Chapter 5

Alkyd Resins
1. Introduction 157
2. Unmodified Alkyds 163
A. Alkyds Based on Phthalic Anhydride or Phthalic Acid 163
2-1. Preparation of Polyfglyceryl phthalate) Alkyd Resin 165
2-2. Preparation of Linseed Oil-Modified Poly (glyceryl phthalate) Alkyd Resin
by the Fusion Process 169
2-3. Preparation of a Soya Oil-Modified Polyfglyceryl phthalate) Alkyd Resin
by the Solvent Process 170
2-4. Preparation of an Alkyd Resin with Benzoic Acid to Control Molecular
Weight 171
B. Alkyds Based on Other Acids 173
2-5. Preparation of Glyceryl Adipate 175
2-6. Preparation of a Trimellitic Anhydride-Based Alkyd Resin No. 3712NT .. 179
3. Modified Alkyds 180
3-1. Preparation of Polyester Amide by the Reaction of
N,N-Bis(2-hydroxyethyl)linseed Amide and Dibasic Acids 182
4. Alkyds Modified with Vinyl Monomers 184
4-1. Preparation of a Styrene-Modified Linseed-Trimethylolethane Alkyd 184
5. Alkyds Modified with Other Thermosetting Resins 186
6. Miscellaneous Alkyd Preparations 187
References 187

1. INTRODUCTION
Alkyd resins are prepared from polyhydric alcohols (three or m o r e
hydroxyls), polybasic acids, and m o n o b a s i c fatty acids (saturated and
unsaturated) [1]. They are soluble in h y d r o c a r b o n solvents a n d are used in
the coating industry. Polyesters prepared from dihydric alcohols are not
included in the area of alkyd resins in this chapter and have been described
in Vol. I of this series [2].

157
158 5. Alkyd Resins

Alkyd-type resins were first described in 1847 by Berzelius [3], who

obtained a brittle resinous polymer by the reaction of tartaric acid and
glycerol. In 1853 Berthelot prepared the glycerol ester of camphoric acid
[4]. In 1856 von Bemmelen [5] studied resins obtained by heating glycerol
with succinic acid, citric acid, and a mixture of succinic and benzoic acids.
Other early investigators were Dubus [6], Lourenco [7], and F u r a r o and
Danesi [8]. In 1901 Smith [9] described a solid transparent glycerol
phthalate resin that was insoluble in water but soluble in hot glycerol.
Removal of the glycerol in vacuo afforded a resinous mass containing
glycerol and phthalic anhydride in a molecular ratio of approximately 2 : 3 .
Further heating caused the resinous material to yield a puffy brittle mass.
General Electric Laboratories carried out a series of intensive investigations
on the glycerol-phthalic anhydride reactions leading to the production of
useful resins of the heat-convertible type as summarized in the work of
Callahan [10], Friberg [11], Arsem [12], Dawson [13], and Howell [14].
The latter workers found that replacing some of the phthalic anhydride
with monobasic acids leads to more flexible resins with better solubility
properties. Kienle [15, 16] in 1929 and 1933 prepared glycerol-phthalate
resins containing some unsaturated fatty acids; these came into use as
protective coatings that were cured by air drying or heating at low baking
temperatures. The commercial production [17] of phthalic anhydride by the
catalytic oxidation of naphthalene accelerated progress in commercially
manufactured alkyd resins. Other developments that helped in the progress
of alkyd resin technology were the introduction of new solvents; lauric acid;
soya and tall oil fatty acids; maleic, fumaric, and isophthalic acids; and
polyhydric alcohols such as pentaerythritol, dipentaerythritol, and tri-
methylolethane. The structure of a typical phthalic anhydride alkyd resin
may be represented as

\
/ C - C - C -
O-

o=c
(CH )„
2

CR' = C R " - ( C H ) m - R
2 η

Gel permeation chromatography of alkyd resins has been reported

and the molecular weight distribution of products has been studied [18].
/. Introduction 159

Molecular weights (determined by the Rast method) are also found to depend
on the cooling schedule, and data have been reported in this area [19].
F u n d a m e n t a l studies on the glycerol-phthalic anhydride reaction were
first m a d e by Kienle [15] who found that the gel point occurs at about 7 8 %
esterification.
A n explanation of the cross-linking behavior in systems with more than
two functional groups reacting at esterification was first formulated by
Carothers. In simplified form his equation states that as the molecular
weight becomes infinite (at the gel point), ρ = 2 / / , where ρ is the extent of
the reaction and / is the average degree of functionality or the average
number of functional groups per molecule, considering only the use of
stoichiometric equivalents of interacting functional groups. Excess func­
tional groups such as hydroxyl are not truly reactants since there are no
carboxyl groups that they can react with. In systems with a functionality of
3 or more, gelation can be avoided by limiting the extent of the reaction or
using proportions that deviate from stoichiometric proportions. This
method is commonly used with monofunctional reagents (fatty acids) to
reduce the overall functionality. For example, the Carothers equation when
applied to stoichiometric a m o u n t s of glycerol and phthalic anhydride is

2 moles glycerol + 3 moles phthalic anhydride

+ 3 χ 2COOH = 12 (1)

6
12 functional groups
/ = j = 2.4 (average number of functional groups per
s
molecule reacting)
2 2
ρ = - = —— = 8 3 % (extent of reaction where gelation should occur;
* ' 7 8 % found by Kienle [15]) (2)
When / = 2, ρ = 100%, and the equation predicts that no gelation occurs
when bifunctional c o m p o u n d s are used. Therefore, alkyd chemists tend
to use formulations in which / = approximately 2.0 in order to get alkyd
resins which will not gel during manufacture. In other words, the molar
equivalents of hydroxyl should equal the molar equivalents of carboxyl
groups. In actual practice an excess of hydroxyl equivalents is used to give
specific properties, especially in baking coatings. For example, a typical
alkyd with 2 0 % excess of hydroxyl and a functionality of 2 is prepared from
phthalic anhydride, 1.0 mole (2 equivalents); glycerol, 1.0 mole (3 equiva­
lents); and soya fatty acids (soyal oil), 0.5 mole (1.5 equivalents).
Flory [20] and J o n a s o n [21] have also derived equations to describe the
gelation point of alkyd resins.
160 5. Alkyd Resins

TABLE I Representative Alkyd Resin Starting Materials

M.p. B.p. Sapon. Equiv.

Raw material (°F) (°F) Mol. wt. no. wt.

Polyhydric compounds
Glycerin — 554 92.1 — 31
Ethylene glycol — 386 62.1 — 31
Diethylene glycol — 473 106.1 — 53
Propylene glycol — 374 76.1 — 38
Trimethylolethane 395 — 120.1 — 40
Trimethylolpropane 136 — 134.2 — 44.7
Pentaerythritol 504 — 136.2 — 45.5

A cids-A nhydridesa

Phthalic anhydride 270 544 148.1 — 74

Phthalic acid 375-410 — 166.1 — 83
lsophthalic acid 650 — 166.1 — 83
Terephthalic acid Sublimes 570 — 166.1 — 83
Trimellitic anhydride 334 — 192.1 — 64
Trimellitic acid 419-423 — 210.1 — 70
Maleic anhydride 266 — 116.1 — 49
Fumaricacid 548 — 116.1 — 49
Adipicacid 306 — 146.1 — 73

Oils
Linseed — — — 188-196 280
Soya — — — 189-195 280
Dehydrated castor — — — 188-194 293
Safflower — — — 188-194 293
Tall — — — 170-180 285

a
Operations with all acids or anhydrides should be carried out in a well-ventilated
hood using proper personal protection (gloves, apron, chemical goggles).

