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Патент USA US2406206

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Patented Aug. 2Q, 1946
UNITED‘ v‘sm'i'Ejs . PATENT ,oFmE
' '
Melvin,De ‘Groote‘, University City, Bernhard ~ -~
_ Keiser, Webster Groves, and Arthur F. Wirtel,
.Kirkwood, M0.,’assignors toiPetrolite Corpora
. j . tion, Ltd.,,VVilmington, DelL, a. corporationlof
, N0 Drawingr" Application July6,-1943, " '
.c‘ciaims. (01. 260-5406)
matter, ourxpresentt-application being a'continu
slightly above the boiling pointlof'water, for in
for use as a demulsi?er in the resolution of crude
inch gaugehpressure, {and at anyv temperature,
chemical product that is. particularly adapted
suresvup to or including .200 pounds perfs'qliare
Qneobject, of our ‘invention is to provide a new
Oxidation may take-place at atmospheric pres’
sure or, superatmospheric ‘pressure, ‘i. .e., jpres
quently matured as U. S. Patent No. 2,340,308,
etc;, it may be of thelorganic type which produces
peroxide such as alpha-pinene, linseed oil,» etc.
.ation-in-part of our pending application Serial
No. 444,468, ?led May 25, 1942,, which subse
dated February 1, 1944,
leate, cobalt ricinoleate, manganese ricinoleate,
_ fl‘his invention, relates to a new'composition of
.Another object of our invention is to provide
stance, 1209 >C.,,u‘p to any temperature which
doesv not produce undue decomposition by ,pyro
a. practicable method‘ for manufacturing said »
' g'Ifhereaction.
time of blowing
be_ fairly brief,
new chemical product. or compound.
Although one of the primary objects of our ‘in
example, 8-10 hours; or it may be quite exten
sive, for instancevas long as 10-12-14 days, the
vention is to provider-a new compound or compo
longer time periods-being employed ‘generally
when the temperature is just slightly abovethe
boilingpoint of water and when'ioxidation is
sition of matter that’ is ‘an ef?cient' vdemulsi?er
for crudeloil emulsionsof the. water-in-oil type,
with air at atmospheric ‘pressure.
a '1 ‘ I
the 'said compound or composition of matter is
adapted for use in other arts, as hereinafter in
Mild oxidation, 1. e., oxidation as exemplified
icated. It may also haveadditional ‘uses in 20 bythe exposure of a ?linof castor oil to air, for
other ?elds which have notvyethbeen, investi
an extended period of time, such' as weeks,,or
even months, (see Chemical Technology‘ ‘and
Analysis ‘of_ ‘Oils, Fats,-~-and Waxes, byLewko
‘ V'_I>‘he composition of ' matter; herein ‘described,
witsch, sixth edition,- volume T2‘, -page~=406)' -, “pro
particularly when it ' is intended 'to "be, used ‘ as a
demulsi?er for‘petroleum' emulsions "oi the W9;
ter-in-oil type, may be obtained by the 'hydroxy
acetylation of-blown or oxidized ricinoleic acid
compounds, or compounds of the kind herein
after-described. _More- specifically,“ the compo
sition of matter herein contemplatedxandrpa-r
duces" relatively-small modi?cations of ‘certain
important tiiidices, such as the iodine‘valua'the
acetyl'value, and the saponi?cationivalue. *If
drastic oxidation takes place, either bycontinued
' mild oxidation, i-or-by-more vigorousroxidatiozi'
30 from ‘the very beginning of the reaction; asin-l
duced by-either, a higher reaction-temperaturelor
the presenceof a catalyst, then there is obtained
ticularly for use as a demulsi?er, is obtained by
treating oxidized ricinoleic‘acid-‘compounds with
a concentrated solution of hydroxyacetic acid, or
an oxidized .oil ,_ having-l; characteristics which
anhydrous hydroxyac'etic'acid'in the ratio of at > -
clearly-indicate that ‘drastic oxidation‘ has taken
least two ,moles of the- hydroxyacetic, acid- and
not more thanS moles of; the hydroxyacetic acid
for each ricinoleyl: radical present-prior to dras
relatively low iodinevalue, such as '70 or less, ‘and
tic; oxidation.- ,That is to say, if one were to; start
with jav pound mole of oxidizedztriricinoleimione
would employ at least six :poundmoles and, not
more than-,vninelv-pound moles of;~jhydr0Xyacetic
i It is well known that oxidized oils can be ob
place; vThese indic'eslot. drastic oxidation farevia
may be as low as 40, or thereaboutsj?a»'sapon
i?cation value of 215 to 283,.or thereabouts; an
acetyl value oflapproxim’ately 160-200; anin
40 creased viscosity such that the material may be
hardly mobile at ordinary temperatures; a spe
ci?c gravity of almost one, or a tri?e over oneat
times;,an increased refractive index; and,.in' the
ricvinolein, -diricin_olein and _ polyricinoleic ‘acids.
