United States Patent Office 3,423,341

Patented Jan. 21, 1969

2
brittle resin. Propylene glycol behaves similarly, also yield
3,423,341 ing a glassy product. By way of contrast, however, di
PROCESS FOR MAKING OL MODIFIED AL ethylene glycol forms a soft resin that is soluble in both
KYO RESNS WHEREN ALL REACTANTS methanol and water.
ARE ADDED IN ONE CHANGE
Robert J. Klare and Grant O. Sedgwick, Minneapolis, Thermosetting, heat convertible resins result when one
Minn., assignors to Ashland Oil & Refining Company, or more of the reactants (i.e., the alcohol or the acid)
Ashland, Ky., a corporation of Kentucky contain more than two reactive groups (i.e., more than
No Drawing. Filed Dec. 11, 1964, Ser. No. 417,795 two hydroxyl groups in the alcohol and/or more than
U.S. C. 260-22 13 Claims two carboxyl groups in the acid). Such polyfunctional
int. C. C08g 17/16 O reactions are capable of forming three dimensional mole
cules. These resins are characterized by their ability to
ABSTRACT OF THE DISCLOSURE
form insoluble, infusible gels under the influence of heat.
A typical example of this type of reaction is that between
Oil-modified alkyd resins are prepared by forming a phthalic anhydride and glycerol. In this reaction, gelation
mixture of alkyd resin forming ingredients in a reaction 5 takes place so sharply that the reaction must be stopped
Zone, said mixture having a remaining ratio of at least short of the gel point. As a consequence, unmodified
about 1.07 at a selected alcoholysis temperature and a glycerol phthalate has known only limited commercial
selected superatmospheric steam pressure; reacting said Se.
mixture at said selected alcoholysis temperature and said Between these two extremes, it is possible to produce
superatmospheric steam pressure to thereby produce an 20 alkyd resins having properties that can be tailormade for
alcoholysis product, releasing said steam pressure and almost any particular application by reacting various com
esterifying said alcoholysis product thereby producing an binations of monohydric alcohols, dihydric alcohols and
oil-modified alkyd resin, polyhydric alcohols with various combinations of mono
armiscess...Sec.Simr
basic acids, dibasic acids and polybasic acids. Because of
25 the extensive permutations and combinations that are
The present invention relates to an in situ alcoholysis possible, a wide variety of alkyd resins are currently be
process. In a second aspect, the present invention relates ing produced from an even wider variety of ingredients.
to a process for making oil-modified alkyd resins wherein However, it is not meant to imply that resins can always
alcoholysis and esterification are conducted sequentially be made with ease in meeting some new demand. Often,
in a single reaction zone and wherein all reactants are 30 the exercise of a considerable amount of inventive skill
added in one charge. is involved.
The alkyd resins comprise one of the most versatile Because of the considerable expense involved in the
groups of synthetic resins known. They can be readily preparation of carboxylic acids and alcohols in pure form,
adapted to the production of a wide variety of coatings. those skilled in the art have long sought cheaper ways of
Consequently, in recent years they have been used in the preparing alkyd resins. These prohibitively high costs
paint field in a greater volume than any other single class dropped considerably after the development, some years
of resins. One of their most outstanding qualities is their ago, of the alcoholysis principle which enabled manufac
ability to impart distinctive properties of beauty and flex. turers to use oils of fatty acids (i.e., glycerides) rather
ibility to both varnishes and enamels. These properties than pure fatty acids and glycerine themselves. At the
are retained to a considerable extent even on prolonged 40 present time, all of the well known drying oils and their
exposure of the varnish or enamel to weathering. Indi corresponding fatty acids are used to modify the proper
vidual resins of the group (i.e., alkyd resins), while pos ties of alkyd resins.
Sessing these primary characteristics, naturally are de According to techniques that are currently used in
signed to differ widely from one another. the manufacture of oil-modified alkyl resins, a polyhydric
The primary reaction involved in the preparation of all alcohol (e.g., pentaerythritol) is first reacted under al
alkyd resins is esterification. Thermoplastic, nonheat con coholysis conditions (e.g., at atmospheric pressure and
Vertible resins are obtained when both the alcohol and 450 F. using a catalyst) with a glycerol ester of fatty
acid reactants (the primary reactants are carboxylic acids acid (e.g., soybean oil). During the alcoholysis reaction,
and alcohols) possess two and only two reactive groups the polyhydric alcohol reacts metathetically with the fatty
in their molecular structures (i.e., a dicarboxylic acid and 50 acid portion of the glycerol ester. Subsequently, and often
a dihydric alcohol). Such a reaction is bifunctional and in a separate vessel, the other alkyl resin ingredients
produces chain molecules of relatively large molecular (e.g., phthalic anhydride) are added to the alcoholysis
Weights. The ends of the chains can terminate in either product. This mixture is then esterified to form the desired
a free carboxyl or free hydroxyl group. To obtain a neu alkyl resin. The purpose of the alcoholysis step is to
tral resin, these free groups can be further esterified with obtain a fatty acid-containing molecule having at least
a monohydric alcohol or a monocarboxylic acid. These one reactive (i.e., free) hydroxyl group. The free hydroxyl
linear polyesters are usually produced by the direct ester groups on these molecules can then react with polybasic
ification of a Saturated dihydric alcohol (e.g., glycol) with acid and thereby become part of the resin network. If
a dicarboxylic acid (e.g., succinic acid or phthalic anhy the alcoholysis step were eliminated (i.e., by putting all
dride). Resins are obtained only if the alcohol and acid 60 of the resin forming ingredients together), the reaction
contain the proper structure to yield chains of certain kinetics are such that the polybasic acid would, under
spacial complexity. Otherwise, crystalline or fiber prod these conditions, react preferentially with the polyol, leav
ucts are produced. For example, the product formed as ing the oil as a separate constituent (often as a separate
a result of the fairly complete esterification of phthalic phase). The net result would be a useless combination of
acid with ethylene glycol at room temperature is a hard, 65 oil and oil-free polyester which would probably be gelled.
