722 Macromol. Chem. Phys.

201, 722–732 (2000)

Full Paper: An aminosilane functionalized isocyanurate

of 1,6-hexamethylene diisocyanate (HDI isocyanurate)
was used to formulate coatings. The coatings were formu-
lated using a mixture of the silane-functionalized isocya-
nurate and the unfunctionalized HDI isocyanurate. The
general coating properties and tensile properties were
evaluated as a function of alkoxysilane modified isocya-
nurate. In addition, the thermo-mechanical and rheologi-
cal properties of the films were also investigated. The
moisture-curing process was investigated using FT-IR and
NMR. The results indicates that alkoxysilane-functiona-
lized isocyanurate dramatically enhances the adhesion and
increases the crosslink density.

Proposed crosslinking structure of a polyurethane/polysilox-

ane hybrid coating

Moisture-curing alkoxysilane-functionalized
isocyanurate coatings
Hai Ni, Allen D. Skaja, Robert A. Sailer, Mark D. Soucek*
Department of Polymers and Coatings, North Dakota State University, Fargo, ND 58105, USA
(Received: January 29, 1999; revised: July 26, 1999)

1. Introduction The isocyanate group can also react with water to

Polyurethane and polyurea resins are both derived from afford “moisture-cured polyurea coatings”. The reactions
isocyanate- functionalized monomers or oligomers1). for the moisture-curing process are depicted in Eq. (3) –
Polyurethane resins are typically derived from reactions (5).
of hydroxyl-functionalized oligomers or polyols with an H O
isocyanate as shown in Eq. (1): 0 00
R1NCO + H2O ggs R1N 1C 1OH (3)
H O H O
0 00 0 00
R1NCO + R91OH ggs R1N 1C 1OR9 (1) R1N 1C 1OH ggs R1NH2 + CO2 (4)
Likewise, polyurea resins are derived from reactions of H O H
0 00 0
amino-functionalized monomers or polyamines with iso- R1NCO + R1NH2 ggs R1N 1C 1N 1R (5)
cyanate as shown in Eq. (2):
H O H The isocyanate group reacts with water forming a car-
0 00 0 bamic acid intermediate. The carbamic acid is unstable
R1NCO + R91NH2 ggs R1N 1C 1N 1R9 (2) and decarboxylates spontaneously into an amine and car-

