The Effect of Moisture on the Cationic Polymerization .
Peter C. Hupfield#, Simon R. Hurford# & James S. Tonge*
#Dow Corning Ltd., Cardiff Road, Barry, South Glamorgan. CF63 2YL.
*Dow Corning Corporation P.O. Box 994, Midland, MI 48686-0994
Abstract
In applications that require high speed processing
the role of oxygen in the inhibition of acrylate
polymerization is well documented. Cationically cured
systems, whilst maintaining reaction rates similar to that of
acrylate systems, are not inhibited by oxygen, for example
epoxides and vinyl ethers. However, cationic
polymerization is known to be influenced by the presence
of nucleophiles such as water. In most industrial
processing environments water, in the form of bulk water
or water vapor, is an uncontrolled operating parameter
which is subject to seasonal variations. The effect of bulk
water and water vapor on the cure kinetics of both model
monomer and industrial coatings has been studied and are
presented in this paper. Techniques such as GPC, gel point
determination and pilot plant trials were also used to
determine the impact of bulk water and water vapor. The
influence of counter ion nucleophilicity of the iodonium
salt photocatalyst in the presence of water was also
determined to assess the potential for photocatalyst
modification in controlling the impact of water on the
polymerization rates.
Introduction
The startling success of radically initiated acrylate
based coatings over the last 25 years has led many groups
to try and emulate their performance. The heirs apparent to
the acrylate empire are cationic cured systems based on
epoxy and vinyl ether groups. Like their acrylate
counterparts radiation cured systems based on epoxy and
vinyl ether have many of the benefits outlined in this
conference i.e. 100% reactive solids, low temperature
cure, high production speeds, low manufacturing
footprints, etc. The additional promise in cationic cure lies
in the lure of high speed ambient cure over the oxygen
inhibited radical processes. The aim of this paper is to
define the extent to which the label “ambient cure” can be
applied to cationic cured monomers and silicone polymers
containing cationically curable groups, such as epoxies and
vinyl ethers.
A brief review of the chemical literature quickly
provides the most obvious potential chemical deficiencies
in any given cure systems. In radical systems these would
be recombination, or oxygen quenching of the radical
species, while in anionic cure systems oxygen and
moisture sensitivity might be anticipated. With cationic
chemistry (Scheme One) polymerization proceeds in the
absence of nucleophiles, until the monomer is consumed.
The cationic centers responsible for polymerization are not
reactive towards one another unlike free radicals and hence
have much longer lifetimes. Cationic polymerization will
continue outside the irradiation zone (dark cure), even
when the initiating species are no longer being created,
providing chain transfer and termination reactions do not
occur due to the presence of nucleophilic species. During
ambient UV curing there is the ever present, and
uncontrolled nucleophile water. The water will be present
either dissolved within the liquid coating, chemically
bound to substituents within the coating, such as fillers or
pigments, or will be present in a gaseous state. The
monomeric and polymeric systems studied here, have low
water solubilities and contain no filler, pigments, etc.,
hence the effect of moisture on cationic polymerization is
controlled by the permeability of water vapor.
Photodegradation of aryliodonium salts should
not be greatly influenced by the presence of water,
although potentially it may behave as a hydrogen donor in
the photogeneration and liberation of Bronsted acid. In the
protonation step (or polymerization initiation) water may
play a solvating role, but it is not believed it plays a
significant role in the number of initiating sites. The effect
of water becomes apparent when an oxonium or
carbonium center has a choice between monomer and
water/nucleophilic impurities. From an industrial point of
view the question then becomes: are the concentrations
and nucleophilicity such that the kinetics of these reactions
are of concern in the chosen application? In applications
with high functionality levels, high catalyst concentrations
and relatively slow cure rates, such as epoxy can coatings,
small amounts of nucleophilic impurities are manageable
and sometimes desirable acting as a chain extender. In
application where low functionality is necessary, due to
cost or performance requirements, any reduction in cure
due to moisture is undesirable.
The literature on cationic polymerization
illustrates the benefits and disadvantages of water in “true”
catalyst formation and in chain transfer/termination
reactions [1]. Many authors acknowledge the role of water
in UV cationic systems but few address it specifically.
Two notable exceptions would be the work of Brann [2]
and Hanrahan [3] where the performance and
characterization of cationically cured cycloaliphatic epoxy
coatings were studied. Brann found a higher irradiation
dose was required to reach the same state of cure, as
measured by performance testing, at humidity levels less