absence of other coloring matter, aiyellow'to
deep orange color. The color at times may be a
questionable index, since some oxidized f-castor
They are producedby the common ‘practice of
oils are bleached to.v make, them; particularly
tained from castor oil, ricinoleio acid and various
derivatives of ricinoleic-acid, such as:' Mono
blowing or ‘oxidizing castor oil and similar fatty
adaptable for useas plasticizers in light colored’
oils or acids, particularly non-drying , unsaturat-_ '- resinoid bodies.
ed‘ fatty:oils,- by ;me_ans of a-v gaseous medium; 50 Drastically-oxidized castor oil can~be prepared
bywell-known methods, or ‘such products canbe
such as-air, oxygen, ozone, or'ozonized-air. , The.
gaseous medium,,such,as air, may, be»_ moist'or
purchased in the.,op'en ,1 market under 1 various
dm and the; oxidation, may. iake'lplece ‘(in Ethel
trade names, 'suchas ,“blownicastor oil,” “blend-..
may be of a metallic type, such aslead ricino
essed castor oil,”l“oxidiz'edlcastor -'oi1,""‘héavy
presence orv absence, of; a~catalyst.~ ,fIfhe catalystv
vapor, is separated by gravity; and the solvent _
returned to the reacting chamber for further use.
: (sally-oxidized castor oils, which di?er merely in
degree but not;v
The selection of suitable amounts! of reactants
" "
in the manufacture of hydroxyacetylated blown
The color; of ‘these-oils is stilfvlpal'e .orflilght
castor oil is, of course, simple.
colored in comparison with the oil from which
; transparent, particularly in reasonably thin lay- ,
ers, for instance, an inch or less; ' Such’. oils rep-
The blown oil '
,may be analyzed so as to determine its hydroxyl
orv acetyl value. Such value may be interpreted
1, they have been derived. Usually they are fairly‘
derived, both from the water vapor and solvent
, castor oil,” “viscous castor oil," etc. These vari
ous trade names appear to be applied to drasti
onzther basis‘ of‘ ‘each fatty acid radical present.
The acetyl» value or hydroxyl value may not cor
respond exactly to the alcoholic hydroxyl radi
5 resent greater or lesser degrees of ‘partial oxida
' tion in the sense that there is a drastic change
1 in comparison with the chan’gethat takes place I
calsi attached! to‘ each high molal fatty acid acyl '
1 when a ?lm of castor oil isexposed t‘o‘air.
radicalibut‘ such‘value does correspond, at least,
For the sake of di?erenti’ati‘on, oilsdfthe kind‘ ‘ approximately. The reason is that there may be
previously described will be“ referredto as pale is ‘present anhydrides, or possibly, some compounds
of unknown nature or stability, which affect the
i blown,’ drastically-oxidized castor oils; and the
same terminology is intended to ‘apply ‘to all“, hydroxyl. value determination. For convenience
other ricinoleic bodies of the kind hereinafterd'el- ' - ins-the present instance, one may consider blown
triricinolein in the same manner that it is'scme
1 scribed. In addition to pale blown, drastically-y
‘ oxidized castor oil, there is also another type of‘ 20 times convenient to consider triricinolein, i. e.,
the kind described in U.‘ S. Patent No. 2,023,979, I > as if it were a trihydric alcohol. For practical
td-S'tebr'," dated December'lcl v19335. The ‘product ' purposes; of’ course, there is no economical justie
?c'ation for‘ obtaining-a technicallyv pure blown
described'in said S‘teh‘r patent is characterized by
triricinolein and subjecting such material to hy
the fact that drastic voxi'dationvis continued‘ past ~
droxyacetyl-ation instead ‘of employing blown
the stage‘ ‘where’ a pale blown oil is obtained and
whereas a matter of fact, a-superoin’dized prod- ‘
deter almostsemi-livery consistency is obtained.
