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Patented Jan. 20, 1948
2,434,656
UNITED STATES PATENT‘ OFFICE
2,434,656 '
PROCESS FOR PURIFYING ~MODIFIED '
ROSIN
Irvin W. Humphrey, Wilmington, Del., .assigmor'
to‘ Hercules Powder Company, Wilmington,v
Deh, a ‘corporation of Delaware
N0 Drawing. Application June"17,.1944,x
Serial No. 540,901
12 Claims. (Cl. 260-105)
2';
Thisinventionrelatesto a processlfor re?ning
a modi?ed rosin. More particularly, it'relates to
a ' process for re?ning Fdeh’ydrogenate'd rosin:
D'ehydrogenated ordisproportionated rosin is
ordinarily‘ prepared from wood rosin or gum rosin
which-hasbeen‘re?ned' by one or more familiar
processes prior to-dehydrogenation.
of considerable importance. ' The amount of ' the
lowest boilingfraction should correspond to‘ not
less than about 5%‘ byweight of‘the original de
hydrogenated rosin and preferably to between
about 5%‘ and about v30% by, weight of the orig
inal dehydrogenated vrosin. In. certain preferable
Dehydro
cases it will representabout 10%. by weight of)
the original dehydrogenated- rosin. Likewise, the
obtained; since,‘ in addition to‘ the puri?cation
highest boiling or nonvolatilefraction, which gen
effected through the prior-‘re?ning treatment, the 10. erallyis allowed to remain undistilled, should rep
dehydrogenationtreatment ‘itself may lead to sub
resent at least'about 5%, and preferably between
stantial ‘changein or destruction of minor constit
about 5% and about 25%’,jb‘y weightofthe orig;
uents in the rosin so‘that their presence is no
inaldehydrogenated rosin. It‘ also will be found
genated ‘rosin of a very high grade thus may be
longer noticeable.
desirable in certain cases ‘to have this fraction cor
Although ‘dehydrogenated rosin of a- veryhigh 15 respond to_about.10'%‘ by weight of ‘the original
quality thus‘may‘ be prepared; it has been found
undistilled'rcsinn Accordingly, .the- fraction. of
tobe unsatisfactory for vcertain uses; Thus, when
intermediate boiling range generallywillrepre
analkali metal soap‘ even of a dehydrogenated,
sent from about 50%‘,to- about 90% by weight of
highly puri?ed'rosin is‘ employed as emulsifying
the originaldehydrogenated-rosinr and,‘ in cer
agent in the emulsion polymerization of vinyl 20 tain preferable cases, it will contain about 80%
compounds, and particularly-in the copolymerim
by weight of-the initial. dehydrogenated rosin.
tion of butadiene and styrene, undesirably low
This intermediate boiling fraction represents a
yields of‘ polymer are obtained; Such low yields
new and highly improvedrdehydrogenated rosin
heretofore have prevented‘ the use of dehydro
which possesses numerous advantages over de
genated rosin soaps "in the emulsion polymeriza 25 hydrogenated rosins heretofore known .to. the art,
tion offsuch vinyl compounds, although its avail
particularly as an emulsifying agent in the form
ability and‘low cost‘otherwise would render it of
of-its alkali metal soap for the emulsion polymer
considerable practical utility in such application.
ization of unsaturated vinyl‘compounds such as
It has been discovered in accordance with this
butadiene, styrene, etc.
invention that the properties of dehydrogenated‘ 30 Now, having set forth the broader aspects of the
rosin maybe improved substantially in respect to
invention and its purposes, certain speci?c em
this and other applications by a speci?c and par
ticular process of fractional distillation.
bodiments thereof will be illustrated by the follow
ing examples. In the examples, all proportions
and quantities of materials are expressed in parts
Now, in accordance with this invention, dehy
drogenated or disproportionated rosin is subjected 35 by weightiunless otherwise speci?ed.
toidisti'llation under reduced pressure and thereby
Example I
separated into a lower boiling fraction comprising
at ‘least‘about 5% by weight of the original dehy
A palladium-on-carbon catalyst was prepared
drogenated rosin, an intermediate boiling. fraction
and a distillation residue consisting of‘ at least 40 by treating 225 parts of 6-16 mesh Columbia Ac
tivated Carbon’ (cocoanut charcoal) with a‘ dilute
about 5%. by .weight‘of vthe. original dehydrogen
acidic aqueous solution of PdC12 containing an
ated'rosin. Although‘ the entire undistilled dehy
drogenat'edrosin is unsatisfactory after saponi?
