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Патент USA US2115679

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Patented Apr. 26, 1938
2,115,679
UNITED ‘STATES PATENT ‘OFFICE
2,115,679
.
METHOD OF REFINING ROSIN
Leavitt N. Bent, Holly Oak, Del., assignor to Her
cules Powder Company, Wilmington, Del., a.
corporation of Delaware
No Drawing. Application October 7, 1935,
Serial No. 43,985
18 Claims. (Cl. 87-2)
My invention relates to a method of re?ning
This discovery is an entirely distinct and sepa
rosin, and more particularly to a method where— rate phenomenon from the action of acids in en
by color bodies may'be removed from rosin.
hancing the selective solvent action of resorcinal
As is well known, both wood and gum rosin shown by the~prior art, since the selective color
5 contain visible color bodies which darken the body solvents which I use in admixture with
rosin and, where present in any substantial quan
resorcinol are incapable of dissociating to pro
tity, substantially limit the use of the rosin.
duce hydrogen ions to more than a very slight
Further, wood rosin in addition to visible color extent, if at all. Furthermore, the prior art ad
bodies usually contains certain color bodies which, dition of acids to resorcinol is in no way sug
10 while normally invisible or latent, under certain gestive of my discovery, since the acids admixed
‘conditions become dark and color the rosin or with resorcinol by the prior art are not selective
product in which it is contained. The normally solvents per se for the color bodies of rosin,
invisible or latent color bodies will, for example, and only one of them can in any way be made a
darken in the presence of air and alkali, and selective solvent. The exception is oxalic acid,
15 hence will operate to darken, for example, soaps, which in ethyl alcohol solution is a selective‘
sizes, limed varnishes and the like, in which wood solvent for the color bodies of rosin.
,
rosin may be included as an ingredient.
The method in accordance with my invention
The presence of visible color bodies in rosin involves the treatment of rosin containing visible
and the presence of latent color bodies more par
20 ticularly in wood rosin, where present in any color bodies, and in the case more particularly
of wood rosin, also latent color bodies, with a
substantial quantity, limit the use of rosin in va
substance having a capacity for selectively dis-‘rious arts and hence various methods, of vary
solving color bodies in rosin and incapable of
ing degrees of e?lciency, have been developed
for the removal of ‘such color bodies-from rosin,
25 and especially from wood rosin, in order to in
crease its scope of use and in order to e?’ect the
re?nement of low grade rosin, or rosin contain
ing substantial quantities of visible and/or latent
color bodies.
30
One of the methods for‘ the removal of color
bodies from rosin used by the prior art involves
dissolving rosin in a suitable solvent, such as
gasoline, treating this solution with a selective
solvent for the color bodies in the rosin which is
35 immiscibletherewith, and then separating the
re?ned rosin. Resorcinol has been shown by the
prior art to be a useful selective solvent for the
color bodies of rosin, and it has been shownthat
the addition of an acid, such as sulfuric, phos
40 phoric, acetic, oxalic, salicylic, citric or tartaric
acid, to resorcinol improves its selective solvent
action. The action of these acids in improving
the selective solvent action of resorcinol appears
to depend on their property of dissociating to
45 produce hydrogen ions, since this is the only
property which is common tov the group listed.
Now, I have made the discovery that an ad
mixture of resorcinol and another material other
than resorcinol, which is also a selective solvent
50 for the color bodies of rosin, is a more eifective
selective solvent for the color bodies of rosin
than either material used ‘alone. Furthermore,
such a mixture is more effective than‘ could be
predicated as an additive result of the selective
“ 55 solvent action of the ingredients per se.
5
10
15
20'
’
substantial dissociation to produce hydrogen
ions, i. e., having a hydrogen ion dissociation con
stant‘ less than about 1><10—5, in admixture with 25
resorcinol, which likewise has a capacity for se
lectively dissolving color bodies- from rosin. The
substance in admixture with resorcinol will be
one normally a liquid or in liquid form as, for
example, dissolved in a solvent, and generally 30
will not react with resorcinol, but will function
in admixture therewith as an, independent se
lective solvent for the color bodies of rosin,
though in some cases slight reaction may occur. .
The proportions of resorcinol and substance in- 35
dicated may vary widely and, if desired, they may
be in proportion to form a, eutectic mixture,
when such may be formed.
