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Hydrogenation of acrylonitrile–butadiene copolymer

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Cite this: Catal. Sci. Technol., 2013,

latex using water-soluble rhodium catalysts
3, 2689
Yin Liu, Hanmiroo Kim, Qinmin Pan* and Garry L. Rempel*

Received 16th April 2013,
Accepted 2nd July 2013
DOI: 10.1039/c3cy00257h
www.rsc.org/catalysis
Hydrogenated acrylonitrile butadiene rubber (HNBR) is a high-performance elastomer which has found
important applications in the automobile and petroleum industries. Compared to current NBR solution
hydrogenation technology, direct hydrogenation of NBR in its aqueous form (i.e. NBR latex) is a
‘‘green’’ strategy as it is energetically favorable and environmentally friendly. Two water-soluble
rhodium based catalysts, RhCl(TPPMS)3 (TPPMS = monosulfonated triphenylphosphane) and
RhCl(TPPTS)3 (TPPTS = trisulfonated triphenylphosphane), were investigated for NBR latex
hydrogenation. The NBR in aqueous latex could be hydrogenated using the RhCl(TPPMS)3 catalyst,
attaining HNBR with as much as 95 mol% CQC bond removal. A limited fraction of CQC bond
reduction was observed when RhCl(TPPTS)3 was used as the catalyst. Using the RhCl(TPPMS)3 catalyst,
the hydrogenation reaction could be conducted at mild temperature with no addition of organic
co-solvent. The presence of Rh metal in the resultant HNBR confirmed the phase transfer of the
RhCl(TPPMS)3 catalyst and was considered as a crucial factor for achieving a successful reaction. The
observed influence of process conditions on the activity of hydrogenation has led to an extrapolation
of a mild reaction condition mechanism for the RhCl(TPPMS)3 system. Additionally, in-house NBR latices
with different gel content were synthesized and investigated in the hydrogenation experiment for
comparison. One of the major observations is that the high gel fraction in NBR could greatly limit the
hydrogenation reaction which could be a reasonable explanation for the low conversion of CQC bonds
reported previously.

1. Introduction carbon–carbon double bonds (CQC bonds) in NBR were

reduced while the unsaturated carbon–nitrogen triple bonds
Hydrogenation of unsaturated diene-based polymers constitutes (CRN bonds) remained unchanged (Fig. 1). The high manu-
an important process in polymer chemistry because of the desir- facturing cost of HNBR caused by the cumbersome hydrogena-
able properties of the materials obtained.1,2 The hydrogenation of tion procedures such as obtaining solid NBR from NBR latex,
acrylonitrile butadiene rubber (NBR) to produce hydrogenated-
NBR (HNBR) represents an excellent example since (1) HNBR has
improved chemical, physical and mechanical properties com-
pared to NBR. It imparts excellent resistance to oxidative and
ozonolytic ageing, improved resistance to oils and fluids at high
temperatures and reduced gas permeability; (2) the ethylene–
acrylonitrile co-polymer, which has a similar chemical structure
to HNBR, is difficult to synthesize by conventional polymerization
(i.e. low degree of polymerization).
Currently, most HNBR is manufactured via a solution hydro-
genation process where NBR was dissolved in a certain organic
solvent and hydrogenation was achieved by using H2 gas in the
presence of a precious metal based catalyst (e.g. Pd based supported
catalysts and Rh based organometallics).3 During the reaction, the

University of Waterloo, Waterloo, Ontario, Canada N2L 3G1.

E-mail: qpan.uw@gmail.com, grempel@uwaterloo.ca Fig. 1 Schematic of NBR hydrogenation.

This journal is c The Royal Society of Chemistry 2013 Catal. Sci. Technol., 2013, 3, 2689--2698 2689

