close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2406337

код для вставки
Patented Aug. 27, 1946
2,406,337 '
UNITED STATES A PATENT OF’FICE '
' 214116.337
MODIFICATION OF FATTY oILs V
Laszlo Auer, South Orange,‘ N; J.
No Drawing. Application januaryaz3, 1943,’v V
>
'
vSerial N0.47_3,396
'
,,
f
_
I
22 Claims. (01. 260-407) _
1
~In addition, it should be noted that esters of
fatty acids other than the natural glycerin esters
(fatty oils) may be used, for example, synthetic
glycerin esters of fatty acids, and fatty acid esters
formed with other polyhydric alcohols, such ‘as
GENERAL FIELD or INVENTION ANDMSTATEL
MENT OF OBJECTS
This invention relates to‘ the modi?cation of
fatty oils’, and especially to dryin'g'and semi-'ldr'ya
ing fatty oils.
‘
glycols, pentaerythritol, mannitol, sorbitol, etc.
Fatty oils are employed in‘ a number of differ
ent industries, such, for instance,‘ as the coatings
and. plastics industries, and it is'a ‘general object
For convenience, all such materials are herein re
ferred to merely as fatty oils.
The process may be ‘employed on fatty oils
of this invention to modify and improve the prop
erties of fatty oils for various industrial purposes.
themselves or on various mixtures of materials
Briefly, the invention contemplates treatment
of a fatty oil, for instance, linseed oil, withpoly
or varnish bases of oleo-resinous types, Whether
used clear or pigmented. Reference herein to
“varnish base” means all or part of the varnish
containing fatty oils, ‘for instance, on varnishes
hydroxy benzenes, such as dihydroxy and trihy- '
droxy benzenes, the mixture being heated to ele 15 solids or ?lm forming ingredients.
'
vated temperatures. I have secured particularly
- Fatty acids may be added to the'reaction mix
good results with resorcinol, which isadihydroxy
benzene. Full description ofthe treatment pro
cedure is given hereinafter.
I
I
' According to the present invention, it is possi
ture, if desired.
formed with the treated oil.
‘Y
' >
'
TREATMENT PROCEDURE AND CONDITIONS
As above noted, the treatment process involves
20
heating the fatty oil, or the material containing
ble to achieve a number of advantages in the
treatment of fatty oils. For example, it is possi
, ble to materially improve the drying character
istics of the fatty oil, and also to improve water
and alkali resistance of ?lm coatings or the like
'
same,‘ in the presence of a polyhydroxy benzene,
especially dihydroxyv and trihydroxy benzenes.
Particularly good results have been secured by the
" use of resorcinol which is a dihydroxy benzene;
and with'pyrogallol, which is l, 2, 3‘trihydroxy
-
The foregoing and other objects and advan
The quantity of treating agent employed ‘may i
tages Will appear more fully hereinafter, espe
be‘
varied over a considerable range, depending
cially from consideration of examples given. Be
fore proceeding with description of the treatment 30 upon the extent of'modi?cation desired, the tem
benzene.
'
‘
y'
‘
~
perature,.the particular fatty'oil being treated,
procedure, reference is now made to the-fatty oil
etc.‘ ‘From'a small fractional percentage,‘ for in
materials to which the invention is applicable.
stance, from about 0.05% or 0.1% up to about
The process may be employed on fatty oils gen
30%, may be used, although ordinarily from
erally, including drying oils, semi-drying oils, and
about 0.5%-to about 5 or 10%,‘for instance, 2%
non-drying oils. The following is a typical list 35 is
quite effective.
.
. .
of such oils:
"
'
Tung oil
‘ In connection with treatment temperature, it
may be saidthat in general temperatures from
about the lowest dissolution temperature of the
40. modifying agent up to about 350° C. are usable,
although the temperature should not be above
the pointgat which the fatty oil appreciably de
Oiticica oil
Dehydrated castor oil
Linseed oil
Perilla oil
composes.
Poppyseed oil
Soya bean oil
Walnut oil
Rapeseed oil
>
a
>
r
-
,
V
4,5, with other factors such astemperature. percent
age of treating agent, etc. ' Ordinarily thev time
‘should be at least 30 minutes and mostvusually
several hours,,for instance, from about 1 hour to.
Pine seed oil
Olive oil
Corn oil
Cottonseed oil
Coconut oil
Babassu oil
about
50
Hydroxylated oils‘such as ‘castor oil, etc.
Fish oils (train 'oils)
'
Thetime of treatment will- vary in accordance
,
‘
5hours.
»
.
»
v
,
»
it
i
In connection with treatment procedure, it is
pointed out that the treatment of a'fatty oil may
be effected by adding the treating agent and heat
ing the oil under conditions mentioned above. If
desired, the treating agent may} also be,.mixed
55 with a varnish base or other composite material
I
_
2,406,887
4
3
'Wherever the two-stage type of procedure is
incorporating a fatty oil material, such composite
adopted, it may be advantageous to carry on the
‘ material then being heated under conditions such
as those discussed above.
?rst stage, at relatively low temperature, under
pre-condensation conditions, especially when em
ploying certain of the treating agents contem
Agitation may advantageously be used during
any mixing procedure, in order to aid thorough
dispersion of the treating agent.
plated, such as resorcinol which displays a marked
tendency to sublime. A reflux condenser will be
found effective in reducing the eiiect of sublima
The treatment may be carried out under vary
ing atmospheric conditions, both with respect to
pressure and also with‘ respect to the gas in con
By proceeding in this‘ way (pm-condensation at
tact with the reaction mixture. Thus, under some 10
. relatively low temperature followed by additional
circumstances, the fatty oil or the mixture con
heating at a higher temperature), loss of treat
taining the fatty oil may be heated under vacuum,
and under other conditions, atmospheric pressure p 7 ing agent is prevented or at least reduced.
The term f‘pre-oondensation” (initial or pri
may be used, and also superatmospheric pressure.
It is frequently of advantage to exclude thelair
mary'condensation) , as used herein, means treat- ‘
tion.