Thus, the product constituting our present in
venti’en is- the ‘compound or ‘compounds obtained
'than-thepale blown castor oils, for‘ ‘the ‘reason ; which-‘represent, in‘ essence, a polyhydroxyacetic
tliat'ceftain side‘reac'tionsoccur with-the forma ‘30 acid derivative of blown castor oil. The 'unhy
Such’ products are-usually much d'ark'eriin color ‘
tion of dark ooIored-by-products; and asa're'sult, ‘ ' phenated expression “polyhydroxyacetic acid” is
employed to reform polymeric derivatives of hy
the transparency of the oil has greatly‘ decreased ‘
or disappeared, and ‘it is ‘apt to be opaque in ‘
35 ricinol'ei'c acid. Suchacid's are/obviouslyrester
Attention is’ directed particularly to‘ U. ‘S. Pat
droxyacetic acid in the same ‘way that poly
ricinoleic acid refers to ‘polymeric derivatives of
2,183,487, dated December 12, 1939, to'
acids produced by self-'esteri?cati'on.
acids and their relationship to hydroxyacetic
‘acid is“ readily shown'by the following formulas:
to the “oxidation of castor- oil'i‘n- a mannerthat is
particularly desirable;
. '_
The constitution of such polyhydroxyacetic
Colbetli, to theextent‘ that it‘ discloses details as
A Ourjpreference- is to subject a pale'blo'wn cas .40
tor oil of ‘the following characteristics,‘tolhy
OH»(C_H2COO)1;H '(.-n being at. least 2 and not
- over 10')‘
“In the present‘instance; however, thei’polyhy
droxya'cetic acids, in "View of‘the previous ‘limi- '
tation, are" concerned onlyw'ith the species in
which the formula takes ‘either one or the other
‘The production or‘ hydroxyacetylated 'bl'own '
castor ‘oil ‘or ‘similar ‘compounds, "is comparatively
'si‘mpleandis comparable to the manufacture ‘of
acetylated castor .oil, except thathydroxyacetic
’ acid'crits' equivalent,such as the vanhydri-de or
of two forms;
What ‘has been said previously may suggest
placed byk'the’bl‘own ‘product. In ‘View of, ‘the
an ioversimpli?cat-ion of a rather complicated
structure, 1which results’from the reaction or re
acetyl or‘ hydroxyl value of blown castor oil, the
7 actions indicated. For instanca'theexamination
am chloride, is employed; and‘ castor oil is 're
principal reaction is obviously ‘an esteriflcation
reaction in which ‘the 'reactionjis hastened or
of 'the'reaction between'hydroxyacetic acid and
castor‘ oil, orhydroxyacetic acid and blown castor '
oil'indicates that water is’formed and'must ,be
removed. Actually, the water formed may not
- caused to‘go to completion by removal or any'wae
ter'rcrmed. "The usual procedures for promotion ‘
of 'esteri?cation are'wellknowmand involve one ‘
necessarily be removed instantly, and ‘thus, the
perature' high enough “to 1 eliminate “any " water ' .
Likewise, ‘for reasons of economy, it may be‘de
or more of the following‘: "Employment of a ‘temé'. 65 water may undergo certain obvious vreactions.