Macromol. Chem. Phys. 201, No. 6 i WILEY-VCH Verlag GmbH, D-69451 Weinheim 2000 1022-1352/2000/0603–0722$17.50+.50/0
Moisture-curing alkoxysilane-functionalized isocyanurate coatings
bon dioxide. This amine reacts with another isocyanate
group producing an urea crosslink. Water is similar to a
secondary alcohol in its reactivity. The reaction rate is
mainly controlled by temperature, humidity and catalysts.
For the reaction of an isocyanate with an alcohol, the
commonly used catalysts in coatings are tertiary amines,
especially diazabicyclo[2.2.2]octane (DABCO), and
organotin compounds, especially dibutyltin dilaurate
(DBTDL)1).
Polyurethane and polyurea coatings are classified as
aromatic or aliphatic, depending on which type of isocya-
nates is used. Coatings based on aliphatic isocyanate
exhibit excellent light and weather stability and as a con-
sequence are principally used for outdoor application.
The polyol- or amine-functionalized unit can be varied as
well, leading to resins which have excellent mechanical
properties. In addition, the urethane and urea groups
impart excellent abrasion and solvent resistance. As a
consequence, polyurethane/polyurea coatings are widely
used in the furniture, flooring, railway, automotive and
aerospace industries2).
In the aerospace industry, polyurethanes are typically
used as a component of aircraft-coating systems. Cur-
rently, the coating procedure of an aluminum substrate
for aircraft involves several steps3). A chromate conver-
sion coating, usually consisting of hexavalent chromium
in acidic media, is applied to prevent corrosion. A wash
primer of passivating chromium pretreatment is then used
to aid adhesion of the primer to the surface. A two-com-
ponent epoxy-amine system is coated as a primer on the
wash-primer layer and followed by a topcoat of polyur-
ethane. A two-component polyurethane consisting of a
solution of HDI and a polyester polyol is applied as a top-
coat. In this procedure, chromate is a known carcinogen
and as a consequence its application will be minimized.
A relatively recent approach for aircraft coatings is the
“Unicoat” system developed by Hegedus and co-work-
ers4). The concept of an unicoat system is to replace one or
more steps with a self-priming coating system, especially
to eliminate the usage of chromate. The self-priming coat-
ing is a two-component polyurethane system. Non-chro-
mium passivating pigments such as molybdate and zinc
723
phosphate are used to protect the aluminum substrate from
corrosion. A reduction in volatile organic compounds and
application costs over the traditional multi-step aircraft
coating systems were reported4). However, adhesive fail-
ure has undermined the coating system5).
Organofunctional alkoxysilane, R91Si1(OR)3, pos-
sesses an alkoxy group 1Si1(OR)3 and an organic group
R9, which has been utilized in the past as an coupling
agent for composites and an adhesion promoter in coat-
ings. Alkoxysilane primers have been applied to metal
substrates to improve adhesion and corrosion resistance
for various coatings6–9). Walker6) used five organofunc-
tional silanes as pretreatment primers on aluminum and
steel substrates for epoxide and polyurethane coatings,
vastly improving the initial, wet and recovered adhesion.
The adhesion was also improved by addition of alkoxysi-
lanes to epoxide and polyurethane coating formulation.
Alkoxysilanes can also have a moisture curing process
as depicted in Eq. (6) – (8). The alkoxy group may react
with water to form a silanol and an alcohol. The silanol
group by then condense to form siloxane groups with the
elimination of water or alcohol.
3Si1OR + H2O ggs 3Si1OH + ROH (6)
3Si1OH + 3Si1OH ggs 3Si1O1Si3 + H2O (7)
3Si1OR + 3Si1OH ggs 3Si1OS1Si3 + ROH (8)
Further hydrolysis and condensation reactions form a
silicon oxide network producing a silicon gel. The pro-
cesses are determined by many factors: pH, temperature,
solvent and concentrations. Brinker and Scherer10) sum-
marized the effects of these factors on the hydrolysis and
condensation processes. Among these factors, pH plays a
key role. Siloxane hydrolysis is very slow in neutral con-
dition; it can be catalyzed and accelerated either with
acid or with base.
In our previous study11, 12), the alkoxysilane-functiona-
lized isocyanurate was synthesized through the reaction
of HDI isocyanurate and 3-aminopropyltriethoxysilane
(Eq. (9)):
724
The reaction was analyzed by NMR experiments and
Electrospray Ionization-Mass Spectroscopy (ESI-MS). In
this study, the functionalized isocyanurate (2) is used
with HDI isocyanurate to prepare a hybrid unicoat coat-
ing system. The alkoxysilane has potential to function
both as an adhesion promoter and an organic resin modi-
fier. The monofunctionalized HDI isocyanurate(2)/HDI
isocyanurate (1) hybrid coating formulations were studied
in terms of viscosity. Curing of the coatings was investi-
gated spectroscopically using both FT-IR and NMR. The
