Crosslinking of unsaturated polyesters

6 Unsaturated polyesters
6.1 Crosslinking of
unsaturated polyesters
As mentioned before, unsaturated polyesters are polyesters which have a certain content
of unsaturated compounds bearing olefinic double bonds. This definition excludes poly-
esters containing aromatic double bonds or alkyd resins containing unsaturated fatty
acids. In nearly all products, the olefinic component is a polycarboxylic acid or a derivative.
And nearly all unsaturated polyesters contain maleic anhydride (MA). During preparation
of unsaturated polyesters, most maleic anhydride is incorporated by forming fumaric es-
ters. Fumaric acid is the trans-isomer of maleic acid (cis-ethylene dicarboxylic acid). Fuma-
ric esters are formed predominantly because the molecule contains less energy than the
cis-structure. Fumaric esters are susceptible to free-radical polymerisation and are polyme-
rised together with co-monomers. The latter are reactive vinyl compounds, the most im-
portant of which is styrene. Combinations of unsaturated polyesters with other co-mono-
mers (e.g. vinyl toluene or methacrylic esters) are employed but are of minor importance.
The polymerisation reaction must be started by initiators: peroxide compounds.
The initiator reaction consists in the decomposition of the peroxy group to form
free-radicals. The most suitable peroxides are described in Figure 6.1.
The reactivity of initiators is improved by redox reactions. The redox compounds,
called accelerators, are either organic cobalt(II)salts or tertiary aromatic amines. As a rule,
the cobalt compounds are combined with ketone peroxides (e.g. cyclohexanone peroxide,

Figure  6.1:  Peroxide initiators for crosslinking of unsaturated polyesters

Ulrich Poth: Polyester and Alkyd Resins

© Copyright 2020 by Vincentz Network, Hanover, Germany

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Unsaturated polyesters

methyl ethyl ketone peroxide). The reaction of organic cobalt(II)salts with peroxides is
shown in Figure 6.2.
The tertiary aromatic amines (e.g. N,N-dimethylaniline) are combined with acyl per-
oxides (e.g. benzoyl peroxide). The reaction of aromatic tertiary amines with acyl peroxides
is shown in Figure 6.3.
Where cobalt(II)salts are combined with ketone peroxides, the initiator reaction con-
sists of the reduction of peroxide group to a hydroxyl anion and an alkoxy free-radical. The
alkoxy free-radical adds across the double bond of the fumaric ester, producing an ether
group and a new free-radical. This initiator reaction is shown in Figure 6.4.
The new free-radical reacts preferentially with the co-monomer (e.g. styrene), and
free-radical chain propagation commences. However, the reaction swiftly leads to recombi-
nation with other free-radical chains or free-radicals of fumaric esters.
This reaction sequence is the most probable, because of the different polymerisation
parameters for fumaric esters and styrene. The values in the e/Q chart of the polymerisation

Figure  6.2:  Reaction of organic cobalt (II) salts with peroxides

Figure  6.3:  Reaction of aromatic tertiary amines with acyl peroxides

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 Crosslinking of unsaturated polyesters

(parameters for styrene are e = - 0.80 and Q = + 1.00 (these are the standard values for
both) and for fumaric ester e = + 1.50 and Q = + 0.75. Q stands for the activation energy
of the free-radical and e is the polarisation tendency of double bonds. The values shown
are highly conducive to alternating co-polymerisation. No homopolymers are formed dur­
ing the crosslinking of unsaturated polyesters and styrene.
Co-polymerisation leads to relatively dense but extended molecular networks. These
are necessary for good chemical and solvent resistance. The extension and density of the
molecular networks vary with the free-radical concentration and content of fumaric esters
and the size or molecular weight of the unsaturated polyester. The free-radical concentra-
tion depends on the content of initiator, the content of accelerator and the temperature.