amount of ‘PdClz’ equivalent to 2.8'parts palla
dium. After the palladium had ‘deposited on the
cation for use in’emul'sion polymerizations,‘ because
of the undesirably‘l'ow yields of polymer that re 45 carbon, the catalyst was heated at a temperature
between 200° and 260° C.‘for a period of 6 hours
sult', the intermediate boiling fraction thus pre
pared is of surprising value in this respect. Sub
while in a stream of" hydrogen gas to remove
water and'any‘ acid present.
stantially higher yields'ioi‘polymer are obtained
when soapsof the intermediate boil-ing fraction
Fifteen. hundred parts .of. N . wood rosin‘ then
which have been preparedaccordingto this inven 50 were heatedin the presence of '175 parts of the
tion. are emp1oyed,.than when corresponding soaps
ofundis'tilled .dehydrogenated rosin. areused as
polymerization agents,
above catalyst'to a temperature within the range
of 260°‘to 270° C. for 2%; hours. An atmosphere
of nitrogen gas was maintained over the’molten
In .accordancewith'this, invention, the rela- rosin during, the heating. toupreventi-any, reac
tiveamountsofthe .various fractionsare .a matter 55 tion between the hot rosin and atmospheric'ox'y
2,484,656
4
3
gen. At the end of-the heating period the rosin
Example II
was allowed to cool slightly and was then de
A sample of K wood rosin was dehydrogenated
according to the method described in Example I.
The dehyrogenated resin, after removal from the
canted from the catalyst. The dehydrogenated
rosin thus prepared had an acid number of 155,
and its color graded WG.
Eleven hundred parts of the vdehydrogenated
rosin were placed in a, still having a capacity of
3000 parts. The still was heated by Dowtherm
Vapor, maintained at a temperature su?icient to
catalyst, was distilled at a pressure of about 1 mm.
mercury and thereby separated into two fractions
and a residue.
The lower boiling fraction
amounted to 13% of the original dehydrogenated
rosin.
The
intermediate
boiling
fraction
distill the rosin. The rosin was distilled under an 10 amounted to 52% of the rosin and the residue
absolute pressure of approximately 5 mm. mer
corresponded to 35% of the original dehydro
cury. As the distillation progressed, the temper
ature of the surrounding heating medium was
genated rosin.
Ten parts of the intermediate boiling fraction
raised progressively so that the distillation tem
were mixed with 400 parts of water and neutral
perature of the rosin was correspondingly in 15 ized by the addition of sodium hydroxide. To the
creased. The distillation temperature was meas
neutral soap solution thus formed, there were
ured as the temperature of the vapors leaving the
then added 0.6 part of potassium persulfate, 1
still.
part of lauryl mercaptan, 50 parts of styrene,
The ?rst fraction was collected from the time
and 150 parts of butadiene. The mixture was
distillation commenced until the temperature of 20 sealed in a glass container and gently agitated at
the vapors reached about 250° C.
The fraction
represented 19% of the dehydrogenated rosin
a temperature of 50° C. for a period of 14 hours.
The resulting emulsion then was run into an open
placed in the still and amounted to 209 parts. The
vessel containing 20 parts of a 2% aqueous solu
second fraction, which corresponded to 72% of
tion of phenyl-beta-naphthylamine, the excess
the dehydrogenated rosin originally placed in the 25 butadiene was removed by stripping, and the poly
still, then was collected from the end point of
mer precipitated by the addition of an excess of
the ?rst fraction until the vapor temperature
saturated salt solution. The precipitated polymer
reached about 278° C. The residue, which was
was washed thoroughly with water and then with
allowed to remain in the still, contained all higher
alcohol, and dried and weighed.
boiling or nonvolatile components of the original 30
When tested in this manner, the use of an
dehydrogenated rosin and corresponded to 8%
intermediate boiling fraction led to the formation
by weight of the original dehydrogenated rosin.