resultant coatings were evaluated in terms of general
coating, tensile and rheological properties. The adhesion
was monitored as a function of alkoxysilane content.
2. Experimental part
2.1 General information
The HDI isocyanurate was obtained from Rhone Poulenc,
Inc. (Tolonate HDT-LV) and Bayer Corporation (Desmodur
N-3300, unstabilized). Tolonate HDT-LV was only used in
the moisture-curing process, which was monitored by FT-IR.
The p-toluene sulfonic acid monohydrate (p-TSA, Aldrich),
N,N-dimethylacetamide (DMAc, Aldrich) and methanol
(Burdick and Jackson) was used as received. Absolute etha-
nol (McCormick Distilling) was dried over molecular sieves
(Aldrich, 4A). The monofunctionalized HDI isocyanurate
was prepared as previously described. Air-sensitive materials
were transferred and weighed in an inert-atmosphere dry-box
under argon.
2.2 Instrumentation
A JEOL 400 spectrometer was used to record 1H and 13C
NMR spectra and a JEOL 270 spectrometer was used to
record 29Si NMR spectra. All NMR spectra were determined
in CDCl3 at ambient temperature. The FT-IR spectra were
obtained from a Bruker IR spectrometer (Equinox 55, resolu-
tion: 2 cm–1). Liquid samples were placed on potassium bro-
mide plates; and solid samples were mixed with potassium
bromide powder and then pressed as KBr pellets. The X-Ray
diffraction data were recorded with a Philips MPD Multipur-
pose diffractometer. A zero-background quartz slide was
used as a substrate. Radiation used was Cu Ka (k = 1.5418
A). Viscosity measurements were performed on a Carri-Med
CSL-100 rheometer with a parallel plate geometry. The ther-
mal properties were measured by a Differential Scanning
Calorimeter (DSC, Perkin Elmer Model 7) with a heating
rate of 10 8C/min. Viscoelastic properties were obtained with
a Dynamical Mechanical Thermal Analyzer (DMTA, Rheo-
metric Scientific) with a frequency of 1 Hz and a heating
rate of 3 8C/min over a range of – 100 8C to 200 8C. The gap
distance was set up at 5 mm for rectangular test specimens
(length 10 mm, width 9 – 11 mm and thickness 0.05 –
0.1 mm).
H. Ni, A. D. Skaja, R. A. Sailer, M. D. Soucek
2.3 Methanol termination reaction of monofunctionalized
isocyanurate
The monofunctionalized isocyanurate 2 (8.03 g, 0.02 equiv.
1NCO, normality) was dissolved in methanol (6.4 g, 0.2
mol) and stirred at 25 8C for 168 h. The reaction was moni-
tored by FT-IR until the (1NCO) groups (2 270 cm–1) disap-
peared. The remaining methanol was removed by vacuum at
ambient temperature to afford 3.
1
H NMR: d = 3.64 (1COOCH3), and d = 3.14
(1CH2NHCOO1).
13
C NMR: d = 157.2 (1COOCH3), and d = 57.2
(1COOCH3).
29
Si NMR: d = – 45 (1Si1).
The 3 (2 g) was dissolved in DMAc (2 g) and the solution
was used to cast films for analysis of the curing schedule.
2.4 Reaction of Alkoxysilane with Water
The methanol-terminated monofunctionalized isocyanurate
(3, 1.0 g, 1.21 610–3 mol) was dissolved in absolute ethanol
(3.0 g). Distilled water (0.0164 g, 9.1 610–4 mol) and the
catalyst p-TSA (0.0115 g, 6.04 6 10–5 mol) were added into
the solution with a molar ratio, Si : H2O : H+ = 1 : 0.75 : 0.05,
respectively. The mixture was stirred at 25 8C and 29Si NMR
was recorded.
2.5 Coating formulations and film preparation
The monofunctionalized isocyanurate (2) was formulated
with HDI isocyanurate (1) as shown in Tab. 1. Acetone was
added into the formulation to adjust the viscosity as shown
in Tab. 2. The formulation of coatings for casting coating
films and viscosity tests are listed in Tab. 1 and Tab. 2. Alu-
minum panels (alloy 3003 H14, Q-Panel Lab Products) were
degreased with acetone; the films were casted on the alumi-
num panels with the thickness of 152.4 lm (6 mil) by a
drawbar for the four formulations in Tab. 2. The films were
set in a closed box with a stable humidity of more than 95%
and at ambient temperature for 3 – 4 days (until surface
became tack-free). Then they were put into a closed oven
and further moisture cured at 88 – 90 8C under 100% humid-
ity for 10 h. The cured films were stored for three days under
ambient atmospheric conditions before testing.
2.6 Mechanical properties
All mechanical tests were performed in standard procedures
according to ASTM standards, including indentation hard-
ness (Tukon hardness, ASTM D 1474-85), pencil hardness
(ASTM D 3363-74), crosshatch adhesion (ASTM D 3359-
87), pull-off adhesion (ASTM D 4541-85), reverse impact
resistance (2794-84) and tensile properties (ASTM D 2370-
82). The tensile properties test was performed on an Instron
Universal Tester Model 1 000. The dimensions of films for
tensile testing were 0.05 – 0.12 mm in thickness, 13 – 17 mm
wide, and an initial length of 40 mm. A crosshead speed of
20 mm/min was applied to determine elongation-at-break,
tensile modulus, and tensile strength. Six samples were
tested for each film. The data are reported as the mean of the
data set, with an uncertainty based on the standard deviation.
Moisture-curing alkoxysilane-functionalized isocyanurate coatings 725