Figure  6.4:  Initiator reaction with unsaturated polyester

Figure  6.5:  Copolymerisation reaction

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Unsaturated polyesters

A particular advantage is that styrene can act as a solvent for the unsaturated polyester
resin. However, the styrene is incorporated into the film matrix during co-polymerisation,
so it acts as a reactive solvent. Thus, the content of volatile organic compounds is low, and
the entire system is environmentally friendly as a result. This is furthermore the reason
that the system can be applied to form high film thickness without problems (up to 500 µm).
And, besides coating applications, the unsaturated polyesters are suitable for plastic parts
and laminates (glass-fibre-reinforced plastic, assembly parts, and ships’ hulls).
Unsaturated polyester systems containing a combination of acyl peroxides and tertiary
aromatic amines can react at lower temperatures but suffer from the disadvantage of
possible discolouration. These products are mainly used for putties and fillers.
It is also possible to crosslink unsaturated polyesters with reactive monomers. In such
cases, initiation can take place by adding cumene hydroperoxide and organic cobalt(II)salts
or peresters (e.g. tert.-perisononanate) without accelerators. Products initiated in this way
are relatively stable when stored at ambient temperatures.
As a rule, the peroxides are not added until just before the system is ready to be ap-
plied. The accelerators are already incorporated during manufacture of the coating mate-
rials. The aforementioned aromatic tertiary amines may already have been added to the
delivery form in the case of unsaturated polyesters. The pot-life of the finished material
varies with the type of unsaturated polyester, the initiator and the accelerator.
If large quantities of fully initiated unsaturated polyester remain after the application
process, there is a risk that large amounts of heat will be generated (reaction enthalpy)
which could lead to combustion.
The pot-life of activated industrial quantities of UP systems can be compensated for in
different ways. The first employs two-head curtain coating equipment, with two storage
tanks. One contains UP resin and initiator, while the other contains UP resin and accelera-
tor. The reaction does not start until the two components have been cast one on top of the
other, whereupon both materials inter-diffuse. The second, known as the reactive-primer
technique, entails applying a primer containing a binder which forms films by physical
drying only and in addition a necessary quantity of peroxide. This is followed by the un-
saturated polyester containing the accelerator. Here, too, crosslinking starts after a diffu-
sion process has occurred.
The crosslinking of unsaturated polyesters by co-polymerisation with styrene leads to
a decrease in volume. This shrinkage is advantageous in the production of moulded parts,
as they are easy to remove from the mould after crosslinking. However, it is a disadvantage
in coatings application, because the shrinkage may generate loss of adhesion (particularly
on bare metal).
Unsaturated polyesters can be crosslinked by UV light (see Chapter 6.4).
Inhalation of styrene may lead to irritation of skin and mucous membranes. It can im-
pair procreative capacity and styrene is a presumed to be carcinogenic. The occupational

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 Unmodified unsaturated polyesters – “wax polyesters”

exposure limit is 20 ml/m3. Replacements for it are being sought. Alternatives to styrene as
a reactive solvent are vinyl toluene, tert.-butyl styrene, α-methyl styrene, maleic diesters of
lower monoalcohols, and methacrylates. On account of their polymerisation parameters,
vinyl esters react only at elevated temperatures. If polyfunctional reactive solvents serve as
co-monomers, e.g. divinyl benzene or 1,4-butanediol dimethacrylate, networks of high
crosslinking density are formed. However, owing to the poor performance of the alternati-
ves, styrene is still in use, but naturally the necessary precautions must be adopted.
Crosslinking of unsaturated polyesters by co-polymerisation is inhibited by atmospheric
oxygen. It is believed that atmospheric oxygen, by virtue of its ability to form a bi-radical,
becomes attached to the free-radicals on the growing polyester chains, as a result of which
peroxide formation occurs, followed by recombination. The reaction constant for oxygen
addition is much higher than for the co-polymerisation step, as presented in Figure 6.6.
Crosslinking is then incomplete. The upper layers of the coating films become soft and
tacky. However, there are different ways to avoid these effects.

