Technical Paper

Wood coatings

New trends in wood

coatings and fire retardants
Biobased monomers and high performance coatings

Contact:
M.Sc. Andreea Daniliuc
Fraunhofer-Institut fr
Holzforschung WKI
Braunschweig/Germany
T +49 531-2155-308
andreea.daniliuc@wki.
fraunhofer.de

Andreea Daniliuc
Barbora Deppe
Olaf Deppe
Stefan Friebel
Dirk Kruse
Claudia Philipp
Improved, UV-curing wood exterior coatings can
be made from diols. Synthetic routes are available
to use renewable products. Improved fire retardants can be made from encapsulated ammonium
polyphosphate.

n order to look at the possibility of the use of 1,3-propanediol for exterior coatings, a comparison has been
made of polyurethane dispersions (PUD) in which the
polyester composition is the investigated parameter. The
work involved replacing 1,6-hexanediol (1,6-HDO) by 1,3PDO. After polyesterification by melt condensation, the
polyurethane dispersions (PUD) were produced according

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to the acetone process, followed by a chain extension

with a diamine. After removing the acetone, the polyurethane dispersion was adjusted to a solids content of 40%.
Biotechnologically produced 1,3-propanediol (1,3-PDO)
was used as a starting component in the polyester synthesis. 1,3-PDO is already produced from corn sugar by
means of biotechnology [1]. Work has been carried out
on the conversion of glycerol to 1,3-PDO, which should
lead to a more cost-effective process [2].
Hydrolysis resistance is an important criterion for good
weathering properties of a paint film. The polyester
component has the dominant influence on the paints
performance. Therefore, to assess the influence of the
diol component of the hydrolysis, two polyester based
on 1,3-PDO and 1,6-HDO respectively were examined
for their hydrolysis resistance. In each variant, the acid
component was also varied. In series 1, the same mole
fractions of adipic acid and phthalic anhydride were used.
In series 2, the molar ratio of adipic acid to phthalic anhydride was 1:2.

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Technical Paper
Wood coatings
Hydrolysis Resistance
The hydrolysis of polyester polyols was measured by
the reduction of its molecular weight over time, as the
hydrolysis process breaks the ester bonds of polyester
polyols. The acid groups created reduce the pH value.
Since the hydrolysis is autocatalysed by the pH value, the
mixture was buffered to a constant value of pH 4. The
change in molecular weight of the polyester was determined at 80 C. The reduction of the molecular weight
indicated that the molecular weight distribution index of
the polymer only changed little. Thus, the hydrolysis of
the ester groups was shown to be independent of the
molecular weight and occured from the chain ends.
Taking the molecular weight/initial molecular weight ratio
(Mn/Mn0) as a quantitative measure, the molar mass of
1,3-PDO-based polyester polyols decreased by hydrolysis
to 47% (series 1) and 61 % (series 2) of the original value
compared to 49 % (series 1) and 66 % (series 2) for 1,6HDO based polyesterpolyols. The hydrolysis rate was much
lower than originally expected, because of the smaller
molecular structure of 1,3-PDO. The higher proportion of
phthalic anhydride had a much stronger influence than
the choice of the diol in series 2 (see Figure 1), because
the phenyl group sterically shielded the ester bondings.
Additional studies have shown that the hydrolysis stability can be further enhanced by other sterically hindered
monomers such as isophthalic acid and neopentyl glycol,
but this, however, reduces the elasticity of the film.
The 1,3-PDO and 1,6-HDO-based PUD were formulated as
exterior wood varnishs. They were mixed with a commercially available acrylic resin in a ratio of 1:3. Pine sapwood was then coated with these products. The total
film thickness was approx. 100 m. The coated samples
were weathered using fluorescent UV lamps and water in
a QUV machine according to DIN EN 927-6.
The weathered samples are shown in Figure 2. After the
QUV weathering, the pure acrylic dispersion displays
were visually slightly more damaged than the two PU
blends. The durability of the two PU blends cannot be
visually distinguished using this weathering method.
In a further test, pine sapwood was coated with pure
1,3-PDO-PUD and with a 3:1 blend with a pure acrylic dispersion. The coated samples were subjected to natural
weathering according to DIN EN 927-3. The results after 15

Results at a glance

In order to look at the possibility of the use of

1,3-propanediol for exterior wood coatings, a comparison has been made of polyurethane dispersions
(PUD) in which the polyester composition is the
investigated parameter.

