5 ALKYD RESINS

W. T. Elliott

5.1 INTRODUCTION
Alkyd resins are low molecular weight esters formed when polyhydric alcohols react with
polybasic and monobasic acids. The term 'alkyd' was first used by Kienle in 1927 to describe
the reaction products of polyhydric alcohols (AL) with polybasic acids (KYD). These crude
reaction products were hard, brittle, insoluble materials of no obvious utility. When
monobasic fatty acids were included in the reaction mix, the product became a solvent-
soluble film forming 'oil-modified' alkyd. The 'oil-modified' adjective was subsequently
discarded, and the new resins were known as alkyds. When a new generation of useful
film-forming polyesters appeared in the 1960s and 1970s they were christened 'oil-free
alkyds' to distinguish them from their very-similar grandparents. While much of the content
of this chapter is relevant to both alkyds and polyester coating resins, the term 'alkyd' will
be reserved for the fatty acid-containing variety.
For many years alkyds were the predominant solvent-soluble surface coating polymers.
They were economical, and their structure could be modified to provide products suitable
for a very wide range of substrates, application methods and cure conditions with acceptable
chemical resistance and durability. The excellent pigment-wetting properties of alkyds and
the availability of new types and grades of pigment designed to exploit their potential, led
to a revolution in methods of paint manufacture in the late 1950s and early 1960s.
Alkyd resins and the demands made of their formulation and manufacture have been a
major factor in the progress of polymer science. It is fitting that alkyds should have been
the model polymers used by Carothers, and by Florey and Stockmeyer in their pioneering
development of gel point theory in the 1940s.
Since about 1960 the position of alkyd resins as the predominant type of paint binder has
been eroded principally by the growth of acrylic resin types. Self-crosslinking acrylic resins
rapidly replaced alkyds in tinplate finishes and white goods coatings. Acrylic lacquers and
acrylic melamine baking enamels made possible durable 'metallic' finishes containing
aluminium flake and replaced alkyds in automotive topcoats. During the same period,
water-based coatings steadily replaced solvent-based systems, particularly in broad wall
applications, with a resulting fall in alkyd consumption in the architectural field. Improve-
ments in water-based systems and development of new types of coating resins, concerns
about the possible hazards of solvents to painters and to the environment, and increases in
factory painting, particularly of building components, continue to reduce the share held by
alkyd resins. Despite these considerations, alkyd-based coatings look like being around for
a long time yet.

76
P. Parsons et al. (eds.), Surface Coatings
© Chapman & Hall 1993
 ALKYD RESINS 77

Alkyds remain a surprisingly large component of the paint industry's usage of resins. An
educated guess based on reported production statistics suggests that alkyds were used in
about 20 percent of the paint volume sold in Australia in 1990. This is due to a number
of reasons. They are a single-pack system that is stable in the can for a long period; they
are inexpensive on a cost/performance basis; and they are exceedingly versatile in
performance. They can be modified to give properties ranging from fast hard-drying,
low-flexibility products to slow-drying, soft, flexible films. Modifying resins, such as rosin,
phenolics, styrene and acrylates, extend the drying perfomance characteristics even further.
Modifying with polyamide resins yields thixotropic alkyds. Products of very high exterior
durability and gloss retention result from copolymerization with silicone intermediates.
As alkyd resins are polyesters, they are subject to normal ester hydrolysis-that is,
sensitivity to water, acid and alkali, particularly when they are dried by oxidation. On the
other hand, the ester structure confers good ultraviolet and heat resistance, leading to
superiority in gloss and colour retention, when compared to, say, epoxy (poly ether) esters
of similar oil length.

5.2 CHEMICAL PROCESSES INVOLVED IN ALKYD TECHNOLOGY

5.2.1 Esterification reactions

When an alcohol reacts with an organic acid, an ester and water are formed.

RCOOH + BOR' (1)

acid alcohol ester water

where R = organic group and R' = different organic group

The reaction is reversible, and the water must be removed for the ester formation to
proceed. As the equation shows, the reaction takes place between the hydroxyl group of the
alcohol and the carboxyl group of the acid. These are the functional groups in the
esterification reaction.
Esters are also formed when alcohols react with acid anhydrides. This reaction results in
formation of an ester without the formation of water.

o o

ROH + <\~-rQ- II=©

ROC

0 (2)
II~
o
H-OC
II
o
alcohol phthalic anhydride phthalate monoester

Phthalic anhydride is a component in the majority of alkyd resins. Its anhydride ring opens
to form a monoester at about 160 C. The acid group remaining in the phthalate monoester
0

starts to react at about 180 C.0

If phthalic anhydride (a difunctional acid) is reacted with an alcohol molecule with two
hydroxyl groups (a difunctional alcohol), a linear polyester is formed.
78 SURFACE COATINGS

---
0
II H H H H 00 H H
~" /C" I I I I ~ ~ I I
I II 0 + HO-C-C-OH HOC-C O-C C-O-C-C OH + nH20
I I
"- ~
I I / I I
~/ "C/
H H H H H H
II n n+l
/
~-
(3)
0 n
phthalic anhydride ethylene glycol poly(ethylene glycol phthalate)

Because there are n + 1 moles of ethylene glycol and n moles of phthalic anhydride, the
polyethylene glycol phthalate molecule is terminated by hydroxy groups. Its average
molecular weight is also determined by the molar ratio between the components.
If a molecule of glycerol is reacted with a molecule of a monobasic (fatty) acid, a
monoglyceride is formed-conceptually shown as follows:
If the ethylene glycol in equation (3) is replaced by the monoglyceride, an alkyd resin

CH 20H CH200CR
I I
CHOH + RCOOH CHOH + (4)
I I
CH 20H CH20H

glycerol fatty acid monoglyceride water

results.

H 2COOCR RCOOCH2
I I

-
HOCH HC OH
CH 200CR
I O=C
/0"
c=o I °II °II I
"~
CHOH + / C O=C C-O-CH2 + nH 20
I_I
I
CH20H
n+l - "
~
n
/-
~-~
" n
(5)

monoglyceride phthalic anhydride alkyd resin

The result is the so-called 'theoretical alkyd'. Sadly this idealized formula displays an order
not present in the real alkyd resin, which will contain molcules with a diversity of molecular
weights, shapes and compositions. However, because the average effective functionality of
the reactants is 2, in theory at least, a non-gelling resin results. Putting this more formally:
F f art total number of reacting groups
unc IOn I YAY = total number of molecules (5A)
When FAv<2 the proportions of the mix should theoretically not lead to a gel.
As in equation 3, the average molecular weight of the polymer is controlled by the ratio
between the difunctional acid and the effectively difunctional alcohol components. Exam-
ination of the idealized structural formula shows that the resin molecule is terminated by
hydroxyl groups which are present in 'excess' over the number of acid groups. These excess
hydroxyl groups cannot react because there are not enough acid groups present. The
formula above can therefore be rewritten (for the case where OH groups are in excess)
 ALKYD RESINS 79

F _ 2 x number of acid groups

(5B)
AV - total number of molecules
This concept of average functionality is a basis on which a practical approach to formulating
non-gelling resin formulae can be based and which will be considered later.
As mentioned earlier, esterification reactions as shown in reactions I, 3, 4, and 5 are
reversible. It is useful to regard the reactants and reaction products (in a closed system at
temperatures above 180· C) as existing in a form of dynamic equilibrium in which ester
groups continually form and separate without changing the overall concentration of water,
alcohol, acid or ester group. A similar process can be observed when an ester is heated with
any of the components of the esterification reaction.
5.2.2 Alcoholysis
When an ester is heated with an alcohol, alcoholysis takes place. Lead, calcium and alkali
metals in the form of oxides, hydroxides or metallic soaps are used as catalysts.

CH 2COOR CH20H CH 2COOR

I I ----. I
CHCOOR + 2 CHOH ~
3 CHOH (6)
I I I
CH 2COOR CH20H CH20H

triglyceride glycerol monoglycerides

(eg. vegetable oil)

The equation given above is an idealized result. In fact an equilibrium mixture containing
triglyceride, diglyceride, monoglyceride and glycerine is formed, the main component of
which is alpha- monoglyceride. It is possible to determine the amount of monoglyceride
formed during the alcoholysis reaction. However, in practical alkyd production the end point
is usually taken as the point at which solubility in alcohol is reached. If in doubt a trial
esterification with phthalic anhydride can be carried out. If the result of heating the formula
quantity of phthalic and alcoholysis product to 240· C is a clear non-grainy pill, equilibrium
is accepted to have been reached. Alcoholysis products are used as an economical source
of fatty acids in alkyd resins.
5.2.3 Acidolysis
When an ester is heated with an acid, an acidolysis occurs.
COOH
I

RCOOCH 2
COOH
I
~
~COO-CH2
----. I
Rcoo6H +~ RCOO-CH + RCOOH (7)
V-
~

I COOH I
RCOOCH 2 RCOO-CH 2
triglyceride isophthalic acid acidolysis fatty acid
product
80 SURFACE COATINGS

The end point of the acidolysis is usually taken as the point at which the acidolysis mix is
clear hot.
As with alcoholysis, the product is a random mixture. Acidolysis is frequently used as a
me~ns of rapidly incorporating acids of low solubility such as isophthalic acid, into alkyd
reSIns.

