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Патент USA US2134429

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‘Patented 0.1.25, 1938 Y
I
e
‘
Mamet
. UNITED STATES PATENT OFFICE
RESINOUS ESTERIFICATION PRODUCTS OF
INNER ETHERS AND METHODS OF MAK
ING SAME
‘
‘
Kenneth R.‘ Brown, Tamaqua, Pa., assignor to
’
Atlas Powder-Company, Wilmington, Del., a
corporation of Delaware ~
No Drawing." Application Mal-en 11, 1938,
Serial No. 195,380
‘ 21‘ Claims; (01. 260-8)
.fId‘his invention relates to a new type of syn- may contain such non-functional substituents as
‘thetic‘ resin,‘and to the method of ‘making‘the’ are compatible with the ring formation and do
same, and more particularly‘it relates to a novel not prevent the resinifying esteri?cation of the‘
resinous material comprising ‘the esterification- hydroxyl groups during the reaction. The non
product of a resinifying polycarboxylic ‘organic ‘ functional substitution may be performed on the 5
acid, either alone or in combination with a fatty " inner ether or on the hexahydric alcohol before
oil acid, i._e.,‘ an aliphatic long chain saturated or
unsaturated monobasicj acid, and an inner ether
derivable from a straight chain hexahydric alco-
inner‘ ether‘ formation. ‘In this way, the proper
ties of the resinous esteri?cation product may be
varied, ?rst, by control of the number of esteri
. loholbyintramolecular condensation.
'
~
‘
This application is a continuation of my prior
‘ . ‘ applications,
Serial Nos. 758,865,
758,866,
758,867 ?led December 22, 1934.
?able hydroxyl groups in the polyhydric inner 1o,
ether and, secondly, by the character of the non-
and
~
‘
functional substituent.
‘
‘
‘
The inner ethers may be de?ned as cyclic car
One object of my invention is to provide a ‘ban-oxygen compounds containing one cyclic oxy-‘
15, synthetic resinous product of novel characteris- gen per ring (known as an oxido ring) and derived 15
‘ tics and constitution which‘ has wide applicability
from a hexahydric alcohol by intramolecular 0011-
in the‘ industries and‘ great utility in plastic and
densation. If only one molecule of water is re
coating compositions.
moved
U
‘
‘ '
‘
‘
_
"
by
the, intramolecular
condensation,
<
a
Other ‘objects, including the "novel ‘method of " monoanhydro derivative containing only one car
20, making the resinous product, will appear from a‘ hon-oxygen ring is obtained. If the condensa- 20
“ consideration of the‘sp‘ecification and claims.
‘ -
tion ‘removes two molecules of water from the
‘This invention contemplates “the production 01" alcohol, a dianhydro‘ compound containing two
resinous materials comprising the esteri?cation
carbon-oxygen rings, which may or may not be‘
products ‘of a resinifying polycarboxylic organic
of the condensed type, is obtained. The number
25 acid (a polycarboxylic organic acid capable‘v of
‘ withstanding resiniiication temperatures without
decomposition] prior to resin formatiom'and an
of members in the ring and the number of oxido 25
rings in the inner ether which are Possible de
pend upon the‘ arrangement of the , hydroxyl
inner ether of astraight chain heXahydric al- 'gl‘oups in the Chain of the hexahydl‘io alcohol
coho].
30
“
d
‘ "
I
j
‘
,from which the inner ether is derived.
The resinifying polycarboxylic organic acid may
“ be either aliphatic ‘or aromatic, or a mixture of‘
two or more polyca'rboxylic acids of either or both
classes may be employed. The‘ anhydride may
be used in;place ‘of the acid and the term “poly35. carboxylic organic acid’,’ as employed herein ineludes ,the anhydride‘ thereof. As an example of
‘.the aromatic polycarboxylic.‘ acids, the use of
which in many instances" is ‘too be preferred,
phthalic acid may be mentioned. In the case of
40 an aliphatic polycarboxylic acid, the acid may be
saturated‘, or unsaturated, and may or may not
If the
hydroxyl—bearing carbon atoms through which 30
the intramolecular condensation takes place are
separated by only one carbon atom-,fi-membered
carbon-oxygen rings only are possible; if they are
separated by two carbon atoms, S-membered rings
are obtained; vand if they are separated by three 35
carbon atoms, then G-membered rings are formed.
Whether in any particular intramolecular con
densation a mono- or di-anhydro compound is
formed depends generally upon the conditions of
the reactiomancl it is possible to‘form dianhydro 40
compounds containing different membered car~
contain » hydroxyl ‘groups. ‘Succinic, glutaric,
bun-oxygen rings, for example, a compound con
adipic, suberic, azelaic, pimaric, malic, tartaric,
taining‘a 4- and a 6-membered ring. As a result‘
4- maleic, fumaric", mucic and citric acids are ex-
3. amples of ipolycarboxylicialiphatic acids which
are
applicable for
use.‘
'
,
,
of the condensation of the hexahydric alcohols, 45
a mixture of the various inner ethers may be
formed.
‘
d
.
‘
.
\
,
The ‘inner- ether. of the straight chain hexahy- ., Of the hexahydric straight-chain alcohols from
“ \dric alcohol forming the esteri?cation product which the inner ethers arederivable, mannitol
50 with the polycarboxylic organic acid may be em- and sorbitol, due to their availability, are espe- 50 r
‘
ployed directly in the reaction; or advantageously
the inner ether may be formed under‘ the condi-
cially suitable. In order that the structures of .
certain of the inner ‘ethers may be illustrated,
tions of and‘during the esteri?cation reaction by
utilizing the polyhydricalcoholas the initial ma-
some ‘of these‘which maybe formed from the
‘hexahydric straight-chain alcohols have been
‘ ‘55 ,terial.
The inner-ethers maybe unsubstituted‘or
chosen as typical.
,
l
2,134,429
2
The 4-membered oxido ring, known as an oxi
dopropan ring:
CHr-‘CHOH~—CH—(CHOH)|—CH|OH
O/
O
The 5-membered oxido ring, known as a furan
ring:
CH:—(OHOH)z—CH—(CHOB)—-CH;OH
CHOH
The S-membered oxido ring, known as a pyran
ring:
CH|—(CHOH);——/CH—~CH:OH
/
//
example, by simple heating at temperatures of
140° C. or upwards. Preferably, however, the
heating is carried out in the presence of a de
hydrating catalyst of either a basic or acidic 30
nature at temperatures of 140° C. and upwards.
The ethers. when formed, are preferably puri
CHOH
fled by vacuum distillation.
When the hexahydric alcohol is employed as
onon
CH
40
may be obtained from the polyhydric alcohol
under any suitable dehydrating conditions, for
0/
or
35
alcohol may be used and the inner ether formed
during the course of the resin-forming process.