of an amount of polymer which corresponded to
In order to test the puri?ed dehydrogenated
73% of that theoretically obtainable. A similar
rosin in emulsion polymerization, a portion of the
test upon the original, undistilled dehydrogenated
35
middle fraction or, in other words, of the fraction
rosin led to the formation of only 46% polymer,
which was distilled between about 250° C. and
indicating that by the distillation of the dehydro
about 278° C, was saponi?ed with aqueous alkali,
genated rosin according to the present invention,
using an amount of alkali equivalent to 200% of
a 160% improvementin the yield of polymer had
the amount theoretically necessary for neutrali
been obtained.
zation, and the concentration of the resulting 40
Example III
solution was adjusted to 2.5%. To 20 parts of
this 2 5% solution were added 0.30 part potassium
K wood rosin was dehydrogenated according to
persulfate, 0.08 part isoamyl alcohol, 6.8 parts
the method of Example I and separated by frac
butadiene and 2.25 parts styrene. This mixture
tional distillation under reduced pressure, into
was sealed in a glass tube, and its temperature 45 10% of a low boiling component, 80% of an inter
maintained at 50° C. for 16 hours while the tube
mediate boiling component, and 10% of a distilla
was rotated slowly to agitate its contents. At the
tion residue. When tested in the emulsion poly
end of the heating period, the polymer was pre
merization of butadiene and styrene according to
cipitated by the addition of saturated salt solu
the method of Example II, the use of the inter
50 mediate boiling fraction resulted in the formation
tion, washed, dried, and weighed.
The intermediate boiling fraction when tested
of 73% polymer. On the other hand, the use of
in this manner led to a yield of 96% of the amount
the low boiling fraction and of the residue, when
of polymer theoretically obtainable.
tested in an identical manner, resulted in the
It is evident from this value that the distillation
formation of much lower amounts of polymer.
of dehydrogenated rosin provides a product which
From the results indicated in the preceding
is of marked value in the emulsion polymerization
three examples, it is apparent that the distilla
of vinyl compounds, such as butadiene and
tion of dehydrogenated rosin according to the
styrene.
present invention leads to a marked improve
In order to provide further illustrations and
ment in its eifectiveness in the emulsion polymeri
embodiments of this invention and to indicate the
zation of vinyl compounds such as butadiene and
valuable improvements that may be obtained in
styrene. That this improvement is due to the
accordance with the method thereof, the following
distillation and not to other possible factors is
three examples also are presented. In these ex
demonstrated by Example IV, in which the use of
amples, the dehydrogenated rosin has been sep
the intermediate boiling fraction led to much
arated by distillation into fractions of varying
higher yields of polymer than did the use of
proportions in order to illustrate the relative im
either the low boiling fraction or the residue.
provements that may be obtained under various
Example IV
conditions. From the results shown by these eX
One
hundred
twenty
parts of a palladium-on
amples, it is evident that the proportion of the
activated carbon catalyst were added to 1200 parts
dehydrogenated rosin which is collected in the
of molten Nelio gum rosin. The rosin and catalyst
intermediate boiling fraction has a signi?cant
then were heated under a nitrogen atmosphere
effect upon the properties of this fraction, and
for one hour at 260° to 285° C.
that highly advantageous improvements may be
One thousand parts of the dehydrogenated gum
obtained by the distillation of dehydrogenated
rosin according to the present invention. ,
75 rosin thus produced, were mixed with 33 parts
5
6
of *maleic ‘Ianhydrlde ‘ and ‘heated, ‘with agitation;
at*1-’70° to ‘180° 'C. ='for ‘four 1-hours- under a :carbon
relative > sizevofithe, intermediate boiling‘ ‘fraction,
dioxide atmosphere. " The - product? then‘ was 'frac
and similar factors. In general, it has been'found
thattwhen the pressure during the distillation is
tionally distilled at an ab'solutenpressure 'of'73
‘maintained .within‘ the range of about >5-10 mm.
'mm. ‘mercury and thereby‘separated'iintoflthe ‘5 mercury;athe:distillation maybe carried outsatis
Jfractions'shown‘in the-following table. “fl‘hetem
perature of distillation shownlinirtheitable lislth'e‘
temperature of %-the' vapor‘“leaving‘thevmolten
‘factorily within *thextemperature range of about
'210°¢'C.::to; about 275° ‘C. when .the measured tem
perature'isrthatofthe vapors leaving the boil
v"rosin.