5.2.4 Hydrolysis
When an ester is heated in a sealed system with water, the ester is hydrolysed. Traces of
mineral acid or alkali metals can be used as catalyst, but uncatalysed reactions are preferred
as they yield purer products.

CH 2COOR CH 20H
I I
--+ CHOH
CHCOOR + 3H2O ~ + 3RCOOH
I I (8)
CH 2COOR CH 20H

triglyceride glycerol fatty acid

(oil)

This process is used in commercial production of fatty acids and glycerol.

5.2.5 Transesterification
When two esters are heated, they undergo transesterification. Transesterification cannot be
avoided during alkyd processing, but the rate is thought to be slower than alcoholysis,
acidolysis or hydrolysis.

R'COOR A + R"COORs R' COORs + R"COOR (9)

ester 1 ester 2 ester 3 ester 4

5.2.6 Other reactions

During processing of alkyd resins a variety of reactions not involving ester bonds take place
which have an effect on the polymerization process. The extent of these reactions is difficult
to determine, but there is no doubt that they occur. Some, such as etherification, cannot
be avoided, others such as formation of maleic adducts are used deliberately. All of them
have an effect on the performance characteristics of the alkyd resin and ultimately of the
paint system.

5.2.6.1 Etherification
When alcohols are heated, they form ethers.

ROH + ROH (10)

 ALKYD RESINS 81

In the presence of acids the speed of reaction is high even at temperatures around
130· C as occurs during preparation ofbutylated amine formaldehyde resins, for example.
In alkyd cooking, lower concentration of hydroxyl groups and competing esterification
reactions seem to produce lower levels of etherification than the higher reaction temper-
atures would lead one to expect.
During alcoholysis, because solubility of alcohols in vegetable oils is poor, high
concentrations of alcohol can exist for some time at quite high temperatures, and some
etherification must occur. The resulting polyol dimers have high functionality-particularly
in the case of polyols like pentaerythritol, dipentaerythritol has a functionality of 6.

CH 20H

2HOCH2 - "
/
C-

CH 20H
CH 2 OH
.--
---. HOCH2 -C-CH 2 -O-CH2 -C-CH 20H
/
CH 20H
/
+ H 20

(11 )
pen taerythritol dipentaerythritol

Even at low concentrations such highly functional components have an effect on viscosity
and acid value out of proportion to their concentration.

5.2.6.2 Cracking products

During monoester formation a variety of volatile byproducts, usually with offensive odours,
are given off. Among these are acrolein, a very poisonous lachrymatory liquid.

CH 20H CHO
I
CHOH
I
CH 20H
.-- I
---. CH
II
CH 2
+ 2H 2O
(12)

glycerol acrolein

Fatty acids and rosin undergo decarboxylation.

RCOOH ---. + RH
(13)
CIS fatty acid carbon dioxide C I7 hydrocarbon

Unsaturated fatty acids also undergo chain scission near double bonds, forming shorter chain
acids and hydrocarbons. The presence of oxygen, or prior exposure of the fatty acid to
oxidation, greatly increases the amount of breakdown and the variety of by-products leading
to formation of short chain aldehydes, ketones, alcohols and acids. It is easily shown that
the presence of the cracking products formed during alcoholysis has a deleterious effect on
drying properties and on the stability of pigmented systems.
82 SURFACE COATINGS

5.2.6.3 Dehydrated castor oil

Castor oil is the glycerol triester of ricinoleic acid. On heating above 180· C ricinoleic acid
undergoes dehydration to form a mixture of conjugated and non-conjugated fatty acids. The
reaction is accelerated by mineral acids.

OH
I
CH 3 - (CH2)4-CH2-CH-CH2-CH=CH- (CH 2),-COOH
ricinoleic acid

t!1 H+
CH3 (CH2)4-CH2-CH=CH-CH=CH (CH 2hCOOH + H 20 (14)
(conjugated)
+
CH3 (CH2)4-CH=CH-CH2-CH=CH (CH 2),COOH + H 20
(unconjugated)
dehydrated castor oil fatty acids

The ricinoleic acid moieties in the oil can also be dehydrated, forming esters containing a
mixture of esterified fatty acids with conjugated and unconjugated double bonds. Some
unsaturation is lost due to formation of dimer acids.
5.2.6.3.1 Reactions of double bonds
Other than the cracking reactions mentioned above, double bonds undergo at least three
types of reaction: conjugation, autoxidation, and interaction between alcohols and ethers.
(i) Conjugation, in which isolated double bonds move into conjugated positions.

CH3 (CH 2) 3 CH= CH CH2CH = CH (CH 2) S COOH

(15)
non-conjugated acid
~ CH 3 (CH 2hCH=CHCH=CHCH2 (CH 2)sCOOH
conjugated acid

This reaction is certainly expedited by free radicals which can result from a small amount
of oxygen pick-up.
Example
Diels Alder addition (1:4 addition)
Because it has an acid group functionality of 3, the adduct produces a higher viscosity than
the equivalent amount of a difunctional acid. Small amounts of maleic anhydride are
sometimes' added to alkyd cooks to form adducts for this reason.
Fatty acids or their esters, each with two conjugated double bonds can interact to form
dimers by Diels Alder addition. If drying oils are heat-treated, conjugation of some double
bonds occurs, followed by dimerization.
 ALKYD RESINS 83

CH3
I
(CH2h
CH3 I
I
O~ (CH2h O~ / ~"
/C-CH CH
/C-CH
o II I o I II
+ CH 'C-CH CH
'C-CH
~ II O~ ,,~/
(16)
o CH
I I
CH (CH 2)g
II I
CH COOH
I
(CH 2)g
I
COOH
maleic conjugated 1:4 maleic adduct
anhydride fatty acid

CH3 CH3
I CH3 I
(CH2h I (CH2 ) 3
I
CH (CH 2h 6
II
CH
"/H"
C CH
2 I I II
CH HEAT C H CH (17)
II /"c/
CH CH I
I ~H (CH 2 )g
(CH 2)g I I
I (CH 2)g CO OR
COOR
I
COOR
esters of conjugated acids dimerized esters

Heat-bodying results in viscosity increases and faster-drying resins. Tung oil or tung oil fatty
acids heat-body very rapidly, and the oil forms a gel in about 10 minutes at 240· C.
Dimerized fatty acids are made commercially and are used in polyamide resins.
(ii) Autoxidation reactions
Autoxidation and the attendant formation of hydroperoxides and conjugation are dealt with
in the 'vegetable oil' section of this volume. The reactions described there for crosslinking
vegetable oils are paralleled by those causing air-drying of alkyds. In the autoxidation
reactions leading to formation of 'air-dried' alkyd paint films, the 'functional groups' are the
84 SURFACE COATINGS

double bond systems of those fatty acids containing two or more double bonds. As the
number of such fatty acid moieties in an alkyd molecule increases, the rate of cure increases.
Autoxidation plays an important part in formation of cracking products alluded to above
and in heat-bodying. It is essential, therefore, to avoid contact with oxygen during alkyd
processing if consistent products of acceptable colour are to be produced.
(iii) Interaction between alcohols and ethers
Alcohols react with ethers through an alcohol interchange reaction similar to the
alcohol!ester interchange dealt with above.

(18)
ether A alcohol B ether C alcohol D
If the new alcohol is volatile, it can escape from the system and the equilibrium shifts to
the right. This reaction has a number of applications in alkyd technology, the most
important of which is the crosslinking of alkyds by amine resins such as etherified urea
formaldehyde or melamine formaldehyde resins.

(CH 2)9
I
COOH
hexa(methoxymethyl) hydroxy functional cured resin (19)
melamine polyester
(eg alkyd)

In this reaction the hydroxyl groups are the functional groups of the alkyd. Alkyds intended
for this application have a higher hydroxyl excess-that is, a higher hydroxyl functionality
than air-dry alkyds.
The reaction is catalysed by acids, which may be provided by the terminal carboxyl groups
of the alkyd. The reaction rate at room temperature is usually low enough to give an
extended shelf life to the alkyd/amino resin paint system. Baking times of 30 minutes at
120 to 150 C are normal for such coatings.
0

The alcohol!ether interchange reaction is also used in alkyd manufacture as a means of

incorporating preformed silicone resins, thus forming silicone alkyds.

RI Rl
I A I
ROH + CH30Si-O --------. ROSiO + CH30H
I I (20)
R2 R2
hydroxy function methoxy silicone silicone methanol
alkyd intermediate intermediate alkyd
 ALKYD RESINS 85

The alkyd intermediate may be modified with drying oil fatty acids if an air-dry paint is
required, or the silicone alkyd may be hydroxy functional to allow crosslin king by melamine
resins, for example.

5.3 ALKYD PROCESSES

Practical manufacture of alkyd resins is dependent on processes for esterifying the
polyalcohols and poly and monobasic acids in a controlled manner to yield a homogeneous
thermoplastic product, which can be 'dissolved' in a solvent for futher processing.
As shown above, for polymerization to take place two difunctional reactants must react
(see equations 3 and 5). If one is present in excess, the molecular size of the polymer is
controlled by the molar ratio of the reactants. If a difunctional reactant reacts with a
trifunctional reactant, molecules of 'infinite' size can be formed with some molar proportions
of reactants. A molecule of 'infinite' size is Florey's definition of a 'gel'.
At the end of the alkyd polymerization process an essentially linear (i.e. thermoplastic)
structure is required. This can be achieved by having an average functionality of 2 or less
for the reacting components at all times.