 3,423,341
3 4.
It has now been discovered, and this discovery forms ventors that the minimum effective remaining ratio at
a basis for the present invention, that oil-modified alkyd which alcoholysis will take place is about 1.07.
resins can be prepared (e.g., from glycerol esters such The remaining ratio for a given system can be found
as linseed oil) by an in situ alcoholysis process wherein by reference to the following equations:
all of the ingredients are brought together at one time.
In order for the in situ alcoholysis process to be effec X-(AY)(Y)
tive, certain conditions must be met and certain pa T 56,100 (1)
rameters must be kept in mind.
Briefly described, the in situ alcoholysis process of the X--P-C
present invention involves charging all of the essential O R=2 . (2)
alkyl resin forming ingredients to a reaction vessel. The
formulation employed is controlled in the manner here wherein the terms are defined as follows:
inafter described. The ingredients are then heated to an
alcoholysis temperature under superatmospheric Steam AV=Acid value of reactants at esterification equilibrium
pressure. When alcoholysis is complete, the steam pressure W=Weight of reactants at esterification equilibrium
is released and the reaction mixture is then allowed to X-Equivalents of unreacted acid at esterification equi
esterify to the desired specifications. librium
One of the advantages of the present in situ alcoholysis P=Equivalents of hydroxyl groups in the initial charge,
process has been found to be the shorter cycle times excluding those in the oil
involved. The second addition of ingredients (required 20 C=Equivalents of acid groups in the initial charge, ex
by the prior art) is eliminated and esterification times cluding those in the oil
have been observed to be shorter. Products produced by Z= Equivalents of fatty acid in the oil
the inventive process have very consistent qualities (more R=Remaining ratio
so than the prior art products). This is undoubtedly due, By esterification equilibrium, it is meant to refer to the
in part at least, to the production of a more consistent 25 equilibrium which exists under the in situ alcoholysis con
alcoholysis product. Smaller losses of material have been ditions, which conditions are employed to suppress esteri
noted during processing. Molecular weight distribution fication and promote alcoholysis. Obviously, such a pa
of the desired products is more even. The end products rameter has no meaning in the prior art two-step process
have generally lower viscosities which allow for easier where oil and polyol are the only reactants present during
handling. By its very nature, the process is adapted to 30 alcoholysis.
a simplified test for determining when alcoholysis is com Some water is produced during the in situ alcoholysis
plete. In the case of short oil alkyds (i.e., alkyds con by direct esterification. This water formation inherently
taining a minor amount of oil), normal alcoholysis tech helps to increase the remaining ratio. Water can also be
niques involve such a small volume of material that heat included in the initial charge to help raise the ramaining
transfer is very poor. The in situ alcoholysis process offers ratio. However, much of this water will usually be re
an obvious additional advantage in this situation. moved as steam which, in turn, will advantageously Sup
The present inventors have observed that, under ordi press esterification during the in situ alcoholysis. In any
nary circumstances, when all of the ingredients required event, the effect of water (in the liquid phase) on the re
to prepare a conventional oil-modified alkyd resin are re maining ratio is normally small and a large change in
acted simultaneously (e.g., an oil such as soybean oil, a 40 water content is usually needed to see any pronounced
dibasic acid such as phthalic anhydride, and a polyol effect. The overall effect of including more water in the
such as pentaerythritol), a polyester will form from the initial charge of ingredients is to raise the equilibrium
dibasic acid and the polyol. This direct esterification acid value, to raise the remaining ratio, and to raise the
reaction consumes a sufficient number of the hydroxyl pressure (using a closed system and internally generated
groups of the polyol and prevents successful alcoholysis 45 pressures).
between the oil and the polyol. Thus, an oil-modified Higher pressures also increase the remaining ratio. The
alkyd resin is not obtained as the dominant product. effect is significant. With some resin formulations, no ad
Instead, a useless combination of oil and oil-free poly justment in the ingredients is needed to conduct in situ.
ester is produced. alcoholysis, provided the pressure is sufficiently high to
The present inventors have discovered that if this same 50 keep the remaining ratio above 1.07, e.g., at 1.15. How
mixture of ingredients is allowed to react under elevated ever, for many resin formulations, the required pressure
steam pressure, the direct esterification reaction is in is intolerably high and far exceeds the pressure limits of
hibited. Consequently, this allows more unreacted hy conventional reaction vessels.
droxyl groups to remain in the mixture, thereby allow A higher alcoholysis temperature can usually be tol
ing alcoholysis to take place. It has been determined 55 erated using the present in situ process, because etherifi
by then that by controlling the steam pressure, it is cation is curbed by the presence of water. However, as
possible to keep a sufficient amount of free hydroxyl the temperature is raised so is the pressure (if internally
groups available indefinitely to thereby promote the alco generated pressures are used) and it can easily be seen
holysis reaction between the polyol and the oil. It has that an intolerable pressure might be realized for the par
been further noted by them that the presence of water 60 ticular reactor available. Additionally, while higher tem
(either in the liquid or gas phase) does not adversely peratures speed up the reaction, they usually decrease the
affect the desired alcoholysis reaction. After alcoholysis remaining ratio. Ordinarily, the effect is quite small, but
is complete, the steam pressure is reduced, and esterifica sometimes it can be significant. Alcoholysis temperatures
tion follows, thereby producing the desired oil-modified for the in situ process will generally approximate the con
alkyd resin. 65 ventional prior art alcoholysis temperatures. Tempera
In developing the present in situ alcoholysis process, tures of from 300 to 600 F. can be used, although
a method has been devised by the present inventors to temperatures of from 400 to 550 F., e.g., 420 to 490
determine the conditions needed for in situ alcoholysis F. are preferred.
