Documente Academic
Documente Profesional
Documente Cultură
Wood 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
20
07|08 l 2012
www.european-coatings.com
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
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
www.european-coatings.com
07|08 l 2012
21
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
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.
22
07|08 l 2012
www.european-coatings.com
Technical Paper
Wood coatings
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),
www.european-coatings.com
07|08 l 2012
23
Technical Paper
Wood coatings
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].
24
07|08 l 2012
www.european-coatings.com
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.
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).
www.european-coatings.com
07|08 l 2012
Spheromers
functional additives