ingfrosin. ‘These temperature limits are not crit
‘The several fractions ‘then were vItcste'd in lthe lll) icaLihoWeVer, and they ‘may vary somewhat .ac
“emulsion polymerization of‘butadiene and styrene
cording ‘to Jthex purity of the dehydrogenated
‘rosin;the.:proportionof the rosin collected'in the
by" substituting = for‘ the - dehydrogenated - rosin .rof
various fractions, the pressure, and similar fac
that-‘example the = particular ‘fraction ‘under: ‘test.
tors. ‘Foriexa-mple-an' increase in the proportion
‘The ' yield » of- the r polymer :which was then .ob ,15 of zthezdehydrogenated rosin which is collected
inthejntermediate boiling jfraction tends .to
Y-tainediwith:eachdraction‘ is shown‘ in ithePfOI-lOW
‘ing table:
broaden lthedistillation range. The distillation
temperatureslalso increase or decrease with the
accordingrto the methodemployed l in :Example‘i,
T
Fraction
l ‘iPer'g‘yglthof‘ Y
:pressure,‘ according‘ to relationships Well known to
Distillation "em-1: Tom‘ 8 ‘Yr’ ?eld-0f i,
the art. Thus, when the pressure‘is increased,
'
‘Demure
‘ 'drs?ggiiitédi Polymer ‘20 stheitemperatureof distillation is increased, and
conversely when the pressure is lowered, the tem
perature at which the dehydrogenated rosin dis
tillsralsowill be'lowered to a certain extent.
:33 {25 ‘In orderto obtain a product of the highest
113g
,quality,'it isdesirable to minimize contact of l the
1 vpérsomt
"2414
' ‘
From. thegyieldsv of apolymer showntintthisntable,
,itais :apparent . that vthe. three-intermediate [boil
,-ing .-fractions, which ,alternatively could {have
been collected as one fraction,,represent-amarked
.improvement over thelowboiling fraction and
2f the. .residue.
{It .- is. :to .;be appreciated/that when .reference ,is >
rosinwithvthe-atmosphere by means of'a suitable
inert gastsuch as nitrogen,‘ carbon dioxide, or the
like.
The:clehydrogenatedrosin which is employed
‘ 1in;,_accordanee;with.thisinvention is obtained by
contacting ::a: gumlorlwood rosin at a suitable
temperature with anactive hydrogenation cata
:lyst:in;the; absence of added, hydrogen _ and at- an
until the rosin containsat
made in the-preceding, examplesto theamount 35relevatediemperature,
:.least':about 40% :dehydroabietic acid and‘until
‘ of 5 polymer theoretically. obtainable-this quantity
less :thanabout 5%, and preferably less than
‘is ‘calculated . from~the amounts of . butadiene and
1i%,efiabietic-acidremains. Suitable hy
styrene employed landswith thesassumption of m-about
drogenation catalysts 'for effecting this conver
‘complete reaction. The maximum-amount prac 40 : sionrarepalladium, platinum; nickel,‘ copper. chro
tically obtainable in various testing vmethods
lmite, ,andgthe'like. The catalyst may be subknown to . the l art, even under the most favor
~DOI't8d'j01’l a carrier, ‘such as granular alumina,
able-conditions, may fallconsiderably belowthis
I?bI‘OUS‘?SbEStOSQOI' activated charcoal. The de
theoretical value and may vary considerablyfrom
hydrogenation ;or:disproportionation with a pal
.one. test.meth0d to :another. :Although such ,dif .45 »ladium~catalyst,rfor example, may be conducted
:ferences may .render =di?icu1t the expression- of
seither w by va iicatchwise ;or continuous procedure.
test?valueson an absolute basis, the‘. differences
"Thus, in *aabatchwise procedure, the rosin may be
.do not detractfrom the .valuelof any one method
--.contacted-with:from about 5% to‘about 20% by
7 of..test for determining . the . relative effectiveness
~.weight,~b.ased‘on'the weight of the rosin, of a
.of various emulsifying vagentsin lthe polymeriza
3.50 catalyst :consistingof-from 1 to 2 parts palladium
zdeposited‘on 1100 parts activated charcoal. The
irosin and :the ‘catalyst are heated together at
From the preceding examples, "it, is apparent
. tion of. . vinyl compoundsrsuch . as .butadiene ., and
.styrene. .