Calculation of average functionality

Rephrasing equation 5B,
. l'
FunctlOna 2 x equivalents COOR
lty AV = - - " - - - - - - - - (21)
total moles of reactant
The above formula should be used where OH groups are in stoichiometric excess (as is
normally the case for alkyds). If the COOH groups are in excess,
. l'
FunctlOna 2 x equivalents OR
ItYAV = (22)
total moles of reactant

5.3.1 Fatty acid and alcoholysis processes

When an alkyd is to be made in which the polyol is to be glycerol, either glycerol and fatty
acids, or glycerol and the oil may be starting points. As 3 moles of fatty acid plus 1 mole
of glycerol react to form 1 mole of oil, the same composition can be achieved either way
from oil or fatty acid and glycerol.
Formula A (fatty acids) Formula B (oil)
Moles Functionality Equivalents Moles Functionality Equivalents
COOH OH COOH OH
Linseed fatty acids 3 3
Linseed oil 1* o o
Glycerol 3.5 3 10.5 2.5 3 7.5
Phthalic anhydride 3 2 6 3 2 6
Total 9.5 9 10.5 5.5 6 7.5

*The linseed oil is an ester without either acid or hydroxyl functionality, so it is present in reaction B only as a dilutent. 3 moles of linseed fatty
acid react with I mole of glycerol to yield 1 mole of linseed oiL
86 SURFACE COATINGS

In formula A the OH groups are in excess, so formula 20 applies.

9x2
FAV=9:5= 1.89

As FA V is under 2, the composition should not gel.

In formula B also, the OH groups are in excess; formula 20 again applies.
6x2
FAv =-s.s=2.18
As the average functionality is above 2, composition B would be expected to gel, and this
is what happens in practice. Formula B can be made, however, if the process is carried out
in two steps by first subjecting the oil to alcoholysis with the glycerol and then esterifying
the alcoholysis product with the phthalic anhydride (see equation 6).
In practice alkyds such as formula A and B have been made from both fatty acids and
glycerol and via the monoglyceride from oil. While oil is cheaper than fatty acids and
glycerol the process time is longer and the amount of heat used is greater. There is also
a feeling that the fatty acid process alkyd dries faster than the one made by alcoholysis.
When polyols other than glycerol are involved, however, alcoholysis cannot be used unless
a mixture of polyols including the glycerol component of the oil is acceptable. Many alkyds
containing mixed polyols are used and particularly the alkyds containing pentaerythritol,
which are usually made by alcoholysis.

5.3.2 Acidolysis process

As described in section 5.2.3, acidolysis is used to improve the reaction rate of dibasic acids
of low solubility. It is mostly used with long oil isophthalic acid resins and is limited to
formulae containing at least 1 mole of oil per mole of insoluble diacid (equation 7).

5.4 ESTERIFICATION
The esterification stage of alkyd resin manufacture is a condensation reaction-that is, water
is evolved as a by-product. Because the esterification is an equilibrium reaction, the evolved
water must be removed to force the reaction to completion. Two techniques are normally
used to remove the water. These are called the fusion and the azeotrope (or solvent)
processes.

5.4.1 Fusion process

This is the longer-established process of the two and involves fusing the components at an
elevated temperature. The reaction mixture in the kettle is continually and vigorously
sparged with an inert gas (usually nitrogen or carbon dioxide). This has two effects: the hot
reaction mixture is protected from attack by oxygen, and the evolved water vapour is
continually removed from the kettle.

5.4.2 Azeotrope process

Azeotrope processing involves the addition of small quantltles of hydrocarbon solvent
(normally xylene or toluene) to the reaction mixture. At the elevated processing temper-
atures, a water/solvent azeotrope is formed, which is condensed externally to the kettle. The
water and solvent are separated, the solvent being returned to the kettle and the water run
to waste.
 ALKYD RESINS 87

5.4.3 Comparison of fusion and azeotrope processes

Fusion
(a) Simple equipment is required, so there are lower capital costs.
(b) The use of inert gas can cause problems with loss of components by sublimation and
physical entrainment. However, there are times when removal of, say, phthalic
anhydride is necessary, and under these circumstances the sublimation effect can be used
to advantage.
(c) The kettle temperature can be controlled independently of the loaded components.
(d) Scaling from one kettle to another of different size or shape may require reformulation
because of variation in loss of components.
(e) The bubbling action of the inert gas improves agitation.
Azeotrope
(a) This needs complex condensation and separation equipment, so there are higher capital
costs.
(b) Loss of components is minimal, and often superior resin colour is achieved as the
refluxing solvent cleans the upper areas of the kettle, preventing charring.
(c) The kettle temperature is controlled by the quantity of refluxing solvent.
(d) Scaling from the kettle to another of different size presents fewer problems.
(e) The presence of solvent reduces the viscosity of the alkyd, enabling better agitation. This
yields better water removal and a faster reaction speed.
(f) Presence of solvent reduces the concentration of reactants and causes corresponding
reduction in reaction rate.
5.4.4 Process control
The esterification reaction is normally controlled by viscosity increase and acid value
decrease. Samples are taken from the batch at predetermined intervals after processing
temperature has been reached. The time intervals are typically 30 minutes for fast-bodying
batches, and hourly for slower bodying products. ('Bodying' is a term used for viscosity
increase.)
The samples for viscosity measurement are diluted with solvent, which is usually the same
solvent and in the same ratio that the batch is to be finally manufactured. The viscosity is
usually determined by the Gardner-Holdt method. Acid value is determined by titrating with
alcoholic potassium hydroxide solution.
An important aid to controlling batches is to plot viscosity against time on semi-log graph
paper. A batch processing normally appears as a straight line, and by extrapolation it is
possible to judge whether the processing temperature should be increased for slow-bodying,
or reduced for fast-bodying batches. Steps can also be taken to start cooling earlier if the
bodying rate warrants this action. In processing it must be remembered that the viscosity
determination takes approximately 20 minutes to carry out, with the batch continuing to
increase in viscosity during that period. When processing by the azeotrope method the
sample taken from the reaction will contain a percentage of reflux solvent, and this has to
be allowed for when testing.
At a predetermined viscosity and acid value, the batch is cooled and thinned with solvent.
It is then tested for non-volatile content and adjusted with further solvent into the viscosity
and non-volatile specifications.
5.5 ALKYD RESIN PROCESSING
5.5.1 Safety
Alkyd processing involves handling viscous flammable materials at high temperatures in
88 SURFACE COATINGS

substantial quantities. A number of the raw materials are corrosive, poisonous, teratogenic
or capable of sensitizing some individuals. Plants and processes must be designed to keep
these hazards away from the operating personnel. Personnel involved in development must
get agreement on safety issues before introducing new materials or processes in plant or
laboratory,
5.5.2 Environment
Fires, leaks, buildups of contaminated solvent and caustic resulting from cleaning operations
all put the environment at risk. All vents to atmosphere must be through an incinerator or
scrubber system. Any water to sewer has to be adjusted to meet requirements of the relevant
authority and must contain no solvent and meet requirements for suspended solids pH and
biochemical oxygen demand (BOD).
Nothing should be allowed to enter a production site that does not leave it in saleable
product. Production schedules and processes must be adjusted to bring this about. Raw
materials must be handled in bulk or in recyclable containers. The alternatives are too
expensive in the long term to contemplate.
5.5.3 Quality
Reproducibility must be a pre-eminent objective of the maker of resins for the paint
industry.
Resins are used as pigment dispersants and suspending agents and form part of a dynamic
system in which individual components of the paint system compete for positions on the
pigment surface. The quantity of material on the pigment surface is very small-less than
the amount of batch-to-batch contaminant. The effect of contaminants can be disastrous for
the paint system, particularly if the product is a tint base.
Factors affecting reproducibility include variations in raw material; part bags are a
particular unrecognized source of trouble and go hand in hand with materials held in stock
for extended periods. Products not often made present raw-material problems as well as
being unfamiliar to the operators.
Consistent weighing accuracy across the range of material quantities required for an alkyd
formula would require a separate device for each material, but this is impractical. About
0.5 percent of the quantity being measured is a reasonable objective. Of more importance,
however, is providing exactly the same quantity of each material for each batch; that is,
consistency is as important as accuracy. Without this, formula adjustments are not possible.
Modifications should not be made unless absolutely necessary. Troubles will be avoided
if the same kettle, batch size and even position in the production cycle can be used for each
product. Otherwise, variations in heat-up time, agitation, gas flow, heat-bodying, colour,
reflux rate and so forth cannot be avoided. Nowhere is this more obvious than in fusion
process, where variable losses between batch sizes make different formulae essential.
5.6 RESIN MANUFACTURING EQUIPMENT
Because of the tendency to replace one resin type by another, new plants for alkyd
manufacture will very likely be used for polyesters and even amino resins and solution
acrylics. In the long term, a plant built with all wetted parts of 316 stainless steel (contact
with copper and copper alloys must be avoided for acrylics) metering pumps with mechanical
seals and variable speed drive and remote control valves, all under computer control, is the
most economical. Such a plant consists of the following.
5.6.1 Preweigh
The extent of the preweigh area depends on the amount of bulk liquid storage. Liquids
 ALKYD RESINS 89