The same type of resinous product is formed in
both cases, since upon saponi?cation, an inner
ether is obtained from both resins and the hexa
hydric alcohol cannot be regenerated in the case
where it is utilized as the original reactant. As
the most convenient method of obtaining the
inner ethers is by internal condensation of the
polyhydric alcohol, usually the intermediate step
involving the preparation and separation of the
inner ether is dispensed with, and the polycar
boxylic organic acid is reacted directly with the
polyhydric alcohol. If desired, the inner ether
20
30
may be mentioned that mannide and isomannide
have been used for two de?nite chemical indi
viduals, but I prefer to consider the terms “itan"
and “ide” as descriptive of the classes of mono
and di-anhydro ethers of polyhydric alcohols.
As pointed out, the inner ether may be em
ployed directly in the reaction with the resinify
ing polycarboxylic organic acid, or the hexahydric
CHOH
15
ether: thus, mann-itol, mann-itan, mann-ide;
dulc-itol, -itan, -ide, etc. In this connection, it
CHOH
CH-CHzOH
The dianhydro compound containing two con
densed S-membered oxido rings, known as furo
furan rings:
45
the original reactant, the evidence points to the
fact that the intramolecular condensation form
ing the inner ether takes place before the hy
droxyl groups are esteri?ed, but the esteri?ca
tion may possibly take place ?rst. If the latter
does occur, however, it is to be understood that 40
it falls within the scope of the invention and
within the claims. The claims reciting the
esteri?cation of the inner ether are to be under
stood to include not only the use of the inner
ether as the original reactant but also the use 45
of the hexahydric alcohol from which the inner
- ether is formed.
0/
The useful resinous properties of these esters
derive from the fact that they are mixtures of
or
o
noon
on,
on
on,
o11—'—ono11
It is to be understood, of course, that the
structural formulae given above showing the
various rings are merely by way of example, and
that the ring formation may take place between
60 any of the other non-adjacent hydroxyl-bearing
carbon atoms of the alcohol. With most hexa
hydric alcohols, and particularly with those espe
cially applicable for use, the inner ether con
taining the furan ring appears to be the main
product obtained as the result of the intramo
lecular condensation reaction under usual condi
tions, although smaller amounts of the other inner
ethers of both the mono- and di-anhydro type
may be present. The inner ethers of the various
70 hexahydric alcohols may also be designated by
names derived from the stem of the parent alco
hol by adding the characteristic suiilx, “itol”, for
the parent alcohol; "itan" for the cyclic mono
anhydro derivative or inner ether; and “ide”
for the dianhydro derivative, the dicyclic inner
large aggregates built up by esteri?oation from 50
much smaller polyhydroxy inner ether and poly
basic acid units. In the elaboration of these
large molecules, condensation takes place with
the formation not only of straight chains, but
also of branched chains and so-called tridimen
sional molecules which result from the tying to
gether of two or more straight or branched
chains by a polybasic acid link.
It is known that the reactivity, and particu
larly the esteri?ability, of hydroxyl groups is 60
aifected and diminished by steric hindrance, and
that in general the reactivity of functional
groups such as hydroxyl or carboxyl decreases
with increase in the size of the molecule to which
they are attached. Accordingly, the use of sto 65
ichiometric proportions of acid and hydroxyl in
the production of these resinous esters does not
lead to neutral, completely reacted preparations,
but gives mixtures of large molecules containing
uncombined hydroxyl and carboxyl groups. 70
Also, this effect is more pronounced, the more
hydroxyls, and hence the more reactive posi
tions, in the polyhydroxylic starting material,
since
tri-dimensional
molecules
form
more
readily and have in their structure hydroxyls 75
' mm»
“andcarboxy1s3which are‘ inqqdnger ‘ in‘ a posit'fdn parent‘ polyhydric alcohol therein; or where’jde- '
,
“
to react. PSO that” where; tor'instance, hex‘ahy
-
h
,
3‘
‘ rivatives ‘of more than one polyhydric alcohol are
dric straight chain‘alcoholsare usedaslstarting ‘present in the resin, ‘the‘equivalentnof resin-is
t
materiaLonly ‘aiffraction‘joi the total ‘hydroxyl‘ ‘the ‘weight ‘of resin ‘ having; therein the‘ esteri?ca~ ‘
j. presentds active ‘in the resin-‘forming‘esteri?ca- ’ tion product of inner‘ethers, the sump: themol
‘
‘f tied-{1h the ?rst place; the original ‘six hydroxyls
, ‘fractions of which is one,‘ "
: are diminished by two; dueato ‘the formatlodof
, ‘ ‘the‘tetrahyd‘ric,monoanhydro‘derivative, In‘tlie,
.‘
‘second ‘place, reaction "proceeds ‘ at r such ‘ a ‘ rate
,‘
,
. ’ ‘
‘
“ ‘ Thefact that. the e'ste‘rificatlon reaction does,
not involve all‘the, normally esteri?able‘ hydro‘xyl‘ .
"ligroups' of ‘the hexahydric "alcohol when that com-<9
‘andfin
a‘ ‘manner ‘that, under“ the conditions pound is‘ employed as the initial reactant, ‘and
.‘ such as 'de‘scribedtln' ‘the examples, j‘only ‘in ‘the the fact that‘jupon sappnification of the esteri»
‘neighborhoodot 21/2‘or thefremalni‘rig “4 normally‘ ?cation‘ product,‘ "the inner etherand not the
esteri?able ' ‘hydrox'y‘ls‘, can "be" reacted‘. Increas
hexahydric alcohol, is recovered,‘ show clearly
ing‘ the prcportion‘fof organic‘ acid used above that‘ ‘ tinder‘. the ‘conditions “ of esteri?catijon, the
515' this amount,favorsitheformation ‘of more pan
hexahydric alcohol undergoes an intramolecular
'
‘ tially‘ ester‘i?ed" phlycarboxylic "organic acid‘ resi
dues, “and “hence ‘ a :‘resirious‘ester “of higher
condensation ‘tc‘form an inner ether, ‘which prod
ess‘?obviously reducesVthe number‘ of ,hydrOXYl '
‘ ‘ acid‘ number‘witho‘ut increasing effectively ‘the
‘
.1720
‘ :
groups in the‘niolecule. by two for each o‘xido-‘ring
‘Hformed.
l‘ ‘ In‘the ‘preferred, method “of ‘ manufacture
‘ ‘where ‘a resinof low ‘acid ‘number 'is‘d‘esired,‘ the
fhexahydric alcohol‘or the innerether and the
organic__ acid are‘erh‘plo‘yed in proportions ‘so that
‘
‘
V
,
,
a
‘
' ‘ The‘ esterification reaction‘maybe carrlediout‘
in any. suitable manner and, at any elevated“
temperature which results in the formation of
resinous; 'esterl?ed ihner ‘ethers. The“ optimum
the amount‘ of‘ acid: is ‘equivalent‘to ‘not ‘more ‘temperature for the“ reaction will depend upon \
than about Lone-half off" the totarhydroxyls in . the ‘reactivity of the ‘organic acid‘ qr‘, acids enl
the hexahydrie alcohol, ‘ hence, ‘aboiit‘ three‘ car
ployed,gand the‘ 'mixture‘ of, the‘ reactants‘ is
boxylfequivalents' ‘are used. ‘The proportionfoi’ maintained at the elevated temperature untiljthe
8 acid 'used can‘be advantageously reduced to the esteri?cation, is "substantially epmplete. . The ‘re~
neighborhood‘ofy two and one~guarter carbcxyls. action ,will take place in "the absence of a cata
‘when thelatter‘proportions ‘of’ acid are used in ‘ ‘lyst’, but if‘itris ,desiredjtoreduce, the length of 3'0.