sirable to use a highly concentrated hydroxy
acet'ic acid'instead of the anhydrous material as
the selected reactant. ‘In such instances, the
su'l‘fon'ic acid in'sm'all'amountsacts as a'catalyst;
sometimesit is expedient to pass-‘an ‘inert'dried 70 water would ‘readily enter into hydrolytic reac
formed, :forinstance, 120-1800 ‘ (3.; ‘sometimes the
presencecf .a strong "acid, "such as a benzene- ,
gas‘through the reaction mixture“; at other times
esteri?cation ‘may "be conductedin the presence i
ofahighiboiling water-insoluble"solvenusuch .as ‘
xylene or ‘the like, which assists in'removing the ‘
tions'with the blown castor 'oil,'and thus, the
producte'or composition which is actually hydroxy_
acetylated, may include compounds comparable
vttrric'incrleic acid, 'polyricinoleic ‘acid, monoricino
water in; thefoiimrcf jvanori the.’ condensate so 75 lein‘and diricinolein. Generica‘lly, ‘the expression
T“superglycerinated fa if’ucr; l'superglycerintted
'triricinolein" refers to thei'mixture in whichsthe
monoglycerides and 'diglycerides .are present.
Speci?c terminology indicated inthe present in
stance would be :superglycerinated' blown caster
HYnnoxYecnmArEmBLown GASTOR 0n.
Example 3,
._ ‘v Thesame procedure is employed asin the-two
preceding examples, except that . 83.5 rounds of
hydroxyacetic acid are employed, i..el., amount
oil.ULikewise,-the acids and polymerized acids
obtained from ‘the blown :‘caston oil,iare"so'me
.which would result theoretically in av mixture of
the dimeric and trimeric radicals.
itimes reierred'to as ‘a “blown castoroil'estolide.”
(See U. S. Patent No. 2,079,762, dated May 11,
1 .,
~ . v‘Q:Hirimoxim'cniryns'rini, BLOWN CASTOR'QIL _' ’
1937,’ to De Grooteand Keiser.) ' In addition to
"the other productsv formedlby hydrolysis, glycerol
must be included.= It is not intended in the pres
Example 4
x _~ '
" I The same procedure is followed as in Examples
‘1. to 3, precedingjexcept that anhydrous hydroxy
entrinstance toclaim the product obtained ‘by
iacetic'acid is employed and water is removed im
hydroxyacetylation of glycerol,‘ but it" is .to be
noted that ‘such material'may be present co-W mediately upon "formation. : ‘The. productfso '"ob
tained represents polyhydro'xyacetylated blown
generically, for reasonslindicated. Earlier ref
i'erences to the compounds herein contemplated,
castor oil,v orimore especially, polyhydroxyacet
and ' particularly for use as a demulsifier,vv include
:ylated' blown vtriricin’c'ile'in, ‘in the presence-of a
polyhydroxyacetylate‘cl 'Iderlva'tives- of blown ric
‘minimum amount ‘of .polyhydroxyacetylated "co
inoleic acid compounds, and such‘. expression 1s
now suitably quali?ed-so as‘ to be limited‘to blown
It is well known that the exact composition-‘of.
ordinary oxidizedicastor oil "is not known.‘ This
'hasbeen a‘ matter ‘of commentfrom time to" time
in the? literature, including the- patent literature
dealing-‘with the arts in which blownj‘castor oil
is contemplated‘. In» view ofv-such fa'cts,it be
castor‘ oil, blown tri-ricinolein; blown superglyc
erinatedlcas'tor oil, and blown castor ‘oil estolides,
and other speci?c compounds mentioned subse
'quently. The preferred example isthe cogeneric ;v
mixture obtained by’the polyhy'droxyacetylation
comes even'rmore' ‘ difficult‘ .toi'attempt' to" indicate
the “nature of they products ' obtained: by hydroxy
acetylation of blown ‘castor oil-or-the like; 'As has
of blown castor-"oiL- *One mayvemploy super
glycerina'ted blown castor oil obtained by reaction
‘between blown castor oil and g'lycerine,_ in the
been previously indicated; esteri?cationg‘and quite
'pr'oportion‘of one‘. o'rijtwo moles of. glycerol‘pjer
mole of-rblown castor 'oil.‘ This simply means that
the product is obtained by rearrangement instead
frequently, .‘ hydrolysis,‘ enters ‘into the ‘reaction,
and. it is‘ quite probable, especially when aque
ous hydroxyacetic acid is employed, thatrear
of hydrolysis. ' 0bvi'ou‘sly,gone '- may also employ
'rangemennas exempli?ed by vthe formation'pf
vtechnically pure blown mon'oricinolein, technical
ly‘ pure lblown ‘diricin'olein, " and technically pure ;~ .estolidesjlm'ay
The‘ polyhydroxya'cetylated
take place:
‘I ’
‘blown ricinolei'c‘ acid.‘
V i
, r
contemplated as new‘ compositions of matter; and
particularly for-'use as demulsi?ers, may- be 'ob
Although it is believed,'in view 0t what has been
said, that no' further description is necessary in
regard ‘to the manufacture of hydroxyacetylated
blown ricino'leic- ‘acid compounds, the following
examples are included by way of illustration:
HYnaoxYAcarYmrsp, Brown CASTOR 011.