'
,
a
merit under conditions of the type just mentioned
from the reaction mixture, and this-may beldone -
during any stage of treatment, either by employ-e I 1 at vtemperatures below the sublimation point and
for a time suchthat upon subsequent heating of
ing Vacuum or by blanketing the surface of the
the treated oil to higher or heat bodying tem
V‘batch with some non-oxidizingbr inert'gas, for
instance, CO2, S02, HzS, or nitrogen. Still fur 20 peratures the resorcinol no longer tends to sub
lime to any‘ great extent.
ther, exclusion of air may be obtained by carry
ing. out .thejreaction in a closed vessel (but not
EXAMPLES
necessarily under a positive pressure), in which
'
.
Inv order'to- demonstrate the process linseed oil
event vapors or the like released from the reac
tion' mass may‘ serve to dispel or exclude the air. ~ 25 and'resorcinolwere selected'as typical of the start
ing materials and treating agents, these two being
I, have found vacuum'treatment to. be particu
usedin' mostJof the examples given below.
larly effective, for instance, from about 100- m-ms. ‘
To determine the most advantageous treat
Hg to about 450 mms. Hg internal pressure, al
ment conditions, several comparative series of
though higher or lower pressures ‘are also useable.
experiments were? carried'out, all utilizing resor
_ With regardto the foregoing atmospheric con
cinol andhnseed oil. An analysis of these ex
conditionsin the reaction vessel, it‘may be noted
periments will aid in an understanding of the in
thatcertainof the gases mentioned may be vem
ployed for their supplemental effect on the: re
. First, note that resorcinol has a boiling point
action, in which event, if desired, the gases may
of 27.615? 0;, and melts at 116° C. When molten,
be bubbled through the reaction mixture.
,
vention.
'
'
'
it. dissolves quite easily in fatty oils and even
at temperatures below- its melting point, it is'sol
In general, it may be‘pointed out that increas
ing any one of the variables: temperature; time
or percentage of modifying agent, usually in
creases‘the rate and/or extent of the reaction.
uble inv many fattyoils.
’
In‘ spite of the fact that the boiling point of
is comparatively high, it sublimes out
The modifying'agents herein claimed may be 40 resorcinol
of‘ fatty oils at temperatures below its boiling
employed (either simultaneously or sequentially)
in combination with others disclosed, for instance,
in- various of my 'copending applications and
issued patents, some of which are mentionedhere
inafter;
.
V
'
,
point. ‘Furthermore, its boiling point is below
the usual and preferred temperature range for
bodying fatty .oils or for cooking varnishes.
45
‘In addition, supplemental treatments'may be
, applied to the oil, either during or following the
COMPARATIVE'EXAMPLES 1 T0 5
Because of the foregoing characteristics, it is 1
advantageous to adopt‘ some means or procedure
reactionwith the agents here contemplated, many
for‘ reducing loss ofv the treating agent by subli
of‘ such supplemental treatments also being dis
mation" or‘ boiling. With this in mind, a series
cussed fully’in" copending applications and issued 60 of' experiments were carried out in one liter'alu
patents below mentioned. For instance, the modi
minum beakers provided.v with covers, using resor-'
?ed oil products may be vulcanized with sulphur
cinol and alkali: re?ned linseed oil, in-400 gm.
or sulphur chloride or similar vulcanizing agents.
batches, each" being heated at a different tem
Attention’ isv directed ~ to my copending applica
perature, as? is'indicated in Table No. I-A here
tion Serial No. 461,789, ?led October 12, 1942', 55 below, showingireaction conditions and the re
which discloses treatment of fatty‘ oils- with
sulting viscosities of‘ the treated oils. All vis
cosities given herein are expressed in terms of
the Gardner Holt scale.
7
phthalic anhydride and resorcinol;
‘
In all cases of this series 2% of‘ resorcinol was
-Where a fatty oil is being treated to prepare
it for incorporation in- a varnish base of the oleo 80 used and the temperature was maintained for 2
'?uorescein and also with a combination 0
resinous type, oneparticularly advantageous pro
hours.
'
'
cedure is as follows: In this case the treating
Table No. I-A
agent may initially be added to and dispersed in
ALKALI REFINED LINSEED OIL WITH RE's'oRoiNoL
IN COVERED KETTLE
the fatty oil at relatively low temperature, for‘ in
stance, fromwabout 75°;C. to about 200‘ CL; and’ 05
then when’ the oil is incorporated in’ the varnish
Ex. No
Temperature
Viscosity
sl??glgtgn
A
A
3+
Slight.
Considerable.
Do.
or, varnish base, additional heating maybe ap
plied‘ at higher temperatures; in order to. carry
out the‘ full degree of modi?cation of the‘ oilv
contemplated.
_
Even when treating a fatty oil alone, itv may' be
' advantageous to divide the, treatment‘ into two
stages, the ?rst of which is carried on at' a rela
tively low temperature, and the latter of which
is carried on at a higher temperature.
.
A _______ __
75
(The same
heating).
oil
without
B+
Do.
S
Do.
A
The foregoing series‘ indicated thatv sublima
2,406,887
5
tion increased in general with increase in tem
perature.
Following the initial treatment of the several
The cold water test was carried outby immers
ing one half of each panel‘ (carrying the varnish
?lm) in cold water for 24 hours; and observing
batches as mentioned above, varnishes were pre
the milkiness of the ?lm and the rate of recovery
pared with the treated oils, the several varnishes 5 t0 the original condition. The hot water test was
then being subjected to drying and water tests
Carried out in a similar manner, except that the
with results indicated in Table No. I—B herebepanels Were immersed in boiling Water for 15
low. The varnishes were prepared with ester
minutes; the milkiness and rate of recovery again
gum, each being of 25 gallon length, and each
being OhSBI‘W-Id.v
varnish was cooked at 3009 C_ to a Viscosity Of 10 The columns under the “Cold water” and “Hot
about C to D, at 50% solids when thinned with
Water” headings indicate the following:
mmera’l _spn:1ts' ,The e°°¥<mg rttme requlred to
Con=arbitrary scale of condition of ?lm when
reach thls vlsee‘slty 1s mdlea'ted m the table be‘
?rst removed after the test, No. 1 indicating the
1°w-
best condition,
,
_
\ -
A1“ explanatlon of the deslgee'tiens under the 15 Rec=arbitrary scale representing rate of recov
drymg an‘? other test eelu'mns 1S glven after the
ery to original condition after withdrawing
table, but it is here pointed out that the followfrom the test, No. 1 indicating the best rate_
mg as well as ‘other tables, appearing In the DI‘BSON==arbitrary scale of the condition of- the ?lm
em specl?ea'twn’ Include (In addition to num'
after standing overnight (following immersion
sent
bered‘examples)
letteredmxamples which repre- 20
blank or “control’ experiments, 1. e., an
period)’ No.