than 35 % RH. At 70% RH the cure was reduced to 25 %
of it’s original low humidity level. The humidity effect
was also dependent on the nature of the polyol diluent, but
unaffected by high levels of moisture scavengers.
Hanrahan differentiated between through cure and surface
cure and found that humidity and temperature had the
greatest effect on surface cure, and little effect on through
cure. It should be noted that these systems are typically UV
epoxy can coatings which fall into the category cited above
as high functionality, relatively slow cure speed. In a
general reaction both oxonium (I) and carbonium (II)
species, produced by epoxy and vinyl ethers respectively,
theoretically react with water to yield hydroxyl
functionality with liberation of Bronsted acid (Scheme 2).
This acid is then available to create a new initiation site,
hence the term chain transfer.
Studies by Williams found that the cationic
polymerization process was retarded by water [4].
Williams, like Brann, found that the rate of cationic
polymerization was reduced, in his examples, by as much
as a thousand fold. It was observed however, that the
molecular weight of the polymers remained unchanged if
left for a sufficiently long period of time. It was argued
that equations (I) and (II) in scheme 2 could be considered
as an acid /base equilibrium. At the concentrations
anticipated it was cited that the equilibrium lies to the right
hence there is no tendency for the solvated proton to
initiate a new monomer (chain transfer) in the reverse
reaction. This qualitatively fits the behavior seen by some
researchers [5] and explains the often ill defined role of
water in cationic systems. A further complicating factor is
the stability of the ion-pair complex in the particular
polymer system studied. A considerable stability difference
would be anticipated between a very low dielectric non-
coordinating polydimethylsiloxane and a highly polar
ether/ester epoxy can coating. Williams went further to
develop a model based on the probability of finding one or
more water molecules within a distance x of ion pair
complex determining the extent to which polymerization is
inhibited. This model should hold for other nucleophiles
such as alcohol’s, another common impurity. The effect of
alcohol on cationic polymerization was clearly
demonstrated by Crivello [6] who studied the affect of t-
butanol on the viscosity of cyclohexane oxide
polymerization reactions. Crivello found a sharp decrease
in cationic polymerization on increasing t-butanol level.
There are many striking chemical and physical
differences between cationic systems which may also
control the extent to which nucleophiles affect
polymerization. The epoxies monomer and oligomers
based on ethers and esters form a more rigid matrix(high
Tg). In such systems reaction (I) enables propagation of
unreacted monomer to what otherwise might have been
considered a trapped center, thus increasing the degree of
conversion. Vinyl ethers tend to form low Tg flexible
polymers hence cation trapping would be less of an issue
and high conversions are usually seen [7]. The oxonium
center formed by water reacting with a carbonium ion, or
protonation of an epoxy, does not propagate reactions with
vinyl ether monomers. In silicone epoxies [8] and silicone
vinyl ether [9] systems the Tg of the systems is one of the
lowest of commercially available polymers, hence
reactivity difference can be attributed to the functional
groups themselves. Silicones present unique conditions in
that they have very low water solubilities, yet very high
water vapor permeability. When this high permeability is
combined with very high surface area to volume ratio
encountered in thin film coatings, you have a system in
equilibrium with the prevailing atmospheric conditions.
Table 1 gives the concentration of water vapor available to
react with cationic centers within epoxy and vinyl ether
silicones.
Table 1 Variance in Atmospheric moisture
Dew Point (F) [H20] (g/Kg)
40 5.2
50 7.8
60 11.2
70 16.1
80 22.7
This paper is aimed at identifying the impact of
moisture vapor on cationically cured coatings.
Experimental
Isobutylvinylether (IBVE) and vinylcyclohexene
oxide (VCHO) were purchased Aldrich chemicals and
were distilled and stored under nitrogen prior to use. The
preparation of the vinylether and epoxy functional
siloxanes are described elsewhere [8,9].
Irradiation studies were done using a Fusion
F300 UV lamp system fitted with an 1H bulb and a P300
power supply. Samples were irradiated in a sealed quartz
tube which had been inerted with nitrogen. The samples
were cooled using a deionised circulating water bath.
Samples were worked up by quenching in isopropanol and
neutralizing with calcium carbonate. These were then
filtered and the solvent removed under reduced pressure.
Irradiation doses were measured with an EIT UVICURE
High Energy Integrating Radiometer. Gel Permeation
Chromatography (GPC) analyses were obtained using the
following experimental set up: Perkin Elmer ISS-100
autosampler; Perkin Elmer 250 series GPC pump; two
300 x 4.6 mm, 5um Phenomenex columns; Beckman
Model 156 RI detector and chloroform as the mobile
phase. Samples were prepared in HPLC chloroform
(1mg/ml).
