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Патент USA US2134388

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Patented ,_
Y " 1UNlTEo
. I I‘ _ Q rrarnonorj alz??lgmm
. ,Glidden Company, clevelandhohio, a corpora’ " .
‘ ‘a tion of Ohio
'No Drawing.‘ Appllcation‘Aprll 2, 1935. We.»
Renewed‘ March 26.11am;j
7 v
10 Claims. “('ci. ‘260419;
October'25, pending application Ismail #11343, ‘med ‘March
I This application is a continuation in part of.~ my I‘
applications ‘Serial #749,991, ?led
1934, and Serial #113473, ?led March 19, 1935.
19, 1935, I 'havetdisclosed that this reactionnis
generic'for phenols.
This invention relates to the esteri?cation of
5 phenolic hydroxylgroups with high-boiling, rela-‘
' tively unreactive organic acids, and has particular
ing such esteri?cations whereby such‘esters are
obtained economically and successfully. In. par- '
10' ticular, it refers to a method of esterifying phe-.
nolic hydroxyls with mixed, anhydrides of high
V .
vhydride'of a'high-boiling and alow-boili'ng car‘ .
I "
boxylic acid; ‘and that this reaction islikewise
generic for all-phenolic hydroxylgroups whetherv ‘ ' > I
in freeph'en'ols'or in phenolic-resins.
‘By a higliéboili'ngcarboxyliczacidisnieant‘in 10
the foregoing“ and in the claims sin-acid of, this
and low-‘boiling acids. under such conditions that
low-boiling acid is formed anddistilled \O?, leav
ing an ester of the high-boiling"_acid. v _.
prepared by'the action on a phenol of'a mix'edané v5v
reference to a new and novel method for conduct- '
'“‘ ' Ihave‘now discovered that similar esters maybe, . -
' class which boils at above ‘200°.'centigrade,at at-.
' - '
mospheric pressure. Examples offsuch acids are
rosin,v linseed oil and otheroil fatty acldsrstearic
In the; production of phenyl esters, ‘various ' ' ._ ‘acid,
‘methods havebeeri used.v [Withthe active low
benzoic acid. ,This is, of course’, not‘ a 15 ». a
list of the acids I havefouncl tobe of ‘ w
molecular‘weight acids such as acetic acid,.the ’ value;
esters have’ been prepared by reacting the anhy- By
dride directly withgthe' phenol, in the presence of going and in the claimsis meant an-‘acidof this a ,
' 20 a condensing agent suchas caustic soda. 5 The
vclass'~wrlch_ boils at below 190“ centlgrade at at- 20. ‘
f ester is then separated from thereactionmixture > mospheric pressure. Acetic ‘acid is the acid of this} 1
' by any available method.
class which‘ has beenfoun'd to havethe greatest
As the molecular weight of the acids increases,“ value,
although propionic and > chloroacetic -__acid
In the case of~_,,the '
‘their reactivity ’ decreases.
25 straight chain saturated acids, this is particular- ‘
‘are likewise
1y true; and the anhydrides of acids with ‘more
than '1 carbon atoms (caprylic acid andhigher)
’ It; has beeen foundconvenient to preparethe ‘25,
mixed anhydrides by ‘V distilling low ‘boiling ‘car-j
will not esterify phenols by a simple direct reac
tion under normal operation conditions. It is
30 necessary, in such cases, either torea'ct the phe
nols with the acid chloride, or to react themwith
the acids in the presence of reagents which will
-' form the acid chlorides in situ (e. g. phosphorous
anhydride and a high-boiling carboxylic’ acid.
Preferably one imolecula'r weight. of the de
‘sired "high-boiling ,carboxylic acidv and one mo- 30,
oxychloride, thionyl chloride). “In either case,
35 hydrochloric acid‘ is evolved; this (aid is extremely
boxylic' acid'from a mixture of a'low-boiling acid '
' lecular'weight'of the ‘desired loweboiling acid an- ~ .
' > hydride are placedin thevesseland oneniolecular
weight of, the‘low-bo'iling“ acid from 'which the -
anhydride is derived is distilled oiI while the'e's- _
corrosive, and must be separated from the reac-. ' cape of- substantial amounts of the low-boilingan; 35
tion mass. Furthermore, the acid' chlorides, and
the carrying agentaare rather
expensive; and ~
the commercial preparation of these ’ esters is
40 therefore not feasible. by this method.‘
i ’
It has been ‘proposed-to esterify'phenols at ex
, tremely high temperatures with acid anhydrides;
hydride is prevented.’ ,Thislatter'maybe ‘accom-== '
plished by the‘use'of' asuitablqdisltilling column,‘
the design or ‘which is [well ‘know‘nin' the arts.‘
_ ~ '
To the mixedanhydride' ‘so obtained‘is added
the phenol or, phenolic resin theJesterof which is 40
desired and low-boiling acid is)again distllledifi‘qm.
the‘ mixture 'or solution. {This is-continued until
but, in addition to the di?iculties encountered in
the reaction, it is extremely di?icult to separate -'the esteri?cationfis complete',, 'T'Offcourseg'itfis
45 the esters from the free acids liberated.