Figure 1: Variation over time of Mn/Mn0 of polyester polyols in a buffered solution

months weathering are shown in Figure 3. The plane areas of the samples are in both cases free from any damage.
Since the initial elasticity of the PU-blends is higher than
that of the pure acrylics, the visual damage occurs at a
later stage. To improve the durability of exterior wood
coatings, for example, the hail resistance, the use of a
blend of pure acrylics with a flexible polyurethane dispersion is highly recommended. Both the 1,3-PDO and
the 1,6-HDO-based PUD significantly extended the durability of the acrylic dispersions tested.

Biobased UV-coatings
The method of synthesis of UV-curable polyester polyurethane dispersions for furniture coatings was as follows.
The first step was the synthesis of a polyesterpolyol.
The diol component was predominantly 1,3-propanediol. Other biosourced diols such as glycerol, pentaerythritol or castor oil may also be used. The main building
blocks were Diacids such as phthalic acid, isophthalic acid
and adipic acid. In principle biosourced diacids such as
furandicarboxylic acid, succinic acid and difatty acids can
also be used, i.e. the polyesterpolyol can be made of
100% natural resources. The second step was the addition of an isocyanate such as isophorone diisocyanate
(IPDI), hexamethylene diisocyanate (HDI) or others to
give an isocyanate-terminated polyesterpolyol. For dispersions that require a high light fastness, aliphatic isocyanates are preferred to aromatic ones. The advantage
of IPDI is that it gives particularly good film hardness. A

Ways of making the constituents from renewable

sources are being developed
Improved fire retardants can be made from encapsulated ammonium polyphosphate (APP)

Figure 2: Results after 2016 h QUV-weathering (DIN EN 927-6) left: acrylate;

centre: blend with 1,3-PDO-PUD; right: blend with 1,6-HDO-PUD. The right-hand
sample of each series is the non-weathered reference sample.

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Technical Paper
Wood coatings
self-emulsified dispersion was achieved by the addition
of dimethylol propionic acid (DMPA). In the next step, the
NCO-groups of the polyurethane prepolymer were reacted with hydroxyacrylates such as 2-hydroxyethyl acrylate
(HEA), 2-hydroxyethyl methacrylate (HEMA) and pentaerythritol triacrylate (PETA) or a mixture thereof. Typically,
the level of double bonds was in the range of 1.8 to 3.0
mmol/g polymer. After neutralising with, for example,
triethylamine, the PU-resin was dispersed in water.

Renewable sources
Figure 3: Results after 15 months natural weathering (DIN EN 927-3) left: pure
1,3-PDO-PUD; right: 3:1 blend with acrylic / 1,3-PDO-PUD

Figure 4: Possible synthesis route for bio-based 2-hydroxy acrylate

To date, hydroxyacrylates have been made from petroleum. Figure 4 illustrates the future scenario for bio
method for the production of 2-hydroxy acrylate. A demonstration plant for biobased acrylic acid production is
due for completion this year with a production plant following in 2013 [3]. Bioethanol can be used to make ethylene oxide as part of the process.
Bio-sourced pentaerythritol triacrylate is using commercial pentaerythritol and bio-sourced acrylic acid as shown
in Figure 5. If these building blocks are available in the
future, waterborne UV-curing polyurethane dispersions
with a natural content of 55 to 80 % will be possible.
UV-dispersions produced in the laboratory were formulated with a photo-initiator (a-hydroxyketone), defoamer
and a wetting agent. The total solvent requirement (butyl
glycol) is less than 25 g/l to achieve a minimum filmforming temperature of < 5 C.
The coating has a gloss of 95 % measured at 60 . And its
wood-grain-enhancement properties are excellent. The
lacquered wooden plate was subjected to a standard test
DIN 68861-1 (for furniture surfaces) and rated as category
1B. The pendulum hardness according to Knig (DIN EN
ISO 1522) lies between 70 and 133 s.