Some of the typically used raw materials are shown in Table I.

The manufacture of alkyd resins usually involves alcoholysis of the oils
with a polyhydric alcohol followed by a batch process in which the first step
is the esterification to a specified end point and then solution into a solvent
thinning tank. The esterification may be done in the absence (fusion process)
or presence (solvent process) of solvent, but in both cases an inert gas
(nitrogen or carbon dioxide) must be bubbled through the reaction mixture
to facilitate removal of water of esterification and to minimize oxidation.
The fusion process has the advantage that there is less of a fire hazard and
that there is a lower equipment investment involved. However, the solvent
process requires less time in clean-up of the kettle, entails lower raw
material losses, and gives a lighter colored product.
1. Introduction 161

Fig. 1 Alkyd resin processing equipment. [Reprinted from "Amoco TMA as Primers for
Alkyd-Melamine Enamels and Acrylic Lacquers," Tec. Bull. TMA 25a. Amoco Chemical
Corp., Chicago, Illinois, 1974.]

The equipment used is either stainless steel or stainless steel clad and is
corrosion resistant. An example of a typical equipment set-up is shown in
Fig. 1, where the sparge is either nitrogen or carbon dioxide.
Other manufacturing equipment has been described by Martens [23] and
Hovey [24]. Typical laboratory and manufacturing equipment is described
in a review by M o n s a n t o [25, 26]. Continuous methods of producing alkyds
have not gained widespread usage [27].
Quality control in the manufacture of alkyd resins involves appropriate
rapid tests to determine the acid number, viscosity of solutions of known
concentrations in mineral spirits or xylene ( G a r d n e r - H o l d t viscosity tubes
used for comparison), color (Gardner 1933 Color Standards), and cure
time. A target range 2-5 units above the acid number units of gelation is
desirable. Most manufactured alkyd resins have an acid value (number of mg
of potassium hydroxide required toneutralize 1 gm of resin) of less than 15.
Once laboratory results have established the relationship of acid number
and solution viscosity to reaction time, both are plotted on graph paper and
are used in manufacturing operations (see Fig. 7). N o m o g r a m s for alkyd
manufacture have also been published [26].
The first alkyd resins sold commercially were by the General Electric
C o m p a n y under the trade name 'Captai." The production of alkyds has
4
162 5. Alkyd Resins

risen from 100 million lb in 1940 to 545 million lb in 1957 [28] to 734 million
lb in 1973 [29]. In 1973 the phthalic anhydride-type alkyd resins amounted
to 691 million lb and the other polybasic acid types amounted to 43 million
lb of resin used. In addition, styrene alkyd polyesters amounted to 32
million lb.
The unmodified glyceryl phthalate alkyd resin has only limited solubility
unless it is reacted during its preparative stage with oils or fatty acids. The
oil used is either a drying, semidrying, or nondrying oil. In addition to
glycerol, pentaerythritol is the most important of the lesser-used polyhydric
alcohols. The resulting resins are more durable than the glyceryl alkyds and
are faster setting. Other polybasic acids such as sebacic and adipic are used
to give soft resins that are useful as products that are polymeric plasticizers
for harder materials [30].
Today alkyds are a m o n g the most important and widely used resins in the
coating field. They are outstanding in terms of their economy, versatility
of formulation and application, and durability. Large quantities of oil-
modified glyceryl phthalate alkyds find use in interior and exterior enamels,
paints, automotive finishes, industrial finishes, marine coatings, and
appliance enamels [30]. Often the oil-modified alkyds are coreacted with
either styrene or silicones to give resins with modified properties. The alkyd
resins can also be combined with other resins such phenolic resins, a m o n o
resins, epoxies, acrylics, and polyurethanes to give special coating
materials. Alkyds are also used for molding materials that require good arc
and arc track resistance, insulation resistance, good flammability ratings
(UL94-VO), and excellent mechanical, thermal dimensional, and electrical
properties [31]. Miscellaneous uses of alkyds have been summarized by
Martens [32].
Some of the typical reactions that take place during an alkyd resin
preparation and curing are: (1) esterification, (2) alcoholysis, (3) ester inter­
change or transesterification, (4) etherification, (5) free radical addition
reactions, (6) Diels-Alder reactions, (7) decarboxylations, and (8)
polymerization via free radical initiation during curing (air-drying alkyds).
The addition of other resins such as urethane, epoxy, or phenolic resins
to the final resin can lead to further condensation reactions with hydroxyl,
carboxyl, and olefinic reaction sites.
A typical formulation for an alkyd paint is shown opposite.
Some important reviews [34, 35] and m o n o g r a p h s [23, 25, 32] on alkyd
resin production provide additional details.
The safety considerations involved in alkyd resin manufacture, including
plants, processes, and materials has recently been reviewed [36]. It is sug­
gested that this reference be consulted before getting involved in alkyd resin
synthesis.
2. Unmodified Alkyds 163

White gloss enamel [31] Parts

Composition
Acrylic-modified T M A Resin [74% solids ( N V M ) ] a
270
Cymel XM-1116 b
86
(add before water)
is added)
Water 300
Triethylamine 18
Rutile titanium dioxide c
257
Combine and pebble mill for 24 hr. Then add 150 parts water to give 1081 parts enamel.

Properties
The initial viscosity in a #4 Ford Cup (sec) 29
Initial pH 7.7
Pigment : binder ratio 0.9:1.0
Melamine:resin ratio 3:7
Wt.7o NVM 50.2
The bake cycle is 20 min at 350°F to give a durable, weather-resistant coating.

α
T M A , trimellitic anhydride; NVM, nonvolatile material.
b
Available from American Cyanamid Co.
0
TiPure R-900, available from Ε. I. du Pont de Nemours & Co.

2. UNMODIFIED ALKYDS

A. Alkyds Based on Phthalic Anhydride or Phthalic Acid

The earlier alkyd resins (glyceryl phthalate) were all of the heat-convertible
variety; i.e., on heating the resin was converted to a nonfusible type [15].
More recently an unmodified alkyd refers to a resin prepared from a dibasic
acid, a polyol, and an oil or fatty acid. In some cases a monofunctional acid
such as benzoic acid has been added to reduce functionality [23]. Oxygen- or
air-convertible alkyd resins are prepared by replacing part of the polybasic
acid with the proper a m o u n t of an oxidizable unsubstituted fatty acid or
acids such a linolenic, oleostearic, or others that are commercially available.
With these two types of systems, alkyds are used to prepare coatings that
cure u p o n baking or air drying.
Alkyds are very versatile and can be blended with many other resins
[37-39]. However, alkyds are not highly chemical resistant and are affected
by water [40]. They have fair resistance to petroleum solvents and oils
but are removed (dissolved) either by polar solvents (ketones, esters) or
164 5. Alkyd Resins

chlorinated c o m p o u n d s . Alkyds are thermally stable to about 300°F but

become brittle at this temperature.
Kienle and Hovey [41] studied the reaction of phthalic anhydride (3.0
moles) with glycerol (2.0 moles) and found that by titration of aliquot
samples the free acidity is reduced to approximately one-half within one
minute after the start of the reaction, as shown in Fig. 2.
Kienle and coworkers also found that phthalic acid gives similar results to
phthalic anhydride and reacts at a similar rate once 5 0 % esterification has
been attained [42]. This is true since both reactions give a c o m m o n
intermediate product as shown in E q . (3).
Infrared spectra of phthalic acid and anhydride based alkyds are shown
in Fig. 3.