In carrying out the treatment, the rosin is de
sirably treated in solution in a suitable solvent 40
therefor which is immisible with the mixture, and
the treatment involves essentially contacting the
mixture with the rosin, or the rosin solution, to
permit the mixture to extract color bodies from
the rosin by selectively dissolving the color bodies 45
therefrom. The treatment may be carried out,
for example, by admixing a solution of rosin with
the mixture and subsequently separating the
rosin solution from the mixture and the color
bodies dissolved thereby by gravity. It may like- 50
wise be carried out by re?uxing rosin in solution
with the mixture and subsequently separating, or
it may be carried out by dissolving rosin directly
in the mixture, by the application of heat, if ‘
necessary, and subsequently precipitating the re- 55
2,116,679
2
?ned rosin from the mixture as, for example, by
partial evaporation of the rosin solvent, by the
addition of a non-solvent oi’ rosin to the mixture,
or by reducing the temperature, etc.
Where rosin is treated in solution in a suitable
solvent, it is essential that the substance asso
ciated with resorcinol be immiscible, or capable of
being rendered immiscible with the solvent for
rosin, as by a reduction in temperature. It is
10 likewise essential that the rosin solvent be im
miscible or capable of immiscibility with resor
cinol. On the other hand, where the rosin is
treated by dissolving it directly in the mixture,
the characteristic of immiscibility with the rosin
15 solvent is not essential to the substance used with
the resorcinol.
Examples of selective solvents for the color
bodies of rosin, suitable for use in admixture with
resorcinol in the practical adaptation oi the
20 method of my invention, are i’urfural; a phenol,
as ordinary phenol, o-cresol; furfuryl alcohol; a
chlorohydrin as ethylene chlorohydrin; aniline;
methyl thiocyanate; a metallic halide, as tin
chloride or zinc chloride, in a suitable solvent
25 such as ethyl alcohol; an alkali metal acetate
or propionate, in a suitable solvent such as
ethyl alcohol, etc.
>
It will be understood that a solution of a
metallic halide as tin chloride orszinc chloride
30 in suitable solvent, such as ethyl alcohol, is a
selective color-body solvent, and that in certain
cases, as with zinc chloride, where the metallic
halide is soluble in resorcinol, the use of an addi
tional solvent is unnecessary. Likewise, it will
be understood that the solution of an alkali metal
acetate or propionate, in a suitable solvent, is
a selective color-body solvent, and that where
the salt is soluble in resorcinol, as in the case
of sodium acetate, resorcinol can be used as the
solvent. When resorcinol is used as the solvent
for metallic halide or the alkali metal acetate or
propionate, it acts as a solvent for the color,
' bodies 01' rosin and at the same time acts as a
solvent for the added compound, placing it in
45 liquid form, so that it can also act as a color
body solvent.
As a suitable solvent for rosin where the rosin
is to be treated in solution, I may use, for ex
ample, gasoline, petroleum ether, pinene, di
pentene, etc.
In carrying out the method embodying my in
vention, for example, a solution of rosin in a
suitable solvent, as gasoline, is prepared con
taining, say, about 12% rosin, or for example,
55 a solution of rosin such as is obtained by ex
tracting pine wood chips with a suitable solvent,
as gasoline, is washed, or, if desired, re?uxed at,
say, a temperature of about 100° C.-120° C., with
a mixture containing a substance having a ca
60 pacity for dissolving color bodies in the rosin and
immiscible, or capable of being rendered im
miscible with therosin solvent and resorcinol in
amount: within about the range 5%-95%l by
weight. By way 01’ illustration, where phenol is
used with the resorcinol, the phenol may be pres
ent in the mixture in amount from about 5% to
95% by weight, or more desirably within about
the range 10%-50% by weight, and where, for
example, furfural is used, the furiural may be
70 present in amount from about 5%-95%_ by,
weight, or more desirably within about the range
10%-50% by weight.
'
Where it is desired to use a eutectic mixture,
such will be formed, when using, for example,
phenol, by a mixture of 20% resorcinol and 80%
phenol, when using o-cresol, by a mixture of
10% resorcinol and 90% o-cresol, etc., the req
uisite proportions of resorcinol and the other
substance, when such will form a eutectic mix
ture therewith being readily determined.