stored in bulk can be pumped through mass flow meters direct to reaction vessels. If
computer control is provided, addition rate and composition of mix can be programmed,
thus avoiding need for preweigh tanks. In reducing cost and possibilities of contamination,
liquid phthalic anhydride is worthwhile if the quantity handled is large enough. There is
a saving in· heat-up time and consequently in sublimation of phthalic.
Except for quantities small enough to be weighed in a bucket and added through a manual
addition valve, drum stocks of functional raw materials are a nuisance.
Drystocks can be added from bulkabags, and facilities such as quick close hatch and
electric hoist with dialscale of suitable size and accuracy should be provided. Batch sizes
should be written (if possible) around whole numbers of bulkabags. There will be an
inevitable clash if phthalic and pentaerythritol are both in bulkabags, and some conventional
bag stock is probably unavoidable.
5.6.2 The resin kettle
For universal application the kettle should be 316 stainless, with height-to-diameter between
1.5:1 and 2.0:1.9, with dished ends and flush bottom outlet. The vessel and associated
equipment should be approved for vacuum and an operating pressure of at least two
atmospheres above normal.
Efficient agitation is essential, and a continuously variable speed drive can provide
optimum mixing when the kettle is part-charged. It is important to promote top-to-bottom
circulation of the reaction mass to facilitate water removal. Turbulence is valuable to ensure
intimate mixing of incompatible components such as polyols and vegetable oil.
A turbine stirrer with baffles works well, and a comb or foam breaker above highest
charge level is useful. Some adjustment of height to find the best position for the foam
breaker and an intermediate turbine if fitted should be provided.
5.6.2.1 Heating and cooling
If a kettle is to be used for a variety of resin types, a jacketed kettle through which a synthetic
heat transfer fluid is pumped is necessary. If the same furnace is to be used for a number
of vessels, a separate hot oil circulating pump and temperature-controlled loop is necessary
for each kettle to facilitate control of the temperature in the jacket. This avoids hot spots
and allows control of heat input for each process when different product types are being
cooked in different kettles attached to the same furnace. This system allows controlled
heating for batch temperatures from about 50 C to the maximum temperature of the heat
0

transfer fluid, about 300 C. 0

Kettles have also been heated by high-pressure hot water, but very high pressures are
required in the jacket and furnace, and cost-effectiveness is at present doubtful.
Alkyd kettles have been heated by direct firing with fuels ranging from coal and coke
through fuel oil to gas and electricity. In the early years, open kettles of about 200 gallons
capacity (say, 1000 litres) heated on coke, oil or gas fires and stirred by hand were used for
oleoresinous cooks and for alkyds. Significant losses of phthalic and glycerol took place, and
such processes would be environmentally unacceptable in these days.
Cooling is normally effected by pumping water through coils immersed in the reaction
mix. This arrangement tends to produce poor agitation in the space between the coil and
the kettle wall during both heating and cooling. Satisfactory heat transfer areas are available
for heating and cooling, however, and apart from cleaning difficulties, the system is
acceptable. If a cooling jacket is used instead of a coil, there are restrictions on heat-transfer
areas for both heating and cooling.
Cooling water is supplied from an evaporative cooling tower. Attention is drawn to the
fact that during the initial stages of cooling an alkyd from an esterification temperature of
90 SURFACE COATINGS

250· C or higher, the cooling water flashes into steam. This can cause problems with the
cooling water reticulation system and/or damage plastic components if they are present in
the cooling tower.
Inert gas inlets are required near the bottom of the reactor and also above the liquid level.
The inlet in the bottom of the kettle is ideally a ring with many small holes to distribute
the 'sparging' gas over a broad area. The gas inlet tends to fill with resin and block up and
needs to be washed clean with solvent at the end of each batch. For reproducible processing,
gas flow meters are required on these lines. The flow to the top of the kettle can be quite
small-its function is to prevent diffusion of oxygen into the kettle during heatup and
cooling. The flow to the bottom of the kettle can be surprisingly high during fusion
cooking-as much as 150 L per kg of reaction mix per hour, though lower rates will
normally be used. Inert gas pressure can be used to transfer the finished product to the
thinning tank. Inert gas on a production scale is usually nitrogen provided by evaporating
liquid nitrogen. Glass kettles are acceptable for laboratory work.
5.6.2.2 Safety valve and rupture disc
The boiler code requries that reactors be fitted with a safety valve to prevent the vessel from
being subjected to internal pressure above the ticketed limit. Because resin can block safety
valves, a rupture disc designed to blow at pressure slightly above the setting of the safety
valve is desirable. Discharge from safety valve and rupture disc needs to be ducted away
from personnel and fire hazards.
5.6.2.3 Sample valve
Provision needs to be made in the reactor for samples to be taken during processing. This
can be done in several ways. Typically, a small valve can be located in the side of the reactor
below the surface of the alkyd batch. Alternatively, a line in the top of the reactor reaching
down below the alkyd surface can provide a sample by pressure application to the batch
(particularly useful in laboratory cooks).
5.6.2.4 Condensing systems
To cope with all cooking situations a resin kettle must be able to deal with the fusion process,
which involves handling considerable flows of hot sparging gas contaminated with water,
polyol and phthalic anhydride. The environment licence for the plant may require that the
emerging gas be incinerated or scrubbed to specified standards.
Primary clean-up at the kettle usually involves a shower condenser and water scrubber,
which removes most of the sublimed phthalic and the water-soluble polyol. The gas is then
incinerated or passed through activated carbon absorber beds and the scrubber water
recycled with makeup before treatment to adjust BOD, pH and suspended solids.
It is quite feasible to produce alkyds without a special fusion set-up, and in a 'Universal
Kettle' it would probably not be fitted.

5.6.3 Azeotropic distillation

The water of reaction is distilled from the kettle as an azeotrope usually with xylene. The
vapours of this solvent have autoignition temperature well above the limits reached during
alkyd processing and present much lower hazards than aliphatic solvents such as White Spirit
(autoignition temperature under 260· C). Solubility of water in xylene is also low, and this
reduces the water carried back to the kettle in solution.
The azeotrope is condensed, the xylene is recovered and returned to the reactor, and the
water is measured and, after treatment, is discarded.
 ALKYD RESINS 91

In order to minimize return of water to the kettle it is desirable to have the separator
as cold as possible. A near-horizontal condenser with condensate flowing the length of the
condenser provides cool condensate but is more likely to block than the arrangement of
vertical condenser with vapour inlet and condensate outlet and separator at the bottom. In
the latter case, a cooling coil in the separator is helpful, and there are cases on record of
auxiliary separators being used in the return line to the kettle to minimize water return.
5.6.4 Glycol recovery and azeotropic distillation
Oil-free alkyds and the occasional conventional alkyd frequently contain volatile polyols such
as ethylene and propylene glycol. Controllable and reproducible production of these resins
requires a partial condenser or fractionating column to separate water of esterification and
glycol in the period when most esterification occurs. In the final stages of esterification, water
may be removed by azeotropic distillation or by fusion with the gas passing through the
condenser. An automatic decanter can be used to maintain a fixed level of water in the
receiver.
5.6.5 Thinning tanks
Solvent-cut alkyds are normally thinned externally to the reactor, in thinning tanks. Because
the completed alkyd is non-corrosive, the tanks can be made of mild steel. The tanks should
be of sufficient size to hold two batches of completed thinned alkyd. An agitator is essential
for dissolving the alkyd as transfer from the reactor proceeds. Internal coils are used to
provide heating and cooling. Water cooling is used whilst thinning, and heating used for
transfer, filtration, and so on. A reflux condenser is useful to avoid solvent loss.
To avoid static electricity buildup, solvent should be loaded from the bottom of the tank,
and the line from the reactor should enter the solvent subsurface for the same reason. The
tanks should be earthed.
5.6.6 Filtration
After an alkyd has been thinned, it needs to be filtered to remove foreign matter, skins or
gel particles, and catalyst residues. There are several ways of alkyd filtering. The most
common uses plate and frame presses, which consist of a series of frames over which filter
paper can be fitted. The frames are so arranged that the resin must pass through a paper
as it is pumped through the filter.
As an aid to filtering, diatomaceous earth is usually dispersed in the alkyd whilst in the
thinning tank. This prevents the pores of the filter paper being clogged by residue and thus
slowing the rate of filtration.