r ^ > - C O ^

CH2-CH-CH2 VC-OCH CH-CH OH

2 2

or + 1 1 1 • I
OH OH OH >-COH OH
Ο
/ \ II ο

f \ c
~ 0 H (3)
II
ο

Fig. 2 Decrease of free acidity with time (T - = 195°C; solid line, free phthalic anhydride;
broken line, acid number). [Reprinted from R. H. Kienle and A. G. Hovey, J. Am. Chem.
Soc. 51, 509 (1929). Copyright 1929 by the American Chemical Society. Reprinted by
permission of the copyright owner.]
2. Unmodified Alkyds 165

Wavelength (μπι)

Fig. 3 Infrared spectra: (1) glyceryl phthalate (acid), A.V. = 129; (2) glyceryl phthalate
(anhydride), A.V. = 126. [Reprinted from R. H. Kienle, P. A. Van Der Menlen, and F. E.
Petke, J. Am. Chem. Soc. 61, 2268 (1939). Copyright 1939 by the American Chemical Society.
Reprinted by permission of the copyright owner.]

2-1. Preparation of Poly (glyceryl phthalate) Alkyd Resin

[41]

en CO.
> )
CO^
+
CH -CH-CH
I
OH
I
2

I
OH OH
2

C C-OCH CH-CH -C2 2 C-OCH CH-CH 0-

2 2 (4)
II II I II I
ο ο ο οο ο ο o-
I
II
-c c=o
166 5. Alkyd Resins

To a resin flask equipped with a thermometer, mechanical stirrer, con­

denser, Dean & Stark t r a p , and nitrogen bubbler are added 46.0 gm
(0.50moles) of glycerol and l l l g m (0.75 moles) of phthalic anhydride.
The reaction mixture is heated to 195°C for l y h r while a slow stream of
nitrogen is bubbled through it. The acid value is about 170 at this point, and
the product is still soluble in acetic acid, acetone, and other solvents.
Further heating at 195°C for another l y h r causes the resin to set to an
insoluble gel (acid n o . = 119-136). The reaction data are shown in Table II
along with percent esterification data in Table III and Fig. 4. The Dean &
Stark trap in the above preparation contained 7.0 gm of a liquid consisting
of water and some white crystals. Titration with N/25 potassium hydroxide
using phenolphthalein as an indicator showed 0.085 gm of phthalic
anhydride (0.076%).
Since phthalic anhydride is insoluble in most oils (linseed, safflower, and
the like) but soluble in monoglycerides, the oils are first alcoholized with
the polyol (glycerin or others) in the presence of a catalyst to form

TABLE II Isotherms of Free Acidity Change

with Time at 195°C fl

Time Time Free anhy­ Acid

(sec) (min) dride (7o) number

0 0 70.67 535
215 3.58 31.05 235
720 12.16 28.99 218
1320 23.0 27.02 212
2440 40.67 25.25 191
3420 50.0 24.51 185
3980 63.0 23.96 181
4380 73.0 23.42 177
5790 96.5 22.23 169
6780 113.0 21.47 163
8340 139.0 21.02 159
9000 150.0 19.93 151
9720 162.0 19.84 149
10,610 177.0 19.18 145
11,150 186.0 18.31 139
11,340 189.0 17.94 136
11,700 195.0 15.81 119

a
Reprinted from R. H. Kienle and A. G.
Hovey, / . Am. Chem. Soc. 51, 509 (1929).
Copyright 1929 by the American Chemical
Society. Reprinted by permission of the copy­
right owner .
2. Unmodified Alkyds 167

TABLE III Variation of Properties of Products with Time at 195°C fl

Time Time Flow pt. Refr. Acid Sapon. Ester Ester

(sec) (min) (°Q index number number value (%)

0 0 — — (535) — 0 0.0
215 3.58 64 — 235 584 349 59.8
720 12.16 69 — 218 582 364 62.5
1380 23.0 76 1.56 212 583 371 63.6
2440 40.67 78 — 191 570 379 66.5
3420 50.0 81 — 185 589 404 68.5
3980 63.0 82.5 — 181 591 410 69.4
4380 73.0 83 — 177 588 411 69.9
5740 96.5 86 — 169 589 420 71.4
6780 113.0 91 — 163 605 442 73.0
8340 139.0 96 — 159 611 452 73.8
9000 150.0 96 — 151 604 453 75.0
9720 162.0 105 — 149 605 456 75.5
10,610 177.0 106 — 145 608 463 76.1
11,150 186.0 118 1.58 139 614 475 77.3
11,340 189.0 Gel — 136 585 449 77.8
11,700 195.0 Gel 119 574 455 79.3

a
Reprinted from R. H. Kienle and A. G. Hovey, / . Am. Chem. Soc.
51, 509 (1929). Copyright 1929 by the American Chemical Society.
Reprinted by permission of the copyright owner.

monoglycerides. The use of catalysts (litharge, calcium hydroxide, and so

on) at 525°-550°F gives satisfactory results provided a condenser is used to
prevent loss by volatilization of the ingredients. The reaction is complete
when 4 volumes of methanol are soluble in 1 volume of the monoglyceride
product at the boiling point of methanol. Samples are taken every 5 min and
checked. The reaction usually takes about 20 min. The catalyst is usually
0 . 1 - 0 . 1 5 % of the glycerin calculated on the basis of the metal content. The
calcium catalyst is preferred from the standpoint of efficiency and resin
color. After the alcoholysis step the polycar boxy lie acid (such as phthalic)
is added with or without solvent to complete the alkyd preparation. The
reaction is usually carried out at 450°F, and an inert gas is used throughout
the entire process to facilitate water removal and to prevent color formation.
Safflower oil, because of its outstanding quick drying and excellent
initial color with minimum after-yellowing, has come into wider use than
has linseed oil. A n analysis of the properties of the various oils is given in
Table IV.
A typical oil-modified alkyd resin synthesis using linseed oil is given in
Preparation 2-2. M o r e recent examples of alkyd resin preparation are
shown in Table VI.
168 5. Alkyd Resins

5 50

ι1 40

l2 30 ·

20 •

10 ·
10 30 50
01 ι ι ι ι—ι 1 1

0 20 40 100 150 200

Time (min)
Fig. 4 Increase of esterification with time (T = 125°C). [Reprinted from Ν. H. Kienle and
A. G. Hovey, / . Am. Chem. Soc. 51, 509 (1929). Copyright 1929 by the American Chemical
Society. Reprinted by permission of the copyright owner.]