1 _indicating the best condition‘
_
_
experiment carried out with the same on’ under
The alkali resistance test was carried out with
exactly the Same treatment conditions as the
numbered examples, except that no treating agent
somewhat heavier ?lms than for the drying test,
and cold Water entitle? Water tests- For, this PUT‘
was used.
It may also be mentioned that state- 25 pose ?lms of 0003
,
thlckness were apphed to test
merits regarding comparisons of properties, such
as drying characteristics, are always related to
panels which were eheeimmersed in a
aqueous
sedlun? hydree?de selutlon' The eondltwn afterr’
?lms formed with varnishes incorporating the
hours lmmerslen, was Observed aed reeerded’ end
same fatty oil treated under the same conditions
also the co'ndltloh after Overnight immersion.
(both prior to and during the formation of the 30 The results of these two, Observatlons are men‘
varnish itself) but without the presence of the
Gated, m?the eorrespondmg columns wider the
modifying or treating agent,
In the table just below the example numbers
correspond to those in Table No. I-A, the letter
heading Alkali.” The key to the letters in these
columnsls as fellows:
H=hazy
“v” following the example number indicating the 35
Sl.m=slightly milky
varnish prepared with the treated oil.
M=milky
'
Table No. I—B
VARNISHES PREPARED WITH TREATED OILS or TABLE No. I—A
EL No’
Minutes
cooking
_
Vis-
at 300°
cosity
C.
Drying
’
Cold water
'
Set
Hot water
.
DF
TF
%
ON
Alkali
.
48
Con
Rec
ON
164
A
%
1
B
A
3
2
o
.... ._
1
D
A
2
1
1
5
2
1
o
O
D
%
%
%
84
%
84
%
M
%
B
O
o
A
B
A
2
4'
2
1
2
1
1
1
1
5
5
5
1
2
1
1
1
1
190
o
1
2
2
D-
A
1
1
1
5
3
2
cate the following:
'
Set=time in hours to initially set.
‘
DF=time in hours for the ?lm to become dust
free.
'I’F=time in hours for the ?lm to become tack
free.
ON=condition of ?lm after "overnight” drying,
7hrs.
ON
2
Where appreciable dissolution of the ?lm took
place, that fact is noted in the corresponding col- _
umns by ?gures, representing the approximate
percentage of the ?lm remaining. For instance,
M—40 indicates that the ?lm was milky and that
‘40% of the immersed part of the ?lm remained
on the panel, 60% being destroyed.
With the foregoing explanatory comments in
mind, it will be seen from Table No. I—B that
60
The columns under the heading “Drying” indi
2
ON
207
ing a ?lm of 0.0015" thickness was employed. .
5
Bee
203
185
161
All varnish tests in the present series, as well
as in other series of examples mentioned herein
after, were carried out in the following manner.
Initially the varnishes were stored for 48 hours
after the addition of driers (0.3% lead, 0.03%
cobalt and 0.02% manganese, based on the oil
content of the varnish and added in the form of
naphthenate driers). In order to test the char
acteristics of the varnishes, a coating knife yield
2
0011
notwithstanding the appreciable loss in treating
agent during the initial treatment of the oi1 (see
Table I--A),'the varnish ?lms displayed consid
erable improvement in a number of respects as
compared‘ with a ?lm made from a varnish incor
porating the same oil in untreated condition
(compare Example Av with the others). The al
kali resistance and drying characteristics both
display considerable improvement.
the letters representing an arbitrary scale to in
COMPARATIVE EXAMPLES 6 T0 9
dicate the relationship between the several ex 70
In this series of examples alkali re?ned linseed
amples, “and also their relation to the item just
oil was also used and was treated with 2% re
below (the letter A indicates the driest ?lm and
sorcinol, as in the ?rst series. In each case a
succeeding letters progressively decrease in
batch of 400 gms. of oil was placed in a one
liter Erlenmeyer ?ask equipped with a re?ux con
48=condition of ?lm after drying for 48 hours. 75 denser, so as to provide a condition of pre-con
hardness).
'
2,406, 3.37
8
7
densatien and thereby reduce loss of the resor
COMPARATIVE ExAMPLEs 10 To 12 V
cinol. For the re?ux condenser, a ‘straight air
condenser was used, since the ‘relatively high boil
ing point of resorcinol does not necessitate water
In a third comparative series of examples, al
kali re?ned linseed oil was again used and the
percentage of resorcinol was varied in order to
indicate what percentages yielded the best re
cooling. In all experiments of this series the re
?uxing time was two hours. ‘The temperatures
tried di?ered as between different examples. the
results being indicated in the Table II—A here
below,
sults.
~
‘
_ Table No. I,I——A
provided with an air condenser. In each case a
' blanket of CO2 was maintained at the surface
ALKALI REFINED LINSEED OIL WITH RESORCINOL
<
UNDER REFLUX
Ex’ N0’
1
In the exampleslof this series 4,000 gm. batches
of the oil were placed in stainless steel kettles
v10 of three gallon size, the kettles being covered and
of the oil and all of the oils were heated under
Temperature
Viscosity
Extent .of
sublimation
Very little.
6. .
W...
l50° C _________________________ __
A
7..