1 the =react‘ioh, the maximum‘esteri?cation ‘ofvthe time required for the reaction, any of the usual '_
‘ hydroxyls is generally attained‘with the mini‘ ?evsteri?cation ‘catalysts ‘such as, boric anhydride
‘ “ ‘mum amount of uncombined'andpartlally esteri I ‘or ‘zinc‘i‘dust may beused. ’ We'havefound ‘that
‘ ?ed polycarboxylic acid.
‘f _‘j
.
‘ If bnl‘the other‘hand, Bl resin 01“ higher'acid
the‘ quality‘ for ‘the ‘resin may be‘jl ‘improved by
carrying out the reaction inani'nert‘ atmosphere,
s5
number ‘sheared; the amountoi’ acid employed‘ e. g.,\ in ‘carbondioxide' o‘r?nitroge'n.‘ ‘Further
‘ ‘may befincrea‘se‘d torn'otmore .than‘about four
‘ aoid"'equiyalent‘s per rn'ol‘r‘of‘ inner ether. ‘If
» ratios‘greate‘r thah about'4 acid‘equivalents‘ ‘are
‘r
employed,‘
the jresinous product ‘is
,
, the utility‘ of H,
I40
1.‘ impaired» due to‘larger amounts orun‘combined
more, we have found‘itdesirable in certain‘ cases
to‘, ‘remove excess of volatile ingredients ‘andv .un
desirable volatile ' lay-products ‘formed during the
reaction , by letting with inert‘jgases suchas
carbon dioxide" or nitrogen. ‘ ,
' ‘
ahd"'j‘partially" esteri?ed} polycarboxylic acid.‘ ‘ . ,Theprop'erties of these resinous"esterification
‘ These carbo'xyls ‘are ‘distributedibetween uncom‘r
products depend on‘the natureand proportion‘ of v.
‘bin‘e‘d aids and the free ‘carbo‘i'iylsof"thepartlually" the'react‘ants, and'on the ‘methodof, preparation.
esterij?ed ‘polycarboxylic i acid‘ residues,‘ ‘both of 'Ifhus' the color, solubility; behavior,‘ mechanical
which?contribute.to‘ithe‘ high acid number.‘ , The
properties, chemical ls‘tabillty,_.etc;;‘ maybe al
Y ‘higher .thefem'oun‘t. or ; acid “ employed ‘ever, the _‘ terejdhby using‘ different polybafsic aoi'dsgj Malelc,
l 1“
react evenr‘less ‘than the‘ optimum‘ amount‘,~o‘i1acid
., 5.5.
‘
a;
‘l ¢
.
‘ combining ratios‘pointedj‘out above, the higher a for example, ‘gives very light,‘ water~soluble ma; "
. will‘ be the" acid number" of the resin 'duenotlonly terials; and phthalicgives products‘havih'g higher
to theincreaise, inhthejamo‘unt of excess unreacted solubility‘ in hydrocarbon. solvents.’ '‘ Merely "by 50
acid but‘ alsoto the" larger ‘amount of partially . varying the heating time,‘esters ran'gingin chars
esteri?ed lvpolycarboxfylic‘ acid wresidues present; ‘ ‘_ ' acter‘ from. soft, readily.‘ soluble, highlya‘cid nia
Under certain circumstances, we‘may purposely I renal‘ ofl‘low ‘average molecular weight, to highly ‘
polymerized; hard, insoluble-,jv-linfusible ‘products
to ‘obtain‘materialfhaving averylow' acid number may beobtained. ‘In making esters of thistypr,
and somewhat different solvent“ properties than the‘ latter stages‘of the reaction‘, are rpreferably
55,.
the typicall‘lesteri?cation product, ‘oritoreduce carried out‘by heating or curihg inoven‘s. fI'hese ‘ >
j‘ l: ‘to 'avminimum the‘prop’ortion of an expensive ‘resinous esters may be‘ ‘usedfeitherjalone, mixed
with other, materials, and/ordissolved' in‘ suit:
‘V60 thus;
able ‘solvents, foruseYin eoatingfcompositions,“
1 “Thebe‘proportions‘
regulated according
‘ of‘ the components
‘to .therequirement's
used"
ingredient.
"
' r
'
‘
‘l
impregnants‘, ‘binders,f_ adhesives,‘ ‘ insulating“ mas‘; .
“ of thereaction‘, or the properties of the‘ ?nished , terial, molding“ composition‘. and _ the like. They,
‘product, any undesirable excess of anyojfhthe may be rnixedfwith dryihgh‘ils in-the‘ preparation
‘ 1 “.ingred‘ents; being removed by jetting “or; extrac- .
tion‘ with suitable solvents, it being. understood name; A particularly wide application ‘is-‘in the‘
‘ that thiswremovaltaffectsz onlyitthetvuncombined nformulation o‘f lacquers, usingfthere'sino'u‘s’ester,‘ I
‘’ ingredients ‘and does not " diminish‘ “the ' acidity
@due‘to the presence of'partially»v ‘esteri?e‘d-poly
;
“
{basic acid residues. tFor v'mosti vpurposvespit will
70‘
“
be desirable ‘to prepare‘a ‘product which'fco‘n
.
.
,
.
a“ cellulose Yderivatlve such “as the nitrate; ace
tate, or ethyl or, benzyl ether‘, agsolverit',‘ a plasti-V.
esters are heat hardening‘; theyare v‘aluablein» m
tains less‘ than one and preferably lessthan' gradients in baking'enamels'.“ ' otherisimilar ap-'‘
, ‘onelhalf equivalent‘ of- ‘un‘combi‘ned, acid" per‘, plications willoccur ‘toftho‘se having acquaint~
equivalent of resin. “By “equivalentfof resin" ‘is
“ ‘meant thew‘eight of r‘esln‘having the'esterl?ca
“75
tion‘productyof "1‘ ‘molof the inner ether of the
.,
Since] the resinous .
Where phthalicfac‘id'isvone cry-the‘v reactants,
the properties otith'e resin may “be modi?ed by‘
‘
4
2,134,429
the replacement of a portion of the polycar
terial; in a typical instance, the .m'ol ratio of
used herein, includes the air-drying acids, and
the long chain monobasic organic acids contain
ing at least twelve carbon atoms and not more
the monobasic acid to polycarboxylic acid may
than one ethylene‘ linkage.