TABLE IV Component Fatty Acids in Oils used in Coating Compositions 0

Percent acid in various oils

Dehydrated
Fatty acid Linseed d
Safflower* Soybean f
castor 7

Linolenic 52.0 0.0 9.0 —

Linoleic 16.0 78.0 51.0 65.0
Conjugated 5
— — — 22.0
Olein 22.0 13.0 25.0 7.5
Saturates 0
10.0 9.0 15.0 0.6
Hydroxy acids — — — 5.0

a
Reprinted from A. E. Rheineck and L. O. Cummings, / . Am. Chem. Soc.
43, 409 (1966). Copyright 1966 by the American Oil Chemists Society.
Reprinted by permission of the copyright owner.
b
9,11-Octadecadienoic acid.
° Comprises myristic, palmitic, stearic, and archidic acids and small
amounts of other monoenoic acids.
d
Liquid chromatography chart published by Archer-Daniels-Midland,
Minneapolis, Minn. 1961. Mol. wt. 878.
e
W. Ibrahim, J. Iverson, and D. Firestone,/. Assoc. Off. Agric. Chem. 47,
776 (1964).
' R. L. Terrill, / . Am. Oil Chem. Soc. 27, 471 (1950).
 2. Unmodified Alkyds 169

2-2. Preparation of Linseed Oil-Modified Poly(glyceryl

phthalate) Alkyd Resin by the Fusion Process [43]
HO-CH 2

ο ιI
W HOC]
HOCH
11 II
Ο + CH (CH )4CH = CHCH CH=:CH(CH2)7COOCH2
C ^_ _ ^ H ) C H = CHCH2CH = CH(CH ) CO~ ~
3 2 2

C 2 4 2 7

Ο
and related unsaturates (see Table IV)

C C-OCH2CH-CH2-O-C C-OCH2CH-CH2-O-
ô ô I /) \ 0 0 ό
och; X
> I

C- (CH ) CH=CHCH CH=CH(CH ) CH

2 7 2 2 4 3

II
Ο
(5)

T o a resin kettle equipped as in Preparation 2-1 and containing a carbon

dioxide sparge are added 336 gm of linseed oil (0.383 mole, 1.15 equiv.) and
80 gm (0.87 mole, 2.6 equiv.) of glycerin, and the mixture is heated to
225°F. Then 0.15 gm of calcium hydroxide catalyst is added, and the
alcoholysis completed at 45°F in about 30-40 min. (One volume of resin is
soluble in 4 parts of boiling methanol.) The remainder of the glycerin
(28 gm = 0.305 mole, 0.915 equiv.) is added, and after 10 min 250 gm
(1.69 moles, 3.39 equiv.) of phthalic anhydride is added. The temperature
of the reaction mixture is raised to 450°F, and the batch held at 450°F until
the reaction is complete (no condenser used), i.e., until an acid value of 5-7
is obtained and a 5 0 % mineral spirits sample has a Gardner viscosity of W
(Gardner Standard Tubes used). The total processing time is approximately
5-6 hr.
A typical safflower oil alkyd involves the following formulation [44].

Safflower oil, 797 gm Ί

Litharge, 0.4 gm > Alcoholysis
Pentaerythritol, 225 gmj
Phthalic anhydride, 346 gm

After condensation to a resin, the mixture is m a d e up to 7 0 % solids in mineral

spirits. The solution dries in 30 hr to a tack-free film.
170 5. Alkyd Resins

A short alkyd ( 3 5 - 4 5 % oil content and > 3 5 % phthalic anhydride)

prepared from soya oil by a solvent cook procedure is given below (Prepara­
tion 2-3). A short alkyd is characterized by having fast setting and fair air
drying but good baking, adhesion, color retention, and gloss. These alkyds
also have fair flexibility ratings.

2-3. Preparation of a Soya Oil-Modified Poly (glyceryl

phthalate) Alkyd Resin by the Solvent Process [45]
Ο Ο
ÇH OCR
2 CH OH2 CH2OCR
C H - O C O R + CHOH • CH-OH
I I I
CH20CR CH20H CH20H
ο
(Soya oil; see Table IV)

(6)

T o a resin kettle equipped as in Preparation 2-1 are added 160 gm (0.183

mole) of soya oil, H O g m (1.21 moles) of glycerol, and 0.25 gm of litharge
catalyst. The reaction mixture is heated to 233°C while carbon dioxide is
bubbled through the reaction, and the temperature is held at 233°C until the
mixture gives a clear methanol test (alcoholysis is complete if 1 volume of
the alcoholysis product is soluble in 4 volumes of methanol). The mixture is
cooled to 138°C and 180 gm (1.21 moles) of phthalic anhydride is added
along with 18 gm of xylene. The mixture is heated to reflux for approxi­
mately 6 h r until 22.0 gm (1.21 moles) of water is collected in the Dean &
Stark t r a p . Then 440 gm of xylene is added to give a 5 0 % solids solution
with an acid value of 4.0. This resin has 3 7 . 5 % excess hydroxyls and func­
tionality of 1.95. It will form a h a r d film on air drying in 4-5 hr. The use of
0.03-0.07% cobalt naphthenate is recommended as an aid to speed drying.
A medium oil alkyd ( 4 6 - 5 5 % oil content and 3 0 - 3 5 % phthalic anhydride
in final resin) is one that has good water impermeability, fair baking and color,
usual application, and is soluble in aliphatic solvents such as mineral spirits
and naphthas. The modifying oil commonly used here is linseed or soya.
A typical fusion process formation for a medium oil alkyd resin is as
follows [46].
2. Unmodified Alkyds 171

Parts Equivalents

Pentaerythritol 100 2.92

{21% excess OH)
Tall oil fatty acid 200 0.69
Phthalic anhydride 120 1.61
(resin functionality
2.08)

The mixture is heated to 550°F, and after 1 hr of heating nitrogen is

bubbled through until an acid value of 10 is obtained (approximately 6 hr).
The mixture is diluted to 5 0 % solids with mineral spirits.
A long oil ( 5 6 - 7 0 % oil content; 2 0 - 3 0 % phthalic anhydride in final resin)
alkyd resin is one that has good flexibility, solubility, and brush application.
This alkyd resin requires aliphatic solvents such as mineral spirits and is
slow drying.
A typical fusion process formulation of a long oil alkyd is given below [47].

Parts Equivalents

Glycerin 80 2.57
Linseed oil 330 1.22

Both glycerin 80 gm (2.57 moles) and linseed oil 360 gm (1.22 moles) are
heated to 260°C, and then 160 gm (1.94equiv.) of phthalic anhydride is
added. The mixture is cooked until an acid value of 10 is reached, and then
the resin is cooled and diluted to 7 0 % solids with mineral spirits.
As mentioned earlier benzoic acid (or p-tert- butylbenzoic acid) is some­
times added to alkyd resin formulation to control the molecular weight by
acting as a molecular chain stopper [48, 49]. A typical formulation of such
an alkyd is shown in Preparation 2-4.

2-4. Preparation of an Alkyd Resin with Benzoic Acid to

Control Molecular Weight [48]
In a resin kettle equipped as previously described are heated 94.5 gm
(0.65 mole) of alkali-refined soya oil, 23.5 gm (0.26 mole) of glycerin (98%),
and 0.05 gm of calcium hydroxide for \ hr at 450°F with good stirring and
using a carbon dioxide blanket. Alcoholysis is checked by mixing 1 part of
the reaction mixture with 4 parts of anhydrous boiling methanol. A clear
solution of the boiling methanol indicates proper alcoholysis. At this point
172 5. Alkyd Resins

Ο
ÇH2-ÇH-ÇH2 + ÇH.O^R ^ ÇH OH 2 phthalic anhydride ^
OH OH OH CH—OCR 4 5 0
° F
CH-OH benzoic acid
II I
Ο CH OCR 2