_ -.-
200°C _____ __
B
reflux preliminarily for two hours at 200° C. and
thereafter for an additional period at 300° C. for
a time suf?cient to increase the body to from
1 about Z4 to Z6 viscosity. Results of this series ’
of examples are indicatedin Table No. III-—A.
Do.
8._ .__.,_
250° C ..>
-_
U
DO.
9 _______ _,
300° C _________________________ __
'I‘
Do.
B ....... ..
(‘The same 011 without heating
and not re?uxed.)
.
A
Table No. III-A
ALKALI REFINE’D LINSEED OIL WITH VARYIN G
.
As in Examples 1 to .5, the treated oils .of Ex
amples 6 to 9 were also‘ used in preparing ester
gum varnishes of 25 gallon length, the formula
tion being the same as described above. These
varnishes were then tested and the results are
PERCENTAGE OF RESORCINOL
Ex. No.
Percentage
Time at 300° C.
Viscosity
0.5% ______ ._ .8 hrs, 10 mins___-___
2.0%., .... ._ 8 hrs, 40 mins___._....
.
indicated in Table ‘II—B just below, incorporating
columns and distinctions corresponding to those
described above.
Table No.’ II-B
4.0% ______ __
‘Z5
Z4
7 hrs ______________ __
Z6
No agent_.__ 8,hrs., 20 mins _____ __
Z5
From the above it will be seen that lower than
‘VARNIS'HES PREPARED WYITH TREATED OILS OF TABLE NO. II-A
Minutes
Ex N0
'
-
cooking
‘
_
Drying
Vis-
‘
at 300°
cosity '
C.
,
Set
Cv
V
189
Cold water
Hot water
Alkali
V
v
a
‘
DF .. Tl?‘
ON
48
0011
Bee
ON
'
Con
____ __
V),
%
B
A
3
1
1
l
C
%
%
1
C
A
2
2
2
5
2
1
210
D
____ _-
%
%
B
A '
2
1
1
6 '
'1
1
105
190
D
C
_____ i.
l
1A
2
A
A
l
l
1
1
l
l
5
5
l
3
l
2
,7 hrs.
ON
about 4% of resorcinol does not materially ac
celerate the rate of bodying.
The faster bodying of the varnish of Example
911 may be partly'explained by the fact that the
oil here employed (see Table II-A) had a much
To demonstrate drying and other characteris
tics of these treated oils, 25 gallon length ester
gum varnishes were again prepared and cooked
higher viscosity than the other oils, indicating
that at least a portion of the bodying took place
during re?uxing.
5
V
‘
ON
210
% D
I 2 D-
l -
Rec
in a manner similar to those described above,
'
except that the viscosity attained was about from
50 C to E. The properties of these varnishes are in
dicated in Table III-B just below.
ance were quite satisfactory and further that
Table No. III—B
The foregoing table shows that cold and, boil
ing water resistance and also the alkali resist
VARNISHES PREPARED WITH TREATED OILS or TABLE NO. IIL-A
_
Minutes '
EX N0 , cooking‘
'
‘
at 300°
C.
95
_
Drying
Cold water
Hot water
Alkali
Vis
cosity
Set
DF
TF
ON
48
Con
‘Rec
ON
Con
>
Rec
ON
7 hrs
ON
C
1%
3
4
B - A
2
2
1
6
5
5
116
C‘
1%
2
3
B
A~
2
2
l
5
2
.2
S1. m_--_
90
D
1%
3 -
8
D
A
1
l
1
6
5
5
H _____ __
Do.
135
E
V2
1%
A
2
2
1
5
1
1
1-1 _____ __
Do.
2 'D—
M_______ Gone.
Do.
From the foregoing, it may be noted that while
the drying of the varnishes made with treated
oils was distinctly improved. The drying of the 65 the resorcinol, When used in low percentages, does
not appear to appreciably accelerate the rate of
varnishes made with oil re?uxed at 150° C. (var
bodying of the oils, nevertheless, considerable im
nish 611) and at 250° C. (varnish 812') was the
provement With'respect to rate of bodying is ob
best, the former having a slight edge over the
servable in preparing or cooking the varnishes
latter. The drying of the varnishes containing
the treated oils was in all cases extensively im 70 from the pro-treated oils.
The varnishes made with oil containing 0.5%
proved as'compared with the blank experiment
resorcinol (1011i and 2% resorcinol (1112) both
showed up quite well in various of the drying and
From the above it appears that pre-condensa
other tests. The varnish containing 2% resor
tion by re?uxing between about 150° C, and 250“
cinol (1112) seems to yield the best results,
C. gives the most ‘advantageous results.
(B1)).
_
a
i
2.406.881
.9 i
10
~
ing the oil under pre-condensation or re?uxing
EXAMPLE 13
Further tests were made. employing different
percentages of resorcinol with linseed oil, the dif
at a temperature of about 150° C. and for a time
ferent percentages having been obtained'b'y di
of abouttwo hours. That these conditions con
stitute about the most favorable balance, when
luting a precondensed concentrate with addi
tional'oil. These tests were carried out in the
and properties, is further evidenced by the results
of another comparative series of examples given
following manner:
.
considering the various diiferent ‘characteristics
'
justbelow.
.
‘
>
.
Initially a batch of alkali re?ned linseed oil
was treated with 2% of resorcinol ‘under pre 10
COMPARATIVE EXAMPLES 14 '1‘0 17.
condensation conditions at a temperature of 150°
p In this series of examples alkali re?ned lin
C. for 2 hours. This treated batch was then dilut
seed‘oilwas'again used and in each example 2%
ed with additional alkali re?ned linseed oil in
of resorcinoiwas employed as'the treating agent.
order to secure test batches incorporating the fol
lowing percentages of resorcinol,
The batch of each example was preliminarily
15
Example N0.
heated ‘under reflux‘for two hours, the re?uxing
temperature being different aslbe't'we'en‘ the, sev
eral examples. Thereafter, the 'ltreated oil "of
' ‘ Resorcinol
13a _________________________________________________ ._
each batch was heat bodied at 300° C. for a time
‘ Per cent
‘
1.0
of about'31/4 hours. (The viscosities obtained in
20. the given time are indicated in Table IV—-A just
0.5
0.2
0.1
138 _________________________________________________ _.
below.