If a resin of the air-drying type is desired, a
portion of the polycarboxylic acid (which in the
production of air-drying resins should comprise
10 phthalic acid or anhydride, either aloneor in
and the viscosity in solution decrease while the
solubility, the compatibility with oils, the soft
ness, and the weathering resistance increase. By
choosing suitable proportions of the 'polycarbox
ylic and monobasic acids, the properties of the
admixture with the resinifying, aliphatiopoly~
product may thus be varied-from those of an
almost insoluble and infusible resin to those of
seed oil, perilla oil, China-wood oil, menhaden
oil, and thelike.‘ These acids may be employed
in pure form, mixed, or containing small amounts
of non-drying, aliphaticnacids. '
"
In the production of ‘air-drying resins, the
ratio of polycarboxylic'organic acid to air-drying
acid employed in the process may vary widely,
depending upon the properties desired in the
resinous material. Thus, with a large proportion
of ‘air-drying acid and a small amount of poly—
carboxylic acid, a productv is obtained which has
properties clearly ‘related to that of a drying
oil. By increasing the polycarboxylic acid and
decreasing the air-drying acid, the viscosity of
the resinous product is increasediand its solu
35 bility is decreased until, with a very small
amount of air-drying acid and a large amount of
polycarboxylic acid, .an insoluble and infusiblc
product is obtained. In the preparationof resins
suitable for synthetic enamels, for instance, a
' satisfactory inol ratio of linseed oil acids to
phthalic anhydride is in the
.60 to .80, preferably .75.
neighborhood of
I
.
Furthermore, valuable properties are imparted
to the inner ether resins described herein where
45 the polycarboxylic ‘ organic acid, comprises
phthalic acid or anhydride, either aloneor. in
admixture‘ with the resinifying, aliphatic poly~
carboxylic acids set forth'above, when a mono
basic, semi- or non-drying acid is reacted in
place of a portion of the polycarboxylic organic
acid.
‘
‘
k
The monobasic acids contemplated for use are
long chain acids containing at least twelve car
bon atoms and not more than one ethylene link
P age. The saturated acids, including those whose
formulae may be represented by CnHZnOZ, where
n is at least 12, for example ‘lauric, myristic,
palmitic, and stearic acids, as well as the un
saturated acids containing only one ethylene
60
be from .3 to .9. As the proportion of the mono
basic acid is increased, the tendency to gelation
carboxylic acids set forth above) may be re
placed with an air-drying acid. As examples of
air-drying acids may be mentioned linoleic, lino
lenic, eleostearic acid, and other acids character
ized‘ by a plurality of double bonds and the prop
erty of drying by atmospheric oxidation. Such
acids may be obtained synthetically or by saponi
?cation of the common‘drying oils-such as lin
20
' ing on the properties desired in the resinous ma
boxylic acid by a fatty oil‘ acid, which term as
linkage, for exampleoleic and ricinoleic acids,
fall within this class. These acids do not possess
the non- or semi-drying oils.
-
,;
.
,
It is known’thatin fatty oilacid- odl?ed
glycerol base resins, .whoselgreatest usefulness
lies in the ?eld of coating compositions, the vis
cosity decreases as thefatty oil-acid content of
the resin is increased. Coating compositions,
particularly pigmented types, demand the use
of resins having viscosities highenough to keep 20
the pigment satisfactorily suspended during stor
age.
This requirement sets an upper limit to
the fatty oil-acid content of technically useful
resins. A high ‘drying acid content is, however,
desirable, since it confers increased weather re 25
sistance and quicker and more extensive drying
powers on the ?nished composition.
Similarly,
> high semi- or non-drying oil-acid content con~
fers increased weather resistance in the ?nished
composition. :Furthermore, resins prepared from
bility and cheaper solvents.
,
The use of polyhydroxy cyclic inner ethers in
the preparation of fatty oil-modi?ed resins 35
greatly increases the viscosity in ordinary lac
quer solvents, and thus permits the preparation
of technically valuable resins of much higher
fatty oil-acid content than has hitherto been
The air-drying resins are particularly appli 4.0
cable in formulating synthetic enamels compris
disclosed.
'
1
,
I
-
ing the resin, a solvent, a pigment, and a slew.
tive, with or without a plasticizer. The semi
or'non-drying oil-modi?ed type resins are par
ticul‘arly applicable in .the formulation of baking
enamels comprising the resin, a solvent and a
pigment, with or without a plasticizer. The fatty
oil-modi?ed type‘ resins are also particularly use
fulin the formulation of lacquers, and for this
purpose, may be combined with plasticizers, col
oring agents and cellulose derivatives of the type
previously mentioned. They may also be ‘used
in paints, varnishes, binders, adhesives and im
pregnants with the usual ingredients. Other uses
of the fatty oil-modi?ed resinous materials, and
the incorporation therewith of other materials,
will naturally suggest themselves to those famil
iar with the ?eld.
'
'
The following speci?c examples are given to
characteristic air-drying properties. Theymay
vention and the character of the products derived
therefrom.
vegetable, such as castor oil, coconut oil,’ olive
oil, lard, tallow, soya bean oil, corn oil, cotton
100 parts of phthalic anhydride are mixed with
60 parts of mannitol, this ratio corresponding
to 4 equivalents of/acid per mol of hexahydric
alcohol. The dry mixture is introduced into a
reaction vessel and quickly heated to 128° C.,
cottonseed oil being known as beta fat.
The
monobasic acids contemplated herein may ‘be
70 used either pure or in the form of mixtures,
which mixtures may contain small amounts of
glycerides and more-unsaturated acids.
The ratio of resinlfying polycarboxylic organic
acid to monobasic semi- or non-drying acid em
75 ployed in the process may vary widely, depend
(it)
illustrate the manner of carrying out my in».
be obtained synthetically or more conveniently
by saponi?cation of the natural oils, animal or
seed oil, and the like, the acids derived, from
30
high semi- orinon—drying oil-acid content reac
tion mixtures have the advantage of high solu
'
.
Example 1
causing the mixture to melt. . The molten mass '
is heated at the rate of 21/2° C. rise in ?ve min
utes until a temperature of 177° C. is reached.
The rate of temperature rise is then 'lecreased
to 1'’ C. in ?ve minutes until a temperature of
218"’ C. is reached.
The resulting product is
9,134,429
then. poured" into a mold.‘ The resin is dark
brown in color and hasa softening point of
112°
C.
>
-
After twenty more minutes of heating at 160° C.,
gelatinization takes place. The product is a light
-
Example 2
brown resin.
organic solvents. Its softening point is 89.5° C.