CH OCR
2

Soya oil

are added 3 9 . 0 g m (0.42 mole) of glycerin (98%), 113.0gm (0.76 mole) of

phthalic anhydride, a n d 16.7 gm (0.14 mole) of benzoic acid (95%) [glycerin:
phthalic anhydride 2 . 4 : 3 (20% excess glycerin)]. While carbon dioxide is
bubbled through, the reaction mixture is heated slowly from 290°F to 440°F
over a 1-hr period, a n d heating at 440°F is continued until the acid number
of 13.6 is reached. T h e product is diluted t o 5 0 % solids with xylene to give
a resin that air dries in 215min (with the aid of 0.5 gm lead or 0.05 gm cobalt
naphthenate-type catalyst) to a dry, hard film. Baking for \ hr at 250°F
speeds the curing time to 33 min. (Due to toxicity, lead salts are not
preferred.)
Trimethylolpropane [ C H C ( C H O H ) ] ( m . p . 58.8°C) can be substituted
2 5 2 3

for glycerin in many alkyd resin preparations to give improved heat and
light stability t o the final products. Some typical formulation (1-4) are

Formulations

Parts by weight (1) (2) (3) (4)

Soybean oil 39.1 29.9

Glycerin 20.9 — — —
Trimethylolpropane — 30.2 33.6 31.86
Phthalic anhydride 140 140 39.7 35.6
Tall oil fatty acids — — 26.7 32.5
2. Unmodified Alkyds 173

shown belo w an d ar e prepare d b y th e solven t coo k procedur e t o a n aci d

number o f 14-1 7 [50] .
The molucla r weigh t distributio n i n alky d resin s prepare d usin g casto r oi l
or hydrogenate d casto r oi l ha s bee n reporte d [51 ]

B. Alkyd s Base d o n Othe r Acid s

Kienle an d Petk e wer e amon g th e firs t t o stud y th e effec t o n th e rati o an d
properties o f alky d resi n formatio n o f acid s othe r tha n phthali c aci d o r
anhydride. I n al l case s wher e eithe r aliphati c o r aromati c acid s wer e use d
the greates t tim e involve d th e firs t hal f o f th e reaction . Th e aci d value s nea r
gelation wer e betwee n th e calculate d value s fo r th e dime r an d tetramer . Th e
percent esterificatio n attaine d a t gelatio n wa s abou t th e sam e fo r th e
different dibasi c acid s (approximatel y th e sam e a m o u n t o f wate r evolved) .
A summar y o f som e othe r acid s i n compariso n t o phthali c anhydrid e i s
shown i n Tabl e V .
The infrare d spectr a o f th e alky d resin s fro m th e aliphati c acid s ar e
similar a s see n i n Figs . 5 an d 6 .
Recent catalys t studie s o n preparin g phthali c anhydride-base d alkyd s
indicate tha t i n a stud y o f hydroxyethylphthalate s th e us e o f th e aluminu m
salt (an d N a C 0 ) gav e th e alky d resi n wit h th e bes t propertie s (goo d hard -
2 3

ness an d goo d fo r coatin g meta l parts ) [52] .

Spectroscopic studie s showe d tha t residue s forme d i n th e preparatio n o f
phthalic-anhydride-based alky d resin s containe d mainl y meta l phthalate s
[53]. A summar y o f thes e resin s i s give n i n Tabl e VI .

2 ' ' 5 ' 8 11 "TÏ"

tgnelevaW h (μιη)

Fig. 5 Infrared specta: (1) glyceryl maleate, A.V. = 231; (2) glyceryl succinate, A.V. = 182.
[Reprinted from R. H. Kienle and F. E. Petke, J. Am. Chem. Soc. 62, 1053 (1940). Copyright
1940 by the American Chemical Society. Reprinted by permission of the copyright owner.]
174 5. Alkyd Resins
o ^
<N OO
Λ > —< O
O
rH h O O O
Ο ^<N !Λ !Λ
> Ο
< S ON ^ O
NO «O
U
NO ·/"> O —
t Ό
oo r-' od
r- NO
s
Tf
i^i o m ONON «/n
α
o
U
32
<
ο
3 ο
03 w O oo fN m o
M in
-h -h -h -h (N
O ON ON ON «y-i
•S g .s O Tf m r- r-
o3 C H
NO NO OO Ο Ό
α
ci O w
-Si Je 5
S X
ω
2 S: s
CQ
<
f—
««Ι
•o
r- ^
Ë O m
o 2 c
··-> *on _.
J-i
0D,3 -faS 0C!3
-—
ρ α c
£ ^ W
(l) <u V-i
.S -α ·
ω ω ω τ 1
Ο αo *ce (β S
ϋ û^ cuiU^
J-,
Λ
<>
l .S
£ a 3 -S 3 ex ~
DH 1/ 1 ^ C/ 3 Λ
2. Unmodified Alkyds 175

4 6 8 10 12
Wavelength (μπι)
Fig. 6 Infrared spectra: (1) glyceryl adipate, A.V. = 159; (2) glyceryl sebacate, A.V. = 118.
[Reprinted from R. H. Kienle and F. E. Petke, / . Am. Chem. Soc. 63, 481 (1941). Copyright
1941 by the American Chemical Society. Reprinted by permission of the copyright owner.]

2-5. Preparation of Glyceryl Adipate [54]

Ο Ο
CH -CH-CH + HOC-(CH ) -C-OH
2 2 2 4

I I I
OH OH OH

I
Ο CH-OH
II I
CH 0-(CH ) -C-OCH
2 2 4 2
(8)
Ο
II
Ο O CH-OC-(CH ) -C- 2 4

- C - (CH ) - C - OCH
2 4 2 Ο

In a resin flask equipped as earlier described and equipped with a

nitrogen bubbler are heated 23.0 gm (0.25 mole) of glycerol and 54.8 gm
(0.375 mole) of adipic acid. The experimental data for this alkyd resin are
found in Table V and Fig. 7. The infrared spectra of the product is shown
in Figs. 5 and 6.
The alkyd resins prepared from the aliphatic polyacids [55] (sebacic,
azelaic, and adipic) were used as caulking compounds during World W a r II,
particularly for aircraft. These products also have valuable features as
nonmigrating plasticizers for film formers such as cellulose derivative [56].
176 5. Alkyd Resins
-ο ε
o
ο
7 I su
δ
ο
Ζ
I I ε
Χ Os
ο ο
E4 o
PU
J3 -Ci
Η Χ EU
ο
S
ο ο o
(Ν ΓΝ)
.2
C
ο
Ο
I I
ο
M
ε 2 M
Ο o O OO
U (Ν (Ν .52 θ"\
U O
ε < Q
I I
Q
I f s
3& HJ Ο
ι—I G <Ν
ο CU
ο Ο
(Ν Ο
T3 ω 2
g? Ρ Ό 1Η° ε £
Λ Τ3 xi
-Ρ Ο &ο ι
- ο Λ .2 i-î
o
D se i—1
eg 2 -Β s s s
£ o
B Û O
2 £ U
ω
^ ο ο
2 ο
o ^
O
2 PQ Q
c .5 ο
| 8
Η σ\
Ο-ι Η —ι
3 0 0
12 00 g 00
O ^ Q
sis
-2 % ε < d H ν^- } ΕM­ o
£ ^ 3 M ^ w
as r : a
2. Unmodified Alkyds 111

Fig. 7 Reaction data for glyceryl
54.8 gm; Δ , temperature; • , acid
F. E. Petke, J. Am. Chem. Soc.
Society. Reprinted by permission
Time (min)
adipate with proportions of glycerol 23.0 gm and adipic acid
value; O, water evolved. [Reprinted from R. H. Kienle and
63, 481 (1941). Copyright 1941 by the American Chemical
of the copyright owner.]