. that a substantial ' improvement inthe proper
ties ,of'dehydrogenated rosin may. .be obtainejdiby
about:150°‘C. to about 800° C. for about 1 to 5
hours. In" the’ continuous process, the molten
distillation under reduced pressureand withsep- ' 55 ,vrosinsisrflowedover the supported palladium cata
l'lysti-at a temperaturewithin the range of about
aration of the dehydrogenated ‘rosin intoatjleast
2259'tolabout:300°'C..for a period of time from
about‘5‘% of a'low boiling fraction, an interme- ‘
ab‘outzl?rminutes to‘ about 1 hour.
-A varietyofdehydrogenated rosins may be
IIIyandlV, the. intermediate: fraction‘ is of great .60 treated ‘according to the present invention. Thus,
ieitherldehyrlrogenated wood rosin or dehydro
‘ly‘ improved 'value as ‘an emulsifying agent ‘in
diate boiling fraction, and atleast about‘51% of a
distillation > residue.
As shown'by ‘Examples. II,
the polymerization of butadiene andpstyrene, by
comparison either" with the‘undistille'd ‘dehydro
' genated rosin“or'withmhe"low-boiling fraction :and
bgen-atewgumvrosinTmay be‘re?ned according to
the ‘herein-disclosed process.
The wood rosin
preferably. is :re?nedaprior to the dehydrogena
ii? tionlandisubsequent distillation althoughlit will
"the residue.
be apparent that :asubstantial improvement‘in
‘The’ pressure‘ employed “for the'dis‘tillation
:should be’ low enough vto rpermitvdistill-ation - atea
temperature which» will notcause ‘undue - decom
positionofthehrosin during distillation.’ Accord
. certain'rpropcrties'also maybe obtained by prac
ticing-theiinvention with dehydrogenated unre
?nedwood rosin. "The rosin prior to dehydro
' ingly, pressures below about‘ 30mm. ' mercuryare“ 7o genation may be; re?ned according to one or more
desirable, and it is preferableito?employ-a‘pres
sure of about 10' mm. 'or ‘lower.
‘ The : temperature ‘=- range throughout which the
lintermediateboilingifractionmstills'dependsupon
of the several methods that are well known to
those skilled in-the : art, for. example, by treat
ment with selective solvents, withadsorbents, by
crystallization,:andlthe‘like. Prior to dehydro~
the pressure: employed duringrthe 'distillatioml‘t'he '; ‘7 5 ~genationithe'crosin . :also‘ may‘ have been ‘treated
2,484,656
8
7
with acidic isomerizing agents ".to' effect its iso~
acid to distillation under reduced ‘pressure and
merization.
separating said dehydrogenated rosin into a lower
As illustrated by Example IV, prior to distilla
tion the rosin may have been treated with maleic
anhydride as an aid in removing polymerization
inhibitors or retarders.
This treatment may be
accomplished by heating the dehydrogenated or
disproportionated rosin with m-aleic anhydride,
boiling fraction consisting of at least about 5%
by weight of the dehydrogenated rosin, an inter
mediate boiling fraction, and a distillation residue
consisting of at least about 5% byweight of the
dehydrogenated rosin.
‘
2. The process of re?ning dehydrogenated rosin
which comprises subjecting a dehydrogenated
5% of maleic anhydride based on the Weight of 10 rosin containing at least about 40% dehydro
abietic acid and no more than about 5% of abietic
the rosin, to a temperature of about 100° to about
acid to distillation under reduced pressure and
200° C. for a period of, for example, about 1 to
separating said dehydrogenated rosin into a lower
about 3 hours.
"
usually in an amount of from about 1% to about
If desired, the intermediate boiling fraction
boiling fraction consisting of about 5% to about
may be collected during the distillation as one or 15 30% by weight of the dehydrogenated rosin, an
intermediate boiling fraction consisting of from
more fractions. The intermediate boiling frac
tion may also be redistilled, if desirable, to ob
tain an even more highly puri?ed product. In
general, however, this latter additional treatment
about 50%‘ to about 90% by weight of the de
' hydrogenated rosin, and a distillation residue con
sisting of from about 5% to about 25% by weight
will not be found to be necessary, although col 20 of the dehydrogenated rosin.