2.7 Viscoelastic properties Scheme 1: Proposed crosslinking structure of a polyurethane/

polysiloxane hybrid coating
Crosslink density was calculated by the following equation:

E9 = 3 me RT (T S Tg) (10)
where me is the number of moles of elastically-effective net-
work chains per cubic meter of film and E 9 is tensile storage
modulus at corresponding temperature T. This relationship is
effective when T S Tg, and for low crosslinking density elas-
tomers13). For the highly crosslinked system, it can only be
used to evaluate the relative density of crosslinking.
For the stoichiometric networks, the crosslink density can
be estimated by the Scanlon equation

3 4 5
me ˆ C3 ‡ C4 ‡ C5 ‡ ::: …11†
2 2 2
where C values are the concentrations of reactants with func-
tionality more than 2 expressed in moles per cubic centi-
meter of final cured film14). Calculated crosslink density is an
estimated value for a perfect network.

3. Results
The overall objective of this study is to improve the adhe-
sion of the Unicoat coating system. The organic part of
the Unicoat system consists of a hydroxyl functionalized
polyester crosslinked with the isocyanurate of HDI. In Tab. 1. The formulation of functionalized isocyanurate diluted
in HDI isocyanurate
this study, we focused on the HDI isocyanurate. The HDI
isocyanurate was functionalized with an alkoxysilane Sample Functionalized isocyanurate (2) HDI Isocyanurate (1)
group to promote adhesion. It was of interest to test our ———————————— —————————
wt.-% wt.-%
hypothesis on the moisture curing polyurea system before
integrating it into the fully formulated Unicoat system. 0/100a) 0 100
In addition to functioning as an adhesion promoter, the 10/90 10 90
alkoxysilane group can participate in the curing process 25/75 25 75
35/65 35 65
of the bulk coating. The moisture-curing process occurs
with both the isocyanate group and the alkoxysilane a)
0/100 = 0 wt.-% 2; 100 wt.-% 1.
group. Two crosslinking mechanisms are occurring
simultaneously in the presence of atmospheric water. The Tab. 2. The formulation of functionalized isocyanurate diluted
organic moisture-curing mechanism of isocyanate in HDI isocyanurate and solvent acetone
(Eq. (3) – (5)) and the inorganic moisture-curing mechan- Coating Functionalized HDI isocyanurate Acetone
ism of alkoxysilane (Eq. (6) – (8)) result in polyurea/poly- isocyanurate (2) (1) ———
siloxane (organic/inorganic) crosslinked coatings shown ——————— ——————— (wt.-%)
(wt.-%) (wt.-%)
in Scheme 1. In the reaction of isocyanate with water, iso-
cyanate groups disappeared and urea linkage formed as 0/100Aa) 0 95 5
depicted in Eq. (3) – (5). This curing mechanism was 10/90A 9.5 85.5 5
investigated by monitoring the functional groups as a 25/75A 23.75 71.25 5
35/65A 33.25 61.75 5
function of time using FT-IR.
To investigate the moisture-curing mechanism of a)
0/100A = 0 wt.-% of 1; 95 wt.-% of 2 with the addition of 5
alkoxysilane and optimize the curing process, a model wt.-% acetone.
compound was used to monitor the reaction of the alk-
oxysilane (2) with water (Eq. (4) – (6)). The monofunctio- The coatings were formulated through the dilution of 2
nalized HDI isocyanurate was first terminated with in HDI isocyanurate as a function of functionalized iso-
methanol to eliminate the effect of isocyanate group, and cyanurate (0 – 35 wt.-%), as shown in Tab. 1 and 2. A
then an acid catalyst p-TSA was added to accelerate the higher concentration of functionalized isocyanurate, 50
reaction. The condensation products were then monitored wt.-%, was also approached to formulate coating with
by 29Si NMR. HDI isocyanurate. The resultant coating films were brittle
726 H. Ni, A. D. Skaja, R. A. Sailer, M. D. Soucek