6.2  nmodified unsaturated polyesters –

U
“wax polyesters”
Unmodified unsaturated polyesters are prepared from combinations of maleic anhydride
with other polycarboxylic acids, e.g. phthalic anhydride. Mainly they contain short-chain

Figure  6.6:  Oxygen inhibition of polymerisation

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Unsaturated polyesters

aliphatic diols, e.g. ethylene glycol, propylene glycol, 1,3-butanediol, or neopentyl glycol.
The ratio of maleic anhydride to other polycarboxylic acids determines the solubility and
crosslinking efficiency. Typically it is between 4 : 6 and 7 : 3. For more flexible coating
films, the maleic anhydride is combined with adipic acid, or the polyesters contain long-
chain aliphatic diols, e.g. 1,4 butanediol, trimethyl 1,3-pentanediol, or ether diols, e.g. di-
ethylene glycol, dipropylene glycol or higher polyether diols. Higher functional polyols are
unsuitable or, if so, only in small amounts.
The components for preparing unsaturated polyesters are esterified at relatively low
temperatures (e.g. at 180 °C). The products are usually not formulated with an excess of
polyols; the limitation on the number-average molecular weight is imposed by lower de-
grees of condensation. The acid values are high at 30 to 50 mg KOH/g. The reason for not
using an excess of diols and higher functional polyols and for choosing relatively low es-
terification temperatures is to avoid secondary reactions. These secondary reactions take
the form of premature polymerisation of double bonds and Michael addition by OH
groups. The Michael reaction is the addition of hydrogen atoms of terminal OH groups to
double bonds of fumaric esters. This gives rise to side-chains and the molecular weights
increase significantly, as shown in Figure 6.7.
Furthermore, there is the risk that polymerisation may start during dissolution of un-
saturated polyesters in reactive solvents (styrene). GPC analysis always reveals higher
molecular weights than those calculated.
To prevent premature polymerisation, small quantities of inhibitors are added (hydro-
quinone, methyl hydroquinone).
Some formulations (see patent examples) specify fumaric acid instead of maleic anhy-
dride. The disadvantages here are that fumaric acid has a very high melting temperature

Figure  6.7:  Secondary reaction during production of unsaturated polyesters

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 Unmodified unsaturated polyesters – “wax polyesters”

Table 6.1: Example of an unmodified, unsaturated polyester resin

n = m/M building element M m m-‰
10.395 propylene glycol 76 790.0 437.3
3.797 pthalic anhydride 148 562.0 311.1
6.204 maleic anhydride 98 608.0 336.5
sum 1960.0 1084.9
water 18 153.4 84.9
yield (AV = 46) 1806.6 1000.0
polyester constant k'M 1.1874
average molar mass [g/mol] Mn 964
acid value [mg KOH/g] AV 46
OH value [mg KOH/g] OHV 70.4
viscosity (65 % in styrene) [mPa·s] η 1486

(287 °C, in a closed tube) and tends to undergo sublimation. Like isophthalic acid, fumaric
acid is esterified only by reaction at particle interfaces. This leads to broader molecular
weight distributions and higher solution viscosities. Given that maleic anhydride is conver-
ted into fumaric ester during esterification, there would appear to be no advantage to be
gained from the use of fumaric acid.
Commonly, unsaturated polyesters are dissolved at low temperatures, with addition of
inhibitors. The quantity of styrene in the delivery form is between 30 and 50 wt.%.
If an unsaturated polyester resin has an equivalent weight of about 300 g/mol, expres-
sed in terms of the double bonds (see example in the following) and it is diluted 60 : 40
in styrene (molecular weight 104 g/mol), the molar ratio of double bonds to styrene is
almost 1 : 2. This means there is one double bond in the polyester for every two molecules
of styrene (see Figure 6.5).
The following example [101] describes an unsaturated polyester resin (see Table 6.1)
containing phthalic anhydride and maleic anhydride in the molar ratio of 62 : 38, made to
react with propylene glycol in small molar excess, calculated on dicarboxylic acids (1.04 :
1.00). The esterification is carried out until the acid value is 48 mg KOH/g. The resin then
has a number-average molecular weight of 964 g/mol (theoretical). As the polyester mole-
cules contain 3.31 moles of fumaric ester on average, the corresponding equivalent weight
is 291 g/mol.
The unsaturated polyester resin of the example is dissolved in styrene to a concentra-
tion of 55 wt.% solids in solution, and 0.012 wt.% methyl hydroquinone is added by way
of stabiliser.
Such resins are suitable for high-quality coatings. However, ways are needed to prevent
the inhibition by atmospheric oxygen to achieve optimum film properties on the surface.