In my application Serial #749,991, ?led Octo
ber 15, 1934, I have disclosed the fact that a phe
nolic resin containing free phenolic hydroxyl
groups may be esteri?ed by ‘mixing such a phe
50 nolic resin with a di?icultlyreactive acid, and a
low-boiling organic acid anhydride‘, such_as.ace
I '
obviousthat su?icient phenolvorphenolresin must if; I I
be added‘to react‘with the mixedanhy'dride era 45/» ~
product ‘having a high acid'nunib'er will result. ' If
I an excess'of a phenol is used; of course, freephe- ,: a‘ ‘
n01 'will‘remain. , This-can be removed by vacuuinf" . , _
distillation, or otherwise. If an excess ofphenolic "
resin'is‘ used,va1 partial ester will result. ‘ Bypa'r- i50
tial ester is‘meant one which containsin its com-v
tic anhydride, and heating the-mixture in'such a
manner that the free low-boiling‘ acid formed is
position unreacted or unesterified phenolic rhy
distilled oil, while the anhydride a‘nd’high-boiling
It'is important in, the preliminaryidistillation ;; ' j
_ hich results .Iin the mixed 'anhydridesthat a 55.
65 acid are kept in the reaction zone. In my co
droxyl groups.
excess of high carboxylic acid is used the phenyl
4 quantity of low-boiling acid not greatly exceed
ing one mol for each mol of low-boiling anhydride
or phenol resin ester will contain free high-boil
be distilled. If too much is distilled some excess ing acid. When'this is not harmful or when it
anhydride of the high-boiling carboxylic acid will > may be desired such an excess may be used'with- .
result. Since these anhydrides do not react out departing from the spirit of this invention.
readily or satisfactorily onaccount‘of the fact
A convenientand economical method of pre
that by reaction they leavefree acid in the mass ' paring the mixed anhydrides has been here de~
vscribed. It is to be understood that other meth
their ‘formation should be avoided.
Speci?c examples will make clear the mode ods for preparing these starting materials may
of operation, thus permitingthose skilled in the be used.
Mixtures of high-boiling carboxylic acid in?
art to clearly understand the invention. ' It is to
be understood that these examples are to be stead of'on'e high-boiling carboxylic acid may
.be used to produce mixed esters. In the claims
considered in a purely illustrative sense.
the term ‘high#boiling carboxylic acid” is to be
Example ,1
construed broadly enough to include mixtures, 15
In a vessel equipped
suitablewdistilling ; or-individual acidswhich boil above 200° centi
column are added 239 parts of hydrogenated ?sh
In the claims the term “phenolic body” is used
oil fatty acids and 90.5 parts of 95% acetic'an
for substances containing free phe
hydride. The solution is heated until 44 parts
20v of acetic acid have been distilled,‘ the temper- . nolic hydroxyl groups,‘ ,
'While I have shown but one. example of a
' ature at the top of the still head preferably not
phenol, and one of a phenolic resin, and but one
anhydride, it. is, obvious that other low-boiling
exceeding 120° centigrade. "To' the mixed an
hydride are added IOO'grams of a“ cresylic acid
fraction boiling between 208° icentigrade and acid anhydridesIhigh-boiling acids and phenolic
215° eentigrade. The distillation is then con-> ‘bodies may be used, without departnignfrom the
tinued until‘ substantially alljof, the acetic acid spirit‘ of my invention.‘
In the'cla'ims, ‘the term‘ “heat treating” is de
which can‘result from the hydration of the acetic
anhydride originally lused 1 has ‘been eliminated ?ned as heating under such conditions that the
from'the reaction l?ask, The product is then" low-boilinguacid derived from the anhydride is
removed from thefreaction, while theoriginal
30: preferably subjected to reducedlp'ressur'e to elim
reactantsare retained ‘therein. '
i. . .‘
‘inate tracesof acetic'acid anduncombinedphe
‘N01 claim ‘is made. herein for the products re
nols.- In‘the ?nal ‘stages of ‘the. distillation at
atmospheric pressureit is desirable,v to: raise 'the sulting from the practice of this process. Such
temperature of the reactants to approximately ‘ products are claimed in my cQ-pending applica
_‘ tlon," Serial #749,991, above referred to.