to take place. They have discovered that there is a mini The remaining ratio can also be increased (most con
mum ratio (at esterification equilibrium) of equivalents 70 veniently) by adjusting the initial charge of ingredients
of free hydroxyl groups to equivalents of fatty acid groups so that a portion of, for example, the glyceride oil is re
placed by fatty acid and glycerine. This has the effect
in the oil which must exist for in situ alcoholysis to of significantly increasing the remaining ratio without
take place. This ratio has been defined by them as the appreciably changing the equilibrium acid value. If this
"remaining ratio.' It has been found by the present in 75 is done, a lower pressure can be used than would other
 3,423,341
5 6
wise be needed. If all of the oil is replaced by fatty acid economics could be obtained without risking gel forma
and glycerine, no pressure (zero p.s.i.g.) is needed since tion. When a gel forms in a reactor (through an inade
the requirement for an alcoholysis step is eliminated. quate remaining ratio or insufficient pressure), the prod
The equivalents of fatty acid, as well as glycerine, which uct is not only ruined, but there is a considerable amount
are needed to replace an equivalent amount of glyceride of work involved in cleaning the reactor.
oil to maintain a remaining ratio of R at a desired equi It must be realized that it is possible for the calculated
librium acid value of AV is given by Equation 3. remaining ratio to differ from the actual remaining ratio
(especially where, for example, an estimated AV has
B R (3)
been used). Thus, caution should be used in adjusting a
0. conventional resin formulation to in situ processing.
wherein the terms are defined as follows: Therefore, a higher calculated remaining ratio is sug
gested for the initial attempt (e.g., use a remaining ratio
X, P., C and R are as previously defined of 1.20 and 10 weight percent water) so as to avoid the
B=Equivalents of fatty acid which is necessary to re possibility of gel formation.
place an equivalent amount of fatty acid in the oil 5 In determining the completion of alcoholysis, a meth
F=Equivalents of fatty acid in the oil before any of it anol solubility test can be used. The methanol solubility
is replaced by fatty acids test is one of the most common tests used to determine
All unknowns appearing in Equations 1-3 can be de when an alcoholysis reaction has been completed. This
termined from the initial unreacted charge of ingredients 20 test can be effectively used for testing reaction comple
to the reaction zone, with the exception of the equilibrium tion for "in situ' alcoholysis. The procedure involves
acid value, AV. Those skilled in the alkyd resin art will testing the solubility of the reactants in methanol (an
probably have information available to them on the equi ishydrous). When the reactants are soluble a clear solution
obtained; when insoluble, a cloudy solution is otbained.
librium acid value. If not, they can easily determine it by
performing the reaction on a small scale. However, in This test is used because free oil is fairly insoluble in
the absence of such data, an estimated acid value of 90 25 methanol. The acceptable ratio of methanol to reactants
(at 100 p.s.i.g. and 450 F.) can be used to make a crude varies with the oil length and other constituents of the
approximation of the appropriate parameters when using alkyd. Normally, for short oil alkyds, the solutions should
glyceride oils. Once experience has been gained, the be clear at 4 volumes of methanol to 1 volume of react
proper equilibrium acid value can be inserted in the equa ants. For a long oil alkyd, a 1 to 1 ratio is not uncommon.
tions and the relative amounts of the ingredients further 30 Alkyd chemists normally have a feel for what the meth
modified to fit the newly determined requirements to en anol test should be for a particular alkyd. However, it
sure a smooth, yet economical operation. has been found through experience that in situ alcoholysis
The in situ alcoholysis is conducted in the liquid phase is completed at the time when the reaction mixture has a
under steam pressure. Pressures of up to 500 p.s.i.g. can brilliant clarity. No exception to this has been found for
be used, although it will generally be found more con alkyd resins based on phthalic anhydride.
venient to operate with pressures of from 50 to 200 p.s.i.g. When alcoholysis is complete, the steam pressure is re
Pressures below 120 p.s.i.g., e.g., about 100 p.s.i.g., are leased, preferably at a slow rate, e.g., 10 p.s. i. per minute
especially preferred since many reaction vessels currently or slower. A preferred rate of release is 5 p.s. i. per min
used by industry are so limited. The steam pressure can ute or less. If the steam pressure is released too rapidly,
be obtained by pressurizing the reaction zone with live 40 volatile ingredients can vaporize and be lost. After the
steam. However, a more convenient and preferred prac pressure has been released, the ingredients are then esteri
tice is to add water to the initial charge of ingredients, fied attemperatures of from 300 to 600 F., more usually
heat the mixture in a closed system (after first evacuating form 400 to 550 F., e.g., 420 to 490° F. Esterification
air) and bleed off steam to maintain the desired pres is ordinarily continued until the acid value has reached
sure (e.g., to maintain 100 p.s.i.g.) until the desired al 45 Some predetermined level. It is common to continue
coholysis temperature is reached. It has been found that the esterification until the acid value is reduced below 50.
holding the reaction for thirty minutes without releasing Some resins are prepared by continuing the esterification
any steam, and then releasing steam to get the desired to an acid value below 30, and some other resins are pre
temperature, produces no advantages insofar as prevent pared by continuing the esterification until an acid value
ing the loss of volatile materials is concerned. 50 of below 10 has been reached, e.g., below 5. The esteri
In the preferred form of the present invention, water fication can be accomplished under an inert atmosphere
is included in the initial charge to provide the steam (e.g., nitrogen gas). If desired, by-product water can be
source. The amount of water present in the charge should removed during the reaction by using a gas sparge or the
be sufficient to vaporize and maintain the desired pres like.