to evaluate their coatings properties. The viscosity of the The termination reaction was verified by the 1H NMR
functionalized isocyanurate in HDI isocyanurate was spectrum shown in Fig. 1, in which the new proton reso-
measured and adjusted with acetone to a level amenable nance at d = 3.64 indicates the formation of new urea
for casting films. After moisture curing, the general coat- group (1NHCOOCH3), and d = 3.14
ing properties (adhesion, hardness and impact resistance) (1CH2NHCOOCH3). The 13C NMR spectrum shown in
of the polyurea/siloxane hybrid coatings were measured Fig. 2 corroborated the 1H NMR data, d = 157.2
to evaluate the effect of alkoxysilane group on the bulk (1NHCOOCH3), and d = 57.2 (1COOCH3). Fig. 3 shows
film properties. The viscoelastic properties of the Unicoat the degree of cure monitored by 29Si NMR. Fig. 3 b is the
29
system were investigated using DMTA. The glass transi- Si NMR spectrum for the reaction of 3 and water for
tion temperature (Tg) and crosslink density of the hybrid 18 h. The resonance at – 52.8 ppm in Fig. 3 b was
coatings were derived from the tan d and storage moduli assigned to the dimer with the structure as below15):
(E 9), respectively.
OR OR
0 0
1H2C1Si1O1Si1CH21 R = C2H5
0 0
3.1 Hydrolysis and Condensation of Alkoxysilane OR OR
The model compound for this study is methanol-termi- This indicates that the alkoxysilane group of 3 can
nated monofunctionalized isocyanurate, which is pre- undergo hydrolysis and condensation reactions, forming
pared via the reaction of 2 and methanol (Eq. (12)). siloxane linkages during the curing process. Extending

1
Fig. 1. H NMR spectrum of monofunctionalized isocyanurate terminated with methanol (3)

13
Fig. 2. C NMR spectrum of monofunctionalized isocyanurate terminated with methanol (3)
Moisture-curing alkoxysilane-functionalized isocyanurate coatings
Fig. 3. 29Si spectra of (a): monofunctionalized isocyanurate terminated with methanol
(3) and (b): hydrolysis and condensation of 3 with water in solvent ethanol catalyzed by
p-TSA for 18 h
the reaction time (100 h) resulted in the disappearance of
the dimer resonance. However, the higher condensation
forms of siloxane trimer and tetramer were not detect-
able.
The model compound (3) was further used to investi-
gate the cure schedule for the alkoxysilane group. Since
the 29Si NMR data was inconclusive after dimer forma-
tion, 3 was directly casted into film, and monitored in the
extent of its cure as a function of time. The principle
means of evaluating the extent of cure was when the film
surface was tack-free. The cure schedule was determined
as 10 h at 88 – 90 8C under 100% relative humidity. This
cure schedule was used for all the coatings in the study.
3.2 Moisture curing of HDI isocyanurate
The moisture curing of the HDI isocyanurate (1) reactions
(Eq. (1) – (3)) was monitored as a function of time by FT-
IR as shown in Fig. 4. After 72 h, the liquid isocyanurate
was tacky, and between 72 h and 96 h, the tack film vitri-
fid into a tack-free film. As expected, the IR spectra
shows the consumption of the isocyanate group (2 270
cm–1) and the formation of urea groups (3 370 cm–1) with
increasing cure time. The NCO group completely disap-
peared after 432 h, which indicates that the curing pro-
cess was complete. With increasing cure time, the IR
band at 3 580 cm–1 also increased. This band may be
attributed to hydrogen bonding between water and the
urea crosslinks. As the curing process proceeded, more
727
urea crosslinks were available for hydrogen bonding, and
as a consequence hydrogen bonding to urea groups
increased as a function of time.
3.3 Viscosity
The viscosity of the mixed 1 and 2 coatings formulations
was investigated. The viscosity was studied as a function
of 2 with and without solvent (see Tab. 1 and 2), shown
in Fig. 5. The viscosity, as a function of shear rate, indi-
cated that the alkoxysilane-functionalized isocyanurate is
a Newtonian fluid. Generally, the addition of monofunc-
tionalized isocyanurate resulted in an increase in viscos-
ity. However, viscosity was dramatically increased when
the functionalized product content was 35 wt.-%. The sol-
vent acetone has strong effect on the viscosity, especially
for the functionalized isocyanurate system. With 5 wt.-%
dilution of acetone, the viscosity of 35 wt.-% 2 can be
reduced to a spray-application viscosity.
3.4 General coating properties
Tab. 3 shows the mechanical properties of the mixed
coating formulations as a function of monofunctionalized
isocyanurate (2). The formulations were diluted with 5
wt.-% acetone to facilitate film casting. The crosshatch
adhesion was improved dramatically from 0B to 5B with
the addition of 10 wt.-% monofunctionalized isocyanu-
rate. Unfortunately, crosshatch adhesion is a crude meas-
728 H. Ni, A. D. Skaja, R. A. Sailer, M. D. Soucek