Sample Preparation.
The photocatalyst (2.62x10-5 moles) was
dissolved in HPLC grade toluene (1g). To this was added
freshly distilled isobutylvinylether (1g). The resulting
solution was mixed and placed in a quartz tube which was
sealed and inerted with nitrogen gas.
Effect of moisture on the cationic polymerization of
vinylethers.
The photocatalyst (2.62x10-5 moles) was
dissolved in HPLC grade methylethylketone (1g)
containing water. Sufficient water was added to give the
following water to IBVE ratios (No water; 0.0028; 0.028;
0.167). To this was added freshly distilled
isobutylvinylether (1g). The resulting solution was mixed
and placed in a quartz tube which was sealed and inerted
with nitrogen gas.
Synthesis of (3-tolyl)(dialkylphenyl)iodonium salts.
The (3-tolyl)(dialkylphenyl)iodonium triflate and
(3-tolyl)(dialkylphenyl)iodonium hexafluoroantimonate
were prepared using a modified method of Crivello [10].
All products were purified using column chromatography
(Kieselgel 70-230 mesh) prior to use.
Synthesis of diphenylIodonium(tetrakis) pentafluoro-
phenyl borate.
DiphenylIodonium(tetrakis)pentafluorophenyl
borate was synthesized using the method of Priou. [11]
and was purified using column chromatography
(Kieselgel 70-230 mesh) prior to use.
Differential PhotoCalorimetry.
A Dupont 2100 differential photocalorimetry
(DPC) was used to give a 3 second exposure time to a Hg
arc lamp operating at an output of 20mw/cm2 at 25 C.
Michigan Airgas ultra air was used as a purge gas with a
flow rate of 65cc/min. Water was introduced by bubbling
the purge gas through a deionised water bubbler prior to
injection into the DPC cell. Gel point measurements were
made using a Gel-Pointe Microsample-Gelometer(TM)
model GP102-AT. To 10g aliquots of a polymer-catalyst
mixture 1g of MEK was added doped with the appropriate
levels of distilled water.
Results and Discussion
Initial work was done on mono-functional model
compounds, namely IBVE and VCHO. These simple
aliphatic monomers were chosen to enable product
analysis using standard analytical techniques. The
aryliodonium salts used were a combination of purchased
and in house synthesized materials. The results of initial
experiments to ascertain experimental procedures and the
utility of the monomer are shown in table 2. These
experiments were carried out by simultaneously irradiating
all test samples with the same light source. This reduced
lamp aging effects and sample to sample variation. The
results clearly show the decreased molecular wt and
consequently DP and % yield as a function of anion
nucleophilicity. The higher nucleophilicity of
photocatalysts containing the triflate counterion is seen
with respect to the much studied SbF 6-. The
perfluorophenyl borate anion appears to have
approximately the same nucleophilicity as SbF 6- which are
2 to 3 times more effective at polymerization than the
triflate anion in these experiments. The commercial source
of the borate was clearly effected by the carbinol
functional diluent it is supplied in [12].
Table 3 shows the effect of doping the IBVE-
SbF6- based system with water. The monomer has very low
water solubility, hence MEK was chosen as a solvent to
controllably introduce liquid water. The extent of
inhibition can be clearly seen with approximately a 50%
reduction in Peak molecular weight and Mw observed. It is
clear from this simple experiment that water is competing
for carbonium active sites with the available IBVE
monomer, to produce a “termination” step rather than
simple chain transfer as described in the cationic epoxy
systems. It is interesting to note that the polydispersity of
the system is reduced on water inhibition. It is unclear
whether this behavior is similar to that seen in “pseudo
living” polymerization of vinyl ether systems polymerized
by conventional methods [13].
Table 4 shows the results of similar water doping
experiments carried out using vinylcyclohexene oxide.
The results indicate that polymer yields are independent of
water content, but the polymer molecule weights are
reduced. This observation is consistent with a chain
transfer process, and very different from the vinylether
system (Table 3) which shows lower molecular weight and
lower yield, implying a much slower chain transfer or a
chain termination step. In a high speed coating line there is
no distinction between the two states, the coating is simply
not cured to the designed level. The introduction of
solvent in these experiments artificially inflate the water
content of IBVE or VCHO. The water contents are not
high when compared to the amount of water vapor
available within a silicone coating system. The water
concentrations used dramatically illustrate the effect of
water as a nucleophile on cationic polymerization. This
technique of solvent /water doping was also extended to
gel point measurements on vinyl ether and epoxy
functional siloxanes. Figure 1 illustrates the effect of
water concentration on the gel point of a silicone vinyl
ether and a silicone epoxy system.
Figure 1. Gel point times versus water content for
silicone epoxy and vinyl ether polymers. 75
EPOXY GEL TIME 0 wt % H20
EPOXY GEL TIME 0.01 wt % H20
70 EPOXY GEL TIME 0.025 wt % H20
EPOXY GEL TIME 0.05 wt % H20
65
220