0. 05
V
"
'
Heavy bodied oils were prepared'of each of the
,> v
initially prepared, by bodying them to Z-4 to Z-6
.
.
,
'_
‘
J
.
H
L
Table ‘NO. IV-—A
HEAT BODYING
diluted oils, and also of a portion of the 2% batch-j,
viscosity.
'.
.
I
-
0F BESORCINOL ‘TREATED 'ALKALI
'REFINED LINSEED OIL
.
Re?ux
tem-_
perature
'
Varnishes were then prepared with each of the '1'
above heavy bodied oils. These varnishes were
150
prepared with ester gum iii'twenty-?ve ‘gallon
V
3 hrs., 20 min ______ _.
‘200
.
length, and each varnish was cooked to a stand
ard
All
viscosity.
of the varnishes
'
were
‘
tested
v I
in i accordance
> i
The foregoing indicates that re?uxing at about
with the methods set out above‘, and in general
all batches showed improvements in at least cer
tain respects, as compared with a similar varnish
; "150° 0. results in quite‘ rapid bodying during the
subsequentwheat bodying.‘ The relatively high
viscosity (Z-G) secured with.the:oil re?uxed at
300‘? C..(Exarr'1pl'e"1'7)w is apparently due to the.
made in essentially the same way but not con
taining resorcinol-treated oil. Some of the spe
ci?c results were'as follows:
factthatat least a portion: of the heat bodying
gallon
length‘were prepared‘ from 'thelfforegoing bodied
oilsi',"the preparation being according to the form
1115. and process already‘ described above in con
I "
Ester
place?
gum‘
duringcthe
varnishes
re?uxing
oi’ l'tWenty-?ve'
itself.; "
40.took
In cold water resistance, the 2% resorcinol con
taining oil yielded the best results, although these
results were approached by the varnish prepared
with the 0.05% resorcinol containing oil., In the
boiling water test, the results were similar to
those in cold water. -
v
>
45
a
In alkali resistance, the several batches may
Minutes
EX
,
No
'
at 300°
other properties of the varnishes thus prepared
are indicated in the following table. >
Drying
cooking
'
nection with ‘otheriexamples; ,The'drying and
Goldwater
Vis,
.
\
cosity
'
Setx DF% TF7
1
14v _____ __
C. 60
O
ON
B
A
48,
15v _____ __
161; _____ --
90
' 90
D
D
M;
56
3A
M
1
1
D
C
A
‘A
1
2 Y
1711 _____ __
55
O
36
%
1
-B
,A
2
be graded in the following order of percentage,
of resorcinol contained in the oil used, the ?rst
?gure showing the best results and‘ the others
gradually decreasing in alkali resistance: .1%,
0.5%, 0.05%, 0.2%, 2%, and 0.1%.
‘
From this series'of tests it will be seen that
. Hot water
>
'
'
j
0011v
1_' Rec1‘
ON1
.2
1
,
l
Alkali
.
'
1
>
0on,5, ,gRec.
11
1
1
v
'
'
‘
5
5
-
1
l
v5- ,
‘l
ON1
H_'
7hrs
____ __ M.
0N ‘
.
l
1
H _____ __ .M-70. .
S1. m____ Gone.
1
M _____ __
‘
M-20.
The foregoing‘ tableilshows highly “ desirable‘
properties, especially with ‘the’ example‘. (Example
14)‘ employing; 2%,re_sorcinol,';re?uxed for two
' hours at _150°'C.‘ , A" varnish made with this par
ticular oil (140) shows excellent cold water ’re--_
sistance,- good hot water resistance andv good
certain of the properties of the treated oils and 65 alkali resistance.
varnishes made therefrom are not necessarily
proportional to the quantity of resorcinol present.
Therefore, for individual uses and applications,
the concentration most favorable to that purpose
should be selected.
-
'
~
,
7.
Various of the foregoing comparativeexam
ples, indicate that for an all roundtype- of product, an e?ective balance of desirable properties
is secured by the employment of presorcinorl in
an amount approximating 2% and by pretreate
It is tack-free in one hour
and really hard in forty-eight hours.
_As hereinbefqre ‘mentioned, for certain pur
poses it may betdesirable to' treat'the oil not
only with resorcinol' orother polyhydroxy ben-.
70 zenes, but ‘also withsome other agent'or agents;
This may beadraniegeoqswhereit ,i§"d,e§i,red to
improve .eertainsnesifiq; properties, for instance.
. alkali resistance; drying, speed of ‘varnish body
ing, etc. Examples 0 f such composite treatment’
are siyenhamw'r‘; :- -
‘shoe-33'?
il
V
12
,
was prepared in the manner already described,
yielding in the short time of 60 minutes a viscosity
_
of G at 50% solids (cut with mineral spirits).
Although the alkali ‘resistance of the varnish
A-batch of 4,000gms. of alkali re?ned linseed
’ oil‘ was heated with 0.5% sulpho-salicylic acid at
100° C., until the reagent dissolved. Theheating '
was somewhat reduced as compared with a var
nish containing an'oil made with resorcinol alone,‘
bythe conjoint use of maleic anhydride-the body
ing velocity was greatly increased, and in addi~
was carried out. in a ‘three gallon openrkettle with
a blanket of CO2. After dissolution of the sulpho
salicylic acid,2% of vresorcinol was added tothe
tion, the drying, time,jcold water and boiling'wa
oil and a cover applied, with are?ux condenser
~
on the kettle. The oil was then heated at 150° 10 ter ,res‘istancewereah very satisfactory.