Paper
dissolving solid NBR in an organic solvent and separating
solvent/catalyst from the HNBR product greatly limits its
applications.
NBR is synthesized via emulsion polymerization and can be
kept as NBR latex. Direct hydrogenation of NBR in latex form
without using an organic solvent would be more economical
and environmentally friendly. It has been recommended as a
potential ‘‘green’’ pathway to produce HNBR. Hence, direct
hydrogenation of NBR latex has attracted attention from both
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industry and academia where considerable efforts have been
made to realize this process. Research on NBR latex hydrogena-
tion has focused on either a hydrazine-diimide route (i.e.
utilization of hydrazine in the presence of hydrogen peroxide
to produce diimide in situ for CQC bonds reduction)4–7 or a
gaseous hydrogen route (i.e. use of hydrogen gas for reduction
with a hydrogenation catalyst).8–12 The first HNBR latex has
been commercialized by Zeon Chemical under the trademark
Chemisat in 2008 via the hydrazine-diimide route.13 Currently,
the core challenges in catalytic hydrogenation of NBR in latex
form lie in areas including (1) exploration of active catalysts to
achieve desired high conversion, (2) avoidance of the use of an
organic co-solvent, (3) control of cross-linking side reaction,
and (4) recovery of the catalyst.
Catalytic hydrogenations in aqueous media have been
reported since the 1960s.14,15 In the last two decades, increasing
interest in catalysis in aqueous media has been pursued
directly by employing water-soluble transition metal com-
plexes.16 Water-soluble catalysts could intensify the catalytic
reaction by averting the mass transfer limitation in water which
is commonly encountered when using conventional organo-
metallics. The use of water soluble rhodium catalysts such as
RhCl(TPPMS)3 [TPPMS: monosulfonated triphenylphosphine,
PPh2(C6H4-m-SO3Na)], Rh(TPPTS)3 [TPPTS: trisulfonated triphenyl-
phosphine, P(C6H4-m-SO3Na)3] and RhCl(PTA)3 [PTA: 1,3,5-
triaza-7-phosphaadamantane, C6H12N3P] has been the subject
of research for many years.17,18 Some of these catalysts have
provided significant achievements in the hydroformylation of
small olefins.19,20
With the success of the utilization of water soluble catalysts
for small olefin hydrogenation, these catalysts have also been
studied when large olefins (e.g. C6–C10) are used as reac-
tants.21,22 However, the catalyst showed less activity towards
large olefins in the biphasic system. The activity of the catalysts
becomes even worse when they are applied for poly-olefin
substrates. Specifically, the conversion (i.e. the percentage of
CQC bonds hydrogenated to C–C bonds) is insufficient to meet
industrial requirements. Singha et al. first studied the hydro-
genation of a commercial NBR latex using water soluble
RhCl(TPPMS)3 catalysts with the addition of the non-ionic
surfactant Triton-X305.23 They found that only 60% CQC
bonds in NBR could be hydrogenated with a TON (turnover
number, calculated based on the final conversion) between
4.0 and 9.3 h1. After that, Mudalige and Rempel investigated
the hydrogenation of polybutadiene (Mn = 900 g mol1), NBR
(Mn = 6400 g mol1) and styrene–butadiene rubber (Mn =
95 000 g mol1) in an aqueous–organic biphasic system using
2690 Catal. Sci. Technol., 2013, 3, 2689--2698
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Catalysis Science & Technology
water soluble rhodium based complexes modified with the
ligands PPh2(CH2)n–COONa (n = 5, 7).9 Similar low conversions
(50–60%) were observed for all three polymers and massive
leaching of the rhodium from the aqueous phase to the organic
phase was observed.
Recently, Papadogianakis and co-workers demonstrated a
successful catalytic hydrogenation of an unsaturated polymer
polybutadiene-1,4-block-poly(ethylene oxide) (PB-b-PEO) in
mixed micellar nano-reactors formed by dodecyltrimethyl-
ammonium chloride (DTAC) using Rh–TPPTS complexes in
aqueous media.24 An exceptionally high degree of hydrogena-
tion (100%) and activity (TON > 840 h1) was observed. In
addition, its catalytic activity was observed even at a rhodium
concentration of only 1 ppm in water.
In our lab, we observed that RhCl(PPh3)3 catalyst is active for
hydrogenation of unsaturated polymers in aqueous systems
(e.g. NBR, SBR latex) with the addition of extra triphenylphos-
phine (PPh3).11,25 This important finding evokes our interest to
re-investigate the polymer latex hydrogenation using its water
soluble analog catalysts. In this research work, we report the
hydrogenation of a typical unsaturated polymer, NBR, in its
latex form using two common water-soluble rhodium catalysts,
RhCl(TPPMS)3 and RhCl(TPPTS)3, in the absence of any added
organic solvent. Very different hydrogenation behaviors were
observed when using these two water soluble catalysts.
2. Experimental
2.1 Materials
The catalysts, RhCl(TPPMS)3 and RhCl(TPPTS)3, were prepared
by reacting RhCl3 with the corresponding ligand (TPPMS, TPPTS)
in ethanol.26,27 Reagent grade mono-chlorobenzene (MCB) was
obtained from Fisher Scientific (Canada). Reagent grade toluene,
ketones (e.g. acetone, 2-butanone) and alcohols (e.g. methanol
and ethanol) were obtained from Sigma-Aldrich (Canada). All of
the solvents were used as received.
Two types of NBR latices were used in this investigation. The
commercial NBR latex was provided by LANXESS Deutschland
GmbH. The in-house NBR latex was synthesized in the lab
following a standard emulsion polymerization procedure.28
2.2 Synthesis of NBR via emulsion polymerization
Reagent grade acrylonitrile (99%), potassium persulfate, tert-
dodecyl mercaptan (mixture of isomers, 98.5%), hydroxylamine
solution (50 wt% in H2O) and technical grade sodium oleate
(83 wt%) were used as received from Sigma-Aldrich (Canada).
Technical grade 1,3-butadiene (99%) was obtained from Air
Liquide (Canada).
NBR latex was synthesized via emulsion copolymerization.
The polymerization reaction was performed in a 300 mL stain-
less steel autoclave (Parr Instrument, USA). The reactor, chilled
in an ice–water bath, was charged with distilled water, acrylo-
nitrile (monomer), sodium oleate (surfactant), tert-dodecyl mer-
captan (chain transfer agent) and potassium persulfate (initiator).
After assembling the reactor, the mixture was degassed and purged
with nitrogen gas for 30 minutes. Then liquefied 1,3-budadiene
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Catalysis Science & Technology
(monomer) was quickly added and copolymerized with acrylo-
nitrile at 30 1C for several hours. After reaching a desired
conversion, hydroxylamine was added to terminate the reac-
tion. The residual portions of acrylonitrile and 1,3-butadiene
were eliminated by steam distillation at 70 1C under reduced
pressure.
2.3 NBR latex hydrogenation
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The hydrogenation reaction was carried out in a 300 mL high
pressure reactor (Parr Instrument, USA). 100 mL NBR latex
(or with a certain amount of additives such as organic co-solvents,
co-catalyst ligands or surfactants) was added to the reactor. The
catalyst RhCl(TPPMS)3 or RhCl(TPPTS)3 was weighed in a glass
bucket and placed in a catalyst addition device which was
installed in the head of the reactor. After completely degassing
the reactor with N2 gas, the catalyst was charged to the mixture
and the reactor was heated to the desired temperature. The
hydrogen pressure and reaction temperature were kept constant
throughout the reaction period. The hydrogenated NBR latex was
Fig. 2 Typical 1H NMR spectra of (a) NBR and (b) hydrogenated NBR.
This journal is c The Royal Society of Chemistry 2013
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sampled at intervals to measure its hydrogenation degree (hydro-
genation degree is defined in Section 3.1).
2.4 Characterization
The hydrogenation degree in the resultant product was
obtained via 1H NMR. Room temperature 1H NMR spectra of
NBR/HNBR in CDCl3 were taken on a Bruker 300 MHz Spectro-
meter (Bruker BioSpin Corp., Massachusetts, USA) with TMS as
internal standard.
Fig. 2 shows the chemical shifts of the protons in (a) NBR
and (b) HNBR by 1H NMR characterization. For NBR, the peaks
from 4.9 to 5.6 ppm represent the olefinic protons. Among
them, the large peaks between 5.3 and 5.6 ppm are related to
trans hydrogen atoms of butadiene resulting from 1,4-addition
and the small peaks between 4.9 and 5.1 ppm belong to the
hydrogen atoms of pendant vinyl groups which come from
1,2-addition. Meanwhile, all of the aliphatic protons in the CH3,
CH2 and CH microstructures lie between 0.8 and 2.8 ppm. In
HNBR (ca. 95 mol%), it could be clearly seen that most of the
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peaks in the olefinic proton region had disappeared due to the
reduction of unsaturated CQC bonds by H2.
The concentration of rhodium present in the HNBR was
measured using ICP-AES, assuming that it comes from the
catalyst. Before being analyzed using ICP-ACE, the HNBR needs
to be digested:29 400–500 mg of HNBR polymer solid was
weighed out and mixed with hydrochloric acid (1 mL, 37.5 vol%),
nitric acid (5 mL, 62 vol%) and aqueous hydrogen peroxide
(1 mL, 30 wt%). The mixture was digested in a High Pressure
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same as the conversion of CQC bonds. Based on the molecular
weight of the polymer we used, the average number of CQC
bonds in a single polymer chain should be more than a
thousand.
Second, strictly speaking, HNBR should be referred to
completely hydrogenated NBR (no CQC bonds left). In this
research work, the term ‘‘HNBR’’ is used for hydrogenated NBR
with at least 95 mol% hydrogenation degree. Usually, a small
portion of residual CQC bonds should be left for sulfur curing

