was brought up to about 540° F. Samples
tested indicated anacid number of 2-3, where
with other oils having better drying properties.
upon agitation was stopped. The product as
such as sardine and ,menhaden oils, in accordance’
with the method described. It is well known that
these marine oils contain‘ only a minor propor
tion of drying constituents (clupanodonic esters)
and a preponderance of non-drying esters which
ordinarily ‘prevent satisfactory drying of these
marine oils when used alone. For this reason,
indicated above was particularly valuable in that.
I have found that by treating these marine oils
with minor'amounts of polyhydric alcohols, such 20 it was capable of being liillymerizedv to a 2-2
body by merely bringing it to a temperature of
as glycerine, and polybasic' acids, such as maleic
and especially fumaric acid, as described herein
above, it is possible to convert marine oils into oils having excellent drying properties._
While the foregoing examples have been pre
sented with glycerine as the illustrative poly
hydric alcohol, the invention is not so limited
‘ but contemplates the utilization of any alcohols
coming within the field of polyhydric alcohols.
' 570° F.
Even greater quantities of the ‘polyhydric. al-_
cohol and polybasic acid may be employed with
satisfactorily resulting improvement.
Thus, in -
the foregoing example 600 pounds oi.‘ penta-ery
thritol may be employed and 864 pounds of the
maleic anhydride. On the other hand, lower pro- ‘
portions may be used with results that are still
Thus, products having the improved and ad 30 quite advantageous. For example, a good com-.
vantageous characteristics sought by the‘ present '
mercial product results when only 280 pounds of
invention, are prepared by'processes wherein di
hydric alcohols suchv as propylene and ethylene
glycol are substituted for glycerine in the initial
step of alcoholysis. Where; however, the poly
hydric alcohol molecule contains an increasing
number of hydroxyl groups, the results achieved
penta-erythritol and 403 pounds of maleic an
hydride are utilized in the above embodiment.
As indicated above. the advantages of the present
invention are in each instance noticeable down
"to and including quantities approximating one
per cént of the amount of oil used.
are even more advantageous. In general, the
_ ?nal drying oil possesses superior drying qualities.
In an embodiment illustrating the use of the
hexahydrlc alcohols 9300 pounds of linseed oil
forms especially waterproof films and polymer 40 were heated to about 300° F. and 350 pounds of
izes even more rapidly. Thus, where the
mannitol added slowly while heating to ‘about
erythritols as; for example, penta-erythritol, are
480° F. When the product was clear and homo
employed, “bodying" 'su?icient for most purposes
genenus the temperature was raised to: about
takes place merely upon heating the product to
540° F. and 565 pounds of maleic anhydride were
the bodying range. Polymerization is thus sum
slowly added with stirring until the acid value
became very low. By this procedure a product
ciently rapid to materially inhibit side reactions
of ouite improved character was obtained. Sim
and the formation of undesirable products as
ilarly good results were obtained where sorbitol
‘pointed out above.
was substituted for the mannitol above.
Similar results are characteristic'of processes
employing even higher polyhydric alcohols as, for
As previously stated, I find it most advanta
geous to employ about 1 to 7 per cent each of
example, the hexahydric alcohols, sorbitol and
glycerine and the polybasic acid in the process
In accordance with an embodiment of this
invention employing a dihydric alcohol, 14250
pounds of linseed oil ‘were heated to about 450° F.
630 pounds of propylene glycol were added slowly
of this invention. ‘Smaller quantities of these
constituents do not give. the optimum results,
although they generally e?'ect some improvement;
Larger quantities, materially exceeding about 1 ~
to 7 per cent of the glycerine and the equivalent
amount of poiybasic acid, do not improve the
quality of the treated oil, and therefore the ex
in 450°~500° F. At the end of this time the mass
of oil was clear and homogeneous. 812 pounds 60 pense of larger quantities is seldom justified.
As stated above. the glycerine or other poly
of maleic anhydride were slowly added and the
hydric alcohol and the fumaric acid, or other
temperature was brought slowly to 540° F., at
pclybasic acid or anhydridep are employed in
which time there was a strong discharge of
substantially stoichiometrical proportions so that
water vapor. After discharge of. the vapor had
a substantially neutral‘ product is obtained. Ii‘
ceased and the oil became clear, agitation
desired. however, a slight excess of glycerine may
was stopped. In this embodiment about three‘
hours were required to complete addition- of all - be employed ‘to neutralize the acidity which some;
times develops during high temperature treat
the maleic anhydride and completion of the re
action. The product of the foregoing treatment , ment. Also, it is sometimes advantageous to add
possessed an acid number or
The product 70 other’ fatty oils‘oi‘ their acids along with the
polybasic acid in the process of ,‘this invention.
may, however, be varied in accordance with the
In that case, the quantity of glycerine employed
acid number desired or permissible for the pur
with stirring over a period of about- two hours.