sure under the alcoholysis conditions. This vapor (i.e., 55 The resin forming ingredients that can be used in
steam) will suppress direct esterification and allow the in practicing the present invention include all those known
situ alcoholysis to take place. The amount of water used in the alkyd art. Broadly speaking, the formulations in
will be an effective amount ranging from more than evitably include alcohol, acid and oil. Since oil-modified,
incidental impurities up to as much as 20 weight percent glycery phthalate type resins form a most important
(based on the combined weight of all the ingredients in 60 subclass of these resins, it can be expected that the formu
the charge, including water). More frequently, this lation will include glycerine (an alcohol), phthalic anhy
amount will be from 1 to 15 weight percent, e.g., 2 to 10 dride (an acid), and an oil such as soybean oil or lin
weight percent on the same basis. Since water present in seed oil. However, other ingredients can be used.
the liquid phase has no adverse effect on the reaction Typical resin forming ingredients form a wide variety
(usually it gives a slight improvement in the remaining 65 of materials including the fatty glycerides such as linseed
ratio) it is advantageous to include more water than oil, soybean oil, tall oil, safflower oil, and the like; alco
would appear necessary. Then, if desired, the amount of hols such as glycerine, inositol, pentaerythritol, ethylene
water used in each succeeding run can be slightly de glycol, trimethylol propane, fatty alcohols and the like;
creased until an optimum amount is reached. carboxylic acids and anhydrides such as phthalic anhy
Likewise, it is desirable to use a remaining ratio that is drides, maleic anhydride, fatty acids, benzoic acid, iso
higher than the 1.07 minimum. It is preferred to use phthalic acid, chlorendic acid, fumaric acid, and the like.
a remaining ratio above 1.15 to avoid any likelihood of The oils used in making the oil-modified alkyd resins
gel formation. Here again, it is then possible to reduce of the present invention are esters of monocarboxylic
the remaining ratio of each succeeding run by using more acids and mono- and polyhydric alcohols. They can be
oil and less fatty acid and glycerine. Thus, more favorable 75 of natural or synthetic origin and mixtures of oils can
 3,423,341
7 8
be used. The monomeric alcohol portion of these oils will from a total formulation consisting of 63.66 parts of saf
usually contain from 1 to 26 carbon atoms, ordinarily in flower oil, 13.68 parts of pentaerythritol, 0.03 part of
an aliphatic hydrocarbon chain. Where the alcohol por litharge, 25.47 parts of phthalic anhydride, 0.22 part of
tion of the oil is the residue of a monohydric alcohol maleic anhydride, and 0.07 part of triphenyl phosphite.
(e.g., oleyl alcohol), it will usually tend toward the The procedure employed was to first alcoholize a mixture
higher carbon contents, e.g., C12 to C24 monohydric ali of the safflower oil, pentaerythritol and litharge (a
phatic alcohols. Sperm oil is a naturally occurring mix catalyst) at 446 F. under substantially atmospheric pres
ture of glycerides and ester of monohydric long chain sure to obtain a conventional alcoholysis product. Then
alcohols. Conversely, where the alcohol portion of the the remaining ingredients were added to the alcoholysis
oil is the residue of a polyhydric alcohol (e.g., glycerine), O product, along with sufficient solvent (Xylene) for reflux
it will usually tend toward the lower carbon contents, purposes and the material was esterified under conven
e.g., C2 to C6 polyhydric alcohols. For example, Soybean tional conditions at 446 F. By this conventional tech
oil is a mixture of glycerides of the higher (e.g., C18) nique, an oil-modified alkyd resin product was obtained
fatty acids. Oils which are the esters of glycerine are which met commercial specifications after conventional
particularly preferred. The acid portion of the oils will 5 finishing (i.e., an acid number of 10 max. and a color of
usually contain from 1 to 26 carbon atoms, ordinarily in 8 max. (Gardner color scale) at a concentration of
an aliphatic hydrocarbon chain. Oils which are esters of 69-71% nonvolatile in a mineral spirits solvent).
fatty acids, e.g., esters of Cs to C26 and preferably C12 For a fuller treatment of the now conventional two
to C4 fatty acids, are particularly preferred. step process, see Robinson, U.S. Patent 2,123,206 (in
These oils can be broadly characterized as esters of 20 corporated herein by reference).
(1) monohydric and polyhydric, saturated and ethylenic (B) Simultaneous reaction of prior art ingredients
ally unsaturated, aliphatic and cycloaliphatic alcohols,
and (2) monocarboxylic, saturated and unsaturated, ali When all of the ingredients of A above were simul
phatic acids. More preferred are the esters of (1) poly taneously charged to a reaction vessel and heated under
hydric, saturated and ethylenically unsaturated, C2 to C6 25 substantially atmospheric pressure to what would ordinar
aliphatic alcohols, and (2) Cato C24 fatty acids. Especial ily be an alcoholysis temperature, the ensuing reaction
ly preferred oils are the fatty triglycerides, e.g., soybean did not proceed in the desired direction, but rather re
oil, safflower oil, linseed oil and the like, as well as mix sulted in a useless mixture of unwanted materials. The
tures thereof. extent of alcoholysis taking place was insignificant.