C,’ for two hours, to e?ect pre-ccndensation. }
EXAMPLE 21
. For ‘ purposes of comparison two
additional
, Inllthis example-a ‘compound, treatment of still
another type is illustrated. For this purpose a
treated linseed oil was employed as a starting
batches of‘ oil were prepared under similar con
ditions, one such batchbeing alkali re?ned lin
seed oil, without any modifying agent, and the
material, the oilcontaining beta-methyl-anthra-v
' dtherbeing .alkali.re?ned linseed ‘oil containing 7
r ..2‘% resorcinol alone (without the‘sulphoesalicylic
vAll three of'the above oils were then: heat bod
ied to aviscosity of from 2-4 toZ-g? and.25 gal
lon long ester gum varninshes were prepared with
the bodied oils in the mannergdescribed above,
_» the several varnishesbeing'tested in the manner
‘ quinone'as an agent for acceleratingheat body
ing. This oil had a viscosity about the same as
20 alkali re?ned or raw linseed oil.
' Seventy pounds of the treated oil were heated
in a 15 gallon kettle with 2% resorcinol under re
flux for 2 hours at 15010. A 5,000 gm. batch
of the ‘resorcinol treated oil was then bodied at
described above, and giving the-following results?
Table No.-fV-'
..
I
713%‘.
7
Minutes
Messages
‘
-
'
_
Dz)"; Oil Without any agent-" ' __‘__'-__ .
V Ev'___r_. 2% resorcino1__;___.-__=._
,_ ____ __
.172‘
'
T135
,lld
'
‘
_
Alkali »
Fair-k--. VG00d___-_. Gopd______ GoneZhrs.
Good_..__ ___do__-__>_ Fair_..r_.t__, Gone 3% hrs,
300".- Qior two hours and twenty minutes, under
The ioregoing treated and heat bodied oil was
then employed in the preparation of 25 gallon '
long varnishes prepared in the general manner
describedabove. Y Three such varnishes were pre
pared .using different resins, as follows: .
(It may be men
tioned that for the alkali tests in Table V ?lms
a.
Ester-gum.
is in contrast tothe heavier ?lms (.0030) used in
'
‘
>
a
V
I
~
-
The'threevarnishes were then cooked to a vis
cosity of ‘C to H,'at 50% solids ‘when diluted with
‘mineral spirits and when containing the drier
'7
EXAMPLE 19
Arbaich' of‘ 1.200‘ gm. of alkali re?ned‘ linseed
combination hereinabove described. The body;
oil was re?uxed with 2% resorcinol at 150°’ C.
Thereafter, 0.5% of naphthionic acid was added
ing times and viscosities' are indicated in the
z‘iollowingitablep
to the cil'and the temperature raised to 300-’ -C.
"
U
'
"
'
~
> 'Table VI
' for 51/2 hours, under a blanket of cog. This ‘Se-w ' .
Cured a viscosity of Z—'5 and ‘from this "treated ' ' -
pared in accordance with the above description;
yielding after a 21/2- hour cookingatr300° C., a
viscosity of'D,vv at 50% solids. The resulting‘var
'
b. Paranol 1750 (a rosin in'odi?ed'plienolic resin).
0''. Amberol 801 (a rosin modi?ed maleic resin);
of only 7.00.15 inch thickness were. employed, which
oil a 25 gallon long'ester gum varnish was pre
I
a blanket of CO2, yielding a-viscosity of X. t
contributes‘to very‘ good hot
and cold’ water’ resistance ‘and. also greatly; in;
'
V
'
Fain-.. ‘Very goodT l‘v'eryrgooi ‘(iced after 7 hrs.; gone overnight‘
' sulpho-salicylic acid >
-
O
watt
E
0
‘Although; the above table indicates that‘ the
creases the alkali resistance.
wit’;
E
sulpho-salicylic acid slightly decreases the body
ing speed and the drying velocity of the resorcinol
treated oil, it isinotedrthat the presence orthe
'
I
ceglgliglff Xiii?tt Dwmg
18.-.“ 2% resorcinol-F595 sulpho-sal____‘_. V
other examples.)
»
EXLNO.
Resin
7
Viscosity
7
55
21a _________________ __
2lb.- ________________ __
'2le. ________________ _.
Ester gum ______ ._
Para11o1l750
_
Amberol 801...
_.
315
35
K
C
65
I
nish, had substantially improved alkali resistance
compared tovthat of a similar varnishmade with 60 vThe foregoing varnishes were subjected to tests
a similar oil containing resorcinol alone.' The dry
of the types describedrabove’, the results indicat
' ing velocity, cold water. and boiling water re- I
ing that the vcold Water'and boiling water'resi'slh
sistance Were somewhat better than that of the
ance‘were somewhat improved-as compared to
a similar varnish made with oil containing beta
varnish made with an oil treated only with.
resorcinol.
,
_
65 methyl-anthraquinone, but not containing resor
EXAMPLE 20 .
V
A batch of 4000 gins. of alkali re?ned linseed
oil were: treated with. 5% maleic anhydride and:
2% resorcinol, by re?uxing'the reaction mixture
for two hours at 150° C.’v After the precondensa 70
tion period-(there?uxicondenser was eliminated .
' . and thetemperatureiyof the'roil raised to 295° C.‘
cinol. The drying'properties and alkali resist-'
fance were'both substantially improved as ‘com-v
,pared with» the varnishes not containing resor
c-inol.
’
1'
r
'
r
a
The most striking improvement, however, is V
the increasein the rate of bcdyin'g, as compared"
with linseed oil treated with resorcinol alone.
, For purposes‘ of comparison between varnishes
hours and 10 minutes yielding a viscosity 4 ‘ (or
varnish bases) prepared withthe oil treated
1 Here again a 25 gallon long esterigiimwajrinish?
' only ‘with betaemethyleanthraquinone, and with
2,406,337 _
13
1,4. ,
said all further treated‘ with resorcinol, it may be
noted that, if properly pre-bodied to a viscous oil,
it will be found that in the cooking of varnishes
(or varnish bases) the oil (without resorcinol)
will further body fairly rapidly. The addition of
resorcinol to the treated oil (containing beta
methyl-anthraquinone) imparts a slight but still
further increase in bodying velocity. Such accel
eration of bodying is noticeable, for instance with
varnishes (or varnish bases) prepared with‘- ester
hours, and the product at this stagewas a fairly‘
thin
The
clear
treated
oil.‘ oil
' > was thereafter further heated
by continuing heating at 290°,to 310° C. for two.
hours, after which heating the oil was consida
erably thicker.