GEL TIME/(sec)
60
200
55
180
160 50
GEL TIME/(sec)

140 45

120 EPOXY SYSTEM

VINYL ETHER SYSTEM 40
300 310 320 330 340 350
100 3
TEMPERATUREX10 /K
80
60
Figure 3. Gel points as a function of Temperature for
40 silicone vinyl ether.
20
0.00 0.02 0.04 0.06 0.08 0.10 0.12
wt % WATER ADDED 180
VINYL ETHER GEL TIME O WT % H20
160 VINYL ETHER GEL TIME 0.01 wt %H20
VINYL ETHER GEL TIME 0.025 wt % H20
140 VINYL ETHER GEL TIME 0.05 wt % H20
GEL TIME/(SEC)

120
The first point that should be made is the faster 100
gelation/cure of the vinyl ether system under nominally dry
80
conditions. There does not appear to be a dramatic
difference, but it should be noted that photocatalysts 60

containing different counter ions were used. The triflate 40

anion was used for the vinyl ether system, and SbF 6- 20
[14]was used with the silicone epoxy. Table 2 shows that 300 310 320 330 340 350
the SbF6- is some 2 to 3 time more reactive under TEMPERATUREX10 /K
3

identical conditions.
In figure 2 and 3 the effect of temperature on gel
times was measured as function of water content. The
most dramatic effect of temperature is seen on the high
water content silicone vinyl ether systems. The dry and low
water content silicone vinyl ethers show very little change
with temperature which would imply that the
Figure 2. Gel points as a function of Temperature for
silicone epoxy.
effect of temperature on the high water doped systems is
due to reducing the effect of the water rather than boosting
the vinyl ether rate. The gel point measurements are a
closed system so no water is driven off, hence the most
likely scenario is the reduction in association /hydrogen
bonding due to increased thermal agitation.
In a slight variation on a widely used tool in
radiation cure, DPC was used to try and further quantify
the role of moisture in vinyl ether systems. Approximately
1mg samples were subjected to short pulses(3sec) of UV
light in a streaming flow of both dry air and moist air.
Figure 4 shows the 87 % drop in enthalpy from 85.6 to
10.9 J/g for the silicone vinyl ether/triflate system on
changing for “dry” to “wet” air flow. DPC does give you a
more accurate assessment of how the coating might
perform in the environment, but it is difficult to quantify
the level of humidity in the sample chamber, hence
performance changes can only be
Figure 4. DPC of Silicone vinyl ether in dry and moist
air.
20
18
Dry air
16
14
Heat Flow(mW)
12
10
8
6
Moist air
4 0
2 10
0
-2
0 1 2 3 4 5
Time(mins)
related to air flow rates. It is clear from the data presented
here that vinyl ethers have the potential to give very fast
cure under ambient cure conditions even with a less potent
catalyst. The inhibiting effects of water vapor in humid
conditions can lead to serious reductions in cure rates in
vinyl ethers. The extent to which this can be overcome will
depend on the water solubility of the coating, the water
permeability of your coating, the concentration of cationic
centers generated, and the monomer functionality level.
There are mechanical means by which a coating
can be dried on a coating line other than inerting. A
common drying device is the IR heater. Thermal aging of
epoxy can coatings is employed to give the system
sufficient mobility to cure to a higher extent. This is
different from using ovens to dry the air in contact with the
coating as proposed here. In figure 5 we see the effect of
relative humidity on the cure speed of a silicone vinyl ether
/triflate coating system. The inhibition in cure seen in the
laboratory environment (see figures 1 and 3) is clearly seen
on this coating, using both 600 and 1200 watts/in fusion
H bulbs. In table 5 we see the results of an experiment on
the same system fitted with an IR heater and an air
circulating systems. The IR heater, positioned before the
UV light box, provided a “dry zone” prior to irradiation.
The efficiency of the IR drier could be increased by
increasing the power output to the heating elements. Run