Asher (Anton Parr, Austria), under a high ‘‘organic program’’ systems to develop optimal properties that render the HNBR
(program condition, 300 1C and 130 bar for 3 hours). The resistant to hydrocarbons, oils and plasticizers. Still, achieving
rhodium metal concentration in the resultant solution was a high hydrogenation degree is crucial in the hydrogenation of
measured using inductively coupled plasma atomic emission polymeric materials.
spectroscopy (ICP-AES, TELEDYNE, LEEMAN Labs, Prodigy, Third, the hydrogenation degree data obtained from NBR
high dispersion ICP, USA). Commercial rhodium standard hydrogenation were in the absence of any mass transfer effect.
solution (1000 mg L1 Rh in HCl, Sigma-Aldrich) was used as The gas–liquid and liquid–solid (polymer particle) mass trans-
standard reference for ICP calibration.30 fer effects were eliminated by carrying out the reaction by
The micro-structure of NBR or HNBR was measured by varying the magnetic stirrer speed from 100 rpm to 1000 rpm
Fourier-transform infrared (FT-IR) analysis using a Bio-Rad and observing no change in the NBR conversion in the reaction
FTS 3000MX spectrometer. 16 times of uniform scanning with (temperature > 80 1C) above an agitation speed of 600 rpm. To
a resolution of 4 cm1 was conducted in all cases. To prepare be on the safe side, all of the runs were carried out at 1000 rpm.
samples for FT-IR, the NBR or HNBR has to be isolated from The diffusion of the catalyst inside the NBR particles could be
the latex and dissolved in 5% (wt/vol.) methyl ethyl ketone. The negligible since the size of NBR particles is very small (B70 nm,
polymer solution was cast onto a single NaCl crystal disc and measured by dynamic light scattering31). In our experiment, the
dried to form a thin polymer film (o1 mm). catalyst was still pre-mixed with the NBR latex at the reaction
The weight average molecular weight (Mw), the number temperature before adding H2 gas to the system. The ICP-AES
average molecular weight (Mn) and the polydispersity index results showed that the rhodium concentration in NBR particles
(PDI), which is equal to the ratio of the weight average to the did not undergo any obvious change during the hydrogenation.
number average molecular weight, were measured using a gel Initial experiments using commercial NBR latex to afford
permeation chromatograph (GPC, Wyatt Technology Corpora- HNBR latex in the presence of RhCl(TPPMS)3 or RhCl(TPPTS)3
tion, California, USA) equipped with an RI detector (Waters catalysts are presented in Tables 1 and 2 respectively. The
150-CV refractive index detector) and a multi-angle laser light catalysts behaved differently with respect to the hydrogenation
scattering instrument (DAWNs DSP-F Laser Photometer). The
dried NBR solid from the NBR latex was dissolved in THF and
Table 1 NBR latex hydrogenation using the RhCl(TPPMS)3 catalyst
filtered through a 45 mm syringe filter with a 250 nm GHP
(GH Polypro) membrane (Pall Corporation, New York, USA) and RhCl(TPPMS)3 NBR solid [CQCNBR]/[Cat.] Time HD
then 100 mL of the solution was injected into the GPC system Entry (mmol L1) content (g L1) (mol/mol) (hours) (mol%)
using THF as an eluent at a flow rate of 1.0 mL min1 at 30 1C. A 1 0.26 25 1100 12 95
polystyrene standard (Mn = 96 722 g mol1 and Mw = 98 251 g mol1) 2 0.52 50 1100 5 80
3 0.52 50 1100 8.5 95
was used for calibration. 4 1.04 50 550 6 95
5 1.04 100 1100 20 95
3. Results and discussion Commercial NBR latex, total volume = 100 mL, T = 100 1C, PH2 = 1000 psi
(69 bar).
3.1 NBR latex hydrogenation using different water-soluble
rhodium catalysts
First, as we mentioned in the Introduction section, NBR hydro- Table 2 NBR latex hydrogenation using the RhCl(TPPTS)3 catalyst
genation refers to the hydrogenation of CQC bonds in NBR. To
RhCl(TPPTS)3 NBR solid [CQCNBR]/[Cat.] Time HD
accurately describe this reaction process, the hydrogenation Entry (mmol L1) content (g L1) (mol/mol) (hours) (mol%)
degree (HD) is used in this research work and defined as
1 0.26 25 1100 20 20
follows: 2 0.52 50 1100 5 15
  3 0.52 50 1100 10 19
½C ¼ Ct 4 0.52 50 1100 13 21
HD ¼ 1   100% (1)
½C ¼ C0 5 0.52 50 1100 20 22
6 1.04 100 1100 10 15
where [CQC]t is the concentration of CQC bonds at reaction 7 1.04 50 550 14 19
time t and [CQC]0 is the initial double bond concentration. We Commercial NBR latex, total volume = 100 mL, T = 100 1C, PH2 =
can see that the hydrogenation degree is defined as being the 1000 psig (69 bar).

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degree. When using the RhCl(TPPMS)3 catalyst, the hydrogena-
tion degree continuously went up and a HNBR with a 95 mol%
HD could be achieved at the end of the reaction. The 1H NMR
spectrum (Section 2.4) showed that most of the CQC bonds
were saturated during the reaction.
In addition, the infrared analysis of the hydrogenated pro-
duct revealed that no detectable reduction of nitrile unsatura-
tion (no peaks appearance between 3000 cm1 and 3200 cm1)
when the RhCl(TPPMS)3 catalyst is used, suggesting that the oil
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resistant property of the material is not compromised by the
hydrogenation process. The macro gel in the resultant HNBR
could be simply measured by re-dissolving the dried HNBR
into monochlorobenzene. The HNBR product was completely
soluble and no visible gel was observed. All the above results
showed that the RhCl(TPPMS)3 catalyst is a very active catalyst
for NBR latex hydrogenation.
Next, we evaluated the NBR latex hydrogenation using the
RhCl(TPPTS)3 catalyst. It was observed that the hydrogenation
conversion increased slowly during the first several hours and
the extent of hydrogenation leveled off, showing only a marginal
increase thereafter. No desired high hydrogenation degree could be
obtained in the presence of the RhCl(TPPTS)3 catalyst. In addition,
the RhCl(TPPTS)3 catalyst remained in the aqueous phase through-
out the reaction as observed by a reddish aqueous phase.
Although both catalysts are water soluble, the catalytic
behaviors with respect to NBR latex hydrogenation are quite
different. As we understand, the cause of this discrepancy could
be attributed to the intrinsic properties of the catalyst ligand.
Due to the inherent surfactant property of the TPPMS ligand,
the RhCl(TPPMS)3 complex could be accumulated in a high
concentration on the interface.32 Compared to TPPMS, TPPTS
has a larger number of sulfonate groups which makes it much
more hydrophilic. The solubility of TPPTS in water is 180 g L1
which is more than ten times that of TPPMS (12 g L1 in water).33
As a result, the RhCl(TPPTS)3 complex prefers to remain in the
aqueous phase so that only the CQC bonds on the NBR surface
could be contacted and hydrogenated. Since HNBR could not
be achieved when using RhCl(TPPTS)3, the following discus-
sion will mainly focus on hydrogenation results obtained using
the RhCl(TPPMS)3 catalyst. The results obtained from RhCl-
(TPPTS)3 are merely used for comparison.
3.2 The ‘‘location’’ of the catalyst in NBR latex hydrogenation
The distribution of the catalyst is quantitatively measured in
order to explain the different behaviors of these two catalysts.
Compared to analyzing the catalyst concentration in the aqueous
phase, the measurement of the catalyst in the polymer phase
gives more accurate information for the location of the catalyst.
From Fig. 3, it can be seen that a small portion of the
rhodium was detected in the polymer phase after the reaction
when using the RhCl(TPPTS)3 catalyst. The tri-sulfonated PPh3
ligand (TPPTS) based rhodium catalyst is completely soluble in
the aqueous phase. Since the catalyst mainly remains in the
aqueous phase, only the CQC bonds on the interface could
be hydrogenated. The relatively small amount of the Rh/
TPPTS catalyst in the polymer phase during the hydrogenation
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Fig. 3 The change of rhodium concentration in NBR polymer particles through
hydrogenation. Commercial NBR latex = 50 g L1, Rh catalysts = 0.52 mmol L1,
total volume = 100 mL, T = 100 1C, PH2 = 1000 psig, square: conversion, circle:
rhodium concentration.
of poly-butadiene has confirmed that the TPPTS ligand based
rhodium catalyst is prone to stay in the aqueous phase.34
However, the distribution of the RhCl(TPPMS)3 in the hydro-
genation system of the high molecular weight polymer in the
aqueous latex system is quite different from that of RhCl-
(TPPTS)3. More than half of the catalyst diffused into the
polymer particles under our reaction conditions. The catalyst
in the polymer phase was extracted from the aqueous phase
during the reaction. The result here was remarkably different
from the hydrogenation of small organic molecules or the
biphasic hydrogenation of polymers with RhCl(TPPMS)3 where
the catalyst always remained in the aqueous phase after the
reaction.9,35 Although both RhCl(TPPMS)3 and RhCl(TPPTS)3
water soluble metal complexes have been numerously reported
as effective catalysts in aqueous biphasic catalysis for small
olefins, it is evident here that RhCl(TPPMS)3 is more active for
hydrogenation of heavy molecular weight polymer latex such as
NBR latex. To our knowledge, this interesting phenomenon has
not been reported or explained previously. We believe that the
proper relative partition of the RhCl(TPPMS)3 catalyst between
water and the polymer substrate caused successful phase
transfer of the catalyst during the hydrogenation reaction. How-
ever, the attribution of the surfactant to the RhCl(TPPMS)3
catalyst distribution should be minimal based on the hydro-
genation results using the RhCl(TPPTS)3 catalyst.
In addition, we believe that the fraction of catalyst in the
polymer phase should be responsible for the hydrogenation
reaction, particularly for achieving a high hydrogenation
degree. Therefore, in this water–polymer two phase reaction,
using the feed catalyst concentration to calculate TON without
measuring its location would be less meaningful. It is also
worth noting that catalyst transfer is not encouraged in the
biphasic reaction. However, as demonstrated above, the ‘‘phase
transfer’’ of the catalyst (i.e. from the aqueous phase to the
polymer phase in this case) is crucial for achieving successful
hydrogenation of large molecular hydrocarbons.
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3.3 The influence of reaction temperature, pressure,

co-catalyst ligands and co-solvent on NBR latex hydrogenation
The effects of the reaction temperature, pressure and the
co-catalyst ligand on the extent of hydrogenation conversion
were investigated using RhCl(TPPMS)3 and the results are
summarized in Table 3. The hydrogenation reactions were
studied over the range of 85 1C to 130 1C with 0.52 mmol L1
of catalyst loading.
The conversion of NBR is obtained over a reaction period of
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9 hours at different temperatures. The results clearly showed

that the hydrogenation reaction is sensitive to temperature. The
highest conversion was observed at 100 1C. It was also observed
that the conversion decreased with a further increase in tem-
perature above 100 1C. This is probably due to the occurrence of
catalyst deactivation at high temperature.
This result is further confirmed by considering the NBR Fig. 4 NBR conversions versus reaction time at different temperatures.
Commercial NBR latex = 50 g L1, total volume = 100 mL, RhCl(TPPMS)3 =
hydrogenation profiles shown in Fig. 4, where the highest
0.52 mmol L1, PH2 = 1000 psig.
initial reaction rate was observed at the highest temperature
(130 1C). However, under this reaction temperature a rapid
decay in catalyst activity was observed after 2 hours. The long
catalyst lifetime in the Ruhrchemie/Rhone–Poulenc hydro- the results are presented in Table 3 as well. Compared to the NBR
formylation process below the ceiling temperature of 130 1C hydrogenation in organic solvent, a higher pressure is required in
suggested that the observed rapid deactivation of RhCl- the aqueous latex hydrogenation due to the limited solubility of
(TPPMS)3 in the course of hydrogenation is less likely the result H2 gas in water. As the hydrogen pressure was varied over the
of catalyst thermal decomposition.36 A possibility of the catalyst range of 400 to 1000 psig, the hydrogenation degree increased
deactivation caused by unknown impurities has been taken with increasing hydrogen pressure. However, no significant
into consideration and re-investigated using in-house NBR effect on the catalytic performance of RhCl(TPPMS)3 at high
latex (Section 3.6). hydrogen pressures (>1000 psi) was observed.
The NBR solution hydrogenation system using rhodium It has been found that the co-catalyst ligand PPh3 has a
catalysts such as RhCl(PPh3)3 and RhH(PPh3)4 exhibited a first- significant effect on NBR hydrogenation when using the
to zero-order dependence on hydrogen concentration ([H2]) as the RhCl(PPh3)3 catalyst. Mohammadi et al. pointed out that the
system pressure increased.37 The influence of hydrogen pressure addition of extra free PPh3 maintains the hydrogenation activity
on the present latex hydrogenation reaction was investigated and of RhCl(PPh3)3 by preventing the formation of the non-catalytic
dimeric species [RhCl(PPh3)2]2.38 Wei et al. also found that the
addition of extra PPh3 (e.g. PPh3: RhCl(PPh3)3 = 10 : 1 weight
Table 3 The hydrogenation degree of NBR under different reaction conditions ratio) greatly improved the activity of RhCl(PPh3)3 in NBR latex
hydrogenation as PPh3 promoted the diffusion of RhCl(PPh3)3
[CQCNBR]/
in aqueous latex.11 Therefore, the effect of adding extra TPPMS
Catalyst [Cat.] Temp. Pressure [TPPMS] HD
Entry (mmol L1) (mol/mol) (1C) (psi) (mmol L1) (mol%) to the reaction system was also evaluated in this study. It was
found that the highest catalytic activity was observed without
1 0.52 1100 85 1000 0 74
2 0.52 1100 100 1000 0 95 the addition of any co-catalyst ligand and the activity decreased
3 0.52 1100 115 1000 0 87 after the co-catalyst ligand TPPMS was added, showing that the
4 0.52 1100 130 1000 0 60 NBR latex hydrogenation reaction is negatively influenced by
5 0.52 1100 100 400 0 50
6 0.52 1100 100 600 0 78 increasing the amount of TPPMS. From the sharp decrease of
7 0.52 1100 100 800 0 92 the catalyst activity as a function of increasing TPPMS concen-
8 0.52 1100 100 1200 0 96 tration, the NBR latex hydrogenation may be explained on the
9 0.52 1100 100 1000 1.65 75
10 0.52 1100 100 1000 5.20 62 basis of an equilibrium mechanism.39 The competition for a
11 0.52 1100 100 1000 16.5 49 coordination site on the rhodium (i.e. bi-phosphine rhodium
12 0.52 220 100 1000 0 95
complex) between the added free TPPMS ligand and the CQC
13 0.52 550 100 1000 0 95
14 0.52 1650 100 1000 0 87 bond units of NBR leads to a retardation of the hydrogenation
15 0.52 2200 100 1000 0 73 reaction.40
16a 0.52 1100 100 1000 0 33 Additionally, the influence of nitrile was investigated as the
17b 5.2 1100 100 1000 0 95
polymer loading is varied while holding all other variables
Commercial NBR latex, total volume = 100 mL, reaction time = 9 hours. constant (Table 3, entries 13–15). The dramatic slow down in
a
With the addition of acrylonitrile to the NBR latex before hydrogenation.
The molar ratio of RhCl(TPPMS)3 to acrylonitrile is 1 : 10. b 95% Conver- the hydrogenation reaction with the addition of acrylonitrile to
sion is achieved within 3 hours. the NBR latex (Table 3, entry 16) and the measured low catalyst

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Catalysis Science & Technology
retention in the polymer phase (35 mol% with addition of
acrylonitrile) show that the coordination of nitrile to a catalytic
intermediate existed.
The distribution of catalysts caused by the interaction
between the catalyst and the concentrated nitrile group in the
NBR polymer chain was also considered. Comparative experi-
ments of hydrogenation of poly-isoprene latex using these two
catalysts were conducted in our lab and it was found that only
RhCl(TPPMS)3 is active for the hydrogenation of poly-isoprene
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latex.41
3.4 Catalytic pathways of the RhCl(TPPMS)3 systems
The catalytic chemistry of Rh(I) phosphine complexes has been
extensively studied, resulting in a comprehensive understanding
of reaction intermediates that bring about the observed reaction
kinetic behavior.42,43 While an extrapolation of this knowledge to
severe reaction conditions may not be straightforward, it is
proposed that a strong correlation exists between the chemistry
underlying this work and that documented under mild reaction
conditions.
Fig. 5 illustrates a catalytic mechanism that is consistent
both with the experimental results shown in the last section
and our understanding of the coordination chemistry of
RhCl(TPPMS)3 in aqueous solution. First, the RhClH2(TPPMS)3
formed by oxidative addition of H2 on RhCl(TPPMS)3 forms the
five-coordinate dihydride according to eqn (2). Then the reaction
pathway is analogous to the reaction of [RhCl(PPh3)3] in organic
solvents which has been well established.
RhCl(TPPMS)3 + H2 " RhClH2(TPPMS)3
For NBR hydrogenation, the comparative ease of hydrogen
activation compared to addition of a sterically hindered olefin
favors the ‘‘hydride pathway’’ shown in the catalytic mecha-
nism. Mohammadi and Rempel showed in their research that
at 65 1C under 1 bar of H2 the reaction is quantitative towards
Fig. 5 Proposed reaction mechanism for the RhCl(TPPMS)3–NBR system.
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the formation of a dihydride.38 However, given that coordina-
tively unsaturated complexes are often presumed to associate
with solvent, Joo et al. suggested that the formation of mono-
hydridorhodium phosphine derivatives [e.g. RhH(TPPMS)3] to
be a strong possibility [eqn (3)–(5)] which has been extrapolated
from the outcome of the hydrogenation of maleic acid and its
trans-isomer, fumaric acid, in the aqueous phase.44 It has been
known that the addition of an acid or a salt to the polymer latex
could interrupt its balance and cause polymer precipitation.
However, no NBR coagulation or precipitation from the latex
was observed using the RhCl(TPPMS)3 catalyst especially under
a high catalyst loading (Table 3, entry 17) indicating that little
HCl or H+/Cl ions were formed during the hydrogenation
reaction.
RhCl(TPPMS)3 + H2 " RhH(TPPMS)3 + H + Cl+ (3)
RhCl(TPPMS)3 + H2O " Rh(OH)(TPPMS)3 + H + Cl+ (4)
Rh(OH)(TPPMS)3 + H2 " RhH(TPPMS)3 + H2O (5)
In addition, the coordination of unsaturated complexes with
solvent was also considered here. Given the observation of the
transport of the catalyst from the aqueous phase to the polymer
phase during the NBR latex hydrogenation, a consideration that
the nitrile group in the polymer chain may inhibit the hydro-
genation cycle is reasonable. As the nitrile group likely coordi-
nates by s donation of its lone pair of electrons, it may
therefore compete effectively with olefin for coordination to
unsaturated complexes.
(2)
3.5 The effect of adding organic co-solvent
The effect of addition of five different organic solvents (mono-
chlorobenzene, toluene, acetone, methyl ethyl ketone and
ethanol) was examined and is presented in relation to their
effect on the final hydrogenation degree and reaction time of
the respective hydrogenation reactions (Fig. 6). Based on their
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Fig. 6 Influence of organic solvent on the hydrogenation of NBR latex.
Commercial NBR latex with a solid content of 50 g L1, co-solvent/NBR latex =
1/10 (vol./vol.), total volume = 100 mL, RhCl(TPPMS)3 = 0.52 mmol L1, T =
100 1C, PH2 = 1000 psi.
Table 4 The compatibility of different organic co-solvents with NBR and with
water
Solubility Compatibility
Organic solvent of NBRa with water
Mono-chlorobenzene ++  three major differences between our experiments and Singha
Toluene ++ 
Methyl ethyl ketone + +
Acetone + +
Ethanol  ++
a
++: good; +: fair; : poor.
compatibility with water and polymers, these five organic
solvents could be divided into three categories (Table 4).
Mono-chlorobenzene and toluene are good solvents for poly-
mers such as NBR but they are immiscible with water. Acetone
and methyl ethyl ketone have certain solubility for NBR and
compatibility with water. Ethanol is miscible with water but it
cannot dissolve NBR.
First, it is very important to realize that the catalytic system
exhibited sufficient catalytic activity (95 mol% conversion in
9 hours) without the presence of any additional solvent. Lower
activity of the catalyst was found when mono-chlorobenzene or
toluene was used as a co-solvent. With the addition of the
organic solvent, the reaction system changes from a continuous
single phase to two phases. The water soluble catalyst stays in
the aqueous phase while the organic solvent swells the NBR
latex particles to form the organic phase. As a result, the
co-solvent prevents the RhCl(TPPMS)3 from contacting the
CQC bonds in NBR.
Compared to mono-chlorobenzene or toluene, higher con-
versions were observed with the addition of acetone and methyl
ethyl ketone. This is because the presence of these organic
co-solvents causes the NBR micelles to swell and facilitates the
approach of the catalyst to the bulk hydrophobic interior region
of the swollen micelles.
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Catalysis Science & Technology
The fastest hydrogenation reaction was observed with the
addition of ethanol (95 mol% conversion in 3 hours). A similar
phenomenon was observed when alcohol was added for NBR
latex hydrogenation using in situ synthesized RhCl(PPh3)3,31 as
the addition of alcohol increased the efficiency of in situ catalyst
synthesis. Here, the increase in the reaction rate could probably
be explained in that ethanol can counter balance the charges
and reduce the electrical repulsion in the stern-layer of the
micelles which facilitates the diffusion of the catalyst.21 Liu
et al. measured the zeta potential of polymer latices containing
various contents of ethanol. They found that the zeta potential
decreased with increased ethanol content showing a reduction
in the electrostatic repulsive energy of the particle surface due
to the presence of ethanol in the dispersing medium.45 This
finding could be useful for the aqueous biphasic reaction
especially for improving the catalytic performance within the
micellar nano-reactor.
3.6 Hydrogenation of in-house NBR latex using RhCl(TPPMS)3
Singha et al. first studied NBR latex hydrogenation using
the RhCl(TPPMS)3 catalyst. They reported that a maximum of
60 mol% conversion could be achieved.23 However, in our
initial investigation, the hydrogenation conversion did not level
off at around 60 mol% but reached more than 95 mol% over a
reasonable reaction period. After careful comparison, we found
et al.’s results: (1) the type of NBR latex, (2) gel content and (3)
the addition of extra surfactant. As both Singha et al. and
ourselves used commercial NBR latex which normally contains
many additives (e.g. antioxidant, stabilizer), there is a large
possibility that the different hydrogenation behavior could
come from the impact of certain additives in the commercial
NBR latex. We have encountered this issue before when we
used different batches of commercial NBR latex. It has been
observed that some of the impurities within the commercial
polymer latex could significantly affect the hydrogenation
activity of the catalyst or even kill the catalyst.46 Hence, an
NBR latex without the addition of additives was synthesized in
our lab and used for hydrogenation thereafter. The in-house
NBR latex was synthesized through emulsion copolymerization
of acrylonitrile and butadiene. A detailed synthesis procedure is
summarized in the Experimental Section. The micro-structure
of our in-house NBR was measured by FT-IR and compared
with commercial NBR. It was found that the micro-structures
of both NBRs were fairly close. In Fig. 7 the distinct peak
exhibited at 2236 cm1 shows the existence of the nitrile
group (CRN) in the co-polymer. Due to the existence of two
types of CQC bonds, the polymerization of 1,3-butadiene
usually gives rise to three distinct structures, i.e. trans, cis and
1,2(vinyl). The intense peak shown at 969 cm1 belongs to the
vibration of the 1,4-trans double bonds, while the small absor-
bance at 910 cm1 corresponds to the 1,2-vinyl terminal bonds,
which is much weaker than that of 1,4-trans double bonds.
However, the 1,4-cis double bonds which usually show at an
absorbance around 750 cm1 could not be measured quantita-
tively by FT-IR.
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Fig. 7 Typical FT-IR spectra of NBR from in-house NBR latex.
Fig. 8 Commercial NBR latex and in-house NBR latex hydrogenation by RhCl-
(TPPMS)3. Commercial and in house NBR latex with a solid content of 50 g L1,
total volume = 100 mL, RhCl(TPPMS)3 = 0.52 mmol L1, PH2 = 1000 psi.
The results of the RhCl(TPPMS)3 catalyst for the hydrogena-
tion reaction of the in-house NBR latex are presented in Fig. 8.
The hydrogenation behavior (hydrogenation curve and final
conversion) remained practically unchanged for both commer-
cial and in-house synthesized NBR latex at lower temperature,
demonstrating that the RhCl(TPPMS)3 catalyst is tolerant to
additives in the commercial NBR latex under this reaction
condition. However, the hydrogenation behaviors are signifi-
cantly different when higher temperature was adopted. It was
found that high conversion still could only be achieved in the
in-house NBR latex.
Second, the effect of gel content of NBR was also investigated.
The commercial NBR latex is free of gel while the NBR latex used
by Singha et al. has a gel content of 24 wt%. Therefore, we
synthesized in-house NBR latices with different gel content via
using different amounts of chain transfer reagent. The in-house
gel free NBR latex has a molecular weight of 75 610 (Mn) with a PDI
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around 3, while the molecular weight of highly gelled NBR could
not be directly measured by GPC. The conversions were quite
different for these NBR latices (Fig. 8). Only 45 mol% conversion
could be achieved when using NBR latex containing gel. The
mobility of the polymer chains for these latices is expected to be
quite different. For the gel free polymer, the polymer chains are
mobile under the reaction temperature (TR > Tg). However, the
amount of gel formation caused by cross-linking greatly increases
the molecular weight of the resulting hydrogenated polymer and
greatly slows down this movement. It seems that a high gel
fraction had a profound influence on the degree of hydrogenation.
The structure of gelled NBR limits the contact between the catalyst
and the CQC bonds, resulting in low conversion.
4. Conclusions
Two types of water soluble rhodium based catalysts, namely,
RhCl(TPPMS)3 and RhCl(TPPTS)3, were studied for NBR latex
hydrogenation. It was found that both catalysts have activity
towards the hydrogenation of NBR latex. The RhCl(TPPMS)3
catalyst was more active than the RhCl(TPPTS)3 catalyst according
to the maximum final conversion in the reaction. The RhCl-
(TPPMS)3 catalyst results in a more than 95 mol% hydrogenation
of the CQC bonds in the NBR latex in the absence of any added
organic solvent. The inherent surfactant propensity of the TPPMS
ligand enables the RhCl(TPPMS)3 complex to diffuse from the
aqueous phase into the NBR phase micelles. The catalyst concen-
tration in the NBR particles during the hydrogenation also con-
firmed that a high degree of hydrogenation can only be achieved
when the catalyst is transported into the solid particles within the
NBR latex. The observed influence of process conditions on the
activity of hydrogenation has led to an extrapolation of a mild
reaction condition mechanism for the RhCl(TPPMS)3 system. In
addition, in-house NBR latex was synthesized and compared with
commercial NBR latex. High conversion still could be achieved
using the RhCl(TPPMS)3 catalyst, showing that the RhCl(TPPMS)3
catalyst is probably generically active for NBR latex hydrogenation.
It was also found that the gel fraction in NBR greatly affected the
hydrogenation which could be the reason for the low conversion
observed in the previous literature results.
Acknowledgements
This research work was financially supported by Natural Sciences
and Engineering Research Council of Canada (NSERC), the Canada
Foundation for Innovation (CFI) and LANXESS Deutschland
GmbH. Special thanks are also given to University of Waterloo
for its support of author’s research.
References
1 M. P. McGrath, E. D. Sall and S. J. Tremont, Chem. Rev.,
1995, 95, 381–398.
2 G. L. Rempel, Q. Pan and J. Wu, in Handbook of Homogeneous
Hydrogenation, ed. J. E. C. G. de V. Johannes, Wiley-VCH,
Germany, 2006, p. 547.
Catal. Sci. Technol., 2013, 3, 2689--2698 2697

Paper
3 N. K. Singha, S. Bhattacharjee and S. Sivaram, Rubber Chem.
Technol., 1997, 70, 309–367.
4 X. W. Lin, Q. M. Pan and G. L. Rempel, Appl. Catal., A, 2004,
276, 123–128.
5 X. W. Lin, Q. M. Pan and G. L. Rempel, Appl. Catal., A, 2004,
263, 27–32.
6 G. A. S. Schulz, E. Comin and R. F. de Souza, J. Appl. Polym.
Sci., 2010, 115, 1390–1394.
7 G. A. S. Schulz, E. Comin and R. F. de Souza, J. Appl. Polym.
Published on 30 July 2013. Downloaded by University of Saskatchewan on 12/10/2014 14:07:32.
Sci., 2012, 123, 3605–3609.
8 X.-Y. Guo and G. L. Rempel, J. Appl. Polym. Sci., 1997, 65,
667–675.
9 D. C. Mudalige and G. L. Rempel, J. Mol. Catal. A: Chem.,
1997, 123, 15–20.
10 D. C. Mudalige and G. L. Rempel, J. Mol. Catal. A: Chem.,
1997, 116, 309–316.
11 Z. Wei, J. Wu, Q. Pan and G. L. Rempel, Macromol. Rapid
Commun., 2005, 26, 1768–1772.
12 T. Weiss and K. Creutz, US Pat., 20080234437, 2008.
13 New HNBR latex for improved heat and oil resistance,
Sealing Technology, May 2008, p. 2, Retrieved from http://
www.elsevier.com.
14 M. S. Spencer and D. A. Dowden, US Pat., 3009969, 1961.
15 J. Kwiatek, I. L. Mador and J. K. Seyler, J. Am. Chem. Soc.,
1962, 84, 304–305.
16 F. Joó, Acc. Chem. Res., 2002, 35, 738–745.
17 F. Joó, G. Laurenczy, P. Karády, J. Elek, L. Nádasdi and
R. Roulet, Appl. Organomet. Chem., 2000, 14, 857–859.
18 N. Pinault and D. W. Bruce, Coord. Chem. Rev., 2003, 241,
1–25.
19 E. G. Kuntz, Chem. Technol., 1987, 17, 570–575.
20 C. W. Kohlpaintner, R. W. Fischer and B. Cornils, Appl.
Catal., A, 2001, 221, 219–225.
21 M. Li, Y. Li, H. Chen, Y.-e. He and X. Li, J. Mol. Catal. A:
Chem., 2003, 194, 13–17.
22 D. U. Parmar, S. D. Bhatt, H. C. Bajaj and R. V. Jasra, J. Mol.
Catal. A: Chem., 2003, 202, 9–15.
23 N. K. Singha, S. Sivaram and S. S. Talwar, Rubber Chem.
Technol., 1995, 68, 281–286.
24 V. Kotzabasakis, E. Georgopoulou, M. Pitsikalis,
N. Hadjichristidis and G. Papadogianakis, J. Mol. Catal. A:
Chem., 2005, 231, 93–101.
25 G. L. Rempel, Q. Pan and J. Wu, US Pat., 7385010, 2008.
26 F. Joó, J. Kovács, Á. Kathó, A. C. Bényei, T. Decuir,
D. J. Darensbourg, A. Miedaner and D. L. Dubois, in
2698 Catal. Sci. Technol., 2013, 3, 2689--2698
View Article Online
Catalysis Science & Technology
Inorganic Syntheses, ed. M. Y. Darensbourg, John Wiley &
Sons, Inc., Hoboken, NJ, USA, 1998, pp. 1–8.
27 W. A. Herrmann, C. W. Kohlpaintner, B. E. Hanson and
X. Kang, in Inorganic Syntheses, ed. M. Y. Darensbourg, John
Wiley & Sons, Inc., Hoboken, NJ, USA, 1998, pp. 8–25.
28 W. Hofmann, Rubber Chem. Technol., 1964, 1–252.
29 D. P. Moraes, M. F. Mesko, P. A. Mello, J. N. G. Paniz,
V. L. Dressler, G. Knapp and É. M. M. Flores, Spectrochim.
Acta, Part B, 2007, 62, 1065–1071.
30 C. B. Ojeda and F. S. Rojas, Talanta, 2007, 71, 1–12.
31 Y. Liu, Z. Wei, Q. Pan and G. L. Rempel, Appl. Catal., A, 2013,
457, 62–68.
32 N. Sieffert and G. Wipff, J. Phys. Chem. C, 2008, 112,
6450–6461.
33 P. B. Webb and D. J. Cole-Hamilton, in Phosphorus(III)
Ligands in Homogeneous Catalysis: Design and Synthesis, ed.
P. C. J. Kamer and W. N. M. van Leeuwen, John Wiley &
Sons, Chichester, UK, 2012, p. 522.
34 V. Kotzabasakis, N. Hadjichristidis and G. Papadogianakis,
J. Mol. Catal. A: Chem., 2009, 304, 95–100.
35 Y. Dror and J. Manassen, J. Mol. Catal., 1977, 2, 219–222.
36 J. Herwig and R. Fischer, in Rhodium Catalyzed Hydroformyla-
tion, ed. P. W. N. M. V. Leeuwen and C. Claver, Rhodium
Catalyzed Hydroformylation, 2002, p. 196.
37 J. S. Parent, N. T. McManus and G. L. Rempel, Ind. Eng.
Chem. Res., 1996, 35, 4417–4423.
38 N. A. Mohammadi and G. L. Rempel, Macromolecules, 1987,
20, 2362–2368.
39 F. Joo, L. Somsak and M. T. Beck, J. Mol. Catal., 1984, 24,
71–75.
40 A. Bényei, J. N. W. Stafford, Á. Kathó, D. J. Darensbourg and
F. Joó, J. Mol. Catal., 1993, 84, 157–163.
41 P. Piya-areetham, P. Prasassarakich and G. L. Rempel,
J. Mol. Catal. A: Chem., 2013, 372, 151–159.
42 B. R. James, Homogeneous Hydrogenation, Wiley, New York,
1973.
43 F. H. Jardine, in Progress in Inorganic Chemistry, ed.
S. J. Lippard, John Wiley & Sons, Inc., Hoboken, NJ, USA,
1981, pp. 63–202.
44 F. Joo, P. Csiba and A. Benyei, J. Chem. Soc., Chem. Commun.,
1993, 1602–1604.
45 Z. Liu and H. Xiao, Polymer, 2000, 41, 7023–7031.
46 Z. Wei, Direct catalytic hydrogenation of nitrile butadiene
rubber latex, PhD thesis, Department of Chemical Engineering,
University of Waterloo, 2006.
This journal is c The Royal Society of Chemistry 2013