2% hours at the same temperature (290° to 310°
C.), and during this timethe oil became grad-v
112113’ thicken Finally the oil Was of asemi-solid
consistency when cooled to room temperature.
gum. ‘However, the more important improve
ment imparted Ito this treated oil by the further
additionof resorcinol is the improvement in dry
ing and also some of the other properties, for in
stance alkali resistance.
_
.
151
It, therefore, appears that such conjoint treat
similar to that described above in connection
being Pyrogallol (1, 2, 3, trihydroxy benzene) in
stead of-resorcinol. The oil was heated between
only achieves the advantages of resorcinol, but at
the. same time secures other improvements in
, Particularly .useful products may be secured
‘EXAMPLE 25 v
A; batch of linseed oil was heated in a manner
with Example 23, the treating agent, however,
ment with resorcinol and certain other agents not
properties, notably the velocity of bodying.
After cooling overnight, the
batch was again heated for a further period of
20:
by conjoint treatment with a polyhydroxy ben
zene and with other modifying agents such as or
ganic acids (polycarboxylic acids), condensed
170 and 200° C. for 3 hours and then between
280and 300° C. for 4 hours, and ?nally kept at
320° C.»-for
507 minutes. No appreciablewbodying
_
took place until the temperature exceeded about
300° 0., but thereafter the bodying was rapid
and the ?nalproduct, when cold, was a gelat
ring compounds and organic sulfonic acids, ex
amplesof whichare given in my Patents 2,298,
inous solid.
914, 2,298,915, and 2,298,917.
‘
CQMPARATIVE EXAMPLES 22v 'ro 25v
In four examples referred to below, oils were
treated in accordance with this invention, with
The ?nal oil products of Examples 22 to 25 were
somewhat diiferent procedures in each‘ case. 30 employed in the preparation vof batches of var
Thereafter, comparative varnish formulas were
nishes made of 25 gallon length with lime hard
made employing these oils. The treatment of
the oils is ?rst referred to just below under indi
ened rosin, the varnishes being diluted to 50%
solids with mineral spirits. These varnishes were
tested for drying (and other properties and in.
each case, the varnish was tested in four differ
vidual example numbers, following which the
varnish preparation and results are described.
ent forms as follows:
EXAMPLE 22
'
‘
a. Varnish without drier.
A batch of 150 gms. of linseed ‘oil was heated
in a 500 cc. Erlenmeyer ?ask with 71/2 gms. of
resorcinol for 5 hours at a temperature between
Vb. Varnish plus cobalt drier (0.03 ‘cobalt metal
on the basis of oil content).
I
c. Zinc oxide paint made with the varnish with
about 200, and 220° 0., the batch‘ being kept un
out drier
der a vacuum of 26 to29 inches. The tempera
ture was just below the boiling point and the
.
.
(pigment to vehicle solids ratio=1 to 1 by
Weight).
treated oil was-a somewhat bodied clear mobile
'
'
oil. Although no extensive changes Were visible 45
in the oil itself, improved properties were secured
d. Zinc-oxide» paint as per‘ 0, with drier ‘as per b.
in varnishes, as brought out below.
varnishes ‘and paints were also made up from
a medium bodied linseed oil not containing any
<
' EXAMPLE 723
For comparative purposes, a blank series of
modifying agent.
.
In the drying tests one of the most signi?cant
results which showed up was the considerable
3 hours at a temperature from 180° C. to 200° C.,
improvement in all of the varnishes made with
for the purpose of precondensation. Thereafter
treated oils as compared with the blanks, with
the temperature was raised to 285° C. and the
respect to “after-tack.” The varnishes made
product kept at or somewhat above that tem 55 with the treated oils were very much more
“print-free” than is usual with soft oil'varnishes.
perature for5-hours. In the ?nal ‘half of the
In the varnishes not containing cobalt drier,
bodying period, the temperature was between 300
the rate of drying of the varnishes containing the
and 320° C. After about 21/2 hours of the heat
treated oils was also improved as compared with
bodying, the oil started to body very rapidly.
the blanks, the several examples showing up
A batch of 150 gms. of linseed .oil was heated
in an open beaker with 71/2 gms. of resorcinol for
nan/rm.- '24
A batch of 150 gms. of linseed oil was heated
with 15 gins. of; resorcinol in a Pyrex ?ask under
air re?ux. - Solution of the resorcinol had been
attained when the temperature rose to 220° C.
yielding an amber colored oil. At about 306° C.‘
the batch was simmering gently, but developed
some vigorous bumping, so that for a-short time
the refluxing was replaced by a distillation con
60
the following order, the best drying being placed
at the top of the list and being far superior to the
I
following: '
-
Varnish made with oil of Example 24, containing
10% resorcinol.
'
Varnish made with oil of Example za'cnntain»
ing 5% resorcinol.
Varnish made'with oil ‘of Example 25, contain-_
- ing 5% Pyrogallol.
nection; ‘Very little of the material distilled. The
Varnish made with oil of Example 22, contain
re?uxing was continued at 300° C. until, after
ing 5% resorcinol.
11/2 hours, the re?ux condenser was taken o?’,
In
the varnishes containing cobalt drier, the Y
heating being continued under open atmospheric
drying
results were also quite satisfactory, the
conditions at 280° C. to 300° C. for 31/2 hours.
varnishes made with oils of Examples 23 and 22
The total time between 280° and 306° C. was 6 75
(both containing 5% resorcinol) being the best.
,
2,406,337
16'
'
face coating materials-which process comprises
In the ,paints. not containing cobaltdrier. the '
incorporating in the oil up to 30% of a polyhy
droxy benzene as the sole active treating agent,
and heating the mixture at a temperature be
tween aboutv 75° C. and about310° C". for at least
- results were similar to the varnishes, the four ex-
amples maintaining the same order as above
noted, and at least the first three ,(in that order
being improved as compared with‘ the blank and
the four being about equal to the blank).