speeds comparable to those observed at 10 to 20 % RH
could by obtained with this simple drying device. The
approximately 12 inch “dry zone” created by the IR driers
differed in the extent to which they increased the
temperature of the substrate. Using radiant driers required
much higher IR source temperature to achieve
Figure 5. Cure Speed as a function of ambient
humidity.
1200
Cure Speed 600 watts
Cure Speed 1200 watts
1000
Cure Speed (Fpm)
800
600
400
200
20 30 40 50 60 70
Relative Humidity %
the same level of cure speed as a forced air IR lamp
combination. The IR driers with blown air were far more
effective at increasing cure speed and caused minimal
heating of potentially thermally sensitive plastic substrates.
These experiments combined with those in the laboratory,
show the key to fast cure is managing the environmental
water vapor. The high gas permeability is the key feature in
the inhibition of cure mechanism in silicone vinyl ether
coatings. Another obvious means of controlling water is
nitrogen inerting. In Electron Beam curing the silicone
vinyl ether/triflate system exhibited the fast cure you
would expect for a low moisture environment.
Conclusion
The effect of ambient moisture on the rate of
cationic polymerization is dependent on the monomer type
and concentration, the coating permeability, coating
thickness, and water concentration. The extent of these
changes have been measured in both epoxy and vinyl ether
monomers and silicone copolymers. Cationic cured
silicone coating present a unique situation in that they
combine very high water vapor permeability with high
surface area. In epoxy system the role of water is
concentration dependent and varies between chain transfer
and chain termination. In vinyl ethers the role of water
appears to be more of a chain terminator. The rapid
inhibition can be effectively negated with mechanical
drying devices such as IR driers or by blanketing with a dry
gas.
References
1. J. P. Kennedy Carbocationic Polymerization, Wiley-
Interscience, New York 1982 polymerization book
2. B. L Brann,. RadTech Rep. (1990), 4(1), 11-19 The
effects of moisture on UV curable cationic epoxide
3. B. D. Hanrahan and R. F. Eaton Proc. Water-borne &
Higher Solids Coatings Symp., 1988 420.
4. J.V.F. Best, T. H. Best, 7 T. F. Williams, styrene. Trans. photopolymerization of epoxy modified silicones for
Faraday Soc. 1962, 58, 192. The radiation induced application to silicone release papers.
polymerization of α methyl styrene. 12. S. Kerr, “Next generation” UV silicone release
5. A. Ledwith & D. C. Sherrington, Reactivity and coatings. Proceeding of Gorham International conference
mechanism in Cationic Polymerization. In Reactivity, 1996
Mechanism and Structure in Polymer Chemistry,eds. A. D. 13. C. G. Cho, B. A. Feit, & O. Webster, Macromolecules
Jenkins & A Ledwith. Wiley & Sons, London 1974, p. 1990, 23, 1918. Cationic polymerization of isobutyl vinyl
244. ether: livingness enhancement with dialkyl sulfides.
6. J. V. Crivello, D. A. Conlon, D. R. Olson, and K. K. 14. Authors note: the silicone epoxy system does not cure
Webb, Specialty Chemicals, 1998, Oct,401. Accelerators with the iodonium triflate catalyst under normal operating
in UV cationic polymerization. conditions.
7. C. Decker & D. Decker Radtech 94 p 602, Kinetic and
Mechanistic study of the UV curing of Vinyl ether based
systems.
8. R.P. Eckberg & R. W. LaRochelle. UV curable silicone
coating compositions. US 4,279,717
9. S. S. D. Brown, P. C. Hupfield, P. Y. K. Lo & R. G.
Taylor. Organosilicon compounds and compositions
containing them. US 5,270,423.
10. J.V. Crivello & J.H.W. Lam; New Photoinitiators for
cationic polymerization; J. Polym. Sci., Polym. Symp,
1976, 56 (Int. Symp. Cationic. Polym. 4th), 383-95.
11. C. Priou, A. Soldat, &J. Cavezzan. J. Coatings
Technology, 1995,67 (851) 71. Cationic
 Scheme 1 Typical Cationic Reaction Sequence for Vinyl ether and Epoxies.