Fig. 4. FT-IR spectra of HDI isocyanurate (Tolonate HDT-LV) moisture curing as a function
of time. (a) wavenumber region: 2 200 – 3 000 cm–1; (b) wavenumber region 2 800 – 3 600 cm–1

isocyanurate content. The pull-off adhesion increased

from 43 to 173 lbf/in2 with 10 wt.-% content of 2. The
maximum pull-off adhesion was 227 lbf/in2 with a 35
wt.-% 2 loading. This represents a more than 500%
improvement in adhesion over HDI isocyanurate (1) coat-
ings. Impact resistance also increases with alkoxysilane
functionalized isocyanurate content. Pencil hardness,
however, appears to be independent of alkoxysilane-func-
tionalized isocyanurate content. The Tukon hardness is a
more sensitive measurement, and unlike the pencil hard-
ness data did appear to vary as a function of 2. Although
the differences are slight, a maximum of 12 KHN was
Fig. 5. Viscosity at low shear rate (3 s–1) of mixed HDI isocya-
nate and monofunctionalized isocyanurate
observed for a 10 wt.-% loading of 2.

urement and can not differentiate between the 10/90A 3.5 Tensile properties
and 35/65A formulations. Pull-off adhesion, however, is a The tensile strength, elongation-at-break, and modulus of
more sensitive measurement. As an overall trend, the the coating formulations are shown in Fig. 6. Tensile
pull-off adhesion increased with increasing functionalized strength decreased from 63.7 MPa to 49.6 MPa with addi-
Moisture-curing alkoxysilane-functionalized isocyanurate coatings 729

Tab. 3. Mechanical properties of coating films

Functionalized 0/100A 10/90A 25/75A 35/65A

isocyanurate/isocyanurate (w/w)

Crosshatch Adhesion 0B 5B 5B 5B
Pull-off Adhesion (lbf /in2) 43.3 l 10.3 173.3 l 30.8 211.7 l 34.3 226.7 l 41.8
Impact Resistance (lb N in) 24.2 l 3.3 31.6 l 5.9 32.5 l 6.7 35.9 l 7.7
Tukon Hardness (KHN) 10.3 l 0.9 12.0 l 0.2 11.3 l 0.3 10.8 l 0.6
Pencil Hardness 3H 3H 3H 3H

Fig. 7. Dynamic mechanical properties of 0/100A, HDI iso-

cyanurate. E 9, storage modulus; E 99, loss modulus; and tan d =
E 9/E 99

Fig. 8. tan d as a function of 2

Fig. 6. Tensile properties as a ratio of HDI isocyanurate (1) to

2: (a) tensile strength; (b) elongation at break; (c) tensile modu-
lus
tion of 10 wt.-% 2. Afterwhich, the tensile strength
remained constant as the concentration of 2 increased.
The elongation-at-break appeared to be independent of 2
content. The tensile modulus, however, followed the
same trend as the tensile strength. At 10 wt.-% loading of
2, the tensile modulus decreased from 1 200 MPa to 800
MPa. As the percent loading is increased from 10 – 35
wt.-%, the tensile modulus returned to the 0 wt.-% 2 level
(within experimental error).
3.6 Viscoelastic properties
The viscoelastic properties of the hybrid coatings films
were investigated using DMTA. An example of the
DMTA data, depicting storage modulus (E 9), loss modu-
lus (E 99), and tan d, is shown in Fig. 7. For clarity, the tan d
and storage moduli E 9 were presented as a function of 2
as shown in Fig. 8 and 9, respectively. The Tg of the for-
mulations was derived from the tan d data. The Tg ranged
from 130 – 140 8C. The film with 25 wt.-% functionalized
HDI isocyanurate (25/75A) exhibited the lowest Tg. It can
be observed from Fig. 9 that there are two transitions in
the storage moduli. The first transition (120 – 150 8C) is
730 H. Ni, A. D. Skaja, R. A. Sailer, M. D. Soucek