As illustrative of the practical adaptation of‘
the method embodying my invention, for ex
ample, 500 parts of a solution of rosin in gasoline
containing about 12% rosin is re?uxed at a tem
perature of about 65° C. with a mixture contain 10
ing resorcinol-within about the range 95%—5%
and phenol within about the range 5%-95%.
The re?uxing is desirably continued for a period
of about two hours, after which the rosin
gasoline solution is separated by settlement, say, 15
at room temperature, 1. e., 20° C.-30° C. from the
resorcinol-phenol mixture and color bodies dis
solved therein. Re?ned rosin is then recovered
from the gasoline-rosin solution by evaporation
off of the gasoline. The rosin recovered will 20
grade H+ to I and will be of a pale color. The
re?ned rosin will be of a paler color than that
obtained by similar treatment with either
resorcinol or phenol alone.
4
As a further illustration, for example, 1,000 25
parts of gasoline-rosin solution containing about
15% rosin is re?uxed with 120 parts of a mixture
comprising 50% resorcinol and 50% phenol for
about
two hours.
After
separation
of the
gasoline-rosin solution from the resorcinol 30
phenol mixture, by settlement at room tempera
ture, the gasoline-rosin solution is given three
washes, each with 170 parts of 80% alcohol by
volume in order to remove residual resorcinol.
0n evaporation 011 of the gasoline from the 35
gasoline-rosin solution, about 100 parts of rosin
grading I in color will be obtained. With similar
procedure, using 120 parts of a mixture of 90
parts of resorcinol and 30 parts of phenol about
107 parts of rosin, grading I in color, will be ob~ 40
tained.
-
As illustrative of the practical adaptation of
my invention using a eutectic mixture, for ex
ample, 500 parts of a gasoline-rosin solution,
containing about 15% rosin, is re?uxed with 60 45
parts of a mixture of 20% resorcinol and 80%
phenol for about 2 hours. The gasoline-rosin
solution is then separated from the resorcinol
phenol mixture and color bodies dissolved therein,
the gasoline-rosin solution washed, if desired, and 50
the re?ned rosin recovered from the gasoline.
In the practical adaptation of the method em—
bodying my invention, iurfural, and the like, may
be substituted for phenol in the above illus
trations; thus, for example, the rosin solution 55
may be treated with a mixture of equal parts
oi’ furfural and resorcinol to obtain a yield of
rosin grading I in color.
,
By way of further illustration, for example,
50-50% mixtures of resorcinol and aniline or 60
furfuryl alcohol, or ethylene chlorohydrin, or
methyl thiocyanate, or a 50% solution of tin
chloride in ethyl alcohol may be used for re?ning
wood or gum rosin with results very substantial
ly greater than can be obtained using any of 65
the ingredients of the mixtures alone. Likewise.
66%-331/;% mixtures of resorcinol and sodium
acetate or zinc chloride, in which the sodium
acetate or zinc chloride is dissolved directly in
the resorcinol, are better selective solvents than 70
any one of these materials alone, and better than
the sodium acetate or the zinc chloride in solu
tion in an ordinary solvent, such as ethyl al
cohol.
For example, say 60 grams of any of the above 75
2,115,079
mixtures may be mixed with, say, 500 grams of
a 14% solution of FF wood rosin in gasoline,
where necessary the mixture being heated to ob
tain a homogeneous solution of the resorcinol in
the other solvent before admixture with the rosin
solution. The selective solvent mixture and
rosin solution are contacted by shaking in a
separating funnel. After desired contact, the
selective solvent mixture and dissolved color
10 bodies are separated by gravity and the re?ned
- rosin recovered from the rosin solution by evapo
ration oil of the gasoline.