Sugarbased methacrylate monomers

for acrylic dispersions

Figure 5: Possible synthesis route for bio-based pentaerythritol triacrylate

Figure 6: Synthesis of a sugar methacrylate starting from glucose

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Novel saccharide monomers exist for acrylic dispersions. For

example, radically polymerisable sugar methacrylates were
synthesized in two-step reactions using low-molecular saccharides, which were copolymerised with commercial acrylic
monomers based on renewable materials. These vinylsaccharides, also from renewable materials, are an alternative to
petrochemical raw materials such as MMA.
3-O-Methacryloyl-1,2:5,6-di-O-isopropylidene--dglucofuranose (MDG), a monomer suitable for the radical
emulsion polymerisation, can be synthesized from glucose in
a two-step reaction by esterification [3]. The acetalisation of
glucose to diacetonglucose (DAG) is state of the art. Protected sugars, which still have one free-hydroxyl group, can be
converted to polymerisable monomers by esterification for
example with methacrylic anhydride. During the work, this
reaction was adapted to give lab-scale batches of 8 kg with
90 % yield and 97 % purity without distillation. Generally,
the homopolymers of these sugar methacrylates exhibit very
high glass-transition temperatures (Tg >160 C) compared to
commercial monomers such as MMA (Tg = 105 C) [4].
The aim is the synthesis of waterborne binders for wood
and wood-based materials based largely on renewable
resources which are present at more than 40 % based on
the solid content of the binder. The properties of acrylic

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Technical Paper
Wood coatings

Figure 7: Degradation profile of a

MDG-containing
copolymer. The
percentage (%)
scale of the
ordinate is related
only to the black
TGA-curve

dispersions can be achieved using an appropriate recipe and

production process. Thus, binders were produced both by conventional emulsion polymerisation and mini-emulsion polymerisation. The lab-scale product thus generated is mainly
suitable for furniture lacquers [5]. The acrylic dispersions were
applied on glass. Film formation took place at ambient conditions. The films were exposed to a light resistance tester for
72 h. No yellowing occurred. The heat stability was tested by
various thermal-analysis methods, such as DSC and TGA-MS.
As shown in Figure 8, the loss of mass is low up to 100 C (<
2 wt- %) and is dominated by water (blue lines). Acetone of
the protecting groups (green lines) is released in the same
amount as water at 130 C (~2 wt- %) and dominates up to
200 C. Subsequently, condensation reactions take place and
water is released again. In general, MDG-containing copolymers are heat stable and for this reason they were tested in
fire retardant coatings (see below).
The coatings of these new binders exhibit a chemical resistance of 1B according DIN 68861-1 without mustard. A
two-layer system of primer and topcoat both consisting of
MDG-copolymers show excellent wood warmth (Figure 9).
Some other properties such as hardness or gloss need to be
improved.
This project was funded by German Federal Ministry of
Food, Agriculture and Consumer Protection (BMELV) via
Agency for Renewable Resources (FNR) within the framework Technische Kunststoffe und Spezialpolymere aus
nachwachsenden Rohstoffen.

tection for flammable substrates by the formation of a voluminous, insulating protective layer by the simultaneous
carbonization and foaming of the ingredients. These socalled intumescent coatings consist of a polymeric binder,
an inorganic acid source (e.g. ammonium polyphosphate),

Figure 8: Steamroller model coated

with two-layer
system of primer
and topcoat both
consisting of MDGcopolymers

Novel fire retardants by encapsulation

Moving on to fire-retardant coatings for wooden facades,
intumescent fire-retardant coatings (IFRC) provide fire pro-

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Technical Paper
Wood coatings