The addition of oils gives resins that may be useful for coated fabric
applications and in lacquers for rubber articles such as cable coatings, and
automotive finishes [55].
In recent years the availability of several aromatic polycarboxylic acids
has been exploited in specialty alkyd resin preparations [57,58]. For
example, trimellitic acid-based alkyds are used in alkyd-melamine enamels
and acrylic lacquers [57]. Isophthalic acid can be used alone or in conjunc­
tion with trimellitic anhydride or phthalic anhydride [59]. Pyromellitic acid
and pyromellitic anhydride have also been suggested as partial replacements
for phthalic anhydride in long or short oil alkyds to give more water-
resistant (also caustic- and gasoline-resistant) coatings [60].
Some typical formulations are described in Table VII.
178 5. Alkyd Resins
O
00
υ
i i J. o o
U
υ
υ
o
c
<
< <
I I
3
P2
o
O
o O
_ — _T Q
<
~ 'n "δ
H
O Tf O o
C o
o
υ 5 00
o
c
<
00
c
LU
ô ô g.
o & £ 2
o o
a, 00 00 Ci
— — o
α D.
O E
o <
ο α O « "35 os
w w
JL 4 $ —
Ό Ό û. 0 > r*- i •
Έ ^ ^ <N E S ' < -s
Ό oo Ό m w
^ >>
O J= ^ ^ ^ ?S "2 "e "ô ^ ! h- o
C ~T ~ "G w c~ ^> TT
g s JE ·§' °· z •
q C/?
o o
o Ξ .a = .2 2 î: -a o e
Q ON Ο ^
^ -E E ~~ ca
o o
H J2 < .5£ ^ .E
 2. Unmodified Alkyds 179

2-6. Preparation of a Trimellitic Anhydride-Based Alkyd

Resin No. 3712NT [57]
ο
II
C-OH
CH 3

+ (CH ) (COOH) + H O C H - C - C H O H + tall oil fatty acids

2 4 2 2 2 —
CH 3

Ο Ο
r^N-C-OH r^^jpC-OR-H
Ο-R-OC-L· ]Lc-OR-C-(CH )4-C-0-R-0-C-L
2 v iJ-C-OR-O-O
II II II II II II II
ο ο ο ο ο ο ο
R = neopentyl (9)
C— derived from tall oil fatty acids
Ο
CAUTION: All operations with trimellitic anhydride (or acid) must be
carried out in a well-ventilated h o o d using proper personal protection such as
gloves, laboratory apron-coat, and chemical goggles. Exposure to trimellitic
anhydride may cause eye or skin irritation or lung irritation (pulmonary
edema).
A resin kettle is charged with 307 gm (1.6 moles) of trimellitic anhydride
( T M A ) , 388 gm (2.85 moles) of neopentyl glycerol, 78 gm (0.535 mole) of
adipic acid, and 304 gm (1.07 equiv.) of tall oil fatty acids [97.6% fatty
acid, 1.2% rosin acid (acid n u m b e r 197)] and agitation and inert gas
sparging is begun. The temperature is raised to 370-380°F over a 1-2 hr
period to control the evolution of water. The temperature is held at
370°-380°F to obtain an acid number of 55-60. (The resin is insoluble in a
conventional benzene-ethanol mixture; therefore, acid numbers are deter­
mined in acetone. T w o to three hours are required to obtain this acid
number after reaching 3 7 0 ° - 3 8 0 ° F . T h e resin is cooled to 3 6 0 ° - 3 7 0 ° F and
held at that temperature until the acid n u m b e r is 50-55 (see Fig. 8). The
total processing time is 5-6 hr, and 1000 gm of resin is obtained. The resin
is diluted with a mixture of 85 parts water to 15 parts te/Y-butyl alcohol and
solubilized with A^N-dimethylethanolamine t o give a p H 7-8 and a 4 0 %
solids (NVM) resin of Gardner Color 2-4 and G a r d n e r - H o l d t viscosity Z-2.
Some additional examples from the recent literature involving aromatic
and alphatic carboxylic acids including polymer (for example, poly(metha-
crylic)acid) for the preparation of alkyd resins are shown in Table VIII.
180 5. Alkyd Resins

! j
! I ι
•
100
! • ;
• Ι
• 1 ί
90 •·:
;
•ί I
Φ
Ρ
; j I
1
•g 80 j
;· ί \
> ·•
C
^ 3823 NT resin (1) : i
<
•

3 70 I 1 ^ 3712 NT resin (2) 1

_j
1-. ^ ;
I ι 1 i

ι
i
*
60 i

I
50 ι \ : 1

r»i H n r» ran σ ρ
' !
1
ι ι : ι : l ι
ι'
40
Reaction time (hr)
Fig. 8 Reaction time by acid number. (1) Heated to 380°F in 1 j hr; held at 380°F for 2 hr,
lowered to 360°F, and held for properties. (2) Heated to 360°F in 1 hr and held for properties.
Resin 3823 NT is similar to 3712 NT but contains TMA (244 gm), neopentyl glycol (352 gm),
adipic acid (123 gm), tall oil fatty acids (362 gm). It is processed in a manner similar to resin
3712 NT. [Reprinted from "Amoco TMA in Primers for Alkyd-Melamine Enamels and
Acrylic Lacquers," Tech. Bull. TMA 25a. Copyright by the Amoco Chemical Corporation,
Chicago, Illinois, 1974. Reprinted by permission of the copyright owner.]

3. MODIFIED ALKYDS
Alkyd resins have been reported to be modified by a variety of starting
materials (rosin acid-maleic anhydride adducts) and other resins with reac­
tive or exchangeable groups. Some typical resins used to modify alkyds are
[61] phenolic resins (OH groups), polyamide resins ( N H groups), epoxy 2

resins [38, 62] (epoxy and O H groups), polyurethane resins ( N C O groups),

amine resins (mealamine-formaldehyde or urea-formaldehyde) [37], and
vinyl resins containing reactive groups.

Ο
xylene
(HOCH CH ) NCR' + R(COOH)
2 2 2 2
140°C

Ο
H-f-OCH CH N-CH CH OCRCO-
2 2 2 2 -OH (10)
COR'
3. Modified Alkyds 181

TABLE VIII Recent Preparations of Alkyl Resins Using Other Acids

Acid or Anhydride Polyol Solvent Catalyst Ref.

Isononanoic acid and Trimethylol propane Xylene — a

phthalic anhydride
Behenic acid and Dipentuerythritol — Tin powder b
phthalic anhydride
Maleic anhydride, Glycerol — — c
trimellitic anhydride,
and maleopimaric acid
Fumaric acid Via epoxy resin — — d
(DER-332)
Poly(methacrylic acid) Pentaerythritol — PbO e
Dimethylterephthalate Glycerol neopentyl glycol — Pb napthenate f
Dimethylterephthalate Neopentyl glycol — Dibutyltin-oxide g
adipic acid
Tetrahydrophthalic Neopentyl glycol — — h
anhydride
Isophthalic acid — — — i
trimejlitic anhydride

L Sadlowski, H. Diefenbach, D. Schmitt, M. Dangschat, and T. Lesar, Eur. Pat. Applic.

a

EP 337087A2 (10/18/89), Chem. Abstr. I l l , 234320e (1989).