Example 7
One mol ofv sorbitol and one mol of citric
acid are heated to 120° C. This ratio of sorbitol
and citric acid corresponds to about 3 equivalents
of acid per mol of the hexahydric alcohol. The
mixture is stirred in an atmosphere of carbon
and held‘at this temperature for four hours,
whereupon it is cast. During this last heating
period, the reaction mass is ‘jetted with carbon
dioxide during the heating. The temperature
dioxide. The resin is ‘dark brown in color, has
of-the reaction mixture is raised to 160° C. in 15
‘an acid number' of 43.4 and a softening point
of 89.40 C. This resin is insoluble in ethylene
dichloride and in ethyl and butyl acetate; par
tially soluble in acetone and toluol ‘and soluble
20 in a mixture of alcohol and toluol.
the course of an hour. The heating is continued
at 160° C. until the reaction mixture becomes too
viscous to stir. This will require about one hour.
‘The product is light brown in color. It is soluble
in water but is‘ insoluble in the common organic 20
‘
Example 3 '
solvents.
i
91.0 parts of mannitol are intimately ‘mixed
‘with 98 parts of maleic anhydride, this ratio cor
responding to 4 equivalents of acid per mol of
25
hexahydric alcohol.‘ 'The mixture is heated in an
‘atmosphere of' carbon dioxide to a temperature
of phthalic anhydride is similarly added and
stirred into the mixture.
40
‘
hexahydric alcohol. The temperature of the
mixture is then raised gradually. with stirring
in the course of three hours, at which point the
resin gels. The resin is insoluble in the usual
organic solvents. The resin, when heat is ap
plied, will soften but will not melt without decom
‘
93.2 parts of sorbitol syrup obtained from the
reduction of glucose and containing 7.03% mois
ture are heated to 90°C. in an atmosphere of
carbon dioxide and 50 parts of maleic anhydride
are stirred in,‘ this‘ ratio corresponding to ap
proximately 2 equivalents of acid per mol of
position.
‘
Example 9
To, one mol of sorbitol, stirred and heated in
an atmosphere of carbon dioxide, 1.125 mols
of phthalic anhydride are added at 125° C. This
ratio of acid to sorbitol corresponds to 2%, equiva
lents of'acid per mol of the hexahydric alcohol.
Heating is continued at a temperature increase
to 150° ‘C. in the course of an hour. During this
carbon‘ dioxide. The resin‘is cast. It is a clear,
40
of 1° C. per minute until a temperature of 200° C. I
almost water white, hard mass, somewhat sticky,
soluble in water,‘ with‘ an acid number'of 177.
‘
It forms a dark brown vitreous mass
when cold.
45 time, the mixture is stirred‘i'n‘ an atmosphere of
Example
30
in‘ an atmosphere of , carbon dioxide to 195° C.
hexahydricalcohol.‘ The temperature is raised
50
This amount of sorbitol
and phthalic and maleic anhydride corresponds
to about 4 equivalents of acid per mol of the
vitreous mass, capable of softening on heating.
Example 4
i
‘Erample 8
Onemol of sorbitol is heated to 80° C. and
temperature is raised gradually to 180° C.‘ in 75
minutes, a stream of carbon‘dioxide being passed
into the reaction vessel during the heating pe
riod. At 180° C., gelatinization occurs. The
1 product. on‘ cooling is an almost colorless, hard,
‘
‘
.
one mol of maleic anhydride is stirred in. The
temperature is raised to 100° C. and one mol 25
of 130°C.‘ At this temperature, ‘the mixture
becomes molten and stirring is started. The
35
The product is soluble in warm
water, but is substantiallyv insoluble in the usual
a. 182‘ parts of dry-sorbitol and 148 parts of
\phthalic anhydride are heated in an atmosphere
of carbon dioxide and with stirring to 120° C.,
this ratio corresponding to 2 equivalents of acid
“ 10 per mol of ,hexahydric alcohol. The mixture is
then heated in the course of an hour to 200° C.
15
5
point the resin is‘insoluble in ethyl alcohol.
'
is reached. The reaction mixture is heated at
this temperature in an atmosphere of carbon
dioxide for four hours. At the end of this time,
101 parts of sorbitol syrup produced by the‘ the resinous product is cast in aluminum pans.
reduction ‘of glucose and containing ‘7% moisture,
80.1 parts‘of ‘succinic acid arevintroduced‘ into a
reaction vessel and mixed at a temperature‘ of
55 100° C., this ratio corresponding to about 2%
equivalents of acid per mol of hexahydric alcohol.
The temperature is then raised at airate of 1/_¢_°
C. per minute until ,a temperature of 195° C.
is‘ reached. ‘The product is dark in color,tough
'I'he‘resin has a softening point of about 130° C.
It is sparingly soluble in a 50~50 mixture of alco
hol and toluol and is insoluble in acetone, ethyl
ene dichloride, toluol, butyl and ethyl acetate and I
alcohol.
Example 10
To one mol of mannltol,~1.125 mols of malic
acid ‘(corresponding to 2.25 acid equivalents per
60 and rubbery when hot, and sets to a brittle mass _ mol of the hexahydric alcohol) are added. The 60
at room temperature.
1
‘
mixture is heated in an aluminum reaction vessel
in an inert atmosphere of carbon dioxide until a.
‘
‘Example 6
210 parts‘ of a sorbitol syrup prepared by the
65 reduction of glucose and. containing 7% mois
ture are heated to 110° C. and 168 parts of tar
‘ ,taric. acid monohydrate are stirred in‘under an
atmosphere of carbon dioxide, this ratio corre
sponding to about 2 equivalents of acid per mol
hexahydric alcohol. 1 The temperature israised
'[70 ‘ofgradually,
with stirring under an atmosphere of
carbon dioxide, to a temperature of 160° C. in
the course of two hours, at the end of which
15
time‘ foaming has ceased. The temperature is
held at‘ 160° C.‘for, twenty minutes, at» which
temperature of 145° C. is reached. Agitation is
then started. Heating is continued so that the
temperature rise is 1° C. per minute until a
temperature of 180° C. is reached. Heating is
continued at this temperature for approximately
seventy-?ve minutes longer. The reaction mix
ture will then tend to solidify. The resinous re
action mixture is insoluble in the ordinary or
‘ganic ‘solvents.
It is also infusible.
‘
Example 11
To one mol of mannitol, 1.125 mols of phthalic
anhydride (corresponding. to 2.25 acid equiva 75
6
2,134,429
lents per mol of the hexahydric alcohol) are
added. The mixture is heated in an aluminum
reaction vessel in an atmosphere of carbon di
oxide until the solids melt. Agitation is then
started. Heating is continued so that the tem
perature rise will be 1° C. per minute. When a
temperature of 200° C. is reached the reaction
mixture is held at this temperature for 41/2 hours
longer, the mixture being stirred in an atmos
10 phere of carbon dioxide. The resinous product
is then cast in aluminum pans. It has a soften
ing point of about 106° C. It is soluble in warm
acetone, partially soluble in a 50-50 solution of
alcohol and toluol, and insoluble in butyl and
15
ethyl acetates, ethylene dichloride, alcohol and
toluol.
