32 polyetheramines

polyetheramines Urethanes Technology International:

Vol. 27, No. 2: April/May 2010
page 32 · © Crain Communications 2010

HYDROPHOBIC POLY-
ETHERAMINES FOR MOISTURE-
RESISTANT POLYUREA COATINGS
By Dr Stephan Göttke,a Dr Fikri recommended, hardly any experimental data
Alemdaroglu,b Dr Werner Bertleff a,c can be found. Most importantly, a direct
comparison of major elastomer properties
between C3- and C4-based polyetheramines is
Polyurea systems have excellent performance missing.
and are therefore used in a broad variety of Based on laboratory spray tests, this paper
industrial applications. These include spray therefore studies whether and in what respects
coatings that seal or cover roofs, pavement PolyTHF amines differ from PPG-based
slabs for bridges, swimming pools, rail beds and polyetheramines.
tunnels. The tests were performed as follows: PSM
Polyurea systems offer benefits in the 3000 type spraying machine by Isotherm; spray
segment of industrial flooring and sealants gun by Isotherm with a No 3 mixing chamber;
because, in contrast to other spray coatings, 120 bar pressure; 70°C, 1:1 mixing ratio by
they may be applied in humid and low- volume; 1.05 index.
temperature conditions and cure fast. As curing segments, one can vary the properties of the Because of its superior hydrophobic
takes just seconds, waiting times are clearly polymer film over a broad range, from highly properties and linearity, the C4 polyetheramine
reduced, for example in rehabilitation projects, elastic and soft to hard and brittle. was expected to contribute to enhancing the
which helps to cut the overall cost. To adjust the desired properties, formulators behaviour of the formulation in hot and humid
Chemically speaking, polyurea elastomers may choose from a selection of isocyanate conditions while improving or at least
are polymers formed by an isocyanate prepolymers and, most importantly, from maintaining its mechanical properties.
prepolymer reacting with diamines that act as different types of polyetheramines that, when
curing agents. The striking features of polyurea appropriately mixed with each other and Properties of PolyTHF amine 1700
elastomers include their ability to readily bridge combined with amine chain extenders, help the C3 polyetheramine D2000, a di-functional
cracks with an elastic coating and their superb broad range of applications of these coatings. primary amine with a molecular weight of about
adhesion to a wide variety of surfaces. With its polytetrahydrofuran amines 2000, is proportionately the most important raw
They are also exceptionally resistant to (PolyTHF amine 1700, 350) (PTMG, C4 basis), material in the curing agent component.
chemicals, high temperatures and mechanical BASF offers polyetheramines that are different Generally it is this polyetheramine, and mainly
strain. Their adhesion to different types of from common amines based on polypropylene the longer-chain polyetheramines such as, in
material is illustrated by coating applications on glycol (PPG, C3 basis) (Figure 2). particular, the tri-functional polyetheramine
concrete, steel, polyurethane foam and wood. They aim to enhance properties like heat T5000, that determine the elasticity of polyurea
Polyureas consist of defined hard and soft and humidity resistance. This approach is based films.
segments as they are known in polyurethanes, a on the success story of PolyTHF, or PolyTHF amine 1700 has a molecular weight
Abb.material.
related 1 TheByPolyurea Reaction
selectively adjusting these polytetramethylene glycol in chemical terms. of about 1700 and, in addition to terminal
O O PolyTHF is used as an primary amine functions, also contains a high
OCN NCO +
H2N NH2 R R' * amorphous soft segment percentage of internal secondary amine
R` R * N N N N n
H H H H in the manufacture of function, so it is also essentially tri-functional.
elastic textile fibers such Table 1 shows the physical data of the
Isocyanate Amine Polyurea as spandex or elastane individual polyetheramines. Table 2 gives the
fibres. The textiles made composition of the polyurea formulations
ß Very fast reaction for spray application ß No catalysts are needed from these fibres remain tested. A standard formulation based on D2000,
highly elastic and are T5000 and DETDA (diethyltoluylenediamine) as
Figure 1 (above): The polyurea curing reaction. Component A: isocyanate also resistant to high a chain extender is compared to formulations in
oligomers and/or isocyanate prepolymers (aromatic & aliphatic systems used) humidity over a broad which T5000 was replaced with 10 percent and
Component B: Multifunctional amines or amine mixes, chain extenders, range of temperatures. 20 percent PolyTHF amine 1700, respectively.
pigments, other additives. The same MDI prepolymer containing 15
PolyTHF amines in percent NCO was used in all cases. To ensure
Figure 2 (below) Polyetheramines polyurea coating comparability of the mechanical data, constant
Although polyamines proportions of hard and soft segments were
C3-chain
Polyetheramines H2N
O NH2 based on maintained (about 40 percent hard segment),
O n
(PPG-based) polytetramethylene and the amine component was adjusted
glycol have been according to the amine equivalent weight of
occasionally described in
a. BASF SE, Ludwigshafen, Germany
C4-chain O NH 2 literature and although b. Elastogran GmbH, Lemförde, Germany
H2N O n
Polyetheramines their use in polyurea c. Corresponding author
(PTMG-based)
Including higher homologues with internal secondary amino groups systems has been PolyTHF is a trademark of BASF.