3. The process of re?ning dehydrogenated rosin
lection of the intermediate boiling fractions in the
which comprises subjecting a dehydrogenated I'OS-r
form of two or more fractions may be found to
in containing at least about 40% dehydroabietic
be desirable in certain circumstances.
acid and no more than about 5% of-abietic acid
Although speci?c embodiments of the inven
tion have been illustrated by the use of batch 25 to distillation under reduced pressure and sep
arating said dehydrogenated rosin into a lower
distillation, it will be appreciated that other Well
boiling fraction consisting of about 10% by weight
known distillation techniques may be employed.
of the dehydrogenated rosin, an intermediate
For example, a continuous still of the ?ash evap
boiling fraction consisting of about 80% by weight ‘
oration type may be employed, with control of
the temperature of volatilization and condensa— 30 of the dehydrogenated rosin, and a distillation
residue consisting of about 10% by weight of the
tion in order to obtain separation of the desired
dehydrogenated rosin.
fractions. Other suitable distillation techniques
4. The process of re?ning dehydrogenated rosin
will be apparent to those skilled in the art.
which comprises subjecting a dehydrogenated
The product of this invention is of particular
value in the preparation of emulsifying agents 35 rosin containing at least about 40% dehydro
abietic acid and no more than about 5% of abletic
of the type hereinbefore illustrated. However, it
acid to distillation under anv absolute pressure of
is not limited to this use since the improvements
less than about 30 mm. mercury and separating
obtained render the product particularly suited
said dehydrogenated rosin into a lower boiling
for applications where the purity or homogeneity
of the dehydrogenated rosin is of moment. It 40 fraction consisting of at least about 5% by weight
of the dehydrogenated rosin, an intermediate boil
is known that the benzenoid properties of dehy
ing fraction, and a distillation residue consisting
drogenated rosin render it useful in preparing de
of at least about 5% by weight of the dehydro
_ rivatives wherein substituents are introduced into
genated rosin.
the aromatic portion of the rosin acid nucleus.
5. The process of re?ning dehydrogenated rosin
As a result of the puri?cation which may be ob
which comprises subjecting a dehydrogenated
tained through treatment of the dehydrogenated
rosin containing at least about 40% dehydrorosin, derivatives of substantially greater purity
abletic acid and no more than about 5% of abietic
may be prepared without an undue increase in
acid to distillation under an absolute pressure of
their cost. This puri?ed dehydrogenated rosin is
therefore of value in the synthesis of amino de 50 less than about 30 mm. mercury and separating
said dehydrogenated rosin-into a lower boiling
rivatives, dye intermediates, detergents, and the
fraction consisting of about 5% to about 30% by
like. The products prepared according to the
weight of the dehydrogenated rosin, an inter
present process are also of value in the prepara
mediate boiling fraction consisting of from about
tion of esters and alkyd-type resins and the like.
A marked improvement for use in emulsion 55 50 to about 90% by weight of the dehydrogenated
rosin, and a distillation residue consisting of from
polymerization can be obtained even when the
about 5% to about 25% by weight of the dehy
rosin has been highly puri?ed prior to dehydro
drogenated rosin.
genation. This is particularly noticeable when
6. The process of re?ning dehydrogenated rosin
the fractionally distilled dehydrogenated rosin is
to be employed in the preparation of emulsifying 60 which comprises subjecting a dehydrogenated
rosin containing at least about 40% dehydroabietic
agents for the mass emulsion polymerization of
acid and no more than about 5% of abietic acid
butadiene and styrene and similar materials.
This is indeed surprising since it would be ex
to distillation under an absolute pressure of less
than about 30 mm. mercury and separating said
pected that the previously obtained high degree
.of puri?cation would render subsequent re?ning 65 dehydrogenated rosin into a lower boiling frac
tion consisting of about 10% by weight of the
treatments of little or no avail.
dehydrogenated rosin, an intermediate boiling
Where in the speci?cation and appended claims
fraction consisting of about 80% by weight of the
the term “dehydrogenated rosin” is employed, it
dehydrogenated rosin, and a distillation residue
is meant to include disproportionated rosin.
What I claim and desire to protect by Letters 70 consisting of about 10% by weight of the de
Patent is:
hydrogenated rosin.
F1. The process of preparing a product capable
upon saponi?cation of forming an improved emul
sifying agent for emulsion polymerization of vinyl
abietic acid and no more than about 5% of abletic 75 compounds which comprises contacting a rosin
1. The process of re?ning dehydrogenated rosin
which comprises subjecting a dehydrogenated
rosin containing at least about 40% dehydro
.