The numerical value of glass transition temperature

Fig. 9. Storage modulus E 9 as a function of 2
the glass transition. The second transition (160 – 190 8C)
is most pronounced in the unmodified HDI isocyanurate
coatings (0/100A), and becomes less apparent with
increasing functionalized HDI (2) content. Fig. 10 depicts
wide angle X-ray data for unmodified isocyanurate (0/
100A), and the highest alkoxysilane functionalized iso-
cyanurate content (35/100A). The remaining formulations
(10/90A, 25/75A) fell in between the 0/100A and 35/65A
data, and were omitted for clarity. The X-ray clearly
shows decreasing crystallinity with increasing alkoxysi-
lane isocyanurate content.
(Tg), the minimum value of storage modulus and crosslink
density calculated from Eq. (11) are listed in Tab. 4. The
Tg kept constant with the addition of 10 wt.-% functiona-
lized isocyanurate (2), and then decreased as the functio-
nalized isocyanurate (2) reached 25 wt.-%. As the con-
centration of 2 increased to 35 wt.-%, the crosslink den-
sity increased to a maximum of 2.54 6 10–3 mol/cm3. The
crosslink density was thus consistent with the Tg data. For
comparison, the crosslink densities for a perfect network
as estimated by Eq. (11) are also listed in Tab. 4. The
crosslink densities of hybrid systems are closer to a per-
fect network than parent polyurea system as indicated by
the ratio of crosslink densities.
3.7 Thermal properties
The thermal properties of the coatings were further inves-
tigated using DSC. The enthalpy change of fusion, glass
transition (Tg), melting point (Tm) and relative enthalpy
change of fusion ratio are listed in Tab. 5. The ratio of
enthalpy change relative to a 100% crystalline sample is
a common method to determine the degree of crystallinity
for polymers16). In the absence of amorphous or pure crys-