It will now be understood that, in accordance
with my invention, I have provided a method for
15 the re?ning of rosin by the removal of color
bodies therefrom involving essentially the use
of resorcinol in admixture with another substance
incapable of substantial dissociation to produce
hydrogen ions, i. e., having a hydrogen ion disso
20 ciation constant not greater than 1.0X10—5, nor
mally a liquid or in liquid form, and having a
capacity for selectively dissolving color bodies
contained in rosin and, where the rosin is treated
in solution, being immiscible or capable of be
ing rendered immiscible with the solvent used to
form the rosin solution, as, for example, furfural;
a-phenol, as ordinary phenol, o-cresol; furfuryl
alcohol; a chlorohydrin as ethylene chlorohy
drin; aniline; methyl thiocyanate; a metallic
halide, as tin chloride or zinc chloride, in a
suitable solvent as ethyl alcohol; an alkali metal
acetate, or propionate, in a suitable solvent, etc.
It will be understood that, according to this
invention, both the resorcinol and the substance
35 admixed therewith operate as selective solvents
for color bodies in rosin, and that acting in con
junction they eifect a greater extraction of color
bodies than can be obtained with the use of either
resorcinol or the substance alone.
40
3
solved therein from the rosin-solvent solution and
separating re?ned rosin from the rosin-solvent
solution.
3. The method of re?ning rosin by the extrac
tion of color bodies therefrom which includes sub
jecting rosin to treatment with a mixture con
taining resorcinol and an organic substance other
than resorcinol in liquid form and having a hy
drogen ion dissociation constant less than
1.0><10—5, said organic substance having a ca 10
pacity for selectively dissolving color bodies con;
tained in rosin, and separating re?ned rosin from
the mixture and color bodies dissolved thereby.
4. The method of re?ning rosin by the extrac
tion of color bodies therefrom which includes 15
subjecting rosin to treatment with a mixture
containing resorcinol and an inorganic substance
in liquid form and having a hydrogen ion disso
ciation constant less than 1.0><10-5, said inor
ganic substance having in liquid form a ca
20
pacity for selectively dissolving color bodies con
tained in the rosin, and separating re?ned resin
from the mixture and color bodies dissolved
thereby.
.
-
5. The method of re?ning rosin by the extrac
tion of color bodies therefrom which includes
subjecting rosin to treatment with a mixture
containing a substance other than resorcinol in
liquid form and having a hydrogen ion dissocia
tion constant less than 1.0><10~5, said substance 30
having a capacity for dissolving color bodies con
tained in rosin, and resorcinol in amount within
about the range 95%-5%, and separating re
?ned rosin from the mixture and the color bodies
dissolved thereby.
6. The method of re?ning rosin by the extrac
tion of color bodies therefrom‘ which includes
subjecting rosin in solution in a suitable solvent
35
to treatment with a mixture containing a sub
It will be further understood that where the stance other than resorcinol in liquid form and
40
substance used with resorcinol is not normally in - having
a hydrogen ion dissociation constant less
liquid form, it will be in liquid form within the
than
1.0><10-5,
said
substance
having
a
capacity
purview of this invention and the claims there
for dissolving color bodies contained in rosin,
for, if it be dissolved in the resorcinol or ad
‘and resorcinol in amount within about the range
45 mixed therewith in a suitable solvent, or other
‘ 95%-5%, said mixture being capable of immisci~ 45
wise lique?ed.
bility with the rosin solvent, separating rosin
This application is ?led as a continuation in solvent solution from the mixture and color
part of the application ?led by me for Method of
dissolved therein, and separating re?ned
re?ning rosin, Serial No. 661,839, ?led March 20, bodies
rosin from the rosin-solvent.
50 1933, which is in turn a continuation in part of
7. The method of re?ning rosin by extraction 50
an application ?led by me for Method of re?ning
of color bodies therefrom which includes sub
rosin, Serial No. 464,103, ?led June 26, 1930.
jecting rosin in solution in gasoline to treat
What I claim and desire to protect by Letters ment with a mixture containing a substance
Patent is:
'
other than resorcinol in liquid form and having
55
,1. The method of re?ning rosin by the extrac
a hydrogen ion dissociation constant less than 55
tion of color bodies therefrom which includes sub
1.0X10~5, said substance having a capacity for
jecting rosin to treatment with a mixture con
selectively dissolving color bodies contained in
taining resorcinol and a substance other than
rosin, and resorcinol in amount within about
resorcinol in liquid form and having a hydro
the range 95%-5%, the said mixture being ca
60 gen ion dissociation constant less than 1.0><10~5,
pable of immiscibility with the rosin solvent, sep 60
said substance having a capacity for selectively arating
rosin-gasoline solution from the mix
dissolving color bodies contained in the rosin, ture and color bodies dissolved therein, and sep
and separating re?ned rosin from the mixture arating re?ned rosin from the gasoline.