5.7 INSTRUMENTATION
Production of addition polymers such as crosslinking acrylic resins and emulsions under
computer control is now commonplace. Because of the high reproducibility of these raw
materials, such resins can be cooked by 'time and temperature' methods and produce very
consistent results. Similar approaches work for oil-free alkyds, and with a small amount of
supervision should also be possible for oil-modified alkyds.
Instrumentation for process control is a field that is developing at the same high speed
as the personal computer. It should be part of the plans for every new installation and should
be regularly reviewed for retrofitting to existing plants. Even if the cooking process remains
under manual control, the following points should be examined.
(a) Raw material quantities: measure using mass flow measurement for liquids and load cells
or similar strain gauges for solids.
92 SURFACE COATINGS

(b) If heat transfer fluids are used for heating:

control the temperature in the main hot oil loop
control the temperature in the hot oil loop for each kettle (interlocked with batch
temperature in the kettle); and
control the batch heat-up temperature curve.
(c) Condenser system: control the reflux ratio in partial condenser and signal when the rate
of water removal and glycol boil-up warrant change to simple fusion or solvent process;
this requires temperature measurement at a number of points in the partial condenser/
packed column and control of the jacket temperature and/or head temperature cooling
coil for reflux ratio control.
(d) Temperature recording: in addition to points already noted, monitor and record the
head temperature in the kettle, the thinning tank temperature and the separator
temperature.
(e) Monitor and record the temperature and flow rate in the cooling water system, the flow
rate in the inert gas system and ammeter readings on agitator motor, hot oil pumps and
cooling water pumps.
(f) Monitor the incinerator operation (or alternately the carbon adsorption system).
(g) Measure and control the rate of reflux return during azeotrope processing; this involves
addition of reflux solvent to maintain the preset rate during heat-up and hold at top
temperature together with calculating a cumulative total of quantity added.

5.8 CLEANING
While alkyd kettles can be cleaned by saponifying the resin residues with hot caustic soda,
the process is not simple. Caustic cleans only the surfaces with which it is in contact. As the
condenser/separator system must be cleaned, the caustic mix is usually foamed over and the
efficacy of the process accepted as an act of faith. The spent caustic must be dumped at
considerable cost, and all traces must be removed by washing the system and boiling out
the condenser separator system.
There seems to be no substitute for a caustic boil in the condenser separator system.
However, this can be done as a separate exercise if caustic solution can be heated-perhaps
with live steam-in the separator condenser system; this requires a much smaller volume than
the kettle as a whole.
The kettle itself can be most effectively cleaned by high-pressure spray using a small
amount of thinning solvent held back from final thinning of the batch. This solvent is
circulated from the bottom of the kettle through the sprayhead to wash all the internal kettle
surfaces while the kettle is still warm. The resulting resin solution is pumped to the thinning
tank, and the process repeated if necessary. The high-pressure spray equipment can be
portable and inserted into the kettle attached to the underside of a dummy manhole cover.
Alternatively a dedicated unit can be fitted with provision to retract it from the reactor when
not in use.
 ALKYD RESINS 93

5.9 MANUFACTURE
Typical instructions for processing a long oil alkyd are given below.
Formulation kg Specification
Soyabean oil (alkali refined) 4500
Pentaerythritol 900 G-H viscosity Z-ZJ
24 percent lead drier 7 Acid value 3-8
Phthalic anhydride 1700 Gardner colour 7 max.
Xylene 150 NVM 69-71 percent
White Spirit 2700
White Spirit 200
Yield 96 percent
(a) Ensure the kettle is clean and empty.
(b) Seal kettle and pull a vacuum of640 mm Hg (16 kPa absolute). Check for leaks. Restore
kettle to atmospheric pressure with nitrogen.
(c) Load oil and start stirrer. Turn on inert gas flow (0.1 m 3 per minute).
(d) Load pentaerythritol through manhole.
(e) Close valve to reflux condenser, open valve to gooseneck, vent through condenser. Turn
condenser water on.
(f) Heat to 225 C. Add lead drier at 200· C on way up to 225 C.
0 0

(g) Hold at 225· C, testing every 15 minutes until soluble 1:3 in ethanol at room
temperature.
(h) When soluble, cool to 150· C and load phthalic anhydride.
(i) Commence heating to 250· C. During upheat arrange system for azeotrope by filling
receiver with water until it flows out of water take-off line. Turn off inert gas flow.
U) Add xylene to reactor.
(k) At 250· C hold under azeotrope, testing hourly for viscosity (70 percent in White
Spirit), acid value, and colour.
(1) At viscosity Y run out approximately 400 L water from separator and apply vacuum.
Tum on cooling water and cool to 200· C. At 200· C, recheck viscosity, which should
be approximately Z. If viscosity OK, dose reactor for pressure, open outlet valve, apply
30 kPa pressure inert gas, and blow to thinning tank loaded with initial White Spirit
charge.
(m) Cool in thinning tank to 80· C. Check non-volatile matter and adjust to specification
with remaining White Spirit.
(n) Filter into drums or bulk storage tank.
Comments
The purpose of step (b) is to get all the oxygen out of the kettle.
(f) Lead soaps react with phthalic anhydride to form insoluble lead phthalate. If any free
phthalic remains in the kettle from the previous batch, it has a chance to react with the
pentaerythritol before the lead is added. Other catalysts, such as lithium hydroxide,
form soluble phthalates and can be added with the oil.
(h) The alcoholysis mix is cooled to 150· C to ensure that the batch does not foam during
addition of phthalic anhydride. Foaming would be an obvious hazard to operators
loading phthalic anhydride. If molten phthalic anhydride is used it can be added to the
closed system at higher temperatures with consequent saving in energy.
(k) To maintain reflux at 250· C, it will be necessary to make periodic additions of xylene.
(I) The vacuum step removes the remaining xylene azeotrope solvent. This step is not
94 SURFACE COATINGS

required if the xylene (which will be about 6 percent of the kettle contents) can be
accepted in the final products.

5.10 CORRECTIVE MEASURES DURING PROCESSING

High acid values during processing can be reduced by glycerol additions. Even in
pentaerythritol-based alkyds, it is better to use glycerol because it is faster reacting and more
readily soluble. If acid value is lower than expected, small amounts of phthalic anhydride
can be added during processing.
Slow-bodying batches should either have the processing temperature increased (in 10 C 0

stages) and/or inert gas flow increased (for fusion process). Excessively fast-bodying batches
should be cooled to a lower processing temperature until they become more controllable.
Batches that finish excessively high in viscosity (or even gel) can be reduced in viscosity
by steam sparging. This reverses the reaction, producing a fall in viscosity or de-gelling. An
alternative method is to add fatty acids to the batch. With this technique, once the viscosity
is lowered it is advisable to add additional glycerol and phthalic anhydride and reprocess
into specification.
While these corrective measures could yield a resin with the correct acid value and
viscosity, they may well cause changes in the performance of the product, e.g. pigment-
wetting dispersion stability or colourant aceptance in paint. Corrective measures should
never be regarded as a normal part of processing, and the causes of variation from standard
should be identified and eliminated.

5.11 RAW MATERIALS IN RESIN DEVELOPMENT

5.11.1 Fatty acids
The fatty acids used in alkyd resins are mixtures of straight chain monobasic acids, which
occur naturally as esters of glycerol in vegetable oils. Some synthetic acids are also important.
Fatty acids are monofunctional. The common acids are:
Equivalent
weights
Lauric acid CH 3 (CH2ho COOH 200
Stearic acid CH 3 (CH 2h6 COOH 284
Oleic acid CH 3 (CH 2h CH:CH (CH 2h COOH 282
Linoleic acid CH 3 (CH 2h (CH:CH.CH 2)2 (CH 2h COOH 280
Linolenic acid CH 3 (CH 2 CH:CH)3 (CH 2h COOH 278
Elaeostearic acid CH 3 (CH 2h (CH:CHh (CH 2h COOH 278
Ricinoleic acid CH 3 (CH 2)5 CHOH.CH 2 CH:CH.(CH 2h COOH 297
Versatic acid 194
A fatty acid must contain two or more double bonds if its esters are to be useful for
air-drying applications. The oils from which the fatty acid mixes are derived are classified
as 'drying' when the triglyceride will form a tack-free film in a reasonable time, 'semi-drying'
when a thin film thickens and eventually gels, and 'non-drying' when exposure of a thin film
to oxidation produces no crosslinking effect. Semi-drying oils contain little or no fatty acid
with more than two double bonds; they are used to produce the most durable and colour
stable of the air-dry alkyds.
Table 5.1 sets out typical compositions for some of the vegetable oils used in alkyds. The
acids are set out in order of increasing air-drying potential. In general, increase in air-dry
 ALKYD RESINS 95

potential goes hand in hand with yellowing tendency. Dehydrated castor oil, however, has
a much lower tendency to yellow than its drying potential suggests.

5.11.2 Other monofunctional acids

Equivalent weight
Benzoic 122
p.t. butyl benzoic 178
Dimethyl propionic 134
2-ethyl hexanoic 144
Lauric 200
Pelargonic 160
Rosin (abietic acid) 340

5.11.3 Difunctional acids

Adipic 73
Azelaic 94
Fumaric 58
Isophthalic 83
Maleic (anhydride) 49
Phthalic (anhydride) 74
Sebacic 101
Succinic (anhydride) 50
Terephthalic 83

5.11.4 Trifunctional acids

Citric 64
Trimellitic (anhydride) 64

TABLE 5.1
Typical compositions of vegetable oils used in alkyd resins
(Changes in variety of seed and growing conditions can produce different fatty acid composition.)