It should be remembered that oil-modified alkyd resins 30 EXAMPLE 1.-(In situ processing of prior
are well known in the alkyd art. Consequently, the initial art resin of run "A")
selection of reactants is a feat well within the skill of
the routineer. See Golding, Polymers and Resins, their By employing the remaining ratio concept and using
Chemistry and Chemical Engineering 295 et seq. (1959). water to suppress direct esterification during alcoholysis,
From the foregoing description, it can be appreciated it was determined that in situ alcoholysis could be ef
that conventional oil-modified alkyd resin formulations fectively used at 450 F. (similar to comparative run A)
can be adapted to the in situ alcoholysis process by using and 100 p.S.i.g. steam pressure (a self-imposed maxi
steam pressure to suppress direct esterification during al mum) if a portion of the safflower oil was replaced by
coholysis. When the remaining ratio is below 1.07 (e.g., a corresponding amount of fatty acid and glycerine. In
0.94), it can be raised to 1.07 or higher by using lower 40 following the in situ technique, 56.24 parts of saflower oil,
temperatures, by using higher steam pressures, by having 7.1 parts of safflower fatty acid, 0.75 part of glycerine,
water present in the liquid phase during alcoholysis, and 25.47 parts of phthalic anhydride, 13.68 parts of penta
by replacing a portion of the oil (e.g., soybean oil) by erythritol, 0.22 part of maleic anhydride, 0.07 part of
the corresponding free acid (e.g., fatty acid) and free triphenyl phosphite, 0.05 part of lithium hydroxide mono
alcohol (e.g., oley alcohol or glycerine). Catalysts can hydrate, and 3.0 parts of water were charged to a reac
be used during alcoholysis and esterification as desired. tion vessel. All of the ingredients were then heated to
Conventional finishing steps can be applied to the prod 450 F. while bleeding off sufficient steam to keep the
ucts as is common in the art. pressure at 100 p.s.i.g. Liquid phase alcoholysis ensued
The present invention is further illustrated by reference and was continued until a 2:1 methanol solubility was
to the following comparative data and the specific ex 50 obtained and an equilibrium acid value of 89 was reached.
amples (which include a preferred embodiment). Unless At this acid value, the remaining ratio was 1.06 (this
otherwise indicated, all parts are by weight and all per represents about the lowest value of “R” that could be
centages are weight percentages. The raw materials used successfully used). The pressure was then slowly released
in the following runs were commercially available ma (at a rate below 10 p.s. i. per minute) and sufficient xylene
terials obtained from the suppliers indicated. 55 was added for reflux purposes. The mixture was then es
RAW MATERIALS terified conventionally at 460 F. under reflux conditions.
The resulting oil-modified alkyd resin, after conventional
Soybean oil.-Once refined, acid value, .5 max., iodine processing, adequately met the specifications currently set
value, 126 minimum for alkyd resins produced by conventional processes (see
Soybean oil fatty acids-RO-11-S 60 comparative run A).
Pentaerythritol-Technical grade
Phthalic anhydride.-Commercial grade EXAMPLE 2
Fumaric acid-Commercial grade To further illustrate the usefulness of using water to
Glycerine.-99.5% Suppress direct esterification and the usefulness of the
Isophthalic acid-Amoco 95 65 remaining ratio concept, the in situ alcoholysis concept
Benzoic acid.-Technical grade was applied to the preparation of another oil-modified
Safflower oil-Nonbreak alkyl resin which had been previously manufactured by
Safflower oil fatty acids-Wecoline SF the conventional two-step technique from soybeam oil,
Linseed oil-Bleached and refrigerated glycerine, pentaerythritol, phthalic anhydride, and fuma
Linseed oil fatty acids.-520 vegetable acids 70 ric acid. Using Equations 2 and 3, the remaining ratio
(A) Conventional prior art process for the conventional charge (no oil replaced by free fatty
acid or glycerine) was calculated to be 0.96. This re
The following run shows how an oil-modified alkyd maining ratio was considerably lower than the minimum
resin is conventionally made. This oil-modified alkyd resin ratio of about 1.07 that is required for in situ alcoholysis.
was prepared by conventional liquid phase techniques 75 Therefore, Equation 3 was used to determine how much
 3,423,341
O
of the oil needed to be replaced by fatty acid and glycerine tion time. The disadvantage is that more fatty acids are
to allow the in situ alcoholysis process to be employed. needed. It is emphasized that etherification is curbed to
It was determined that the new charge must contain a a great extent by the steam employed during alcoholysis.
ratio of free fatty acids to oil equal to 0.107 to give a It is further pointed out that the requirement for addi
remaining ratio of 1.25 at 450 F. (a conventional tional fatty acid is predicated to a large extent on a de
alcoholysis temperature) and 100 p.s.i.g. (a self-imposed sire to keep the steam pressure at a moderate level. Be
limitation). The following procedure was then em cause many conventional reactors now in commercial
ployed. The original formulation was altered only to the use can only be operated safely at pressures which are not
extent of replacing part (i.e., about 10%) of the oil with Substantially above 100 p.s. i.g., a sufficient amount of the
a corresponding amount of free fatty acid and glycerine O oil was changed to fatty acid and glycerine so that a pres
and to the extent of including water in the formulation. sure of 100 p.s.i.g. could be employed. Where pressure
Thus, about 90% of the fatty acids were still to be sup is not a limiting factor, it will be possible to determine
plied by the oil. The remaining ratio was intentionally equilibrium acid values at various temperatures and pres
made higher than needed to make certain that gel for Sures and to accommodate the system accordingly. Thus,
nation was avoided. 5 at any given temperature and pressure, an equilibrium
The new charge (now adjusted to provide a remaining acid value can be determined and then the ingredients
ratio greater than 1.07 at 450 F. and 100 p.s.i.g.) con may be adjusted to meet or preferably exceed the re
sisted of the following: 57.14 parts of soybean oil, 6.10 quired minimum remaining ratio of about 1.07. While
parts of soy fatty acid, 2.19 parts of glycerine, 12.79 higher remaining ratios can be used, there is no signifi
parts of pentaerythritol, 24.58 parts of phthalic anhy 20 cant advantage to doing so except as a precautionary
dride, 0.71 part of fumaric acid, 0.01 part of lithium measure. Even there, as experience is gained, the remain
hydroxide monohydrate, and 4.16 parts of water. All of ing ratio can be lowered toward 1.07.
these ingredients were charged to a reaction vessel. A
vacuum was briefly applied to the reaction vessel to re EXAMPLE 4.