*G. H. Schulte, H. Fischer, R. Hoefer, K. Marten, H. Onusseit, and B. Wahle, German
Patent Ger. Offen DE 3743424A1 (6/29/89), Chem. Abstr. 112, 36788h (1989).
R . Parvani and M. C. Shukla, Pigm. Resin Technol. 20(12), 4 (1991); Chem. Abstr. 116,
C

257394m (1991).
E. Takiyama, Y. Tanabe, M. Akiyama, and M. Arai, Japanese Patent JP61282341A2
d

(1986); Chem. Abstr. 107, 1352243 (1986); T. C. Domide, D. Dobre, A. Radu, C. Berceanu,
and E. Dinculescu, Romanian Patent R090760B1 (1986); Chem. Abstr. 107, 237921S (1986).
Z. Vasicek, K. Hajek, B. Kratky, Z. Ditrych, J. Ruzickova, E. Krejcar, and P. Suran,
e

Czech Patent CS 231384 B7 (1987); Chem. Abstr. 107, 219233q (1987).

T. C. Domide, D. Dobre, M. E. Rosetti, C. Berceanu, A. Radu, and E. Dinculescu,
f

Romanian Patent RO90561B1 (1986); Chem. Abstr. 108, 132785t (1986).

*J. D. Downs, R. L. Drurry, Jr., Κ. B. Moser, and C. D. Roth, U.S. Patent 4,713,436
(1986); Chem. Abstr. 108, 222541q (1986).
υ. Florek, B. Kaczmarzyk, J. Lichecki, D. Halgas, A. Kwiathowski, E. Tyrka, and
Λ

A. Cuber, Polish Patent PL 148764 (1989); Chem. Abstr. 113, 173392J (1989).
' C . J. Coady, Modern Paint Coat. 82(2), 40 (1992); Chem. Abstr. 116, 237389K (1992).

Recently, polyester amides were prepared by heating linseed diethanol-

amide in refluxing xylene with dibasic acids or anhydrides to give modified
alkyd resins [63, 64].
Some typical acids used and the air-dried film properties obtained are
shown in Table IX.
182 5. Alkyd Resins

TABLE IX Air-Dried Film Properties of Polyester Amides*' 6

Sward
rocker hardness Resistance
Dry to Tack to 5 % Resistance
3 10 25 touch free NaOH to xylene
Acid days days days (hr) (hr) (min) (hr)

Terephthalic 5 20 46 1 5 51 220
Phthalic 5 16 32 2.7 21 13 220
Fumaric 20 28 48 3.5 8 4 220
Maleic 8 28 34 32 48 4 32
Itaconic 8 22 38 3 21 4 32
Dimer T — —
_— 90 500 — —
c

Dimer C c
— — 168 500 — —
Azelaic — — — 250 250 9 220
Brassylic — — — 72 500 3 220
Soy alkyd d
8 14 18 2 22 6 0

a
Contains 0.57 Pb + 0.01 % Co naphthenates used as driers.
o
b
Reprinted from L. E. Gast, W. J. Schneider, and J. C. Cowan, / . Am. Oil Chem. Soc.
43, 418 (1966). Copyright 1966 by the Journal of the American Chemists Society.
Reprinted by permission of the copyright owner.
c
Τ = prepared by thermal process; C = prepared by a catalytic process.
d
Sixty-five percent oil-length alkyd.

3.1 Preparation of Polyester Amide by the Reaction of

N,N-Bis(2-hydroxyethyl)linseed Amide and
Dibasic Acids [63]
Method A: Preparation of Af,Af-Z?i5(2-hydroxyethyl)linseed Amide
T o a round-bottomed flask fitted with a stirrer, thermometer, nitrogen
inlet tube, and dropping funnel is added 210 gm (0.2 mole) of distilled
diethanolamine ( b . p . 170°C, 25 1.4740). The contents are warmed to
100°-105°C and 0.13 gm (0.0024 mole) of sodium methoxide catalyst is
added. Linseed methyl ester (29.5 gm, 0.1 mole) is then added dropwise
over a 15-min period. After the addition the reaction is continued under
reduced pressure (20 m m Hg) to facilitate removal of methanol. The reac­
tion mixture is cooled, dissolved in ether, washed with 1 5 % aqueous sodium
chloride, and dried over sodium sulfate. The ether solution is filtered and
the ether removed to afford 34 gm (93%) of a yellow-orange oil.

Method B: Alkyd Resin Preparation

T o a round-bottomed flask fitted with a mechanical stirrer, condenser,
Dean & Stark t r a p , and nitrogen inlet/outlet tubes are added 0.05 mole of
3. Modified Alkyds 183

TABLE X Properties of polyester Amides of HELA and

Dibasic Acids a

Gardner
Iodine
Acid Viscosity Color value Acid no.

Terephthalic »Z10 17 117 13.3

Phthalic >Z10 15 114 6.6
Fumaric Z5-6 12 135 1.0
Maleic »Z10 13 122 21.3
Itaconic Z7-8 15 125 1.4
Dimer T b
V-W c
10 116 8.0
Dimer C b
Z7 14 148 19.0
Azelaic Z6 15 107 17.0
Brassylic Z8-9 15 95 12.1

α
Reprinted from L. E. Gast, W. J. Schneider, and J. C.
Cowan, J. Am. Oil Chem. Soc. 43, 418 (1966). Copyright
1966 by the Journal of the American Oil Chemists Society.
Reprinted by permission of the copyright owner.
b
T = prepared by thermal process; C = prepared by
catalytic process.
c
Fifty percent solids in toluene.

Af,A^te(2-hydroxyethyl)linseed amide ( H E L A ) , 50 ml of xylene, and 0.05

mole of a given dibasic acid. The reaction mixture is refluxed (140°-150°C)
while nitrogen is bubbled slowly through it until the theoretical a m o u n t of
water is collected. The xylene is removed under reduced pressure in a
rotating evaporator to give polyester amides with properties as described in
Table X .
It should be noted that in preparing epoxy alkyd resins the functionality
of a typical epoxy resin (Epon 1001) is 6, due to 2 O H groups and 2 epoxy
groups (4 functional sites). A typical recipe is as follows [65].

Moles used in
alkyd resin

Reaction product of Epon 1001 (Shell Chemical Co.) (1.0 mole) 0.25
and fatty acid (3.0 moles)
Glycerin 0.75
Phthalic anhydride 1.00
Fatty acid 1.00
Functionality/mole = f = 2.0
 184 5. Alkyd Resins

4. ALKYDS MODIFIED WITH VINYL MONOMERS

The unsaturated sites in alkyds are capable of undergoing further
reactions such as Diels-Alder (maleic acid or anhydride [23,66], cyclo-
pentadiene [67]) and polymerization [68] in the presence of catalysts or
other monomers, styrene [69], vinyl toluene [70, 71], methyl methacrylate
[72], acrylic [72], and acrylonitrile [73].
The availability of styrene at low cost in large commercial quantities led
to its use in applications where quick drying, chemical resistance and good
weathering alkyds were required [74]. Mixtures of several monomers also
have been occasionally used provided copolymerization between monomers
is possible [75].
In preparing styrenated alkyds there are four possible methods [76]:

1. Prestyrenation of reactive oil, followed by monoglyceride formation

with a polyol and subsequent reaction with a dibasic acid
2. Prestyrenation of a fatty acid followed by alkyd formation
3. Prestyrenation of unsaturated monoglyceride before alkyd formation
4. Poststyrenation of an oil-modified alkyd

The last method [77] is used in the presence of solvent, and the alkyd is
prepared in the normal fashion, but the reaction is stopped short to allow
further esterification to take place during the styrenation procedure.
Since styrene-modified alkyds are the most important commercially an
example of a typical preparation is decribed below (Preparation 4-1).
R o h m & H a a s C o . has suggested the use of methacrylates in alkyd resin
modification [78].