Saturated Oleic Linoleic Linolenic Total

Oil acid acid acid acid Other WPE drying
Versa tic acid I 100
Coconut 216
Castor 3 3 4 90~ 297 4
TalJ oil fatty acid 1 52 37 10 280 47
Soyabean 13 30 52 5 280 57
Sunflower 12 26 62 280 62
Safflower 7 15 78 280 78
Dehydrated castor 83 8 62 224 280 84
Linseed 10 22 17 50 280 67
Tung 5 8 4 3 80 5 280 87
lC lO branched chain with acid group on secondary carbon atoms. 2Mainly ricinoleic acid. 3Mainly
ricinoleic acid that has not been dehydrated. 4Conjugated diene. 5Mainly elaeostearic acid.
96 SURFACE COATINGS

5.11.5 Tetrafunctional
Pyromellitic dianhydride 55
5.11.6 Difunctional alcohols
1,3-butane diol 45
1,4-butane diol 45
Cyclohexane dimethanol 72
Diethylene glycol 53
Dipropylene glycol 67
Ethylene glycol 31
1,6-hexane diol 59
Neopentyl glycol 52
Propylene glycol 38
Trimethyl pentane diol 73
5.11.7 Trifunctional alcohols
Glycerol (= 95%) 32
Trimethylol ethane 41
Trimethylol propane 45

5.11.8 Tetrafunctional
Pentaerythritol 34

5.11.9 Other resin components

Sodium hydroxide
Lithium hydroxide
Lithium ricinoleate Transesterification catalysts
Litharge
Lead naphthenate
Dibutyl tin dilaurate Esterification catalyst
Maleic rosin adducts
Phenol formaldehyde modified rosin
Triphenyl phosphite-antioxidant, to preserve colour
Phosphoric acid-to preserve colour, produces colourless iron salts
Polyamide resins-to make the alkyd thixotropic
Cardura EI0* (glycidyl ester of versatic acid)

5.12 TERMS USED TO DESCRIBE ALKYDS AND THEIR PHYSICAL

AND CHEMICAL PROPERTIES
5.12.1 Concentration of acid, hydroxyl, and ester groups
In the vegetable oil industry, concentration of acid, hydroxyl, and ester groups is reported
in milligrams of potassium hydroxide per gram of product. This practice was adopted for

*Trade name, SheJi Co.

 ALKYD RESINS 97

resin products including alkyds. Concentration of free acid groups is determined by titrating
a sample with 'alcoholic KOH solution'. (For experimental details, see ASTM D 1639.)
RCOOH + KOC 2 H 5 ---+ RCOOK + C 2 H 5 0H
acid potassium soap ethanol
ethoxide
The resulting acid value is reported in units mg KOH/g. (Note that when an anhydride is
being titrated with alcoholic KOH solution, the result is approximately half that obtained
from the corresponding acid.) Acid value of resins should be compared on the basis of acid
value of the solid resin 'AV NVM'.
Similarly, concentration of ester group is determined by 'saponifying' the ester with an
alkali metal hydroxide (AOH). (For experimental details, see ASTM D 1962.)
RCOOR 1 + AOH ---+ RCOOA + R IOH
Regardless of the alkali metal employed, the saponification value is reported as the equivalent
number of mg of KOH required to completely saponify 1 g of ester.
Finally the hydroxyl value of an alcohol is similarly reported as mg KOH equivalent to the
hydroxyl content of 1 g of alcohol, perhaps because it is traditionally determined by
esterification with an excess of acetic acid and back titration with an alkali solution. (For
experimental details, see ASTM D 1957.) Thus 1 g of an alcohol with a hydroxyl value of
100 mg of KOH/g would be completely esterified by I g of an acid with an acid value of
100 mg KOH/g to yeild 1.968 g of ester and 0.032 g water.
5.12.2 Viscosity
During alkyd processing, samples are taken for viscosity measurement at time intervals
appropriate to the rate of viscosity change. The samples are diluted with solvent, usually the
same solvent and to the same solids content as the batch is to be finally reduced. The
viscosity is measured either by timing the rate of rise of a standard-size bubble in a tube
containing the resin solution at 25 C or by comparing with the rate of rise of a standard
0

bubble tube. (Experimental details will be found in ASTM D 1545.)

If the resin is being 'solvent processed', allowance must be made for the reflux solvent.
A plot of log resin viscosity in stokes (or bubble seconds) against time is usually close to a
straight line and can be used to predict end-point in the final stages of a resin cook. (Bubble
seconds and stokes are non-SI units of dynamic viscosity. 1 mm/s = 1 centistoke. Dynamic
viscosity controls the rate of flow under gravity and so equals kinematic viscosity divided by
density.)
5.12.3 Solids content
The solids-or more correctly non-volatile matter-of resins is determined by evaporating
to dryness a weighed sample of solution and determining the percent residue. (Details can
be found in ASTM D 1644.)
5.12.4 Alkyd characteristics
Any resin development should be undertaken with a clear understanding of the performance
expected of the paint system in which it is to be used. This understanding will extend to
matters of cost and include solvent type, resin solution viscosity, acid value and even type
of oil/fatty acid and oil length. From what has been said earlier, there are a multitude of
models of alkyd paints and the resins themselves to constitute a starting point. The selection
of an alkyd for a particular use requires an understanding of the performance of resins of
98 SURFACE COATINGS

different compositions and characteristics. The information supplied in alkyd manufacturers'

catalogues usually includes most of the following:
(a) oil or fatty acid content-% on NVM;
(b) oil type;
(c) phthalic anhydride content-% on NVM;
(d) resin type;
(e) 'pure drying' or 'pure non-drying' usually means that the resin contains only polyol,
polybasic acid and fatty acid, but the terms are elastic enough to include 'chain stoppers'
like benzoic acid without comment;
(f) modifiers-disclosing presence of rosin, phenol, acrylic, maleic;
(g) solvent type;
(h) non-volatile content;
(i) specific gravity;
G) acid value-usually of the resin solution;
(k) colour;
(I) viscosity as supplied;
(m) viscosity of the resin at a lower non-volatile content-may also be supplied as 'reduced
viscosity' ;
(n) White Spirit tolerance.
Information supplied only in special circumstances includes:
(0) hydroxyl value-needed when an alkyd is intended for crosslinking with isocyanates;
(p) polyol type;
(q) dibasic acid type other than phthalic anhydride.
Data sheets on individual resins will give indications of drier combinations, drying time and
baking schedules with specified crosslinking resins.
The following broad generalizations may be helpful in choosing components for an alkyd
or to indicate which components to replace to obtain a desired performance improvement.
At a given oil length, as the functionality of the polyol increases:
(a) the attainable viscosity of the alkyd increases;
(b) the drying time decreases for a given oil type;
(c) the film hardness increases for a given oil type;
At the same acid content, replacing orthophthalic by isophthalic:
(a) increases the attainable alkyd viscosity;
(b) increases the air dry speed;
(c) Improves the weatherability and chemical resistance.
Esters of primary hydroxyl groups are more stable than esters of secondary hydroxyl
groups, e.g. esters of trimethylol ethane and trimethylol propane are more stable than those
of glycerol. (Stable = resistance to hydrolysis and high temperature acid and alkalis.)
The hardness of an alkyd film increases as the melting point, hardness and crystallinity
of its components increase, e.g. substituting rosin (a brittle solid) for fatty acid increases
hardness. Replacing glycerol m.p. 20 C with trimethylol ethane m.p. 204 C increases
0 0

hardness. Increasing the number of functional groups per molecule involved in the
crosslinking reaction increases cured film hardness and cure speed, so:
(a) A pure 67 percent sunflower pentaerythritol phthalate alkyd dries faster than a pure
62 percent sunflower pentaerythritol phthalate alkyd of the same solids and viscosity;
the sunflower fatty acids are the functional moieties in air-drying here.
(b) A high hydroxyl value coconut alkyd will crosslink with butylated melamine resin faster
and to a harder film than a lower hydroxyl value coconut alkyd of similar molecular
weight.
 ALKYD RESINS 99

For alkyds of given oil length:

(a) Adhesion of the cured film improves as the level of un saturation of the fatty acids
increases.
(b) Water resistance of the cured film improves as level of unsaturation of the fatty acids
increases.
(c) Resistance to yellowing improves as unsaturation of the fatty acids decreases.
(d) Drying time decreases as the proportion of fatty acid with two or more double bonds
increases.
(e) Tendency to skin and gel in the can increases as the level of unsaturation of the fatty
acid rises.
(f) Pigment wetting improves as level of unsaturation of the fatty acid increases.
(g) Adhesion and pigment wetting improve as the hydroxyl value increases.

5.13 ALKYD RESIN FORMULATION

5.13.1 Introduction
A number of approaches to alkyd formulation have been developed in the 60 or so years
since the first alkyds were made. The most elegant predictions of degree of reaction at gel
point derive from the work of Florey and Stockmeyer and deal with polymerization
generally, not only alkyds. Carothers' approach based on average functionality of the
reacting mass is very practical and has been taken up and amplified by Patton, whose factor
K is mathematically related to Carothers' average functionality F by the equation

K=~
A very useful text on the calculation of alkyd formulae is that by Tysall, which deals with
Florey'S and Carothers' approaches in detail.
In practice, alkyd resin formula development is far from an exact science. The procedure
used usually starts with a modification to a known alkyd formula, such as replacing one
polyol with another or one oil with another. A laboratory batch is then cooked, and
depending on the results the formula is modified-increasing polyol to reduce acid value or
other modifications until a satisfactory result is obtained. Alternatively, a starting point
formula is written and cooked in the laboratory, followed by the above process of formula
modification to obtain a satisfactory result.
There are two reasons for this unscientific iterative procedure. First, there is no simple
means of predicting the viscosity of resin solutions; practical experiment is required. Second,
there are inevitably side reactions, as detailed above, which influence acid value at gel point
and which cannot be readily controlled and predicted.
The simple approach of writing formulae with a given percent fatty acid and hydroxyl
excess will be taken. The average functionality will be checked and corrected if necessary
to obtain a desired value of FA v. Procedures for formula modification to correct acid value
and to calculate molecular weight to ensure that viscosity movements are in the appropriate
direction are given below.