In thepaints containing. cobalt drier, the big
gest improvement was indicated in the initial
drying, the best resultin this regard being se
30
minutes.
'
'
'
r
8. A process in accordance ‘with claim 7 in »
which said polyhydroxy benzene is a dihydroxy
. benzene.
.9. A processin accordance with claim‘ '7 in
cured with the paint made with thetreated foil 10 which said polyhydroxybenzene is a trihydroxy
of Example 25 (containing 5% pyrogallol) .
Another signi?cant improvement which showed
I 10. A process in accordance with claim 7' in.‘
up in the tests of the foregoing "varnishes and
which said polyhydroxy benzene is pyrogallol.
paints was that notwithstanding the use of lime’
11. A process for treating fatty oils having dry
hardened rosin asthe resin ingredient; very good 15 ing properties, to improve their ?lm~forming
water resistance was ‘secured, especially-in the
characteristics when usedas varnish base mate
paints made with the oils of Examples25, 23 and
rials, which process comprises incorporating in,
24;,and with the clear varnish made with‘ the
the oil up to 10% of resorcinol as the sole active
benzene.
treated oil of Example 25.
/I
claim:
<
c
7
.
‘I
'
.
20 treating agent, and. heating the mixture at atem
perature between about 75° C. and about r310° C.
r
1.. A process for treating fatty oils having dry: '
for at least 30 minutes.
ving properties to improve their ‘characteristics,
as components of surface coating compositions,’
. ' i
'
12. A process in accordance withclaim 11 in
which at least a portion of the heating is effected
which process comprises incorporating in the oil .
up to 30% of resorcinol as the sole active treating 25
under re?uxing conditions.
agent, and heating the mixture at a temperature
which an initial portion of the heating is effected
at a relatively low temperature under re?uxing
conditions, and in which a succeeding portion
of the heating is eifected at a relatively higher‘
. > V
. between the dissolution point of the resorcinol
and about 310° C. for at least 30 minutes.
2. A process in accordance with claim 1 in
which the heating of the oil containing resorcinol
is effected in two stages,the ?rst of ‘which is con.
tinued- for at least 30 minutes at a temperature
30
temperature su?icient to effect heatbodying. '
14. A process ‘in accordance with claim 11 in
which the fatty oil is'sele'cted from the class
not exceeding about'200° Cr and the second of
comprising drying fatty oils and semi-drying
which is continued for at least 30 minutes at a
temperature above about 200° C.
‘ ‘
13. A process in accordance with claim 11 in
35
Y
fatty 'oils.
7'
~
'
'
v 15. A process in accordance with claim 11 in
3. A process in accordance with'claim 1 in
which the fatty oil is linseed oil.
1
which the heating of the oil containing resorcinol
16. A process in accordance with claim 11 in
is e?ectedin two stages, the ?rst of which is
which the fatty oil is 'soya bean oil. 7
'
~continued for at least 30 minutes at a tempera
17. A process in accordance'with claim 11 in
40'
ture not exceeding about 200° C; and the second
which the fatty oil is a pentaerythritol ester con-i ‘_
; of which is continued for at least‘ 30 minutes at
taining linseed'oil jfatty'acids.
'
a temperature above about 200°‘ C'., said ?rst stage
g 18. A varnish comprising a fatty oil contain“ I
- being carried out under refluxing conditions.‘ ,
ing from about _.05% to about‘30% of resorcinol
as the sole added treating agent, a varnish resin
ll. A process for treating'fatty oils having dry
7 ing properties, to improve their characteristicsas
and
components of surface coating compositions,
which process ‘comprises incorporating in. the
oil up to 10% of resorcinol as the sole active
‘
treating agent, and heating the'mixture under 50'.
refluxing conditionsat a temperature between
about 75° C. and about 250° C. for at least 3.0‘
minutes.
;
.7
.
‘
'
‘
I
'
from about .05% to about 30% of pyrogallol' as’
the sole added'treating agent, a varnish resin.
and aivolatile solvent.
>
'
r
s
-20. A process vfor treating fatty’ oils having
prises incorporating in the fatty oil up‘ to 5% of
?uxed mixture ata temperaturev between about ' '
250°’ C. and about 310° C. for at least 30 minutes.
resorcinol asxthe sole active treating agent, ‘pre
condensing the resorcinol with the oil at a tem
6. A process for treating fatty oils having‘jdry?
ing properties, to improve their ?lm-forming.
peratu're below about 250° C. and thereafter heat
bodyingthe oil by heating the mixtureto a heat
. characteristics when used as components oi'sur
bodying temperature above about 250° C.
,
21..'A process in accordance with claim 4, in
which. the quantity of resorcinol used is between
V V 1/2‘% and 2% of the weight of the oil,
above the boiling 0r decomposition point of the
oil, whichever is lower, for at least‘ 30 minutes.
'7. A process for'treating'fattybils havingrdry-r , ,7
I characteristics when‘ used as components of sur-'
7
characteristics when used ascomponents of sur
face coating compositions which process come
5. A process in accordance with. claim 4.-: and
further comprising additionally heatingthe re
‘ing properties, to improve theiru?lm-formingf
solvent.
drying properties to improve their‘ ?lm-forming '
.
face coating materials, which process comprises
incorporating in the oil up to 30% of ‘a polyhy
droxy benzene as the sole active treating vagent,
and heating the mixture at'a temperature be
tween about 75° C. and about 350°iC. but not
a volatile
19. A varnish comprising a fattyloil-containing '
v22.' A process inaccordance with claim '11; in
whichiat least a portion of the heating is effected
under re?uxing conditions and the temperature
of the re?uxing'being at; least 150° C. ‘and not
more than 200°C. and there?uxing time. being at
1east30
minutesj
'
'
'
‘
Y’ Lemme.
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 400 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа