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Copper photoredox catalyst “G1”: a new high

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Cite this: Polym. Chem., 2017, 8,

performance photoinitiator for near-UV and
5580 visible LEDs
H. Mokbel,a D. Anderson, b R. Plenderleith,b C. Dietlin,a F. Morlet-Savary,a
F. Dumur, c D. Gigmes,c J.-P. Fouassiera and J. Lalevée *a

Received 18th June 2017,
Accepted 14th August 2017
DOI: 10.1039/c7py01016h
rsc.li/polymers
The goal of this paper concerns the development of photoinitiating systems usable in industrial processes
for coating applications (cationic polymerization of epoxide based resins), the manufacture of
Interpenetrating Polymer Networks (IPNs) ( polymerization of acrylate/epoxy blends) and the production
of thick epoxy/glass fibre composites. For these purposes, a copper photoredox catalyst, G1, is proposed
as a high performance photoinitiator. It allows the design of very efficient three component photoinitiat-
ing systems (G1/iodonium salt (Iod)/N-vinylcarbazole (NVK)). The effects of the resin, light source
(LED@375, 395, 405 nm, halogen lamp), G1 concentration, coating thickness (25 µm and 1.4 mm), water
content, formulation stability and hydrolytic stability of the cured coatings were investigated. Examples of
IPNs and glass fibre composites are provided. In the studied applications the G1/Iod/NVK system is much
better than BAPO/Iod/NVK (BAPO – bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide – Irgacure 819)
used as a reference system with good reactivity in the 365–420 nm range. Owing to the catalytic nature
of G1, a reduced G1 content (30 fold less compared to the BAPO content) still leads to a higher practical
efficiency than BAPO in the photopolymerization of a coating. A comparison with other reference
systems based on 2-isopropylthioxanthone or anthracene is also provided and outlines again the very
high performance of G1 for industrial applications.

Introduction required (usually a mercury lamp). This is highly energy inten-

Photopolymerization reactions that transform a liquid
monomer (or a soft film) into a solid material (or a solid film)
upon light exposure are widely employed in many industrial
applications in traditional and high-tech areas such as radi-
ation curing, (laser) imaging, microlithography, stereolitho-
graphy, microelectronics, optics, holography, medicine,
dentistry, nanotechnology, UV cured adhesives, coatings or
composites, drying of inks, ink-jet drop on demand for 3D
printing, manufacture of printing plates, etc. They are green
reactions because they release almost no volatile organic
compounds, and do not need heating.1–10
If radical and cationic photopolymerization processes are
widespread in industry, they usually rely on high intensity UV
light sources and can suffer from oxygen inhibition (for both
radical polymerization and free radical promoted cationic
polymerization). Because of the former, a UV lamp is usually
a
Institut de Science des Matériaux de Mulhouse IS2M – UMR CNRS 7361 – UHA,
15, rue Jean Starcky, 68057 Mulhouse Cedex, France. E-mail: jacques.lalevee@uha.fr
b
Lambson Ltd, Clifford House, York Road, Wetherby, West Yorkshire, LS22 7NS, UK
c
Aix Marseille Univ, CNRS, ICR, UMR 7273, F-13397 Marseille, France
sive since most of the power consumed is released as heat and
only a small part of the emission spectrum is used to generate
initiating radicals or cations. In addition, UV radiation can
cause damage to materials such as plastics, dyes and pigments
and can also cause damage to human cells and tissues. The
use of visible irradiation sources (such as Light Emitting
Diodes – LEDs) to polymerize near UV-sensitive materials can
solve these issues and provide much safer working
conditions.5–10 This would cut costs, avoiding the use of expen-
sive, energy-consuming, photochemical equipment. Near UV
or visible radiation penetrates more deeply through a wider
range of materials than short wavelength UV radiation,
making it possible to reduce energy and the cost of polymeriz-
ation conditions. Dry thin ink films as well as thick coatings,
composites and a deep through cure can be obtained with
LEDs, which are not accessible using existing technologies.
LEDs are also eco-friendly, cheap and do not generate
ozone or emit harmful UV rays. They do not emit infrared
photons and thus generate only very low heat. They have low
operating and maintenance costs, and extremely long life-
times. LEDs are very flexible components that are highly suited
to reactor design. Indeed, their compact design combined with

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their easy and safe handling enables their incorporation in
programmed robots, as well as pulsing and clocking. In other
words, they have the potential to stimulate scientific/industrial
innovation, and preserve the environment, as was recognized
by the 2014 Nobel prize in physics.
Visible light is much less energetic than UV light and often
cannot be absorbed by the usual photoinitiating systems. In
addition, most of the compatible systems exhibit low quantum
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yields for the production of reactive species and are oxygen-
sensitive. Thus, there is an urgent need to introduce new
photoinitiators (PI) or photoinitiating systems (PIS) with
absorption profiles matching the LED emission. However,
there is at present only a very limited number of near UV LED-
curable formulations available on the radiation curing market,
especially in the cationic photopolymerization sector.10 In
recent years substantial academic efforts have been expended
on the development of LED sensitive photoinitiating
systems,9,10 some of this work has resulted in patent
applications.11
In the present paper, we propose a novel photoinitiating
system operating under LED for the radiation curing market.
Our approach is related to the use of a photoredox catalyst.12–16
The first generation of photoredox catalysts was based on Ru
and Ir complexes but they were characterized by several draw-
backs: (i) they are generally very expensive and often difficult
to prepare (more especially for iridium based complexes) and
(ii) they can be toxic. In order to avoid the use of expensive Ru
and Ir complexes, we have tried to develop a new generation of
photoredox catalysts based on cheaper metals (i.e. G1 in
Scheme 1). In this work, G1 is investigated as a high perform-
ance photoinitiator (PI) upon irradiation with near UV or
visible Light Emitting Diodes (LEDs) for the cationic polymer-
ization of epoxides, the synthesis of Interpenetrating Polymer
Network IPNs ( polymerization of acrylate/epoxy blends) and
the manufacture of thick epoxy/glass fibre composites. The
efficiency of G1 based photoinitiating systems (G1/iodonium
salt (Iod)/N-vinylcarbazole (NVK)) is investigated. The effects of
the resin, light source (LEDs at 375, 395, 405 nm, halogen
lamp), G1 concentrations, coating thickness (25 µm and
1.4 mm), water content, stability of the formulation and hydro-
lytic stability of the coatings are investigated. The synthesis of
IPNs and the preparation of composites are discussed. The
G1/Iod/NVK system is also compared to reference systems
based on BAPO (bis(2,4,6-trimethylbenzoyl)-phenylphosphine-
oxide – Irgacure 819), 2-isopropylthioxanthone or anthracene.
Scheme 1 Chemical structures of the photoinitiators.
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As it is shown in this work, the development of photoredox cata-
lysts such as G1 provides a means for creating photoinitiating
systems with unprecedented reactivity. Currently, no photo-
redox catalysts exist on the market.
Experimental section
Materials
The investigated photoinitiators (G1 and BAPO) and other
chemical compounds are shown in Schemes 1 and 2. The
copper complex G1 was synthesized according to the procedure
presented in detail in ref. 17. N-Vinylcarbazole (NVK; used
with the best purity available ∼98%), 3-ethyl-3-oxetane-
methanol (UviCure S130 or TMPO), bisphenol A diglycidyl ether
(DGEBA), hydrogenated derivative bisphenol A diglycidyl ether
(H-DGEBA) and anthracene were obtained from Sigma-Aldrich.
Trimethylol-propane triacrylate (TMPTA) was obtained from
Allnex. Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (BAPO),
bis-(4-t-butylphenyl)-iodonium hexafluorophosphate (Speed-
Cure938 or Iod), bis((3,4-epoxy cyclohexyl)methyl)adipate
(UviCure S128), 7-oxabicyclo[4.1.0]hept-3-ylmethyl 7-oxabicyclo
[4.1.0]heptane-3-carboxylate (UviCure S105), Boltorn H2004
and 2-isopropylthioxanthone (2-ITX) were obtained from
Lambson Ltd.
Irradiation sources
Different visible lights were used for the irradiation of the
photocurable samples: (i) polychromatic light from the
halogen lamp (Fiber-Lite, DC-950; incident light intensity:
∼12 mW cm−2 in the 370–800 nm range), or (ii) LED@405 nm
(Thorlabs, ∼230 mW cm−2), LED@395 nm (Thorlabs, ∼50
mW cm−2) and LED@375 nm (Thorlabs, ∼40 mW cm−2). The
emission spectra of these light sources are given in ref. 18.
Photopolymerization experiments
RT-FTIR procedure. The experimental conditions for the
photopolymerization reaction are given in the figure captions.
The photosensitive formulations (25 µm thick) were deposited
on a BaF2 pellet and irradiated under air or laminate con-
ditions (the formulation is sandwiched between two poly-
propylene films to avoid reoxygenation in the course of the
photopolymerization). The epoxy group content of the model
resin (Scheme 2) and/or the double bond content of TMPTA
were continuously followed by real time FTIR spectroscopy
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Scheme 2 Chemical structures of additives and monomers.

(JASCO FTIR 4100) at about 790 cm−1 and 1630 cm−1, respect-
ively, as shown in ref. 18.
For thick samples (1.4 mm), the polymerization was evalu-
ated in air or under laminate conditions. The evolution of the
epoxy and acrylate characteristic peaks was followed in the
near-infrared range at ∼3700 cm−1 and 6160 cm−1 respectively.
For all the experiments, irradiation starts at t = 10 s. The
final reactive function conversions are denoted as FC (at times
of 400 s and 800 s depending on the experiments).
UV conveyor. The Dymax-UV conveyor was used to cure com-
posite samples. The glass fibres were impregnated with the
organic resin (50/50 w/w%) and then irradiated. The UV
conveyor is equipped with a 120 mm wide Teflon-coated belt
and one UV lamp (mercury–Fe doped lamp). The distance
between the lamp and the belt can be manually adjusted
(fixed at 15 mm) as can the belt speed (fixed at 2 m min−1). Fig. 1 Comparison of the UV-vis absorption spectra of G1 and com-
mercial photoinitiators (BAPO, anthracene and 2-ITX) in DCM.

Results and discussion

Light absorption properties of the studied photoinitiators
The light absorption spectra of G1 and BAPO in dichloro-
methane (DCM) are given in Fig. 1. Their absorption maxima
are located at ∼370–380 nm (Table 1) with the corresponding
extinction coefficients: εG1 ∼ 3200 M−1 cm−1 and εBAPO ∼ 800
M−1 cm−1. For G1, the absorption maximum at 380 nm corres-
ponds to a metal-to-ligand charge transfer (MLCT) transition
with more intense intra-ligand transitions appearing at shorter
wavelengths.19 Interestingly, the absorption spectrum of G1
overlaps well with the emission lines of the LEDs@405 nm,

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Table 1 Light absorption properties of G1 vs. commercial photoinitiators (BAPO, anthracene and 2-ITX): maximum absorption wavelengths λmax,
extinction coefficients at λmax and extinction coefficients at the emission wavelengths of the different LEDs (LED@375 nm; LED@395 nm and
LED@405 nm)
λmax (nm) εmax (M−1 cm−1)
G1 380 3200
BAPO 360 800
Anthracene 359 4200
2-ITX 380 6100
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395 nm and 375 nm. For all LEDs used, the overlapping with
G1 is improved when compared with BAPO (εG1 > εBAPO,
Table 1). The absorption of G1 also ensures better overlapping
with the emission spectrum of the halogen lamp than for
BAPO.
Anthracene and 2-ITX were also chosen as the references
for the cationic polymerization and the evaluation of the
polymerization initiating ability of G1. Compared to these
commercial photoinitiators (2-ITX or anthracene), the absorp-
tion of G1 is still more important especially at 405 nm (e.g.
30 M−1 cm−1 for anthracene, 2000 M−1 cm−1 for 2-ITX and
2200 M−1 cm−1 for G1; Fig. 1 and Table 1).
Cationic photopolymerization of the model resin
Performance of G1 vs. BAPO. The cationic photo-
polymerization of the model resin (Scheme 2) in the presence
of G1/Iod/NVK and BAPO/Iod/NVK in air was carried out using
LED@405 nm. For clarity, the model resin is a blend of
different monomers: UviCure S128 (29 wt%)/UviCure S105
(29 wt%)/UviCure S130 (7 wt%)/Boltorn H2004 (35 wt%). The
photopolymerization profile of the model resin (epoxy function
conversion vs. irradiation time) with G1/Iod/NVK clearly indi-
cates a faster polymerization rate (Rp) and a higher final epoxy
group conversion (FC) than those obtained with the reference
BAPO/Iod/NVK system (Fig. 2A). In addition, a new peak
ascribed to the formation of the polyether network during the
photopolymerization arises at ∼1080–1100 cm−1 in the FTIR
spectra (see e.g. Fig. 2B for G1). For similar weight contents,
BAPO/Iod/NVK is much less efficient, which could partly be
Fig. 2 (A) Photopolymerization profiles of epoxy functions of the model resin in air with G1/Iod/NVK (1.7/4.6/1 w/w/w%) and BAPO/Iod/NVK (1.8/5/
1 w/w/w%) upon LED@405 nm exposure; (B) IR spectra recorded before and after polymerization using G1/Iod/NVK (1.7/4.6/1 w/w/w%).
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ε405 nm (M−1 cm−1) ε395 nm (M−1 cm−1) ε375 nm (M−1 cm−1)
2200 2900 3200
500 700 800
30 60 2800
2000 4600 5500
attributed to the less intense light absorption of BAPO at this
wavelength (ε405 ∼ 500 M−1 cm−1 for BAPO vs. 2200 M−1 cm−1
for G1 – Table 1). Under these conditions, the molar concen-
tration of G1 is lower than that of BAPO ([BAPO] = 4.07 × 10−2
M, [G1] = 1.9 × 10−2 M), which demonstrates the greater reac-
tivity of G1 compared to BAPO. Moreover, G1 afforded tack-free
coatings while tacky polymers were obtained with BAPO.
Study of the dark polymerization: G1 vs. BAPO. The presence
of a possible dark polymerization after a short irradiation
period can be an advantage for the cationic polymerization as
the reaction can continue through a living process. This dark
polymerization process which is an important parameter for
the performance of an initiating system is more efficient using
G1 than BAPO (Fig. 3). In the presence of G1, the polymeri-
zation continues after the light source is removed (60 s of
irradiation: final conversion (FC) increase = 22% for G1 com-
pared to 12% of increase for BAPO after 400 s). This behavior
is ascribed to the greater reactivity of the G1-based system
which can be explained by more intense light absorption pro-
perties of G1 vs. BAPO (εG1 > εBAPO, at λ = 405 nm).
Effect of the G1 concentration. In line with the above
results, the performance of a relatively high concentration of
G1 (1.7 wt%) was excellent, but [G1] must still be optimized.
Under LED@405 nm exposure, G1 appears to be an excellent
photoinitiator whatever the concentration. As seen in Fig. 4A,
using thin films (25 µm), the change of FC is insignificant:
∼2–6%. As expected, in the case of thick samples (1.4 mm)
(Fig. 4B), the performance of G1-based systems increases when
decreasing the photoinitiator concentration. A better polymer-
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G1 is still much lower than that of BAPO ([BAPO] = 4.07 × 10−2

M, [G1] = 1.3 × 10−3 M; [BAPO]/[G1] ∼ 31). These data show the
extreme efficiency of G1 catalyst in terms of photoinitiation
over the well-known BAPO.
The performance of the G1 photoredox catalyst was also
compared to other sensitisers which are well known for their
ability to sensitize iodonium salts. A comparison of the
polymerization profiles obtained in the model resin is given in
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Fig. 5. For example, compared to the use of anthracene or

2-ITX as PIs in combination with an iodonium salt (SpeedCure

Fig. 3 Photopolymerization profiles of epoxy functions of the model

resin in air with G1/Iod/NVK (1.7/4.6/1 w/w/w%) and BAPO/Iod/NVK
(1.8/5/1 w/w/w%) upon LED@405 nm exposure.

ization profile is obtained when using 0.22 wt%: both high Rp

and high epoxy function conversions are found. This result is
probably the consequence of an internal filter effect; i.e., upon
increasing the PI concentration, the penetration of light
decreases. Tack-free coatings are obtained whatever the con-
centration and the thickness of the G1-based system. These
results highlight the efficiency of G1 as a photocatalyst at very
low concentrations which will prove beneficial to reduce both
cost and toxicity issues.
Fig. 5 Photopolymerization profiles of epoxy functions of the model
For comparison, G1 still remains much more reactive than resin in air in the presence of (1) 2-ITX/Iod (0.25/4.3 w/w%), (2)
BAPO even at a low concentration (0.12% for G1 vs. 1.8% for Anthracene/Iod (0.23/4.8 w/w%), and (3) G1/Iod/NVK (0.22/5/1 w/w/w%)
BAPO) (Fig. 4C). In this case also, the molar concentration of upon LED@405 nm exposure, sample thickness = 1.4 mm.

Fig. 4 Photopolymerization profiles of epoxy functions of the model resin in air in the presence of G1/Iod/NVK upon LED@405 nm exposure: (A)
sample thickness = 25 µm, (B) sample thickness = 1.4 mm and (C) comparison of G1/Iod/NVK vs. BAPO/Iod/NVK (the irradiation starts @ t = 10 s);
sample thickness = 1.4 mm, Iod: ∼5 wt%, NVK: 1 wt% in the formulations.

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938), using G1/NVK leads to a dramatic increase of both the Rp
and the final epoxy conversion. The efficiency trend for the cat-
ionic polymerization using LED@405 nm follows the order: G1
> 2-ITX > anthracene. Obviously, this is related to the photo-
redox catalyst behavior of G1 (see Scheme 3) as well as its
better light absorption properties compared to the commercial
photoinitiators (Fig. 1 and Table 1). This result shows that G1
is an excellent photoinitiator for the curing of epoxides.
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Effect of the sample thickness and irradiation devices.
Under the different near-UV or visible LEDs or a halogen lamp,
the G1 based photoinitiating system initiates the cationic
polymerization of a model resin in air. In the case of thin
films (sample thickness = 25 µm, Fig. 6A), the G1-based system
Scheme 3 Photoredox catalytic cycle for the three-component G1/
Iod/NVK system.
Fig. 6 Photopolymerization profiles of epoxy functions of the model resin in air upon different light irradiation devices in the presence of (A) G1/
Iod/NVK (0.22/5/1 w/w/w%) and (B) BAPO/Iod/NVK (1.8/5/1 w/w/w%), sample thickness = 25 µm.
Table 2 Epoxy function conversions obtained in air upon exposure to different near UV and visible light exposure in the presence of G1/Iod/NVK or
BAPO/Iod/NVK based system; G1: 0.22 wt%, BAPO: 1.8 wt%, Iod: 5 wt%, NVK: 1 wt% in the formulations
LED@405 nm
(I∼ 230 mW cm−2)
1.8% BAPO 0.22% G1
a
Sample thickness = 25 µm 59% 88.5%
Sample thickness = 1.4 mm b 88% 99%
a
800 s of irradiation. b 400 s of irradiation.
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exhibited excellent efficiency upon exposure to various LEDs:
405 nm, 395 nm and 375 nm. Each wavelength gave similar
final conversions (epoxy function conversions ∼85–95%,
Table 2), and tack-free coatings. The G1-based system also
worked under very mild halogen lamp irradiation
(12 mW cm−2), but the final conversion was limited to ∼60%,
and tacky polymers were obtained, which can be explained by
the low intensity of this lamp. The best polymerization profiles
were obtained upon exposure to LED@395 nm, which may be
due to the fact that G1 exhibits good absorption properties at
395 nm in combination with a slightly higher intensity of this
lamp compared to that of LED@375 nm (∼10%). As illustrated
in Fig. 6B, the BAPO-based system can also work
under different irradiation devices. A lower efficiency is always
found and both lower polymerization rates and final conver-
sions were observed compared to G1. This might be
attributed to the less intense absorption of BAPO at these
wavelengths (ε ∼ 300–800 M−1 cm−1). Tacky polymers were
obtained with BAPO upon exposure to different LEDs except
for the halogen lamp where the final product was a gel and
not a hard film.
An outstanding performance for the photopolymerization
of the model resin using thick samples (1.4 mm) is obtained at
405 nm (Fig. 7A) due to the higher light intensity of this light
source (∼230 mW cm−2). Nevertheless, when the intensity was
lowered to 40–50 mW cm−2, the performance was reduced in
terms of FC (∼60–70% after 400 s, Table 2) and rates of
polymerization (Fig. 7A). However, the BAPO-based system
LED@375 nm LED@395 nm Halogen lamp
(I∼ 40 mW cm−2) (I∼ 50 mW cm−2) (I∼ 12 mW cm−2)
1.8% BAPO 0.22% G1 1.8% BAPO 0.22% G1 1.8% BAPO 0.22% G1
77% 85% 84% 96% 37% 61%
23% 72% 28% 64% <25%
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Fig. 7 Photopolymerization profiles of epoxy functions of the model resin in air upon different light irradiation devices in the presence of
(A) G1/Iod/NVK (0.22/5/1 w/w/w%) and (B) BAPO/Iod/NVK (1.8/5/1 w/w/w%), sample thickness = 1.4 mm.

(Fig. 7B) had a very low efficiency under LED@375 nm and

LED@395 nm (epoxy function conversions <30%). A relatively
good conversion was reached when using LED@405 nm, but a
long inhibition time was observed. The rate of polymerization
was still very slow compared to what was achieved with G1 and
the molar concentration of G1 was much lower than for BAPO
and afforded tack-free polymers. The suitable absorption of G1
at different wavelengths compared to BAPO (εG1 > εBAPO,
Table 1) made the photopolymerization possible under
exposure to various LEDs. These results clearly demonstrate
the promise of the proposed approach with UV-visible light on
thick samples.
Effect of the water content. The addition of water can play
an important role. It is well known that the addition of water
influences the propagation step in the cationic polymerization:
a favorable effect may be explained by the fact that the Fig. 8 Final epoxy group conversions (FCs) vs. the amount of water
after 800 s of irradiation with LED@405 nm in the presence of G1/Iod/
addition of a small amount of water leads to the generation of
NVK (0.84/4.5/1 w/w/w%) or BAPO/Iod/NVK (1.8/5/1 w/w/w%); sample
reactive species to initiate the polymerization. Conversely, in thickness = 25 µm.
the presence of a lot of water, alcohols can be generated which
can inhibit the cationic polymerization. In the case of
G1-based systems, a relatively low or high amount of water
(∼1.4 → 4 wt%) significantly improves the polymerization pro- Cationic photopolymerization of a DGEBA monomer and its
files of the model resin. The final conversion does not signifi- derivative (H-DGEBA)
cantly change (Fig. 8) and tack-free polymers are obtained. On The G1-based systems are also suitable for the cationic photo-
the contrary, traces of water are highly detrimental for BAPO, polymerization of DGEBA and H-DGEBA (Scheme 2) in air
where the final conversion significantly decreases (Fig. 8) and upon LED@405 nm exposure. In the case of the H-DGEBA
the polymers obtained are tacky. This effect has been already resin, G1 (Fig. 9A) is much more reactive than BAPO (Fig. 9B)
observed in cationic polymerization.3,5 These results show that even without NVK. With the addition of a NVK additive, no sig-
G1 is less sensitive to moisture than BAPO. This will therefore nificant effect was observed for the G1-based system (the
facilitate the storage of G1 containing resin. polymerization rate was slightly improved), which may be due
Stability over time. The G1-based system in the model resin to the fact that the two-component photoinitiating system (G1/
was found to be stable after ∼7 months of storage at room Iod) is already very efficient to initiate the cationic polymeriz-
temperature. It was noted that there was less than a 3% ation without the NVK additive.
change in the epoxy functional group conversion compared to The same behaviour was observed with a DGEBA monomer
the freshly prepared formulation (thin films (sample thickness = in thin (Fig. 10A) or thick (Fig. 10B) samples, but the efficiency
25 µm), LED@405 nm exposure; t = 800 s). This behaviour was lower than in the case of H-DGEBA; the final conversion
demonstrates the stability of the G1-based system in the photo- was limited (FC ∼ 50–70%) which can be explained by the
curable formulation for extended periods of time. This will prove higher viscosity of the DGEBA monomer compared to
beneficial for industrial applications, where formulations may be H-DGEBA. Furthermore, the high viscosity of DGEBA-type
prepared long in advance for final use. epoxides makes their handling and processing difficult which

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Fig. 9 Photopolymerization profiles (epoxy function conversion vs. irradiation time) for H-DGEBA in air upon LED@405 nm exposure; using thin
(25 µm) (A) and thick (1.4 mm) (B) samples in the presence of BAPO/Iod (1.8/4 w/w%) (curve 1), BAPO/Iod/NVK (1.9/4.4/1 w/w/w%) (curve 2), G1/Iod
(0.86/4.3 w/w%) (curve 3), G1/Iod/NVK (0.88/4.6/1 w/w/w%) (curve 4), and G1/Iod (0.25/4.3 w/w%) (curve 5); the irradiation starts @ t = 10 s.

Fig. 10 Photopolymerization profiles (epoxy function conversion vs. irradiation time) for DGEBA in air in the presence of G1/Iod/NVK (0.8/4.6/
1 w/w/w%) or BAPO/Iod/NVK (1.7/5/1 w/w/w%) upon LED@405 nm exposure; using thin (25 µm) (A) and thick (1.4 mm) (B) samples.

can occasionally lead to undesirable mechanical performance lytic cycle does not create coloured photoproducts and allows
due to poor mixing with other components. extensive polymerization at a low G1 concentration. This cata-
The difference between the model resin vs. DGEBA and lytic cycle is detailed in the literature.17b
H-DGEBA can be attributed to the presence of multifunctional
monomers in the model resin. The conversions correspond to
the reactive epoxy function conversions i.e. converting 50% of
these epoxy functions corresponds thus already to a higher
monomer conversion (order of magnitude: 80–90% for the tri-
functional used). In all cases, whatever the resin used, G1 is
still much more reactive than BAPO.

Proposed photoredox catalytic cycle

The original catalytic cycle proposed is depicted in Scheme 3
and is composed of three reactive species: photoinitiator cata-
lyst, Iod and NVK.17a Upon irradiation the copper complex G1
in combination with iodonium salt (oxidizing agent) generates
the radical species through an electron transfer reaction.
A propagation system containing the NVK additive leads to
simultaneous regeneration of G1 and the formation of highly
Fig. 11 Weight loss (%) vs. heating time (hours) at ∼75 °C for the model
reactive cations (Ph-NVK+). The latter can very efficiently resin produced with G1/Iod/NVK (0.22/5/1 w/w/w%) or BAPO/Iod/NVK
initiate the cationic polymerization process. The regeneration (1.8/5/1 w/w/w%), using thick samples (1.4 mm) upon exposure to
of G1 is a key step for an efficient initiation; therefore, the cata- LED@405 nm for t = 400 s.

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Resistance to hydrolysis of the model resin
Resistance to hydrolysis of the cured material may be of impor-
tance if the resins are applied as coatings. In a preliminary
study, pellets of the resins were incubated in warm sonicated
water (∼75 °C). The results were in full agreement with the pre-
liminary study of the water effect.
As shown in Fig. 11, after 56 hours at ∼75 °C, the cured
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demonstrate that the material exhibits poor mechanical and
hydrolytic resistance which is detrimental for many desired
applications. Conversely, the resins produced with G1 exhibi-
ted good remaining mechanical properties: the weight loss is
not significant, and the polymer was still tough even after
257 hours at ∼75 °C. These good mechanical properties endow
the G1-based system with potential applications. These results
are well reflected by the excellent epoxy function conversion

polymers produced with BAPO are mechanically compromised observed in RT-FTIR experiments using G1-based samples
as a result of hydrolytic and ultrasonic stress. These results compared to the reference BAPO one.

Fig. 12 Photopolymerization profiles (epoxy function or acrylate function conversion vs. irradiation time) for IPN synthesis in the presence of G1/
Iod/NVK (0.22/4.8/1 w/w/w%) in TMPTA/S105 (50/50 w/w%), G1/Iod/NVK (0.23/4.4/1 w/w/w%) in TMPTA/S105/Boltorn H2004 (34/33/33 w/w/w%)
and G1/Iod/NVK (0.83/4.5/1 w/w/w%) in TMPTA/S105 (50/50 w/w%) in air, using thin (25 µm) (A) and thick (1.4 mm) (B) samples, upon LED@405 nm
exposure.

Table 3 Epoxy function and acrylate function final conversions (in %) obtained after the photopolymerization of IPNs in air or in laminate, thin
(25 µm) or thick (1.4 mm) samples upon exposure to LED@405 nm in the presence of G1/Iod/NVK: G1/Iod/NVK (0.22/4.8/1 w/w/w%) in TMPTA/S105
(50/50 w/w%), G1/Iod/NVK (0.23/4.4/1 w/w/w%) in TMPTA/S105/Boltorn H2004 (34/33/33 w/w/w%) and G1/Iod/NVK (0.83/4.5/1 w/w/w%) in
TMPTA/S105 (50/50 w/w%)

0.22% G1 0.83% G1 0.23% G1 + Boltorn H2004

In air Sample thickness = 25 µm a Epoxy function 72 79 68

Acrylate function 53 63 32
Sample thickness = 1.4 mm b Epoxy function 80 52 93
Acrylate function 90 84 88

In laminate Sample thickness = 25 µm a Epoxy function 47 50 66

Acrylate function 80 83 86
b
Sample thickness = 1.4 mm Epoxy function 74 52 89
Acrylate function 87 87 86
a
800 s of irradiation. b 400 s of irradiation.

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IPN synthesis
Photopolymerization of a UviCure S105/TMPTA blend (50/50
w/w%). IPNs can be fabricated through a concomitant radical
and cationic photopolymerization of a UviCure S105/TMPTA
blend (50/50 w/w%) in a one-step hybrid curing process using
for example the G1-based system, in air and under laminate
conditions upon LED@405 nm exposure. Using thin films,
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Fig. 13 IR spectra recorded before and after polymerization for IPN
synthesis in the presence of G1/Iod/NVK (0.22/4.8/1 w/w/w%) in
TMPTA/S105 (50/50 w/w%) for a thick (1.4 mm) sample, upon
LED@405 nm exposure; in air.
Fig. 14 Photopolymerization profiles (epoxy function or acrylate function conversion vs. irradiation time) for IPN synthesis in the presence of G1/
Iod/NVK (0.22/4.8/1 w/w/w%) in TMPTA/S105 (50/50 w/w%), G1/Iod/NVK (0.23/4.4/1 w/w/w%) in TMPTA/S105/Boltorn H2004 (34/33/33 w/w/w%)
and G1/Iod/NVK (0.83/4.5/1 w/w/w%) in TMPTA/S105 (50/50 w/w%) in laminate, using thin (25 µm) (A) and thick (1.4 mm) (B) samples, upon
LED@405 nm exposure.
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rapid polymerization profiles were obtained (high Rp and excel-
lent monomer conversion for both epoxy and acrylate func-
tions of UviCure S105 and TMPTA, respectively – Fig. 12A and
Table 3). Tack-free coatings were obtained in any case.
The same behaviour was also observed in the case of thick
samples (Fig. 12B). The best polymerization profile was
obtained using 0.23 wt% G1 which can be explained by deeper
penetration of light at low PI contents. Fig. 13 shows that for
thick samples, a simultaneous consumption of epoxy and acry-
late functions can be carried out in one-step leading to tack-
free coatings. Note that no effect of Boltorn H2004 on the
photopolymerization profiles in air is observed.
While under laminate conditions, the addition of the
Boltorn H2004 resin in the UviCure S105/TMPTA blend
improves the final epoxy function conversions as shown in
Fig. 14 and Table 3. Such results are explained on the basis of
the chain transfer reaction involving the hydroxyl group
present in Boltorn.20 This mechanism results in a decrease in
cross-link density. Therefore, the network structure becomes
more flexible and the mobility of the reactive species increases,
so that the vitrification effect can be delayed and higher epoxy
function conversions are achieved.
Similar to previous reports on the formation of IPNs,21,22
the conversion of TMPTA was higher in laminate than in air.
In contrast the conversion of the epoxy function was lower in
laminate than in air. It may be because the free radical
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polymerization reaction of TMPTA was faster than the cationic
polymerization, and most of the free radicals were consumed
to initiate the free radical polymerization of TMPTA since the
oxygen inhibition effect was prevented by lamination which
reduces oxygen inhibition.
Photopolymerization of the model resin/TMPTA blend
(80/20 w/w%). The investigated copper catalyst G1 also allows
the formation of IPNs through a simultaneous cationic/radical
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Towards composites
Over the last few years composite materials have been the
dominant emerging materials. They exhibit several properties
over conventional ones: light weight, high strength, corrosion
resistance and chemical resistance leading to reinforced
materials for industrial applications.
The composite has been prepared by the impregnation of

photopolymerization of the model resin/TMPTA blend (80/20
w/w%) in air and in laminate using thin or thick samples
upon LED@405 nm exposure. Excellent polymerization pro-
files and high conversion of the epoxy and the acrylate func-
tional groups (Table 4) were obtained. Tack free-coatings were
obtained for thin and thick samples. This result highlights the
dramatic ability of G1 to form IPNs in the presence of only
20% of TMPTA with the model resin (Scheme 2).
an organic resin into a glass fibre and then irradiated. The
results show that G1 is not only more reactive than BAPO for
initiating cationic polymerization but also for IPN synthesis.
These results were also confirmed by our experiments on glass
fibre impregnation (PI resin–glass fibre system) with UV
(mercury–Fe doped lamp) curing. The results are summarized
in Table 5. A fast polymerization was observed using G1, where
the surface became tack-free after the first pass, and within a