and the color bodies dissolved therebyr
8. The method of re?ning rosin by the extrac
65
2. The method of re?ning rosin by the extrac
tion of color bodies therefrom which includes 65
tion of color bodies therefrom which includes subjecting
rosin to treatment with a eutectic
subjecting rosin in solution in a solvent to treat
mixture of resorcinol and a substance other than
ment with a mixture containing resorcinol and a resorcinol in liquid form and having a hydrogen
substance other than resorcinol in liquid form
70 and having a hydrogen ion dissociation constant ion dissociation constant less than 1.0><10-5, said
substance having a capacity for selectively dis
less than 1.0><10—5, said substance having a solving color bodies contained in the rosin, and 70
capacity for selectively dissolving color bodies
re?ned rosin from the mixture and
contained in the rosin, and said mixture being separating
the color bodies dissolved thereby.
'
capable of immiscibility with the solvent for the
9. The method of re?ning rosin by the extrac
75 rosin, separating the mixture and color bodies dis
tion of color bodies therefrom which includes 75
4
2,115,079
subjecting rosin to treatment with a mixture con
taining resorcinol and phenol, and separating re
?ned rosin from the mixture and color bodies
v dissolved therein.
10. The method of re?ning rosin by the extrac
tion of color bodies therefrom which includes
subjecting rosin in solution in a suitable solvent
to treatment with a mixture containing resorcinol
and phenol, separating rosin-solvent solution
10 from the mixture and color bodies dissolved
therein, and separating re?ned rosin from the
rosin solvent.
11. The method of re?ning rosin by the ex
traction of color bodies therefrom which includes
15 subjecting rosin to treatment with a mixture
to treatment with a mixture containing resorcinol
and furfural, separating the rosin-solvent solu
tion from the mixture and color bodies dissolved
therein, and separating re?ned rosin from the
rosin solvent.
-
15. The method of re?ning rosin by extraction
of color bodies therefrom which includes subject
ing rosin to treatment with a mixture containing
resorcinal in amount within about the range
95%-5% and furfural in amount within about
the range 5%-95%, and separating re?ned rosin
from the mixture and color bodies dissolved
therein.‘
16. The method of re?ning rosin by extraction
of color bodies therefrom which includes sub 15
containing phenol in amount within about the jecting rosin to treatment with a mixture con
range 95%-5% and resorcinol in amount within ' taining resorcinol and tin chloride in solution in
about the range 5%-95%, and separating re?ned a solvent therefor, and separating re?ned rosin
rosin from the mixture and color bodies dissolved from the mixture and color bodies dissolved
therein.
a
'20 therein.
17. The method of re?ning rosin by extraction
12. The method of re?ning rosin by the extrac
tion of color bodies therefrom which includes of color bodies therefrom which includes sub
jecting rosin in solution to treatment with a
subjecting rosin to treatment with a mixture con
taining phenol in amount within about the range mixture containing resorcinol and tin chloride in
50%_-10% and resorcinol in amount within about solution in a solvent therefor, separating rosin
the range 50%-90%, and separating re?ned rosin solvent solution from the mixture and color
from the mixture and color bodies dissolved bodies dissolved therein, and separating re?ned
rosin from the rosin solvent.
therein.
,
18. The method of re?ning rosin by extraction
13. The method of re?ning rosin by the extrac
of color bodies therefrom which includes sub
tion
of
color
bodies
therefrom
which
includes
30
jecting rosin in solution in gasoline to treatment
subjecting rosin to treatment with a mixture con
taining resorcinol and furfural, and separating‘ with a mixture containing resorcinol and tin
refined rosin from the mixture and the color chloride in solution in ethyl alcohol, separating
the rosin-gasoline solution from the mixture and
bodies dissolved therein.
,
color bodies dissolved therein, and separating re
14.
The
method
of
re?ning
rosin
by
the
extrac
35
tion of color bodies therefrom which includes ?ned rosin from the gasoline.
LEAVIT'I' N. BENT.
subjecting rosin in solution in a suitable solvent
20
25
30
35
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