5.13.2 Formulating to a chosen oil length and hydroxyl excess

Oil length and type are usually the starting point for developing a new resin:
ru '11 h _ oil content x 100
-/0 01 engt - I . ld
tot a Yle
100 SURFACE COATINGS

~
% latty 'd _ fatty acid content x 100
aCI - I . Id
tota Yle
Variation in hydroxyl excess is used to control viscosity, acid value at the required
viscosity, and overall tendency to gel.
h d
IlL I equivalents ofOH group x 100 100
10 Y roxy excess = . .
eqUIvalents of aCId group
. . equivalents OH
Alternatively the OH:COOH ratIo R = . I COOH
eqUIva ents
To obtain equivalents of OH group and COOH group when oils are used, the amount
of fatty acid or glycerol constituting the oil is used on the basis that for CIS acids
840 g fatty acid + 92 g glycerol---+ 878 g oil + 54 g H 2 0
Thus oil length % = fatty acid % x 1.045
In the ensuing text the following symbols will be used for the terms defined:
fa = % fatty acid
OL = % oil
Mwt = gram molecular weight

M weight of material
= numb er 0 f moIes; M = M
wt
f = number of functional groups per molecule, i.e., the functionality

E = gram equivalent weight per functional group; E = M wt

f
. . weight of polyol in grams
EOH = gram eqUIvalent weIght ofOH groups; EOH = . al 'gh
eqUIv ent weI t
. .. weight of acid in grams
EA = gram eqUIvalent weIght of aCId groups; EA = . I 'gh
eqUIva ent weI t
(Equivalent weights of polyols and acids have been given previously.)
F AV = average functionality (see equation 5B)
The following values of excess hydroxyl will serve as a reasonable starting point for
formulating gylcerol phthalic alkyds of various oil lengths. The hydroxyl value will be
corrected to give an appropriate value of F, as will be seen later.

TABLE 5.2
Ratio R
EOH
(=-)
EA
Alkyd Fatty acid (%) Excess hydroxyl (%)
1 62 o 1.0
2 56 10 1.1
3 46 20 1.2
4 31 30 1.3
 ALKYD RESINS 101

PRACTICAL EXAMPLE
Formulate a gylcerol, phthalic, soyabean alkyd with 50% soya fatty acids and OH:COOH
(R) of 1.15.
Formula for 1000 g of solid resin will be calculated.

1000 g of resin will contain 1000 x 15~0 = 500 g soya fatty acid.
Equivalent weight of soya fatty acid is 280.

500 g soya fatty acid is ~~~ = 1. 786 equivalents.

To maintain the specified OH:COOH ratio 1 equivalent of fatty acid reacts with 1.15
equivalents glycerol to form ester plus 1 mole water.
280 g of fatty acid react with (32 x 1.15 =) 36.8 g glycerol to form (280 + 36.8 - 18 = )
298.8 g ester + 18 g water.
500 g of fatty acid esterified with 65.72 g glycerol yields 533.6 g ester + 32.1 g water.
The amount of glyceryl phthalate needed to yield 1 kg of resin solids is therefore
1000 - 533.6 = 466.4 g ester.
At OH:COOH ratio 1.15: 1, 1 equivalent of phthalic anhydride reacts with 1.15 equivalents
of glycerine to yield glyceryl phthalate ester + 0.5 mole H 2 0.
(0.5 moles of water because 1 mole (i.e. 2 equivalents) of anhydride esterifies to form 1 mole
of water)
74 g phthalic anhydride reacts with (1.15 x 32 = ) 36.8 g glycerol to yield (74 + 36.8 - 9 = )
101.8 g ester + 9 g H 2 0.
We require 466.4 g glycerol phthalate ester.
466.4 = 458
101.8 .
(4.58 x 74 =) 338.9 g phthalic + (4.58 x 36.8 =) 168.5 g glycerine yields 466.2 g phthalate
ester and 41.2 g water.
Thus the formula for the resin is:
Weight Equivalents f Moles
(g) Acid Polyol
Soya bean fatty acids 500.0 1.79 1 1.79
Glycerol I 65.7 2.05 3 0.68
Glycerol II 168.5 5.27 3 1.76
Phthalic anhydride 338.9 4.56 2 2.28
Total 1073.1 6.35 7.32 6.51
Water of reaction = 32.1 + 41.2 = 73.3
Yield = 1073.1 - 73.3 = 999.8
Check OH:COOH = ~:;~ = 1.153: 1
Therefore the average functionality from equation 5B is:
102 SURFACE COATINGS

F '" 2rEA '" 2 x 6.35 '" 1 95

AV rM 6.51 .
The formula will be 'corrected' later to give a more desirable value for F.
The generalized procedure used to develop the above formula was as follows:
1. From table 5.2 find or interpolate a suitable value of R for the oil length required.
2. Calculate the weight of fatty acids (Wfa ) required to give the specified % fatty acid (fa)
in 1 kg resin solids.
3. Find Efa , the number of equivalents in Wfa (look up the equivalent weight of the fatty
acid EA).

E _ Wfa
fa - EA
4. Determine the amount of polyol (W p) required to esterify the fatty acid Wfa at the
required R (look up the equivalent weight of the polyol E OH).
Wp",EfaxRxE OH ... polyol 1
5. Calculate the water of esterification (H 2 0).
H 20 (g) '" Efax 18
6. Calculate the weight of esterified fatty acid Wefa
Wefa '" Wfa + Wp - H 2 0
7. Calculate the amount of polyacid/polyol ester (P E) required for a yield of 1000 g.
PE", lOOO - We fa g
8. Determine the weight Wpe of the polyacid/polyol ester formed when 1 equivalent of
polyacid EpA reacts with R of polyol.
Wpe '" EpA + (R x E OH) - 18 g (9 g for anhydride)
9. Calculate the formula quantities for the polyacid/polyol ester.

Wt polyacid '" !E EpA g

pe
x

PE
Wt polyol '" W x R x EOHg ... polyo12
pe

Wt water formed '" !E x 18 g (9 g for anhydrides)

pe
 ALKYD RESINS 103

10. Tabulate the results.

Equivalents f Moles
Weight Acid Polyol
Fatty acids (Wfa ) E fa
Polyol 1 (Wp)
Polyol 2
Polyacid

Totals
Subtract H 2 0
Theoretical yield

11. Calculate and enter the number of moles of each reactant.

M I _ number of equivalents
o es - functIon
. al'tty F
12. Calculate the yield. Sum the weights of the raw materials and subtract the two lots of
water of reaction. The result should be 1000 ± 0.5 g.
13. Check the OH:COOH ratio.
R = total equivalents of polyol
total equivalents of acid
14. Determine the average functionality FAV'
F _ 2 x total equivalents of acid
AV - total moles
Notes
(a) If the alkyd is to be made from vegetable oil, the quantity of CIS oil needed is
Wfax 1.045. This is less than the weight of esterified fatty acid We fa calculated in step
6 by the amount of hydroxyl excess. This excess polyol must be added as 'Polyol 1'.
The quantity is Wefa - Wt of oil.
(b) A resin starting from oil will require an alcoholysis or acidolysis step before the
remaining ingredients are added. At least 2 moles of polyol for each mole (880 g) of
CIS oil are needed for alcoholysis, and a catalyst (e.g. lithium hydroxide monohydrate
at about 0.25 parts per 1000 parts of oil) should be used.
(c) Acidolysis is appropriate for long oil isophthalic alkyds. About 1 mole of oil is required
per mole of isophthalic to conduct a satisfactory acidolysis reaction. Try 1 hour at
280· C without catalyst followed by cooling to 200-220· C before adding the polyol.
(d) If mixed polyols are to be used as in a long oil pentaerythritol alkyd starting from
vegetable oil there are several possibilities.
The amount of oil can be calculated as in (a) above, i.e. oil = Wfax 1.045. The excess
hydroxyl can be added as glycerol, calculated as III (a), I.e. glycerol
excess = Wefa - (Wfax 1.045).
Alternatively (and usually) the excess can be added as the second polyol. The quantity
IS

[wefa _(Wfa x 1.045)] x equiv: wt of new polyol

eqUlV. wt of glycerol
104 SURFACE COATINGS

or when pentaerythritol is the second polyol

34g
Polyo12 = [Wefa - (Wfax 1.045)] x 32
(e) Where the polyol is to be a mixture, as, for example, 2 moles of glycerol are to be
replaced by 1 mole ethylene glycol and 1 mole pentaerythritol, one can formulate with
the mixture as an entity. In the pentaerythritol/ethylene glycol case the mixture has an
average equivalent weight of 1366+ 62 = 33 and an average functionality F of
4+2=3
2
These figures can be used to simplify the arithmetic. At the end of the calculation the
weight of the polyol mixture is split

x ~ ~~ = 0.6868 pentaerythritol
62
and x 198 = 0.3131 ethylene glycol.
The calculation of the total moles can be done either on a molecular weight of 99, or
on 136 for pentaerythritol and 62 for ethylene glycol. The result will be the same as
far as number of moles is concerned.
Correction factors
Experience has shown that alkyds made with different types of raw materials do not all gel
at the same average functionality. This has led to adoption of particular limiting values of
FA V for different raw materials to ensure that the resins do not gel.
A series of target adjustment factors for F has been derived by Tysall from the work of
Patton and from Bernardo and Bruins. The factors are additive and serve as a reasonable
starting point for various raw-material combinations. They assume that the resin was cooked
to an AV of 8 on resin solids. Add 0.01 for every 2 units of AV above 8.