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Unsaturated polyesters

Initially, building blocks were chosen for the polyester that would yield higher glass-tran-
sition temperatures (e.g. higher than 50 °C) by physical drying. The surface then appeared
solid but had no adequate resistance.
A more efficient method consists in protecting the surface against the influence of atmo-
spheric oxygen by adding paraffin waxes or stearin. The additions vary from 0.1 to 2.0 wt.%,
in accordance with the melt temperatures of the additives of 40 to 70 °C. Products that have
higher melting temperatures require smaller additions. Some unsaturated polyesters already
contain waxes in their delivery form. In other cases, the waxes are added during preparation
of the coating material. The binders in this class are therefore known as “wax polyesters”.
During curing of unsaturated polyesters and styrene, the waxes become incompatible
with the film matrix (gel), they separate out and float on the coating surface. The wax film
on the surface protects the upper film layer against penetration by air and so prevents in-
hibition by oxygen. Thus, the upper film layers, too, can crosslink without failure. There is
another advantage of wax film: it reduces the evaporation losses of reactive solvent (styre-
ne). However, the wax on the surface generates irregular, matte films. The coating layers
must be re-treated by sanding and polishing. This yields films which are very hard and
smooth, have high gloss, and with a bright appearance (filling power). The films have excel-
lent resistance to chemicals, including household agents, such as fruit juices, dressings and
drinks containing alcohol, and water. The UP resin films are not sufficiently weatherable. In
the past, such systems were very popular for wooden furniture treated with closed-pore
clearcoats and pigmented coatings, and flatting varnishes. However, such coatings then fell
out of style and were gradually replaced by open-pore systems which highlight the natural
texture of the wood. Such UP resin systems are now only used for special applications,
among them coatings for pianos. The physical properties of UP resin coatings intensify the
acoustic timbre of these instruments. The systems are also used for automotive dashboards.
However, dashboards are now mainly coated with aqueous polyurethane dispersions.
UP resins of this type are also used for highly-filled putties, mainly for automotive re-
pair coating systems, but in that event without wax, because here the inhibition effect of
atmospheric oxygen plays only a minor role. The UP resins in the class below are also
suitable for such putties.
Typical commercial products: Palatal P 6 (BASF [65]), Roskydal E 65 (Allnex-Nuplex [76]),
Sacopal L 100 w (Krems-Chemie [102])

6.3 “Gloss polyesters”

There is also a way to modify the molecular structure of unsaturated polyester resins with
the purpose of avoiding or minimising the inhibitory effect of atmospheric oxygen. This
approach utilises special compounds which compete against the free-radicals for the oxygen

158
 “Gloss polyesters”

needed for polymerisation. Such compounds are described in numerous patents dating
from the 1960s. They include cycloaliphatic compounds which mainly contain olefinic
double bonds and, more important, compounds which contain allyl ethers.
Suitable cycloaliphatic compounds for the polyols are perhydrobisphenol A (2,2-[4,4'-bis-
hydroxy-cyclohexyl]-propane), and tricyclododecane dimethanol (TCD alcohol DM) and, for
the polycarboxylic acids, tetrahydrophthalic anhydride (THPA), tricyclodecane dicarboxylic
acid (TCD dicarboxylic acid) and endomethylene tetrahydrophthalic anhydride.
Suitable allyl compounds are monoallyl ethers of glycerol and trimethylolpropane and
diallyl ether of glycerol, trimethylolpropane and pentaerythritol. Naturally, the allyl com-
pounds, containing only one OH group, form the terminal groups of the polyester chains.
The structures of the most important compounds are given in Figure 6.8.
It is believed that the activated CH2 groups in the vicinity of the double bond and, in
the case of allyl ethers, in the vicinity of ether oxygen (the allyl position) react with atmo-
spheric oxygen to form hydroperoxides. These hydroperoxides can form free-radicals
which can then take part in polymerisation or enter into recombination reactions. Both
reactions prevent the oxygen from inhibiting the actual co-polymerisation reaction. The
formation of free-radicals of oxygen adducts requires the use of redox accelerators, which
must be added in sufficient quantity, e.g. organic cobalt(II)salts. The possible reactions are
described in Figure 6.9.
The process is comparable to
the oxidative curing of alkyd resins
containing multiple unsaturated fat-
ty acids (e.g. linoleic acid; see Chap-
ter 7.2.1)
Unsaturated polyesters contai-
ning such building blocks co-cross-
link with styrene (or alternative
co-monomers) to immediately yield
hard and glossy film surfaces. To dif-
ferentiate these systems from “wax
polyesters”, they are called “gloss
polyesters”. The measured gloss va-
lues, among others, are high, due to
the high refractive index of styrene.
There is another building block
which can suppress the inhibitory
effect of oxygen, namely 2,2,4-tri-
methyl-1,3-pentanediol. For the pre- Figure  6.8:  Building blocks for avoiding inhibition
paration of saturated polyesters this by oxygen