Example 1
tained in ‘any suitable‘ manner. Hydroxyacetyl
no :ated blowin ,castor' oil prepared ‘ in‘ :anyisu'itable
'man‘nerr-may be reacted further with an. addi
tional amount of hydroxyacetic acid. Another
way of saying the same thing, is that in pre
. ceding Example 1, if desired, the pale blown cas
45 tor oil might have been reacted with 333 pounds
of concentrated hydroxyacetic acid, and upon
1,000 pounds of pale blown castor oil corre
completion of ‘the reaction, it could have been
sponding to the tabular specifications above is
subjected to further reaction with another 333
treated with 666 pounds of concentrated hydroxy
pound lot of the reactant.
acetic acid containing 30% of water. The reac- .
Furthermore, hydroxyacetic acid, that is, the
tion is conducted at 200-250" C. for approximate
monomeric acid, might be converted into the
ly 2% to 4 hours. Completeness of reaction is
dimer or trimer, and such dimerlc or trimeric
indicated by the fact, that elimination of water
acid be employed as a reactant. Then too, one
might employ the obvious functional equivalent
practically ceases by decrease in the acid value
and hydroxyl value of the mixture, and by elimi 55 of hydroxyacetic acid, such as the acyl chloride _
or the anhydride. In other words, although we
nation of free hydroxyacetic acid. The Procedure
have described the preferred method of manu
facturing the new compositions of matter herein
contemplated, and particularly for use as demul
reactants. The amount of hydroxyacetic acid 60 si?ers, it is understood that any feasible proce
dure may be used.
selected in the present instance is calculated to
VAt this point it may be well to restate some
give substantially the equivalent of a mole of an
of the data previously presented in regard to
OH(CH2COO)2H radical for each ricinoleyl radi
is conducted in the usual reaction vessel of the
kind employed for esteri?cation, and may be con
structed of any material which is resistant to the
cal originally present.
thecompositions contemplated. The expression
65 F‘polyhydroxyacetylated” must be employed with
a certain amount of caution, in view of certain
For instance, if one pound mole
of blown castor oil were reacted with 6 pound
Example 2
moles of strong hydroxyacetic acid in the man
The same procedure is followed as in Example 70 ner previously described, it/ is within the realm
of possibility that all the hydroxylacetic acid
1, preceding, except that 50% more of hydroxy
radicals might ultimately be combined into the
acetic acid is used, i. e., approximately 1,000
monomeric’ form. The hydrolysis of the blown
pounds of hydroxyacetic acid, or sufficient .for the
castor oil would result in the formation of glyc
presence of an OI-I(CH2COO):H radical for each
ricinoleyl radical originally present.
75 erol, and one pound mole of glycerol could com
rbineib?itli‘ qtnieemoles-waitiiifdroxyaceticii acid. >
:;radicalsizpresentzpi'iornto dirastioroxfdationi ‘being
The other ‘3 pound molesot hydroxyacetic acid.
couldthen combine with the 3 pound moles of
*biow'nl acids; termed"
airlea'st 211to~ 1 andnot'moi'e Tthan 3213021‘; ,7
hydrolysis orj saponi?
i‘acetylated' rdrasticallyeoxidized caster oilce-Hthe
ratio ‘ofxmonoineric hydroxyacetic acidtm ricini
oleicsacid radicalsipnesent iprior itovdras?e oxidah
cation; ' Witl'i this fact'ilii'i'" mind; ‘it- is obvious that
_ ‘ ~
- 2.. A- new ‘compositional-consisting‘ of: a2 hydroxi
ttached? ii?li's'nece‘ssary
‘tel-describe the iiwenti‘onf-inmolar ratios df'liiii?
droxyacetic acid‘ to‘ ri‘cinoleic ~~aeid~ - radicals orig
inally present. _ Actualim lot course, ‘the iricinoleic
tiom "being at leastvt'o‘l and not more-than: 3
acid is present in combined form, but this is
perfectly obvious, in view"'of"'what has been said.