TABLE 5.3
Monoacids correction factors
Basic value of F = 2
Monoacids Adjustment
CIS fatty acids nil
Lauric coconut pelargonic +0.02
Rosin +0.06
Dehydrated castor oil -0.04
Di acids
PA -0.02
IPA -0.10
Adipic acid - 0.13
Polyols
Glycerol, glycols nil
TMP TME +0.02
PE -0.02
 ALKYD RESINS 105

For example, a soya fatty acid alkyd cooked with pentaerythritol and isophthalic acid with
a target AV on solids of 8-10 should be formulated for a value of FA v of 1.89. This will
give a fair starting point. Because of variations in technique, cooking temperature, stirring,
and losses, one will systematically produce results at variance with these. Experience will
cause you to adopt your own values of F for the polymer compositions you most frequently
use.
The question now arises, how does one modify a formula to adjust FA V to a desired value?
Adjusting FA V to a target value
The traditional method of fine-tuning a formula is to change the hydroxyl excess. If the
formula for FA V is inspected,
F =2 x equivalents acid
Av moles acid + moles polyol
It will be clear that increasing the polyol content reduces FA V and vice versa.
In the practical example given above, the target value for a soya glycerol phthalic alkyd
from the above table should be FA V = 1.98, but was found to be
2 x 6.35
4.07 + 2.44 = 1.95
This can be adjusted as follows:
F = 2EA
AV moles acid + x
where x = moles polyol

F = 1 98 = 2 x 6.35
AV . 4.07 +x

x + 4.07 = ~~9~ = 6.41

x = 6.41 - 4.07 = 2.34 moles
2.34 moles of glycerol = 224.6 g (the former value was 234.2 g)
The drop in glycerol content reduces the yield to 990.2 g and increases the fatty acid
content to 50.5%-not of great significance. It changes the hydroxyl excess to R = 1.134
from R = 1.15. The new formula is:
Weight (g)
Soyabean fatty acids 500
Glycerol 224.6
Phthalic anhydride 338.9
Total 1063.5
Water 73.3
Theoretical yield 990.2
The Paint Research Association (UK) has a computer program that avoids the inaccuracies
inherent in the above approach. Tysall's book, Calculation Techniques in the Formulation of
Alkyds and Related Resins (1982), also gives a method of formulating an alkyd with specified
% fa for and FA V in one step.
106 SURFACE COATINGS

5.14 MOLECULAR WEIGHT OF FINISHED RESIN

The purpose of calculating molecular weight is as a guide to viscosity and particularly to
ensure that formula modifications move molecular weight (and therefore) viscosity in the
desired direction when a formula is being refined. Number average molecular weight (Mn)
can be calculated from the figures tabulated during formula development. (For differences
between number average and weight average molecular weight, see Chapter 1.)
Y
Mn= YxAV
(M - EA) + 56 100
where
Y = yield
M = total number of moles of reactants initially
EA = total number of equivalents of acid initially
AV = acid value of NVM at the end of reaction
Note if the 'yield' is in grams, M and EA are the number of gram moles and gram
equivalents, respectively.
For the resin in the example above (predicted final AV = 8 on solids) before modification,
999.8 999.8
Mn = 999.8 x 8 0.16 + 0.14 = 3333
(6.51-6.35)+ 56100
After modification, assuming the same AV,
990.2 990.2
Mn = 990.2 x 8 0.06 + 0.14 = 4951
(6.41 - 6.35) + 56100
A higher viscosity would be expected, but not a dramatic increase.

5.15 CORRECTING A FORMULA ON THE BASIS OF PRACTICAL

RESULTS
It will usually be found that a resin cook does not give exactly the result required at the
first attempt. A short list of problems would include the following (with solutions suggested
below).
(a) resin gelled at a high acid value.
(b) reached required viscosity, but A V was too high.
(c) resin reached viscosity, but acid value was low and cook was slow.
(d) viscosity stopped rising below figure required and acid value was very low.
The initial response to each of these problems would be to adjust the hydroxyl excess or
the value of FA v' which can be the same thing.
Case a
Reformulate at a lower F AV' If the approximate acid value at gel point is known, see how
much phthalic anhydride would have to be removed to give AV = 0 at gel point.
For a cook with a theoretical yield of 1000 g, the following rough calculation is
serviceable. If AV at gel point is A mg/ g, the amount of PA to be removed is equivalent
of 2A g KOH, i.e.
 ALKYD RESINS 107

A moles of PA _ A x 74 g
56.1 - 56.1
Because the free COOH group cannot be removed without the rest of the phthalic
molecule, we use the molecular weight not the equivalent weight.
Recalculate FA V or R using the lower phthalic anhydride content, and try the cook.
Other things to consider include the cooking temperature-at temperatures above 240 0

C significant fatty acid dimerization is possible especially with linseed oil. If the result is quite
une_xpected, check raw materials and possibilities of oxygen ingress.
Case b
Unless the AV is very much higher than the target, a reduction in polybasic acid should fix
the problem. If the required decrease in AV is A mg KOH/g, reduce the dibasic acid by

5~ 1 x molecular wt dibasic acid g

for each 1000 g theoretical yield.
Case c
This is the reverse of case b. Increase the dibasic acid content by

5~ 1 x molecular weight of dibasic glkg theoretical yield.

It can usually be a little more than the rise necessary-say, A x 1.5.
Case d
This is more difficult. It could be that F AV is much too low. If you know that alkyds (pure
drying) of the oil length formulated regularly reach the specified viscosity, then adjust FAV
and try again. If you are testing new ground, however, you may have to reduce the oil length
and rethink the problem. ¥ou can always try a bit of tung oil and/or a higher cooking
temperature, but this is beyond 'correcting a formula on the basis of practical results'.

5.16 EXAMPLE 1
Formulate a 65% oil length soyabean/pentaerythritol/phthalic alkyd starting from oil with
all added polyol pentaerythritol.
1. Starting point value of R. Although table 5.2 only gives values for glycerol o-phthalic
alkyds, we will use it and rely on the correction process for F to give a better value.
R=l
65
2. Wfa = 1000 x 100 = 650
650
3. Efa = 280 = 2.32
4. Wp = 2.32 x 1 x 30.66
(As this is the glycerol component of the oil, E OH = 30.66, f = 3)
=71.16
5. H 2 0 = 2.32 x 18 = 41.78
6. We fa = 650 + 71.16 - 41.77 = 679.4
(As R = 1, there is no hydroxyl excess, so Wefa is the weight of triglyceride oil, and polyol
1 = 0)
108 SURFACE COATINGS

7. P E = 1000 - 679.39 = 320.61

8. Wpe = 74 + 1 x 34 - 9 = 99
(The equivalent weight of phthalic anhydride is 74 and of pentaerythritol is 34. Only
9 g of water are produced because the diacid is an anhydride.)

9. Wt polyacid = 32~961 x 74 = 239.61

320.61
Wtpolyol=99x 1 x34= 110.09
320.61
Wt water=99x 9 = 29.14
Total water (step 5 and step 9)=29.14+41.78=70.92
10. Weight Equivalents f Moles
Acid Polyol
Soya oil 679.38
This equals
Fatty acid 650 2.32 1 2.32
Glycerol 71.16 2.32 3 0.77
Pentaerythritol 110.09 3.24 4 0.76
Phthalic anhydride 239.61 3.24 2 1.62
11. Total 1070.86 5.56 5.56 5.47
-H 2O 70.92
12. Theoretical yield 999.94

13. Check R = ;:;~ = 1

2 x 5.56
14. FAV = =2.03
5.47
The target value for a soya PE/o-phthalic alkyd, summing the factors from table
5.3, is 2 - 0.04 target FAV = 1.96
Substituting in equation 22
1.96 = 2 x 5.56
3.94 +x
= 2 x 5.56 _ 3 94
x 1.96 .
Moles of polyol = 1.73 (uncorrected 1.53)
The polyol must include the 0.77 moles of glycerol that form part of the vegetable oil, so
the additional 0.2 moles of polyol will all be PE as all added polyol is required to be PE.
0.2 moles PE = 0.2 x 136", 27.2 g
 ALKYD RESINS 109

The formula as adjusted is:

Soyabean oil 679.39
Pentaerythritol 137.29
Phthalic anhydride 239.61
1056.29
Water 29.14
o yield 1027.15
650
% fatty acid 1027.15 x 100=63.3%

which is somewhat shorter than specified.

R is now 5.5;.;t8 = 1.14

If the resin were reformulated using R = 1.14 a much smaller correction would be required
and a percentage fatty acid much closer to 65% would be obtained. In practice it is
worthwhile running a laboratory cook with the formula in its present form and checking
practically that a further change in OH is not required.