APRIL/MAY 2010 URETHANES TECHNOLOGY I N T E R N AT I O N A L

 Urethanes Technology International:
33
Vol. 27, No. 2: April/May 2010
page 33 · © Crain Communications 2010

experiment following
DIN ISO 1817 by
immersion in hot water
at 90°C for various
periods of time. As
Figure 3 shows, the film
obtained from the
standard formulation
takes up water
continually during the
test period of 35 days,
up to a level of 5
percent by weight. In
its components. contrast to this, the formulations
containing 10 percent and 20
Mechanical properties percent of PolyTHF amine 1700,
The mechanical properties of the respectively, initially take up water
standard formulation and the but quickly reach a saturation limit
formulations containing 10 percent at about 1.5 percent.
and 20 percent PolyTHF amine Reduced swelling can be
1700, respectively, were compared assumed to mean a lesser risk of
(Shore D hardness; tensile coating delamination in hot and
strength, elongation (DIN 53504 humid climate conditions. This is
and DIN EN ISO 527); tear due to the more hydrophobic
strength (DIN ISO 34-1); abrasion character of the PolyTHF amine.
(DIN 53516), see Table 2. The No significant differences were
comparison shows the latter to be observed between the PolyTHF
significantly harder and less prone amine levels of 10 percent and 20
to abrasion. There is only a minor percent.
impact on elasticity. This is
remarkable insofar as increased Elongation behaviour after hot-
hardness is typically associated water immersion
with a loss of elasticity. Along with water absorption, the
elongation behaviour of the
Ageing tests in hot and humid polyurea membranes treated as
conditions (90°C) — water above was tested. Figure 4 shows
absorption behaviour that coating elasticity declines
The ageing behaviour of the continually in all three
formulations identified above was formulations over the test period,
compared in a long-term but this process is clearly less
pronounced in the
ß Lower water uptake of PolyTHF® Amine formulations PolyTHF amine
ß Less swelling (less delamination) of the coating material formulations. Here
5
again, the
4 formulations with 10
ß 7 days percent and 20
% Water

ß 21 days
2 ß 28 days
percent of PolyTHF
ß 35 days show only minor
1

differences between
D2000 65,7
0

61,2 51,2
them.
T5000 5,6
PolyTHF® Amine 1700 10,0 20,0
DETDA 28,8 28,8 28,8
Elongation after
Figure 3: Ageing tests in hot/humid conditions immersion in different
(35 days, 90°C), water absorption behaviour chemical media
In another
Figure 4 (below): Ageing tests in hot and humid experiment, the
conditions (35 days, 90°C), elongation behaviour samples were
exposed to chemical
ß PolyTHF® Amine based polyurea coatings stay more elastic
media of different
450 polarity – ammonia
400

350
(10 percent), diesel
Elongation [%]

300 fuel and sulphuric

ß origin
250

200 ß 7 days
acid (10 percent) – for
150 ß 21 days seven days at 23°C.
100 ß 28 days
50 ß 35 days There were no
D2000
0
65,7 61,2 51,2
significant differences
T5000
PolyTHF® Amine 1700
5,6
10,0 20,0
in chemical resistance
DETDA 28,8 28,8 28,8
among all the

URETHANES TECHNOLOGY I N T E R N AT I O N A L APRIL/MAY 2010

34 polyetheramines
polyetheramines Urethanes Technology International:
Vol. 27, No. 2: April/May 2010
page 34 · © Crain Communications 2010
y
400 7 days @ 23°C Table 1 Comparison of major physical properties of PPG polyetheramines (C3)
350 and PolyTHF amines with C4 backbone
300 MW [g/mol] (AHEW)[g/eq.]• Viscosity [mPa.s] Melting point [°C]
250 Polyetheramine D2000 2000 1000 273 @ 23°C -29
Elongation (%)

200
ß Origin Polyetheramine T5000 5000 1940 870 @ 23°C -50
ß Ammonia PolyTHF amine 1700 1700 approx. 670 500-650 @ 40°C +25
150
ß Diesel
100 ß Sulfuric Acid PolyTHF amine 350 350 approx. 165 50 @ 20°C -7
50
• Amine hydrogen equivalent weight
0

D2000 65,7 61,2 51,2 to enhance the Table 2 Comparison of mechanical properties
T5000
PolyTHF® Amine 1700
5,6
10,0 20,0 product properties (at constant hard segment percentage)
DETDA 28,8 28,8 28,8
mainly in humid Standard PolyTHF amine systems
Figure 5: Elongation after immersion in various environmental Component A
D2000 wt% 65.7 61.2 51.2
media (7 days, 23°C) conditions. This is a
T5000 wt% 5.6 - -
major practical benefit, DETDA wt% 28.8 28.8 28.8
formulations. While obviously more for example in PolyTHF amine 1700 wt% - 10.0 20.0
hydrophobic, the PolyTHF amine formulations rehabilitation of Component B
showed resistance results, even for diesel fuel, sewers and of sewage- MDI prepolymer (PPG 2000 based) % NCO 15.0 17.0 17.0
comparable to those of the standard treatment or water- (Hard segment content, % 40 42 42)
formulations (Figure 5). treatment facilities, or
In conclusion, we found formulations in seawater- Shore D hardness 44 52 53
containing PolyTHF amine 1700 (and adjusted desalination plants. Tensile strength [MPa] 16 25 24
for the same proportion of hard and soft Along with PolyTHF Elongation [%] 400 380 340
Tear strength [kN/m] 67 68 70
segments) to produce harder, more abrasion- amine 1700, which is Abrasion [mm³] 187 145 150
resistant films that those containing T5000, the described here and
increase in hardness being accompanied by was extensively tested, we also performed first limit there appears to be a similar trend in
hardly any loss of elasticity. tests on a shorter-chain variety, PolyTHF amine results as for the longer-chain homologue.
However, the major advantage of PolyTHF 350 (molecular weight about 350). Because this Consequently, PolyTHF amine 350 can be
amine based formulations is the fact that they polyetheramine is clearly more reactive, any recommended mainly for use in spray systems
take up significantly less water and therefore addition of more than 5 percent by weight that are slower by nature, or that are applied
show less swelling. This amine therefore helps results in processing problems. But up to this manually.

APRIL/MAY 2010 URETHANES TECHNOLOGY I N T E R N AT I O N A L