Figure 9: SEM of used substances and their composites (1000x magnification)

a carbon-rich source (e.g. polyalcohols such as starch, pentaerythritol) and a blowing agent (e.g. melamine).
In spite of the many advantages, fire retardant coatings
lack sufficient weathering stability. Therefore, their application is limited to indoor use (r.H. < 70 %). Due to the
requirements of national building codes, there is a strong
market demand for fire-protected wooden facades [6].
Substances essential for the intumescent reaction
are sensitive to hydrolysis. For example, ammonium
polyphosphate (APP), as part of intumescent coating,
is hydrolyzed to water-soluble monoammonium phosphate when exposed to relative high humidity. The resulting leakage of phosphate ions leads to a decrease in
fire performance. APP in crystal form II has better water
resistance and higher thermal stability (decomposed at
temperature higher than 275 C) than in crystal form I [7].

Figure 10: Laboratory fire tests with topcoats

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APP II surface treated with different resins and agents

has very low water solubility and improved thermal stability and is commercially available. However, to provide
protection against fire, phosphor-carbonaceous foam
has to form at an early stage of the fire. To ensure the
moisture resistance and temperature-controlled release
of APP, various APP-composites with carnauba wax and
synthetic waxes with different melting ranges were prepared by hybridization process. This process applies fine
powder onto the surface of a core powder. The system
operates by mechanical forces such as impact and shear.
It is therefore not just restricted to chemical laws[8]. The
encapsulation of APP with wax provides improvement
in moisture resistance of coated wood panels as shown
by artificial weathering results according to EN 927. Certain samples remained unchanged. Their fire retardant
performance being identical to unexposed samples after
240 hrs. The protective wax layer did not negatively influence the intumescent process.
Furthermore, to improve the fire retardant performance,
pentaerythritol (PER) was brought by encapsulation of APP
to its immediate proximity. After ammonia was released
from APP, the polyphosphoric acid dehydrated the PER.
Additionally, the APP-PER-composite was encapsulated
with carnauba and synthetic waxes of different melting
range to protect it from moisture. Laboratory-scale fire
tests showed better fire retardant performance of intumescent coatings (IC) with APP-PER-synthetic wax with
melting range from 67 to 118 C than the reference containing pure APP and PER. This result was also confirmed
by TGA measurements. The fire-retardant performance of
APP-PER-carnauba wax composites, with melting range
from 70 to 89 C, was lower than the reference. Figure 9
shows scanning electron microscope (SEM) images of the
pure substances and the prepared composites [9].
10.a) pure APP
10.b) pure PER
10.c) APP coated with 5 % PER 
10.d) APP coated with 5 % PER and 2 % carnauba wax
Moreover, encapsulation overcomes chemical incompatibility such as sensitivity to acids of hydrogen carbonates. Hydrogen carbonate anions react with acidic binder
or phosphate during the production of intumescent coating releasing carbon dioxide. NaHCO3-wax composite
creates the necessary protection layer and NaHCO3 acts
as a blowing agent under heat impact and decomposes
to carbon dioxide. Above 70 C, non-protected NaHCO3
gradually releases CO2. However, the conversion is fast
at 200 C. Disposal of NaHCO3 and thus availability of CO2
is regulated by the melting range of used wax. No gas
formation was observed during production of the IC with
a wax-protection layer with content of 3 % or higher. The
loss of mass determined by TGA was delayed, but the
fire-retardant tests exhibit a decreasing in performance.
The encapsulation level of wax in the composite was
determined by DSC (Differential Scanning Calorimeter)
from the calibration curve as function of normalized enthalpy. For instance, for the synthetic wax with a melting
range from 67 to 118 C, the equation y=-2,4x+0,2 was
used and for carnauba wax with melting range from 70
to 89 C one of the of y= -1,1 -0,7. Two other methods
were used to measure the encapsulation level: conduc-

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Technical Paper
Wood coatings
tivity measurements and gravimetric determination of water solubility. The
core substances of the composites, such as NaHCO3 and APP, are by trend
water-conductive salts.
Further investigations were focused on particle size distribution suitable for a highperformance fire retardant coating, rheology changes associated with the introduced
composites, long-term stability of composites, influence of shear force on the composites during dispersing and a long-term study of natural weathering coupled with
fire retardant performance.