- 3. Anew
' direvious" reference-has
acetylated ,drasticallyroxidizedz :c'astor'» oil; the
7 ratio >01’: monomeric hydroxyaceticacidmadicals
:made: to certain
to ricinoleic acid/radicals present prion to: drastic
Vspeci?cihydroxyacetylated derivatives of blown
micinoleic, acid -componnds-. ., These additional
oxidation being 2*to>v1-.
I members include bl'ovizn,d-iiiicinoleimblownnriormh 15
> ‘
4. ~. Anew composition; aeonsistingnofiai midway
ricinoleina:‘supergzlycerinated blown .oastor oil,
acetylated drasticallyéoxidi-zed caster; 4iil5_;.;_~the
rib-73;, .castor oi}v whic'l'i. has been blown ‘and ‘then ’
lsuperglycerinated; as .diiierentiate'di from: one
“ratio- of- monomeric“ hydroxyacetic :acid radicals‘
to“ ricinoleic; acid‘radicals-v ‘present-prior: toqdisas
“which; is ‘supecglycerinatediand .themblown, ‘ and
tic oxidationbeingrzl/z toil;
also blown ricinoleic acid and blown polyricin .20
iT-he,~-:~herein rdeseribed - ‘chemical: compounds: or
3 ‘ pnoductsaineroi distinctrvalue ass af-break inducer
-5. news-composition, consistingrota hyd-isoxy
acetylated; ‘drastically-oxidized; (caster -:oi-ll; ~ the
ratio; of monomeric hydromacetic v‘acid radicals
to'ricinoleic acid: radicals :present > prior ,to-drastic
in. the doctor treatment of gasoline or the like,
as ‘described.
S-. Patent No. 2,157,223, to
Other additional
oxidation being 3 to! ill
‘ I
16.. Inicthe manufacture of- the compoundbde- V
scribed in-cIa-im1 1,. the steps-oi (a) drastically
oxidizing: :aq =ricino1eic1 acid: compound- selected
f-rom: the-v class“ consistingrof: blown castoit :oil,
uses‘ include. application::asjplasticizera, in: plas
.t;i_c_s;',_ ‘synthetic .resins;,jetc., {and ‘particularly in
the‘ acetate’ type; 715e,, the" cellu-loseacetate; vinyl
blown triricinolein~,:b1own ‘.diricinol-ein, vblown
30 monoricinolein; blown‘ staperglycerinateck castor' ‘
oil‘, superglyceninated blow-n1‘; castoac{\oili blown
- Having thus:>deseribed our inventiomrwhat we
claim as'r-newvand- desire-to
, secure,,
p by
'rici'noleic acid’, blow-n. polyiii-cinoleic acid; and
blown caster oilestolides; and: “(\b) .hyd-roxyacet
1,. Anew composition, consisting of V a: rhydroxyl
ylating said: aforementioned:drastically-oxidized
acetylated drastically-oxidized? fricinoleic a ka'ci‘d 35 'ricinoleicwacid compound; thearatio- of: mono- ‘
compound selected‘ from.‘ the" ‘class? consisting‘ of
meric hydroxyacetic acid towricinoleic-acidmadk
,cals‘ vpresent prior to'drasticIioxidation being’: at
' blown fcastor- oil, blown 'triricin'olein, ‘blown ‘dirii
cinoleimLblown: monoricinoieinr, blown superglyc
. _~1east‘2-to::1‘and netmor?thandizo 1'.‘
‘animated’, castor oil, :superglycerinatedz blown leas
t‘orr 0111-,~ blown ricinoleic acid; blownipolyniclnoleic 40
acid,-,. and blown roaster oil; estolides; the iratiowof
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