Fig. 10. The X-Ray scattering curve

Tab. 4. Viscoelastic properties of the coating films

Sample 0/100A 10/90A 25/75A 35/65A

Tg ( 8C) 139 140 130 137

E 9 (Pa) (minimum) 0.23 6 108 0.286108 0.226108 0.296108
Crosslink density (1) from Rubbery 1.99610–3 2.41610–3 2.29610–3 2.54610–3
Plateau (mole/cm3)
Density (g/cm3) 1.20 1.14 1.14 1.14
Crosslink density (2) from Scanlon 3.08610–3 2.98610–3 3.08610–3 3.14610–3
Equation (mole/cm3)
Ratio of crosslink density (1 over 2) 0.65 0.81 0.74 0.81
Moisture-curing alkoxysilane-functionalized isocyanurate coatings
Tab. 5. Enthalpy change and melting point of coating samples
Sample 0/100A
DHm (J/g) 7.2
Melting point Tm ( 8C) 188.9
Relative ratio of enthalpy change (%) 100
Scheme 2: Proposed interaction between alkoxysilane and aluminum substrate
talline sample in our system, this ratio was used to esti-
mate the relative degree of crystallinity. In the calculation
of enthalpy change ratio, the unfunctionalized HDI iso-
cyanurate was used as a reference. Both melting point
and enthalpy change decreased with the addition of func-
tionalized isocyanurate.
4. Discussion
The HDI isocyanurate and alkoxysilane hybrid system
crosslinked via a moisture-curing mechanism. The
organic crosslinking reactions were established via IR
data. The alkoxysilane crosslinking reactions were estab-
lished via a model compound (3) study using 29Si NMR.
Ultimately, the curing schedule was derived from opti-
mizing coating properties using 3. After the mixed formu-
lations (Tab. 2) were cured via the practical curing sched-
ule, the organic crosslinking reactions were spectroscopi-
cally investigated again using IR. The IR data shows that
under the moisture-curing conditions established using 3,
the isocyanate groups were completed consumed.
From the data, it seems clear that the adhesion was sig-
nificantly enhanced without detracting from the other
731
10/90A 25/75A 35/65A
6.0 3.2 2.1
178.8 163.4 160.4
83 44 29
properties. Instead of using organosilanes as an additive7),
it was incorporated directly onto a monomer. It was also
clear that both the siloxane and isocyanate units partici-
pated in the crosslinking reactions during the film forma-
tion process. The increased Tg and crosslinking density
were observed for the formulations with alkoxysilane
functionalized isocyanurate. The enhancement of adhe-
sion was 400% with the initial 10 wt.-% addition of 2, but
leveled off with further increase of 2. The enhancement
of adhesion can be attributed to the alkoxysilane group.
The proposed mechanism of chemical bonding between
coating film and aluminum substrate is described in
Scheme 2. The chemical bonding may be formed from
the co-condensation of Si1OH and Al1OH producing
Si1O1Al linkage. A similar mechanism was also pro-
posed by Witucki: 1) Silanol hydrogen bonded with
hydroxy group on the substrate; 2) a covalent bond was
formed with the substrate liberating water10). Other forms
of interaction such as polar-polar and hydrogen bonding
may also be responsible for the improved adhesion.
There appeared to be a decrease in Tg (DMTA) and
crosslink density at 25/75A formulation (Tab. 4). There
could be several possible explanations for the results.
One possible explanation involves the fugitive ethanol
732
groups liberated during the hydrolysis of the alkoxysilane
groups (Eq. (6) and (8)). The fugitive ethanol group can
react with isocyanate groups (Eq. (1)), preventing the iso-
cyanate from crosslinking. As more alkoxysilane groups
are added into the coating formulation, the higher func-
tionality of alkoxysilane groups compensates for the loss
of urea crosslinks, resulting in a higher overall crosslink
density. A second possible explanation for this effect is
an interference of the crystallinity of HDI isocyanurate
with measurement of the crosslink density. A separate
study is needed to elucidate this effect.
As shown in Tab. 4, the ratio of crosslink density (rub-
bery plateau to perfect network) for all the hybrid systems
are higher than the polyurea. This may be due to the
increased crosslink density which caused a deviation in
the calculation of crosslink density. It may also be caused
by the ordering (crystallization) which decreased the
mobility of the reactive end groups. It was surmised that
this lack of mobility would retard the crosslinking. In the
hybrid system, the minimum value of the ratio of cross-
link density appeared at 25 wt.-% of 2. It is consistent
with the assumption that the fugitive ethanol reduced the
crosslink density.
The transition in the storage modulus after Tg became
less pronounced as the concentration of 2 increased.
This transition was attributed to the crystallinity in the
HDI isocyanurate polyurea. The crystallinity was
obtained in the X-Ray diffraction data (Fig. (10)). The
crystalline structure is probably due to uniform chain
alignment driven by the hydrogen bonding from urea
group. The relative degree of crystallinity decreased as
the unfunctionalized isocyanurate concentration
increased. The crystalline region of 1 was disturbed by
the addition of the alkoxysilane functionalized isocyanu-
rate (2) and thus the DHm was decreased with increasing
2 as shown in Tab. 5.
Overall, modifying HDI isocyanurate monomer with
alkoxysilane was very successful with respect to improv-
ing adhesion. Optimized coatings properties were
achieved when the modified isocyanurate (2) was formu-
lated with 65 – 90 wt.-% non-functionalized HDI isocya-
nurate (1). What was surprising is, that the adhesion was
enhanced without the degradation to the other mechanical
properties. The tensile properties appeared to be indepen-
dent of 2. The Tg, crosslink density, and impact resistance
were all enhanced with the addition of 2 into the coating
formulations. Extending this concept into a fully formu-
lated Unicoat system is currently being undertaken.
H. Ni, A. D. Skaja, R. A. Sailer, M. D. Soucek
5. Conclusions
The HDI isocyanurate coatings without 2 exhibit a semi-
crystalline structure. The addition of 2 into the HDI iso-
cyanurate coating decreases the relative crystallinity of
the overall coating. Adhesion of polyurea coating is
enhanced by the addition of alkoxysilane modified iso-
cyanurate. The crosslink density, Tg, and impact resis-
tance of the polyurea/siloxane hybrid coating film are
also increased by 2. The tensile properties are indepen-
dent of alkoxysilane modified isocyanurate (2) content.
Acknowledgement: Financial support for this research from
Air Force Office of Science Research grant (AFOSR/NL
F49620-97-1-0218) is gratefully acknowledged. Dr. Glass’s
group is acknowledged for viscosity measurement, and Dr.
Urban’s group for FT-IR detection.
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