4-1. Preparation of a Styrene-Modified

Linseed-Trimethylolethane Alkyd [71]
alkyd resin + styrene •

OCH2-C-C2H5 C-O-CH2-C-C2H5 CH CH-C H

2 6 5

Ο CH -0-
2 CH-CH(CH ) -CH 2 4 3

C6H5

Jn

(ID
4. Alkyds Modified with Vinyl Monomers 185

Method A

To a 1-liter resin flask equipped with stirrer, thermometer, Dean & Stark
t r a p , and condenser are added 130.0 gm (0.88 mole) of phthalic anhydride,
260.5 gm (0.925 mole) of linseed oil (fatty acids), 114.5 gm (0.956 mole) of
trimethylolethane, and 30 ml of xylene. The reaction mixture is heated to
230°C over a 1-hr period and kept there until the water of esterification is
removed and an acid value of 13 ± 3 is reached. The reaction mixture is
cooled to 130°C and diluted to 7 0 % solids with xylene.

Method Β

To 200 gm of the above alkyd resin (70% xylene solution) in a 500 ml

three-necked round-bottomed flask equipped with a thermometer, stirrer,
and reflux condenser is added at reflux over a 2-hr period 140 gm
(1.34 moles) of styrene containing 3.5 gm of di-tert-butyl peroxide. The
reflux is continued for a total of 6 hr, and then the reaction cooled to 130°C
and diluted to 6 0 % solids with xylene.

In the latter preparation the alkyd resin is prepared by the simultaneous

esterification of linseed fatty acids and phthalic anhydride with trimethylol­
ethane.
In another procedure the alkyd resin is prepared in the usual manner by
alcoholysis of the fatty acid with the polyol followed by phthalic anhydride
condensations. Then the alkyd, diluted in xylene to 6 6 % solids, is reacted
with styrene m o n o m e r using di-te/Y-butyl peroxide catalyst [25].

TABLE XI Alkyds Modified with Vinyl Monomers

Unsaturated reactants Reference

Styrene and 2-ethylhexylacrylate-acrylic acid copolymer a

Styrene and 2-hydroxyethylmethacrylate b
Methacrylates c
Hydroxy and carboxy terminated butadiene/acrylonitrile copolymer d
Dimethylaminoethyl methacrylate e
a
J. Kopelent, A. Stejskal, O. Gorgon, and J. Formanek, Czech Patent CS255441
(1988); Chem. Abstr. I l l , 222100g (1988).
b
E. Takiyama and T. Ogura, Japanese Patent JP 01287121 (1989); Chem. Abstr.
112, 181041p (1989).
C
E . Takiyama, A. Kamakura, and R. Ogura, U.S Patent 4,814,365 (1989).
d
P. J. Ruhoff, R. W. Stockstad, J. A. Prévost, L. B. Brandenburger, and R. S.
Edenburg, U.S. Patent 4,914,139 (1990).
e
A. Mashide, H. Watanabe, and A. Sheji, U.S. Patent 5,019,623 (1991).
186 5. Alkyd Resins

Some recent examples of the use of unsaturated resins used to modify

alkyd resins by coreaction with unsaturated sites or by grafting is shown in
Table X I . The examples and references in Table XI are typical of the recent
literature in this area.

5. ALKYDS MODIFIED WITH OTHER

THERMOSETTING RESINS
Nonoxidizing (nondrying) alkyds can be cured to very durable finishes by
baking with amino resins such as urea [79] or melamine-formaldehyde [80].
Phenolic-modified alkyds are used for coatings requiring alkali resistance.
In addition alkyd resins can be modified with epoxies and polyurethanes
or other thermosetting resins to give coatings of improved performance
[81-83]. For example, urethane oils are prepared by reacting diglycerides
with toluene diisocyanate. The resulting oils are used in alkyd resin prepara­
tions or as additives for coatings.
A typical example [84] involves the preparation of an alkyd resin from
phthalic anhydride (712 gm), trimethylolpropane (399 gm), isodecyl alcohol
(277 gm), and xylene (22 gm) and heating (190°-280°C) to remove water
azeotropically and give a resin of acid value 23. The product is diluted with
a 4 : 1 xylene : butyl alcohol mixture to 7 5 % solids. A lacquer is prepared by
mixing 16 gm of the above alkyd resin solution with 3 gm of a methylated
melamine-formaldehyde condensate along with 7.5 gm of titanium oxide
and 0.225 gm of /7-toluenesulfonic acid m o n o h y d r a t e . Sufficient xylene :
butanol (4 :1) is added to give a 5 5 % solids solution. A film of this solution
is dried for 30 min at 120°C. The film is hard and stable to 10% sodium
hydroxide.
Some additional examples of the use of thermosetting resins to modify
alkyds is shown in Table XII along with the references to the patents
describing them.

TABLE XII Alkyls Modified with Thermosetting Resins

Thermosetting resin Reference

Phenol-formaldehyde resin a
Phenol-modified epoxy resin b
7V-(2-hydroxyethyl) ethylenemine and reactive silicon resin c
a
U. Bloecher and E. J. Duwell, European Patent Applic, EP 211591 (1987);
Chem. Abstr. 106, 124672x (1987).
E. Takiyama, A. Yokoyama, and R. Ogura, U.S. Patent 4,814,365 (1989);
b

Chem. Abstr. I l l , 136184f (1989).

H . Umemoto, H. Tanabe, and Y. Taksuchi, U.S. Patent 4,764,569 (1988).
C
References 187

6. MISCELLANEOUS ALKYD PREPARATIONS

1. Imide-modified alkyds [85].
2. Alkyd resins based on glycerol allyl ether [86, 87].
3. Tetrachlorophthalic anhydride alkyd resins with fire-retardant proper­
ties [88].
4. Maleic anhydride-cyclopentadiene adduct (3,6-endomethylene 1,2,3,6-
tetrahydrophthalic anhydride) in alkyd resin preparations [89].
5. Polyethylene glycol-containing alkyd resins [90].
6. Reaction of alkyd resin terminal hydroxyl groups with ketene [91] and
acetic anhydride [92].
7. Oilless alkyds [93].
8. Aminoplast resin for alkyd resin [94].
9. Ultraviolet light-hardenable pigmented alkyd resin lacquer prepara­
tions [95].
10. Zinc chrornate-containing alkyd resin [96].
11. Triphenyl phosphite-containing alkyd resin of improved color and
drying properties [97].
12. Transesterification catalysts in alkyd resin preparation [98].
13. Water-soluble alkyd resins [99].
14. Mill base alkyd resin formulations [100].
15. Water-dispersible alkyd resins [74].
16. Graft copolymers of /?-hydroxybenzoic acid to give mesogenic side
chains [101].
17. Alkyd resins from fish and plant oils [102].
18. Alkyd resins based on soya-bean oil and other vegetable oils [103].
19. Alkyd resins used in linoleum [104].
20. Enzymic synthesis of alkyds [105].
2 1 . Pentaerythritol based alkyds [106].
22. Linseed oil alkyd resins [107].
23. Alkyd resins from dimethyl phthalate [108].
24. Silicon modified alkyd resins to p r o m o t e rapid curing of coatings [109].

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