move air (this improves product color) which was then 25
sealed. The reaction vessel was then heated until the in Again using the remaining ratio concept, a portion of
ternally generated steam pressure reached 100 p.s.i.g. the oil in another conventional oil-modified alkyd resin
Heating was continued to 450-455 F. while releasing formulation was replaced with free acid and free alcohol
steam to maintain the pressure at about 95-100 p.s.i.g. to give a remaining ratio of 1.17. Here, 38.25 parts of soy
The reaction mixture was sampled every 15 minutes until 30 fatty acids, 360 parts of soybean oil, 13.75 parts of glycer
a sample was obtained that had a brilliant clarity. At this ine, 80.65 parts of pentaerythritol, 4.48 parts of fumaric
point, it was determined that the in situ alcoholysis was acid, 155 parts of phthalic anhydride, 0.026 part of lithi
complete. Before proceeding, a sample of the alcoholysis um hydroxide monohydrate, and 16 parts of water were
reaction mixture was taken to test the initial equilibrium charged to a reaction vessel. The procedure described in
acid value assumption. The equilibrium acid value was Example 2 was followed using a steam pressure of 100
determined to be 94. Steam pressure was then slowly re p.s.i.g. and an alcoholysis temperature of 430 F. Four
duced to substantially atmospheric pressure. Then a sol hours and five minutes after the heating began, the al
vent (xylol) was added and the reaction mixture was al coholysis product was clear and had an equilibrium acid
lowed to esterify under reflux conditions at 480 F. After value of 93-95. There was no sign of any gel, and the
esterification was complete, the resulting oil-modified 40 product had a color (Gardner) of from 5-6. Methanol
alkyd resin was finished in a conventional manner and solubility was 2:1. At this point, sufficient xylene was
easily met the specifications for the same product pre added for reflux purposes and the alcoholysis product was
pared by the conventional two-step process. esterfied at 480. F. under reflux conditions. In about two
The simple test used to determine the completion of hours and thirty minutes, esterification was complete. The
alcoholysis is one advantage of the present in situ process. 45 resulting oil-modified alkyd resin, after conventional
When the reaction has progressed sufficiently, a clear finishing, had an acid value of 6 and a viscosity at M-70
sample will ordinarily be obtained indicating such. Other of 50.6 stokes. The final color was 6-7.
wise, a cloudy sample is obtained. In some isolated cases,
the polybasic acid may be insoluble, thereby causing a EXAMPLE 5
precipitate. However, this precipitate can be centrifuged 50
and, if the liquid is clear, the reaction is complete. Again, the concepts were applied to still another resin
formulation which was adjusted to give a remaining ratio
EXAMPLE 3 above 1.07. Here, 39 parts of city water, 536 parts of soy
bean oil, 57.3 parts of fatty acids, 20.5 parts of glycerine,
This example shows the effect of increasing the alco 120 parts of pentaerythritol, 230.5 parts of phthalic an
holysis temperature in an effort to obtain faster reaction hydride, 6.25 parts of fumaric acid, 0.094 part of lithium
times. At 520 F. and 100 p.s.i.g. the equilibrium acid hydroxide monohydrate, and 1.0 parts of triphenyl phos
value for the resin forming mixture described in Exam phite were charged to a reaction vessel. A vacuum was
ple 2 was known from prior experience to be 67. Using pulled on the vessel to remove air and the ingredients
this acid value in Equations 1 and 2, it was determined were heated to 150 F. The reaction vessel was then
that the ratio of free fatty acid to oil had to be about 60
0.47 to keep the remaining ratio above 1.07 (actually sealed and heated to 480 F. Pressure was kept from
going over 100 p.s.i.g. by bleeding off steam as necessary.
about 1.17). Thus, the use of a significantly higher alco
holysis temperature adversely affects the remaining ratio Alcoholysis ensued and was allowed to continue until
samples of the alcoholysis product were clear. The steam
and requires significantly more free fatty acid than is re pressure was slowly released and sufficient xylol was
quired when lower temperatures are used. Based on these 65 added for reflux purposes during esterification. The re
calculations, a portion of the oil was replaced with fatty action mixture was then allowed to esterify under reflux
acid and glycerine and the procedure described in Exam
ple 2 was followed exactly, with the sole additional ex were met. atAfter
conditions 485-490. F. until the desired specifications
conventional finishing, the oil-modified
ception that the temperature employed during alcoholy
sis was 520 F. The oil-modified alkyd resin produced 70 alkyd resin met commercial specifications (i.e., an acid
by this in situ alcoholysis technique was found to be value of from 5-10 and a viscosity of C-D at M-50).
The present invention is still further illustrated by ref
equivalent to the oil-modified alkyd resin commercially erence to the data contained in Table I. These data were
produced from the same ingredients by the conventional
two-step procedure. The advantage of the higher tem obtained by processing a current resin formulation (both
perature employed in this example is in the faster reac 5 with and without adjusting the oil/fatty acid ratio).
 3,423,341
TABLE I.--IN SITU PROCESSING OF AN OIL-MODIFIED ALKYD
Run No.-------------------------------- 11 21 31 41 51 62 71 81 9: Ol 111
Remaining ratio------------------------ .90 0.98 1.06 1, 10 1.12 1.13 1,24 1.22 1,26 1,26 1.50
Percent of total fatty acid supplied by
the oil-------------------------------- 85 85 85 90 90 90 90 90 90 100 100
Pressure (p.s.i.g.)----- - 60 80 80 94 100 100 100 100 100 SO 300
Temperature (F.)---------------- 490 490 490 450 450 450 420 450 420 455 455
H2O included in charge (percent).------- 10 10 10 10 2.5 2.5 2.5 10 10 10 0
Equilibrium acid value----------------- 47.7 60 62,3 78.7 80.5 82 93 91 95 10 138
Charge formulation:
Soybean oil------------------------- 320 320 320 360 360 360 360 360 360 400 400
Soybean oil fatty acid- 77 77 77 38 38 38 38 38 38 O 0
Glycerine.----------- - 8 18 18 14 14 4 14 4. 14 3. 3.