Photoacid
hυ + X- Initiation
H

H
O + O
H +
Protonation
H
+ O
O
+

+O H OH
..
O O
+ +
Propagation

O O
O
+ O
+
Scheme 2 Reaction of Water with Cabocations

H OH
O + O
H + H2O
OH + H+ (I)

H
+ O H2O O +
O
+ + H (II)
OH

Table 2: Polymerization of IBVE. UVC dosage received 0.468 mJ/cm2.

Photocatalyst Peak Mw Mn dp n %
Mwt (Av) Yield
Iodonium triflate 1025 2482 1508 15 1.6 38
Iodonium antimonate 3401 7799 3886 38 2.0 68
Iodonium Borate* 2305 4233 2676 26 1.6 62
Iodonium Borate** 3756 7322 3074 30 2.3 64

* Commercial sample (includes diluent)

** In-house synthesized sample
Table 3: Effect of water on the polymerization of IBVE using the iodonium antimonate catalyst.

Water :IBVE ratio. Peak. Mw Mn Mw/Mn %

Mw (Av) yield
No water 1647 2263 1542 1.46 68
0.0028 1462 2019 1376 1.47 61
0.028 1370 1733 1353 1.28 58
0.167 983 1243 1086 1.14 48

Table 4. Effect of water on the polymerization of VCHO using the iodonium antimonate catalyst
UVC irradiation dose 0.415 mJ/cm2

Water: VCHO ratio. Peak Mwt. Mw(Av) Mn Mw/Mn % yield

No water 791 961 657 1.40 20

0.0028 778 818 610 1.34 26
0.028 590 655 410 1.59 24
0.167 317 308 216 1.42 22

Table 5. Effect of IR blower on cure speed of silicone vinyl ether.

BULB HEATER SETTING WEB CURE

WATTAGE TEMP/F SPEED(FPM)
600 0 84 200
1200 0 84 400
600 40 92 300
600 50 102 500
600 60 98 800
600 70 100 1000