Table 4 Epoxy function and acrylate function final conversions (in %) obtained after the photopolymerization of the model resin/TMPTA blend
(80/20 w/w%) in air or in laminate, using thin (25 µm) or thick (1.4 mm) samples upon exposure to LED@405 nm in the presence of G1/Iod/NVK
(0.21/4.3/1 w/w/w%)

0.21% G1
a
In air Sample thickness = 25 µm Epoxy function 85
Acrylate function 35
Sample thickness = 1.4 mm b Epoxy function 96
Acrylate function 92

In laminate Sample thickness = 25 µm a Epoxy function 85

Acrylate function 95
Sample thickness = 1.4 mm b Epoxy function 99
Acrylate function 89
a
800 s of irradiation. b 400 s of irradiation.

Table 5 Number of passes to be tack-free for impregnated glass fibres with the model resin, H-DGEBA resin and IPNs synthesized using a UV con-
veyor (mercury–Fe lamp), belt speed used = 2 m min−1

Composition At the surface On the bottom

One layer of glass fibre In model resin 1.8% BAPO + 5% Iod + 1% NVK 4 passes 23 passes
0.12% G1 + 4.7% Iod + 1% NVK 1 pass 9 passes
0.22% G1 + 5% Iod + 1% NVK 1 pass 8 passes
0.84% G1 + 4.5% Iod + 1% NVK 1 pass 7 passes
1.7% G1 + 4.6% Iod + 1% NVK 1 pass 9 passes
In H-DGEBA resin 0.88% G1 + 4.6% Iod + 1% NVK 1 pass 8 passes
1.9% BAPO + 4.4% Iod + 1% NVK 4 passes 21 passes
(remains tacky)
In UviCure S105/TMPTA blend 0.22% G1 + 4.8% Iod + 1% NVK 1 pass 1 pass
(50/50 w/w%) 0.83% G1 + 4.5% Iod + 1% NVK 1 pass 1 pass
0.23% G1 + 4.4% Iod + 1% NVK + Boltorn H2004 1 pass 1 pass
In model resin/TMPTA blend 0.21% G1 + 4.3% Iod + 1% NVK 1 pass 1 pass
(80/20 w/w%)

Two layers of glass fibres In model resin 1.8% BAPO + 5% Iod + 1% NVK 4 passes 37 passes
(remains tacky)
0.12% G1 + 4.7% Iod + 1% NVK 1 pass 17 passes
0.22% G1 + 5% Iod + 1% NVK 1 pass 20 passes
0.84% G1 + 4.5% Iod + 1% NVK 1 pass 30 passes
In UviCure S105/TMPTA blend 0.22% G1 + 4.8% Iod + 1% NVK 1 pass 4 passes
(50/50 w/w%) 0.83% G1 + 4.5% Iod + 1% NVK 1 pass 9 passes
0.23% G1 + 4.4% Iod + 1% NVK + Boltorn H2004 1 pass 1 pass
In model resin/TMPTA blend 0.21% G1 + 4.3% Iod + 1% NVK 1 pass 4 passes
(80/20 w/w%)

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Polymer Chemistry
few passes at the bottom of the sample, using one or two
layers of glass fibres. In contrast to G1, the samples based on
BAPO required ∼4 passes to be tack-free on the surface and
many more passes (∼23–37 passes) for curing the bottom.
A brown colour appeared using BAPO, while no significant
change of the colour of the initial composition was observed
using G1. More interestingly, using the IPN approach, only one
pass was enough to produce composites when using one layer,
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and 4 passes were needed with two layers. This behaviour
demonstrates that the G1 catalyst exhibits an outstanding
reactivity for the production of composite materials.
Conclusion
In the present paper, G1 is proposed as a photoinitiator with
outstanding reactivity/efficiency (better than BAPO, 2-ITX and
anthracene) that acts as a photosensitizer for iodonium salt
decomposition in cationic polymerization or as a type II radical
source in free radical promoted cationic polymerization pro-
cesses. G1 is a photoredox catalyst exhibiting high reactivity upon
irradiation with near UV or visible LEDs. The polymerization of
cationic thin (25 µm) and thick (1.4 mm) coatings, the pro-
duction of thick glass fibre composites as well as the synthesis of
IPNs is possible. Owing to its excellent efficiency as a catalyst
only very low loadings of G1 are required. The development of
photoredox catalysts such as G1 provides a new means for obtain-
ing photoinitiating systems with unprecedented reactivity. Other
photoredox catalytic systems are being investigated and will be
presented and evaluated in future publications. The study of the
mechanical/physical properties of the composites obtained is
under way for the final application in the industrial fields. The
high performance of G1 as a cationic initiating system can also
be evaluated for a 3D printing application. Indeed, interesting
data have already been obtained for the latter field.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We thank the SATT Conectus Alsace for the funding of the
project LED_catalyst. The authors thank Dr Jérémie Fournier
from SATT Conectus Alsace for all the scientific discussions.
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