Pentaerythritol- 8. 81 81 81. 8. 81 81 81 81 8. 81
Phthalic anhydr 155 155 155 155 155 155 55 55 55 55 155
Fumaric acid- 5 5 5 5 5 5 5 5 5 5 5
Water------ 65 65 65 65 16 16 16 65 65 65 65
Catalyst.--- 17 7 , 34 .17 .. 7 .7 .17 .17 17 --------------------
1 Vacuum at start up to remove all air from reactor.
2Nitrogen sparge at start up before sealing at one atmosphere nitrogen pressure.
Runs 1-4 illustrate how the minimum effective remain sary to keep the pressure at 100 p.s.i.g.). These resins are
ing ratio is between 1.0 and 1.10. Runs 1 and 2, both considered to be short oil alkyds. A high remaining ratio
having a remaining ratio below 1.0, produced completely 20 is more easily obtained from a short oil alkyd than from
gelled (solid) masses. Runs 3 and 4 (at R= 1.06 and a long oil alkyd (e.g., the alkyds of Table I). At 100
R=1.10) produced usable resins which contained a few p.s.i.g., the long oil alkyds need added water and fatty
gel particles indicating a critical or sensitive region. Runs acid substitution to obtain a sufficiently high remaining
5 and 6 (R above 1.10) both produced very good resins, ratio. Runs 15-17 further illustrate the application of in
indicating that the process was above the Sensitive area situ processing to the preparation of oil-modified alkyds.
of 1.0 to 1.10. These and other runs have indicated the 25 From the foregoing description and examples, it can
minimum effective remaining ratio to be about 1.07. Be be appreciated that conventional alkyd resin formulations
cause R can vary due to errors in calculation and/or er can be adapted to the present in situ alcoholysis technique
rors in charging, etc., the use of a remaining ratio above by employing the remaining ratio concept in conjunction
1.10, e.g., above 1.15, is favored, although economics 30 with the use of steam pressure. The process involves in
may dictate the use of the lowest possible value of R, hibiting the reaction of the polybasic acid with the poly
e.g., about 1.07. hydric alcohol to the extent that enough hydroxyl groups
The effect of temperature can be seen by comparing are available to transesterify with the oil. This is done
run 5 with run 7 and run 8 with run 9. Lowering the by keeping the remaining ratio above a certain value (i.e.,
temperature raises the equilibrium acid value and raises above 1.07, preferably from 1.10 to 2, e.g., 1.15 to 1.6)
the remaining ratio. Conversely, higher temperatures low and by using steam pressure. The remaining ratio can be
er the acid value and lower the remaining ratio. The tem adjusted by pressure, temperature, addition of water, and
perature effect is usually small, but it can sometimes be by replacing some of the oil by equivalent portions of
quite significant. fatty acid and glycerine.
Runs 10 and 11 show how it is possible to raise the 40 The present invention provides a sophisticated batch
pressure high enough to successfully practice the in situ process for preparing oil-modified alkyd resins from con
technique without replacing any of oil with fatty acid ventional ingredients in less time, with fewer manipula
and glycerine. However, as previously pointed out, many tive steps, than has heretofore been thought practical.
available reaction vessels cannot be safely operated at As was previously mentioned, a narrower, more even,
high pressures. Consequently, it becomes necessary to re molecular weight distribution of the resulting oil-modi
place part of the oil. So as to be able to use lower pres fied alkyd resin is obtained when the in situ alcoholysis
SeS. process is employed. Usually, an even molecular weight
The data in Table II further illustrate the use of the distribution makes a more compatible resin and a faster
present in situ alcoholysis technique. drying resin. Thus, the advantages to be obtained from
TABLE II.-N SITU PROCESSING OF OIL-MODIFIED ALKYDS
Run No.------------------------------ 121 3. 141 151 i51 71
Remaining ratio---------------------- 1.30 1.32 1.50 1.15 1.49 2.25
Percent of fatty acid supplied by the
oil---------------------------------- 100 00 100 88 68 100
Pressure (p.S.i.g.)--- -- - 00 100 100 100 00 100
Temperature (F.)------------------- 450 450 450 520 520 450
H2O included in charge (percent).----- 0 0. O 5 5 5
IEquilibrium acid value--------------- 102 8 95 73 73 13
Charge Formulation:
Soybean oil----------------------- 294 520 559 - - -- - - - - - - - - -- -- - - - - - 345

Soybean fatty acid - - -- - - - - - - - - - - - - - - - - -- - - 0.

Linseed oil-------
Linseed oil fatty a
575
73
443
96
Glycerine------- 08 122 22
Pentaerythritol 30 30 202
Phthalic anhydride. 232 232 335
Fumaric acid--------------------------------------------- 3
Maleic anhydride-------------------------------------------------------------------20III
Water----------------------------------------- 0 50 50 50
Isophthalic acid -- - - - -- - - - -- - - - - - - - - - - - - - - -- - - -- - - - - - - - -6i
Benzoic acid.---- --- - - -- - - - - - - - -

Ethylene glycol-------------------------------
1 Vacuum at start up to remove all air from reactor.
Referring now to Table II, runs 12, 13 and 14 are ex in situ alcoholysis are many, i.e., simplified operations,
amples of resin formulations that inherently were capable consistent product quality, smaller losses of materials dur
of giving a remaining ratio above 1.07 at the in situ 70 ing processing, less operator time, etc.