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Unsaturated polyesters

Table 6.2: Example of a "gloss polyester”

n building element M n·M=m wt. ‰
0.45 propylene glykol 76 34.20 140.6
0.40 neopentyl glykol 104 41.60 171.1
0.60 maleic anhydride 98 58.80 241.8
0.40 tetrahydrophthalic anhydride 152 60.80 250.0
0.30 trimethylolpropane dially ether 214 64.20 264.0
sum 259.60 1067.6
water 18 16.44 67.6
yield (AV = 20) 243.16 1000.0
polyester constant k’M 1.2367
average molar mass [g/mol] Mn 1027
acid value [mg KOH/g] AV 20
OH value [mg KOH/g] OHV 20

diol has the disadvantage of eliminating water to form an unsaturated mono-alcohol (as a
chain-end). However, the diol is advantageous for unsaturated polyesters, because it can
help to avoid inhibition by oxygen, in a manner akin to that of allyl ether compounds.
Table 6.2 [103] describes an unsaturated polyester resin containing maleic anhydride
(0.60 moles), tetrahydrophthalic anhydride (0.40 moles), propylene glycol (0.45 moles),
neopentyl glycol (0.40 moles), and trimethylolpropane diallyl ether (0.30 moles) to form
the termination of the polyester molecules (on average 1.3 moles per mole of polyester).
With an acid value of 20 mg KOH/g, the polyester has a number-average molecular weight
of 1027 g/mol. The equivalent weight, expressed in terms of double bonds, is 253.3 g/mol.
Such binders are suitable for wood coatings which are notable for their high gloss, high
hardness, and excellent resistance to chemicals and solvents. They are also used for pig-
mented coatings and putties.

Figure  6.9:  Reaction for avoiding inhibition by oxygen

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 UV crosslinking of unsaturated polyesters

Typical commercial products: Roskydal 500 grades (Allnex-Nuplex [76]), Sacoval L 300 T

(Krems-Chemie [102])
Unsaturated polyesters which, besides maleic anhydride and tetrahydrophthalic anhydride and
other cycloaliphatic polycarboxylic acids, contain significant quantities of long-chain aliphatic
diols, e.g. 1,4-butanediol, 1,5-pentanediol as well as 2,2,4-trimethyl 1,3-pentanediol, and ether
diols such as diethylene and propylene glycol, and higher polyether diols, are ideal for putties
and fillers. Such materials are mainly employed in automotive repair systems. They cure with­
out problems in thicker film layers and can be sanded and reworked after a short time. The
cycloaliphatic compounds generate good adhesion properties. These unsaturated polyester
resins also cure well in thick layers. The films are adequately flexible and can be sanded and
re-worked after a short time. They impart excellent adhesion properties. Particularly good ad-
hesion is provided by alkoxylated bisphenol A as polyol component. In addition, such products
are also relatively resistant to heat. This an important condition for the formulation of primers
which are combined with stoving primer surfacers and stoving topcoats.
Primers for use at ambient temperatures contain a combination of acyl peroxides and
tertiary aromatic amines as this combination confers reactivity at low temperatures
(around 0 °C). While the unsaturated esters already contain the amines in the delivery
form, the acyl peroxides are added mainly in the form of dispersions in plasticisers (pastes
in collapsible tubes) just before the putty is used. As the pot-life of the finished product is
very short, in manual application only small amounts are prepared, by mixing the putty
materials with peroxide hardener.
Typical commercial products: Roskydal E grades (Allnex-Nuplex [62])