'
Example 12
To one mol of sorbitol, .281 mol of maleic
anhydride and .844 mol of phthalic anhydride
20 (corresponding to 2.25 acid equivalents per mol
of the hexahydric alcohol) are added. The mix
ture is heated to a temperature of 125° C. in an
0. p. toluol at 25° C. is about 5.6 poises. The
molar ratio of linseed oil acid to phthalic an
hydride was 0.80.
'
Example 15
One mol of sorbitol and 0.625 mol of linseed oil
acid are heated as described in Example 13. 0.66
mol of phthalic anhydride and 0.14 mol of maleic
anhydride are added. The mixture is heated to
200° C. as in Example 13. After a temperature 10
of 200° C. is reached, heating is continued for
four hours.
The finished resin is soluble in V. M. 8: P.
naphtha, toluol, benzol, acetone, butyl alcohol,
ethyl and butyl acetate, and cellosolve.
The viscosity of a 50% solution of this resin
in c. p. toluol is approximately 3.6 poises at 25° 0.
Example 16
One mol of sorbitol and 0.625 mol of linseed
oil acid are heated as described in Example 13.
0.54 mol of phthalic anhydride and 0.274 mol of
adipic are added. The mixture is heated as in
atmosphere of carbon dioxide. At this tempera
ture, the reaction mixture begins to melt and
Heating is continued so‘ that
the temperature rise will be 1° C. per minute
Example 13.
until a temperature of 200° C. is reached.
The viscosity of a 65% solution of this resin
in c. p. toluol is about 11.5 poises at 25° C?
25 stirring is started.
The
reactionv mixture is heated at 200° C. for four
30 hours, the mixture being agitated in an atmos
phere of carbon dioxide during this heating
period. At the end of this time, the resinous
product is cast in aluminum pans.
It has a
The ?nished resin is soluble in V. M. 8: P. .,
naphtha, toluol, benzol, acetone, butyl alcohol,
ethyl and butyl acetate, and cellosolve.
Example 17
One mol of sorbitol and 0.625 mol of China
wood oil acid are heated as in Example 13. 0.81
softening point of approximately 135° C. It is
sparingly soluble in a 50-50 mixture of alcohol
35 and toluol and insoluble in acetone, ethylene di
chloride, toluol, alcohol and butyl and ethyl ace
tates.
Example 13
mol of. phthalic anhydride is added and the heat
ing continued as in Example 13.
40
0.5 mol of linseed oil acid and 0.75 mol of
phthalic anhydride are heated together to a tem
perature of 140° C. with stirring. 1 mol _of man
nitol is added and heating continued so that the
temperature is raised at the rate of 1° C. per
minute until a temperature of 200° C. is reached.
The heating is continued for 4 hours at this tem
One mol of sorbitol and 0.625 mol of linseed
oil acid are introduced into an aluminum re
action vessel. The mixture is stirred and heated
to a temperature of 120° C. 0.81 mol of phthalic
anhydride is added. After these ingredients are
45 added, the temperature is raised uniformly to
200° C. in 100 minutes. The heating is continued
at 200° C. for 3 hours. The incorporation and
reaction of ingredients is at all times carried out
in an atmosphere of carbon dioxide. The heat
50 ing is stopped and the reaction mixture is cooled
to 150° C. under carbon dioxide. At this tem
perature, the resin is run into aluminum re
ceptacles.
The resin is soluble in V. M. 8: P. naphtha,
55
toluol, benzol, butyl alcohol, acetone, ethyl and
butyl acetate, and cellosolve. When exposed to
the action of the air in thin layers such as those
obtained by the evaporation of solutions in
volatile solvents, the resin dries to a hard, tough,
60 insoluble ?lm. The drying action is accelerated
by the addition oi siccatives. The viscosityof a
65% solution of this resin in c. p. toluol at 25° C.
is about 6.2 poises.
65
Example 14
One mol of sorbitol and 0.64 mol. of linoleic
acid are heated as in the foregoing example,
0.804 mol of phthalic anhydride is added and
the heating continued as there described.
The resin is soluble in V. M. & P. naphtha,
70
toluol, benzol, butyl alcohol, acetone, ethyl and
butyl acetate and cellosolve. The resin has dry
ing properties similar to those of the resin de—
scribed in Example 13.
The viscosity of a 65% solution of this resin in
75
The finished resin is insoluble in V. M. at P.
naphtha, partially soluble in toluol, benzol, ace
tone, and butyl and ethyl acetate.
Example 18
40
perature. All mixing and reaction of ingredients
are caried out in an atmosphere of carbon
dioxide.
The ?nished resin is soluble in V. M. 8: P. r
naphtha, soluble in toluol, benzol, acetone, and
butyl and ethyl acetate. The viscosity of a 65%
solution of this resin in c. p. toluol is about 32
poises at 25° C.
Example 19
182 parts sorbitol and 80 parts beta fat (cot
tonseed fatty acids) are introduced into an alu
minum reaction vessel. The mixture is stirred
and heated to 120° C. 145 parts of phthalic 60
anhydride are added. After these ingredients
are added, the temperature is raised uniformly
at a rate of 1° C. rise per minute until a tempera
ture of 200° C. is reached. The heating is con
tinued at 200° C. for three hours. The incorpora
tion and reaction of ingredients are at all times
caried out in an atmosphere of carbon dioxide.
The heating is stopped and the reaction mixture
is cooled to 150° C. under carbon dioxide. At
this temperature, the resin is run into aluminum 70
receptacles.
The resin is soluble in alcohol, ethyl and butyl
acetates and acetone. It is partly soluble in
toluol and ethylene dichloride and insoluble in
V. M. a P. naphtha. It has a softening point of 75
about‘ 78° on ‘ The viscosity ‘of ak'65%1solution in‘
lof phthalic anhydride 1 are 'addedand the-heating
, ' I1'isic‘ontinued as in,-Example 19.
1‘ 1
lbutyl ‘acetatei's about138 poises at 25° C.‘
a ‘1 'IliThe'lresin =is‘ -‘ soluble in"~alcohol; acetone1'and
‘
‘1
I
_
I
I
“
I
I
I
I
,
1
ethyl-g'and"butyl'jacetates.~
It
is
partly ‘soluble
1 182 parts of is'orbitol andlz?jpartslo£~beta fatb in toluol, ‘and insoluble in‘ ethylene dichloride and
V. M~._-& IP-gnaphtha. A 65% solution ‘of-this
lare heated as, in" 1ExampIe‘11‘19'.“ 133:1‘ parts 1 of ,
. ‘phth'alic janhydride are§added~iand :thei' heating “ resinin butyl acetate has a viscosity of approxi
~ is continued aslinlExa‘mple 19. ‘
1
U
'
- mate'ly 3.1 poises at 25° C. ‘1
‘
~,'I_‘he resin is soluble in1 alcohol, ethylene ‘dichlo
10.
‘ride, acetonelandjbut'yl ‘and ethyl ac'etates’i It
_
is slightly‘ soluble in toluol anddnsolublein-V. M.