alcoholysis conditions without modification. Additionally, Having described the present invention with a certain
these formulations also provided sufficient by-product wa degree of particularity, it will be realized that numerous
ter by esterifying during the in situ alcoholysis to enable changes and variations, falling within the spirit and scope
a steam pressure of 100 p.S.i.g. to be generated and main of this invention, will become obvious to those skilled in
tained in a closed system (steam was bled off as neces- 75 the art. It is not intended that this invention be limited
 3,423,341
13 14
to any of the materials which have been mentioned as modified alkyd resin from a mixture of resin forming
specific examples, nor by any of the specific proportions ingredients comprising a fatty glyceride, an acid, and an
which have been given for the sake of illustration, but it alcohol which comprises:
is intended to claim all novelty inherent in the invention, (a) adjusting the mixture as necessary, by replacing a
as well as all modifications and variations coming within portion of said fatty glyceride with fatty acid and
the spirit and scope of the invention. glycerine to obtain a remaining ratio of at least 1.10,
What is claimed is: Said remaining ratio being the equivalents of free hy
1. The batch process of preparing an oil-modified alkyd droxyl groups to equivalents of fatty acid groups in
resin from a mixture of resin forming ingredients com the oil at esterification equilibrium, at a selected
prising soybean oil, glycerine, pentaerythritol, phthalic an O alcoholysis temperature within the range of 420 to
hydride and fumaric acid which comprises: 490° F. and selected superatmospheric steam pres
(a) replacing part of the soybean oil with an equivalent sure within the range of 100 to 200 p.s.i.g.,
amount of fatty acid and glycerine to thereby obtain (b) reacting said mixture, as adjusted, at said selected
an adjusted mixture having a remaining ratio of at temperature and pressure to thereby form an al
least 1.07, said remaining ratio being the equivalents 5 coholysis product,
of free hydroxyl groups to equivalents of fatty acid (c) releasing said steam pressure to substantially atmos
groups in the oil at esterification equilibrium at a pheric, and
temperature of about 450 F. and a steam pressure (d) esterifying said alcoholysis product to thereby pro
of about 100 p.s.i.g., duce an oil-modified alkyd resin.
(b) charging all of the ingredients in said adjusted mix 20 11. The process of claim 10 wherein steam pressure is
ture to a reaction zone, obtained by including from 2 to 10 weight percent of water
(c) reacting said mixture in the liquid phase at about in said mixture of resin forming ingredients.
450 F. under a steam pressure of about 100 p.s.i.g., 2. In a liquid phase process for preparing an oil
thereby producing an alcoholysis product, modified alkyd resin from a mixture of resin forming in
(d) slowly releasing said steam pressure, and gredients comprising a fatty oil, polyol and acid wherein
(e) esterifying said alcoholysis product to thereby pro Said oil and polyol are first reacted under alcoholysis con
duce an oil-modified alkyd resin. ditions to form an alcoholysis product and wherein said
2. The batch process of claim 1 wherein steam pressure acid and said alcoholysis product are then combined and
is obtained by including water as an ingredient in said ad esterified to produce said alkyd resin, the improvement
justed charge. 30 which comprises: reacting said mixture at a selected al
3. A process for preparing an oil-modified alkyd resin coholysis temperature within the range of 300° to 600 F.
which comprises forming a mixture of alkyd resin form and at a selected superatmospheric steam pressure not in
ing ingredients comprising a fatty oil, an acid and an excess of 500 p.s.i.g. to produce an alcoholysis product,
alcohol, in a reaction Zone, said mixture having a remain said mixture including all of the resin forming ingredients
ing ratio of at least about 1.07, said remaining ratio being 35 and being adjusted, as necessary, to obtain a remaining
the equivalents of free hydroxyl groups to equivalents of ratio of at least about 1.07, said remaining ratio being the
fatty acid groups in the oil at esterification equilibrium, equivalents of free hydroxyl groups to equivalents of fatty
at a selected alcoholysis temperature within the range of acid groups in the oil at esterification equilibrium, at said
300 to 600 F. and a selected superatmospheric steam Selected temperature and said selected pressure; thereafter
pressure not in excess of 500 p.s.i.g.; reacting said mixture 40 (releasing said pressure and esterifying said alcoholysis
at said selected alcoholysis temperature and said super product to produce said oil-modified alkyd resin.
atmospheric steam pressure to thereby produce an 13. The improved process of claim 12 wherein steam
alcoholysis product, releasing said steam pressure and pressure is obtained by including water in said mixture.
esterifying said alcoholysis product, thereby producing an
oil-modified alkyd resin. 45 References Cited
4. The process of claim 3 wherein the remaining ratio UNITED STATES PATENTS
is at least about 1.15.
5. The process of claim 3 wherein the alcoholysis tem 1,979,260 11/1934 Gauerke ------------- 260-22
perature is from 420 F. to 490 F. 2,123,206 7/1938 Robinson ------------ 260-22
6. The process of claim 3 wherein the pressure is from 50 2,181,893 12/1939 Hopkins et al. -------- 260-22
50 to 200 p.s.i.g. 2,369,683 2/1945 Moore ------------- 260-22
7. The process of claim 3 wherein the steam pressure 2,870,102 1/1959 Van Strien ---------- 260-22
is released at a rate at least as slow as 10 p.s. i. per min 3,162,616 12/1964 Dombrow et al. ------- 260-22
late. 3,185,668 5/1965 Meyer et al. --------- 260-75
8. The process of claim 3 wherein steam pressure is ob 55 3,226,348 12/1965 Purcell et al. ------- 260-22
tained by including from 2 to 10 weight percent of water DONALD E. CZAJA, Primary Examiner.
in said mixture of resin forming ingredients.
9. The process of claim 3 wherein air is evacuated from R. W. GRIFFIN, Assistant Examiner.
said reaction Zone prior to producing the alcoholysis prod U.S. Cl. X.R.
uct. 60
10. A liquid phase batch process for preparing an oil 260-29.6, 33.6, 95; 117-167