6.4 UV crosslinking of

unsaturated polyesters
Back in 1955, trials commenced on the crosslinking of unsaturated polyesters by UV light [104].
As here also atmospheric oxygen was observed to inhibit surface curing, the process was
not taken up again until the development of gloss polyesters containing the above-mentio-
ned building blocks (see Chapter 6.3).
The UV crosslinking is started by UV initiators. UV light has wavelengths between 280
and 400 nm. The initiators absorb UV light of different wavelengths to form free-radicals.
These initiate free-radical chain polymerisation at the double bonds of fumaric esters, as
well as at the double bonds of co-monomers.
UV initiators can decompose into free-radicals in the presence of high-energy light, due
to steric effects in their molecules. The most suitable products are benzophenone, ben-
zoin ethers, benzilketals, β-hydroxyalkyl phenyl ketones, β-aminoalkyl phenol ketones

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Unsaturated polyesters

and benzoyl phosphine oxides [105]. For UV clearcoats, the use of between 2.5 and 3.5 wt.%
(calculated on polyester resin) of a β-hydroxyalkyl phenyl ketone has been recommended,
with between 2.5 and 3.5 wt.% (calculated on polyester resin) of a benzoyl phosphine
oxide recommended for pigmented systems [106]. Benzoyl phosphine oxides are suitable
for pigmented systems because they absorb UV wavelengths up to 450 nm, a region in
which, e.g., titanium dioxide is still partly transparent to this light.
Films of unsaturated polyesters (gloss polyesters) cured by UV light contain extended
molecular networks, which lead to high hardness, good flexibility, high gloss values, and
excellent resistance to chemicals and humidity. They are not particularly weatherable.
Unsaturated polyesters for UV curing can be combined with alternative co-monomers,
instead of styrene. These are primarily acrylic esters (monofunctional and polyfunctional
esters), e.g. hexanediol diacrylate or trimethylolpropane triacrylate.
If unsaturated polyesters contain sufficient numbers of double bonds, it is possible to
cure them with UV light, without co-monomers. Such resins are delivered as 100 % pro-
ducts or diluted with solvents (mainly esters, e.g. butyl acetate).
Example of a commercial product: Roskydal 502 BA (Allnex-Nuplex [78])
As UV coatings are deemed to be environmentally friendly and the films are of premium
quality, the systems’ range of applications is being greatly expanded. Their market share
is projected to keep growing in the future. However, in this market the unsaturated poly-
ester resins play only a minor role. The reason is that the double bonds of acrylic esters
are much more reactive than the double bonds of fumaric esters. Consequently, UV cross-
linking is dominated by binders containing acrylic esters, e.g. polyester acrylates (see
Chapter 5.4.3). However, there are polyester acrylates which contain an unsaturated poly-
ester resin segment and terminal acrylic esters.

6.5 Other unsaturated polyesters

If unsaturated polyesters (UPs) prepared from maleic anhydride and other dicarboxylic
acids contain significant quantities of polyethylene glycol, they can be made soluble in
water. Such water-tolerant binders can also be used for UV curing. It is possible to prepa-
re high-molecular weight polyesters which are thinned with water to convert them into a
form suitable for application. However, unlike other UV systems, the water has to be eva-
porated (which consumes energy). As UV crosslinking is highly efficient, the hydrophilic
behaviour of some of the building blocks is not a major problem.
If UP resins are processed without the use of styrene, they offer excellent adhesion
properties. This applies particularly to UP resins containing cycloaliphatic building blocks.
These building blocks were first used for formulating polyesters which surface-cure without
inhibition by atmospheric oxygen. Thereafter, unsaturated polyesters containing such build­

162
 Other unsaturated polyesters

ing blocks (tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride)

were formulated for putties and fillers. Finally, it was discovered that polyesters of such
composition also support adhesion in other coating systems that cannot be cured by poly-
merisation of double bonds. These are expressly called adhesive resins. They consist of
maleic anhydride in combination with phthalic anhydride (hard adhesive resins) or with
adipic acid (soft adhesive resins) and of tricyclodecane dimethanol (TCD alcohol DM). They
serve as additives for can-coating and coil-coating systems, where they improve adhesion.
Typical commercial products: Tego Add-Bond LTH, LTW (Evonik [107])

163