Topcoats reduce migration

The migration of inorganic salts from the intumescent coating can be avoided
by applying a topcoat. The higher its thickness, the better the humidity protection, but at the cost of lower fire performance. The higher topcoat thickness
also reduces the transparency of a wood intumescent coating.
Several commercial topcoats were investigated. Their influence on fire-protection
efficiency was examined in the laboratory. The results showed that, compared
to the reference sample (a pigmented coating was used), all topcoats reduce the
fire-protection performance (see Figure 10).
However, significant differences can be seen between the chosen topcoats,. The
systems TC 1, TC 2 and TC 7 have the smallest influence on the degree of fire
protection observed in laboratory fire tests. Therefore, topcoats TC 1 and TC 2
were chosen for further testing for water absorption.
In outdoor weathering trials, the results obtained are promising, but still do not
meet the requirements. Nevertheless, despite better fire-retardant properties
and humidity resistance that is superior to current commercially available systems, there is still room of improvement.

Novel monomer MDG for fire retardants

Modern flame retardants are adapted to the trend towards non-toxicity, sustainability and environmentally friendliness. Therefore, tailor-made saccharide-based binders were used to in the work on intumescent coatings. Moreover, the polyhydroxylic compound in the intumescent mixture can be partially
replaced by the saccharide-based binder. Hence, the filling grade of intumescent additives can be increased to improve the fire retardant performance.
Waterborne saccharide-containing binders should be salt stable and critical
pigment-volume concentration should be high. Several parameters such as
melting viscosity, polymerization technique, surfactant system and the affiliated particle size and distribution influence the intumescence reaction.
Several 3-O-Methacryloyl-1,2 : 5,6-di-O-isopropylidene--d-glucofuranose
(MDG)-containing binders were tested for suitability in intumescent coatings
with 40 % intumescent mixture consisting of APP, pentaerythritol, melamine
and titanium dioxide. Laboratory fire tests showed better fire retardant performance for MDG-containing acrylic dispersions with a particle size of 100
nm, 45 % of MDG in the copolymer and an increased non-ionic surfactant
content in the surfactant mixture. Also MDG-containing binders with novel itaconate comonomers prepared by mini-emulsion polymerization facilitate the
intumescence reaction. Further investigation on to what extent saccharidecontaining binders could function also as carbon source, are still in progress.

REFERENCES
[1] White G. M., Bulthius B., Trimbur D. E., et al, Patent WO 9910,356 1999.
[2] Nakamura C.E., Whited G.M., Current Opinion in Biotechnology 2003, 14, 454
[3] Klein J., Herzog D., Hajibegli A., Makromol. Chem., Rapid Commun. 1985, 6, 675-678.
[4] Koch U., Yaacoub E.-J., Macromol. Chem. Phys. 2003, 204, 803812.
[5] Vymetalikova B., Deppe O., Zucker aufs Holz, Farbe und Lack, 2007, 10, 24-26
[6] stmann B., Foss A., Hughes A., et al., Dire Mater. 25, (2001) 95-104
[7] Futterer T., Ammonium polyphosphate - a multi-use flame retardant, Speciality Chemicals
Magazine, 26 (2006), 34-36
[8] www.nara-e.de/documents/render.php?aid=16
[9] Derr L., Funktionelle Partikelmodifizierung und Charakterisierung, Diplomarbeit (2009).

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Spheromers
functional additives

Spheromers functional additives

are used in a variety of coating
applications including architectural
and wood paints, clear coats and
industrial coatings.
The perfectly spherical acrylic
beads with a very narrow particle
distribution are inert and easily
dispersed in water and solvent
borne systems.
Spheromers ensures completely
matte paints with zero reflection
even for paints with deep or black
colors. In clear coats dead flat
finishes are achieved with no
altering of transparency.
Addition of Spheromers also
improves stain, burnish and scratch
resistances which result in highly
durable and washable coatings.

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