280-290" centigrade.
1. The‘ process ‘of esterifying a phenolic body
-' Example 2
containing free ' hydroxyl ';groups,. which com- _1
‘A mixture of 344 parts of rosin‘having an acid _ prises
heating it,wi_th_a_mixed anhydride of a
number of 163 and 110 parts of 92-95% acetic
, anhydride are heatedas above described until
"carboxylic'acid boiling below 190° C. and a car
boxylic acid boiling above 200° C., to a tempera
', -63parts of acetic acid; have been distilled.‘ To “Iture above the boiling point of the lower boiling
' the mixed anhydride are added 105 parts of phe
nolic resin previously prepared from 100 ‘parts of .
211mm process v‘of lclaimjlfln which,‘ the mixed v
‘phenol and '12 parts of 40% formaldehyde in the *Tanhydride is suiiicient' to completely‘ esterlfy "all
‘ presence of an ‘acid catalyst and. by vknown
free phenolic hydroxyl groups ‘with the" car
acid boiling above 200° C. '
Upon heating a. ‘homogeneous solution ‘is 1‘ 'boxylic
V 3. The process of esterifying phenolic hydroxyls
formed. The heating is continued until-sub which comprises heating a phenolic body having
stantially all of theremainder of the acetic acid
50 derivable from‘ the aceticanhydride I has. ‘been ' free'hydroxyl groups with a mixed anhydride of 50
a carboxylic‘ acid boiling below 190° .C. and,a
distilled. The product is substantially neutral, *"carboxylic acid boiling above 200° C., to a tem
. and soluble in oils.
_ It is advisable for most’ purposes‘ to'purify the
perature" above the boiling point of the lower»
"fester ‘resin from traces of free acetic acid. {This * boiling'acid, and ‘distilling oi the lower-boiling
‘ ‘may be easilyldon'e by subjectingthe resin ‘to ya
_ reduced‘pressure while still hot. Anyuother suit
able means may be usedt'o accomplishthe same
‘acid as formed.
_4. The process of claim 3, in which the mixed ‘
anhydrideis-su?icient tocompletely esterify all
' free phenolic hydroxyl groups with the carboxylic'." '
In Example 2 the‘ amount-of‘ mixedanhydride
00 .used,
acid boiling above 200° C.
is sumcient to substantiallycompletelyes
terify all. the hydroxyl groups of'the .} phenolic
containing free hydroxyl groups which comprises
‘ resin.‘ ' Were a larger amount to .be'used the final
‘heatingit with a mixed anhydride of acetic acid ;
‘product would contain uncombined high-boiling
‘carboxylic acid? in ,they formof its anhydride.
When this is desirable'for any reason such excess
may be used‘ without departing frornthe spirit
of this invention._ When it is desired to esterify
'only a portion of the phenolichydroxylsa cor
respondingly smaller quantity'of the mixed an
hydride'm’ay bevused. ‘A partial ester will be
r 5. Theprocess of esterifying a phenolic body
and acarboxylic ‘acid boiling above 200°“to a '
temperature above the boiling point of acetic
6. The process -of claim 5 in which the mixed
anhydride is suillcientito completely esterii'y all
free phenolic hydroxyl groups with the carboxylic
acid boiling above._200° C.
materialsithat theflow-bo‘iling anhydride should
7. The process of esterifying a phenolic body
containing free hydroxyl groups which comprises
heating it with a mixed anhydride of aoeticacid
be used to an’amount substantially equal molec
75 ularly to the high-boiling carboxylic acid.’ If an
perature above the boiling point of acetic acid;
formed in this case.
It is apparent for the greatest, economy of
and a carboxyllc acid boiling above 200° to a tem
and distilling of the acetic acid from the reac- -'
tion mixture as formed.
10.. The process of esterifyinz a phenolic body ‘
which comprisesheating it with a mixed an- ‘
8. The process of claim 7 in ‘which the mixed hydride of acetic and oil fatty acids to a tempera
anhydride is‘ sufiicient ‘to completely esterify all ture above the boiling point of acetic acid. dis
free phenolic hydronl groups with the carboxylic tilling of! acetic acid from the reaction mixture. 5
acid boiling above 200° C.
- .
as formed, the‘ mixed anhydride being present
9. The process of esterifying a phenolic body in such quantity that the high-boiling v‘portion
which comprises heating it with a mixed an
thereof is suiiicient'to completely esterify all free
hydride of acetic and oil fatty acids to a tempera
' phenolic hydroxyl groups.
10 ture above the boiling point of acetic acid, dis
tilling oi! acetic acid from the reaction mixture
as formed.
osoan A. ‘mi,
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