10
.
I
' 138.5 parts of phthalic anhydride and105 parts
. & P. naphtha;
65% solution ‘of- 1the' resin in; ‘I oleic acid are heated together-in an aluminum
. butyl acetate‘has' a1 viscosity of§1about wl2i'poises - reaction lves‘selto a ‘temperature of 140° C. ‘with
lI'1ig1at25‘I’C...
~
‘>1 .
>1
\. sti‘r'ring;~‘182 ‘parts ‘of mannitol are" added’ and
l
ammbzézz
I
. "heating is continued 1so that‘ the temperature is
“"182 parts of‘sorb'itol andl65-“parts‘of1beta fat.‘I ~raised
at‘ therate 'of_ :1° C. per-‘minute until a
‘ ‘I I "are heated as in ‘ Example‘ 19lf1..l2511‘parts' off "temperature
of1200° C. is "reached. The heating‘
“ ‘phthali'c anhydride‘ are added andthe heatingis?I'I ‘1 i‘s1continued'at‘this temperature forthree hours.
All mixing'and reaction of ingredients are carried
in Example 19.
a.continuedas
20
I The resin‘ is soluble ‘in ‘acetone; alcohol; ethyl-"6“out in any ‘atmosphere of “carbon dioxide. The
"reaction mixture is cooled toI150° C. under ‘car
I‘eneh‘dichloride'jand butyl ‘andethyl acetates. It
~1i'1bo‘n dioxide, ‘at‘which> temperature the resin is
"s partly soluble‘in toluol‘ andlin'soluble in 'V.
'1‘‘I&I‘P.naphtha'.
.1
‘
‘I
I.
v
1
1
‘
.
run" into aluminum receptacles.
;
I (‘The viscosity of. a 65 % solution in l'outylac'etate=»I
is about 3.1 poisesat 25"‘ c.
‘
The'resin is‘s‘oluble in a'cetonef alcohol; and 25
»j butyl ‘and ethyl acetates. Itfis insoluble in
' ethyl
1 '1*ene"‘dich1oride,;V. M. &“P. naphtha and toluol.
‘Example 22
1‘1A;‘651% solution ‘of-this resin‘in' butyl ‘acetate
‘ 91 parts of sorbitol and 145 parts of‘stearic acid ‘ ‘has‘ a~viscosity of approximately 6;’? poises at
‘
‘
‘
'
30 are heated as in~Example;J‘1_ "1110iparts of 25" c.
continued.
phthalic anhydrid'e
as in Example
are jadde
.19. .. " mi heating is
'
1
.
'
'
Example
28
30
I
fss-j-partsror phthalic anhydride and 88.5‘ parts
1 . The resin is ‘soluble in} ‘acetone, 1 butyliand .‘ ethyl ' v.of palmitic acid‘ are heated as in Example 27.
' ‘acetates, ethylene dichlorid‘ejV.
& P.lnaphtha-, I ,91 partsof mannitol are ‘added and the? heatin
. ‘
35 alcohol. and“: toluoLT ‘1‘A‘I‘65% 's‘olu‘tion'of the resin 1
in butyl acetate‘ hasaviscosityof about“ 1.1
poises.at,25° C.f
“
l
l
.
‘
.1
,
'I
‘
.
is‘ continued as in‘ Example 27. .
1
i‘
The‘resin is ‘soluble in acetone, ethylene di
1 ' chlorideand butyl and ethyl acetates. 11It is part
rmampzerzs
1 . ly soluble in‘ toluol' and insoluble ‘in V. M.1 8; P.
naphtha and alcohol. A 65%‘ solution of-this
‘182 parts of SOl'bltOl and 112 parts of coconut resin“ butyl acetate has a‘ viscosity of approx“ 40
oiljh'aclds‘ are-“heated as" inv Example 19'.‘- 1118.5
parts i‘ of phthalic anhydride are “added -‘ hdtheat;
mately 712 poises at 25° C. 1 > ‘1
f
' l ‘
“Considerable ‘modi?cation is» possible in the
mg is‘ continued as m Example 19.
-II » he ‘resin is» solubleli 9‘1IIbutyl ‘andwethyl"acetateslj ~1choice of the ingredients employed in the esteri?
‘acetone-‘,‘alcohol. and ethyleneidichlo‘ride; ‘It isI‘I 'cationreaction as'well asin the manipulative
*step's utilized. in‘ the processes, without departing
"1..
ubl'e
insoluble
inl'toluol.
‘in 3V." MiltzgP-anaphtha?
. 6I5_%‘1solution- of
and~
vthe-resin
partly “sole
in‘ ‘ from the‘es'sential features of theinvention. ‘
45
Q
- butyl‘ja‘cetate hasiaf‘vis’cositypf about 5.1I'1Ppoises, . i"-11W1'iatIclaim is: 1
‘1'. “Thewprocess of making‘a resinous material -_
'
at 25°C.,
1‘
‘
’
"
"
I
I
I
j
amamplefzr?
,I
11182 parts of-ls'orbitollandf1
1 1'comprising an. esteri?cation product-of an inner
Tether; which comprisesheating together ‘under 50
parts 01 corn; esterifyin'g conditions ‘.resinifying polycarboxylic
oil acidsv are heated as in Example 19.31; 148 parts
‘aoidysaid ‘acid comprising phthalic acid when
of phthalic'anhydri'de are added‘ and ‘heating is'1 iatt'y oil acid is present in the reacting, mixture.
continued as, inEX'ample 119. -. ~
Ci Lt ‘1
' andapolyhydroxyinner ether‘ derivable from -
a straightchain hexahydrio alcohol by intra
irnol'ecular condensation thereof, the number of
partly‘ soluble‘in toluolYandV. M." & P.1‘1naphtha. equivalents of ‘acid present in the reacting mix
-A 65% 'solutionlof this resin inbutyl acetate'has ture being not more than about 4 equivalents Der
I ‘The resin is soluble in acetone‘,‘alc0hol, ethylene
dichloride, vand butylwand ethyl acetates‘; It is
c0‘
\ a viscosity‘
of.
“ about 2.4 poises at 25°
'
C.‘
'
mol
of
ether.
-
1
I
.' 1'
.
.
l
l
'
I
12.‘ ‘The process ‘of making‘aresinous material
comprising an esteri?cation product'of an inner
. ‘ 1182 ‘parts 10f ‘sor'bitol and'IIOeparts"of1-oleic1acid » ether“ "which comprises ‘heating together vunder
‘ are‘ heated 1aslin="ExamplIe-'19. ‘148 parts of Iesterifying conditions phthalic acid and a poly
hydroxy inner ether derivable from a straight
11phtha1ic anhydride are addedand heatingis con
-
tinuedasinExjample
119.“
.1
‘
1
>
‘1
'
.