The ‘temperature during addition was kept with
pose intended, although as indicated above it is
’ is generally made suiiicient to-in'surc that a neu
trahsubstantially acid-free product'is obtained.
usually desirable to produce a product having a'
low acid number approximating zero. A slightly 76 In. any .case, ‘as previously noted. the ?nished
8 h
product has substantially the appearance of an
thereof which arel-now'considered especially ad
. oil of the type used as a starting material, when_
vantageous, the scope of the invention is not
limited to these specific embodiments and i'ea-'
polymerized to the same viscosity. It differs from
the starting oil chie?y in its rapid drying char
tures except as indicated in the _ “pended?
acteristics and the waterproofness of the ?lm 5 claims. .
formed therefrom. In many instances, as with
marine oils, the odor of the oil is substantially
1. A process of manufacturing improved drying
improved by the treatment. Also, the unpoly- . oils capable of bodying rapidly to a fast drying
WhatIclaim is:
merized oil obtained in accordance with this in
product, which comprises heating a fatty ‘oil
vention differs. from the original oil in being 10 having drying properties with approximately
capable of much more rapid polymerization.
from 1 to 7 per cent on the weight of the oil
It will be noted that in the foregoing illus
' of a polyhydric alcohol until reaction is sub
trative embodiments some of which are carried
stantially complete and esterifying the reaction
'out at the limits of the stated range, the pro
product with approximately 1 to 7 per cent on
portion of polycarboxylic acid utilized may vary 15 the weight of the oil of a polybasic acid of the '
_ somewhat from the proportion of the polyhydric
class consisting of polycarboxylic acids and their
alcohol. As will be understood from the above
anhydrides, ‘to form an oil‘ of low acid number.
‘this, follows from the stoichiometricai relation
2. The method of claim 1 wherein the poly
ship necessary to form the optimum product
having~a low acid .number. .It will be further 20
understood that in preparing such products the
,stoichiometric'al proportion of 'polycarboxylic'
hydric alcohol is glycerine.
3. The method of claim 1 wherein the. poly
basic acid is maleic acid.
4. The method‘ of claim 1 wherein the poly
acid which is approximately su?icient to esterify " basic acid is fumaric acid. I
.the free hydroxyl groups introduced, without any
5. The method of claim 1 wherein the poly
appreciable excess of carboxylic groups will de as hydric alcohol is penta-ery‘thritol.
pend upon the relative molecular weights of the
6. The method of claim 1 wherein the fatty
~ reactants and their molar combining ratio. Ac
oilissoya beanoil.
cordingly while the range “of 1 to 7 per cent is.
relatively critical in the case of the polyhydric
alcohol it is relatively less critical as applied to‘ 80
the polycarboxylic acid and represents more of.
_ an approximation in preparing oils of optimum
low acid nu ber.
It is further important to point out that many
f v
7. The method of claim 1 wherein the fatty
oil is linseed oil.
8. The method-‘of claim 1 wherein the fatty
oil is manhaden oil.
' 9. The ‘method of claim ‘1 to which is added '
the step of heating the esteriiiéd product to a
temperature of approximately from 550° to 600°
somewhat similar products may be obtained by 35 F. to develop the desired viscosity.
substituting a fatty acid of a drying or semi
drying oil as a starting material provided that
10. A process of manufacturing ‘improved dry
ingjoils capable of bodying rapidly to a fast
drying product which comprises heating a fatty
esteriiication with the polyhydrie alcohol is car
ried out to a degree equivalent to that repre
oil having drying properties with approximately
sented by the product of (alcoholysis mentioned 40 from .1 to 7 per cent on the weight of the oil
above. In other words, the drying or semi
of a polyhydric alcohol until reaction is sub
' drying oil fatty acid may be reacted with a
stantially complete ‘and reacting the reaction
polyhydric alcohol with the latter ingredient in
product with an amount of polycarboxylic acid .
excess. The excess of polyhydric alcohol should - falling within the range of approximately 1 to 7
amount to from about 1 to 7 per cent on the 4" per cent on the weight of the oil and Just suiil- .,
cient to form a product of low acid number. '
weight of the total amount of the reactants
which are theoretically required ‘to produce a 1
11. A process of manufacturing improved dry
ing oils capable of bodying rapidly to a fast dry
‘may then be reacted with a quantity of poly
ing product, which comprises heating a fatty oil
carboxylic acid stoichiometrically corresponding 50- having drying properties with approximately
completely esteriiled oil. The resulting product
= to the amount of hydroxyl groups theoretically
from 1 to 7 per cent on the weight of the oil
present in‘ the oil; As in the earlier described
process. the amount of polycarboxylic acid ac
of appolvhydric alcohol until reaction is sub
stantially complete and esterifying'the reaction
- cordingly ‘falls within the approximate range of , product with a polybasic acid of the class con
1 to 7'per cent onthe amount of the oil ester 5" sisting of polycarboxylic- acids and their anhy- .
present. Advantageeusly, however, the quan
tity of polycarboxylic acid employed is suillcient <
.drldes. said acid being added in approximatelyv
that combining proportion just suilicient to ester- -
ify all of the free hydroxyl groups present in
the reaction. mixture and to form an oil of low
“9 we number.
‘12. A process of manufacturing improved dry
in: oils capable of'bodying rapidly to a fast dry
groupspresent in the reaction
ing product which comprises heating a fatty oil
having drying properties at a temperature ap
be'apparent from the foregoing that “5 proximating 450.- to 5000 c. with about a per
wbythetermpolybasicacidasusedinthepresent cent of glycerine until react-ion is substantially
complete and esterifying the reaction product at.
M17‘. the so-calied polycarboxylic acids and
a temperature approximating 540° F. with a
their obvious equivalents such as they acid an 70 polyblsic acid of the
consisting of poly
carbonlic acids‘and their anhydrides, said acid
ippiicetion is a continuation-in
’ or I!!! mllcatim
N0. 392L555, ?ied
being added in approximately that combining
. Whilem.
my invention
to certain
described with
75 turewand to 1am an oil ot'low'acid number.
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