2,434,656
10
with an active hydrogenation catalyst in the ab
acid to continuous distillation under reduced pres
sure and separating said dehydrogenated rosin
into a lower boiling fraction consisting of from
about 5% to about 30% by weight of the dehy
drogenated rosin, an intermediate boiling fraction
sence of added hydrogen to form a dehydrogenat
ed rosin containing at least about 40% dehy
droabietic acid and no more than about 5% of
abietic acid, subjecting the dehydrogenated prod
uct to distillation under reduced pressure and sep
consisting of from about 50% to about 90% by
arating a lower boiling fraction consisting of at
weight of the dehydrogenated rosin, and a distil
least about 5% by weight of the product, an in
lation residue consisting of from about 5% to
termediate boiling fraction, and a distillation resi
about 25% by weight of the dehydrogenated rosin.
due consisting of at least about 5% by weight '10
11. The process which comprises subjecting a
of said product.
dehydrogenated rosin containing at least about
8. The process of preparing a product capable
40% dehydroabietic acid and no more than about
upon saponi?cation of forming an improved emul
5% of abietic acid to continuous distillation under
sifying agent for emulsion polymerization of vinyl
reduced pressure and thereby separating said de
compounds which comprises contacting a rosin 15 hydrogenated rosin into from about 5% to about
with an active hydrogenation catalyst in the ab
30% by weight of a lower boiling fraction, from
sence of added hydrogen to form a dehydrogenat
about 50% to about 90% by weight of an inter
ed rosin containing at least about 40% dehydro
mediate boiling fraction, and from about 5% to
abietic acid and no more than about 5% of abietic
about 25% by weight of a distillation residue, and
acid, subjecting the dehydrogenated product to 20 reacting said intermediate boiling fraction with
distillation under reduced pressure and separat
ing a lower boiling fraction consisting of from
an alkali.
12. The process which comprises subjecting a
dehydrogenated rosin containing at least about
about 5% to about 30% by weight of said product,
an intermediate boiling fraction consisting of
40% dehydroabietic acid and no more than about
from about 50% to about 90% by weight of said 25 5% of abietic acid to fractional distillation under
- product, and a distillation residue consisting of
reduced pressure and thereby separating said de
from about 5% to about 25% by weight of said
hydrogenated rosin into about 10% by weight of
product.
a lower boiling fraction, about 80% by weight of
9. The process of preparing a product capable
an intermediate boiling fraction, and about 10%
upon saponi?cation of forming an improved emul
by weight of a distillation residue, and reacting
sifying agent for emulsion polymerization of vinyl
said intermediate fraction with an alkali.
compounds, which comprises contacting a rosin
IRVIN W. HUMPHREY.
with an active hydrogenation catalyst in the ab
sence of added hydrogen to form a dehydrogenat
ed rosin containing at least about 40% dehydro
abietic acid and no more than about 5% of abietic
acid, subjecting the dehydrogenated product to
35
REFERENCES CITED
The following references are of record in the
?le of this patent:
UNITED STATES PATENTS
distillation under reduced pressure and separat
ing a lower boiling fraction consisting of about
Number
Name
Date
10% by weight of said product, an intermediate 40 2,072,628
Brennan et a1 ______ __ Mar. 2, 1937
boiling fraction consisting of about 80% by weight
of said product, and a distillation residue con
sisting of about 10% by weight of said product.
10. The process of re?ning dehydrogenated
2,201,237
Littman __________ __ May 21, 1940
2,247,399
2,277,351
Palmer et a1 _______ __ July 1, 1941
Pohle et a1 _______ __ Mar. 24, 1942
OTHER REFERENCES
rosin which comprises subjecting a dehydrogenat 45
ed rosin containing at least about 40% dehydro
Littman, Jour. Amer. Chem. Soc., vol. 60 (1938),
abietic acid and no more than about 5% of abietic
pp. 1419-1421.
Certi?cate of Correction
Patent No. 2,434,656.
January 20, 1948.
IRVIN W. HUMPHREY
It is hereby certi?ed that errors appear in the printed speci?cation of theiebove
numbered patent requiring correction as follows: Column 3, line 42, for “25%”
reed 2.5%; column 8, line 55, for the numeral “50” read 50%; and that the said
Letters Patent should be read with these corrections therein that the same may
conform to the record of the case in the Patent Of?ce.
Signed end sealed this 30th day of March, A. D. 1948.
THOMAS F. MURPHY,
Assistant Oommissioner of Patents.
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