'
‘ chain hexahydric alcohol by intramolecularcon
65
1‘ vTh‘e‘resin is ‘soluble-in~ ethyl and-butyl acetates- “ densat‘ion thereof, the number of equivalents of
’ and=acetonef
It is ‘slightly? soluble in- toluoljandv acid present in thereacting mixture being. not
“alcohol; ‘andq‘insoluble‘ in ethylene "dichloride -. 'more‘ than about vliequivalents per molof ether.
and ‘VFM. & P.‘ naphtha. ‘ A_‘50% solution ‘of this I i3.~-The process of making a resinous material
‘ Iresin in butyl acetate has a viscosity of about comprising an esteri?cation product of an inner 70
‘1 ether which co'mprisesrheatingv together under
1.6 poises at 25°‘ C.
7 1~E:cample 26
esterifying conditions phthalic acid and a poly
‘ 'hydroxy inner ether derivable from‘ a straight
1 182 parts ‘of sorbitol‘and 175 parts‘ofricinoleic 1 1chain‘hexahydric' alcohol by intramolecular con~
densation thereof, the number of equivalents 01> 75
"acid are heated as .in Example 1941120‘ parts
8
v
'
‘
2,134,439
acid, present in the reacting mixture being from
acting mixture being from 2.25 to 3 equivalents
2.25 to 3 equivalents per mol of ether.
per mol of ether.
4. The process of making a resinous material
comprising an esteri?cation product of an inner
ether which comprises heating together under
esterifying conditions phthalic acid, a resinifying
aliphatic polybasic acid, and a polyhydroxy inner
ether derivable from a straight chain hexahydric
alcohol by intramolecular condensation thereof,
the number of equivalents of acid present in the
reacting mixture being not more than about 4
equivalents per mol ofether.
-
5. The process of making a resinous material
comprising an esteri?cation product of an inner
ether which comprises heating together under
esterifying conditions phthalic acid, a resinifying
aliphatic polybasic acid,,and_a polyhydroxy inner
ether derivable from a straight chain hexahydric
alcohol by intramolecular condensation thereof,
the number of equivalents of acid present in the
reacting mixture being from 2.25 to; 3 equivalents
per mol of ether. ,
»
6. The process of making a resinous material
comprising an esteri?cation product of an inner
ether which comprises heating together under
esterifying conditions phthalic acid, a resinifying
aliphatic polybasic acid, fatty oil acid, and a
polyhydroxy inner ether derivable from a straight
chain hexahydric alcohol by intramolecular con
30 densation thereof, the number of equivalents of
'
comprising an esteri?cation product of an inner
ether which comprises heating together under
esterifying conditions maleic acid and‘a poly
hydroxy inner ether derivable from a straight
chain hexahydric alcohol by intramolecular con
densation thereof,'the number of equivalents of
acid presentv in the reacting mixture being not
more thanabout 4 equivalents per mol of ether.
12. The process of making a resinous material
comprising an esteri?cation product of an inner
ether which comprises heating together under
esterifying conditions phthalic acid, maleic acid
and a polyhydroxy inner ether derivable from a
straight chain hexahydric alcohol by intramolec
ular condensation thereof, the number of equiv
alents of acid present in the reacting mixture
being not more than about 4 equivalents per mol 20
of ether.
13. The process of making a resinous material
comprising an esteri?cation product of an inner
ether, which comprises heating together under
esterifying conditions phthalic acid, fatty oil acid,
and a polyhydroxy inner ether derivable vfrom a
straight chain hexahydric alcohol by intramolec
ular condensation thereof, the number of equiv
alents of acid present in the reacting mixture
being not more than about 4 equivalents per mol ;
acid present in the reacting mixture being not
of ether.
more than about 4 equivalents per mol of ether.‘
'7. The process of making a resinous material
14. The process of making a resinous material
comprising an esteri?cation product of an inner
having air-drying properties and comprising an
ether, which comprises heating together under
esterifying conditions phthalic acid, fatty oil acid,
esteri?cation product of an inner ether which
comprises heating together under esterifying con
ditions phthalic acid, a resinifying aliphatic poly
basic acid, an air-drying acid, and a polyhydroxy
inner ether derivable from a straight chain hexa
40 hydric alcohol by intramolecular condensation
thereof, the number of equivalents of acid pres
ent in the reacting mixture being not more than
about 4 equivalents per mol of ether.
8. The process of making a resinous ‘material
45 having air-drying properties and comprising an
esteri?cation product of an inner ether, which
comprises heating together under esterifying con
ditions phthalic acid, maleic acid, an air-drying
acid,‘ and a polyhydroxy inner ether derivable
50 from a straight chain hexahydric alcohol by in
tramolecular condensation thereof, ‘the number
of equivalents of acid present in the reacting mix
ture being not'more than about 4 equivalents per
mol of ether.
55
'
11. The process of making a resinous material
9. The process of making a resinous material
comprising an esteri?cation product of an inner
ether which comprises heating together under
esterifying conditions resinifying aliphatic‘ poly
basic organic acid and a‘ polyhydroxy inner ether
60 derivable from a straight chain hexahydric alco
hol by intramolecular condensation thereof, the
number of equivalents of acid present in the re
.acting mixture being not more than about 4
equivalents per mol of ether.
‘
straight chain hexahydric alcohol by intramolec~
ular condensation thereof, the number of equiv
alents of acid present in the reacting mixture
being from 2.25 to 3 equivalents per mol of ether. 4 U
15. The process of making a resinous, material
having air-drying properties and comprising an
esteri?cation product of an inner ether which
comprises heating together under esterifying con
ditions phthalic acid, van air-drying acid and a ,
polyhydroxy inner ether derivable from a straight
chain hexahydric alcoholby intramolecular con
densation thereof, the number of equivalents of
acid present in the reacting mixture being not
more than about 4 equivalents per mol of ether.
16. The process of making a resinous material
having air-drying properties and comprising an
esteri?cation product of an inner ether which
comprises heating together under esterifying con
ditions phthalic acid,‘ an air-drying acid, and a
polyhydroxy inner ether derivable from a straight
chain hexahydric alcohol by intramolecular con
densation thereof, the number of equivalents of
acid present‘in the reacting mixture being from
2.25 to 3 equivalents per mol of ether.
17 . The resinous esteri?cation product made in
basic organic acid and a polyhydroxy inner ether
derivable from a straight chain hexahydric alco
hol by intramolecular condensation thereof, the
10.
ether which comprises heating together under
esterifying‘conditions resinifying aliphatic poly
number of equivalents of acid present in the re
60
accordance with the process set forth in claim 1.
18. The resinous esteri?cation product made in
accordance with the process set forth in claim 2.
19. The resinous esteri?cation product made in
accordance with the process set forth in claim 3.
20. The resinous esteri?cation product made in
accordance with the process set forth inv claim 9.
21. The resinous esteri?cation product made
in‘ accordance with the process set forth in claim
10. The process of making a resinous material
comprising an esteri?cation product of an inner
35
and a polyhydroxy inner'ether derivable from a
,
.
,
,
KENNETH R. BROWN.
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