Top Catal (2012) 55:637643
DOI 10.1007/s11244-012-9843-x
ORIGINAL PAPER
Green and Simple Method for Catalytic Hydrogenation
of Diene-Based Polymers
Yin Liu Jialong Wu Qinmin Pan Garry L. Rempel
Published online: 6 July 2012
Springer Science+Business Media, LLC 2012
Abstract Catalytic hydrogenation of diene-based poly-
mers is investigated in bulk form with different types of
homogeneous and heterogeneous catalysts. Among these
catalysts, we found that RhCl(PPh3)3, which could be
promoted by its co-catalyst ligand (PPh3), was able to
diffuse into the bulk polymer. It was shown that a required
high conversion (95 mol %) was achieved within a few
hours for the hydrogenation of acrylonitrile-butadiene
rubber, styrene-butadiene rubber, and polybutadiene rubber
using this catalyst. As an example, the hydrogenation of
NBR in bulk form was investigated with respect to the
effects of reaction temperature, pressure, and catalyst
loading in an attempt to understand the hydrogenation of
the bulk polymer.
Keywords Bulk polymer hydrogenation
Diene-based
polymers
Rhodium catalyst
Solvent free reaction
1 Introduction
Diene based polymers, e.g., natural rubber (NR), polyiso-
prene (PI), butadiene rubber (PB), styrene butadiene rubber
(SBR), and acrylonitrile-butadiene rubber (NBR), are some
of the most important polymers which are widely used as
rubber in industry.
Catalytic modification of these polymers, including
hydrogenation, hydrosilylation, and hydroformylation etc.,
Y. Liu
J. Wu
Q. Pan (&)
G. L. Rempel (&)
Department of Chemical Engineering, University of Waterloo,
Waterloo, ON N2L 3G1, Canada
e-mail: qpan@uwaterloo.ca
G. L. Rempel
e-mail: grempel@uwaterloo.ca
is of great importance in providing efficient synthetic
routes for the production of novel polymers with desirable
physical properties and functional groups that could widen
their range of application [13]. Among them, the hydro-
genation of diene based polymers has been most exten-
sively investigated [4]. The hydrogenated polymers have
been widely used as advanced rubber components due to
their superior mechanical thermal stability and oxidative
resistance [5, 6].
Currently, the catalytic hydrogenation of polymers is
carried out commercially in polymer solutions in the
presence of transition metal catalysts. The polymer has to
be dissolved in a suitable organic solvent such as mono-
chlorobenzene (MCB), acetone or tetrahydrofuran (THF).
The usage of a large amount of organic solvent not only
increases the cost of the process but also raises environ-
mental concerns. Significant research has been carried out
to improve this process by developing new catalysts [79]
or performing the hydrogenation reaction in an environ-
mental benign media such as ionic liquids [10, 11] or
aqueous systems [1215]. Compared with the aforemen-
tioned methods, performing the hydrogenation reaction in
the bulk polymer allows a higher production capacity for a
reactor of a given size. With the absence of solvent, the
process will be more environmental friendly. However, the
diffusion of the catalyst in the bulk polymer is greatly
restricted. Therefore, as we know little research has been
conducted on bulk polymer reactions, especially hydroge-
nation. Gilliom was the first to study catalytic hydrogena-
tion of polystyrene-block-polybutadiene-block- polystyrene
(PSPBPS) and 1,2-polybutadiene (1,2-PB) in bulk form
using entrapped catalysts, RhCl(PPh3)3 and [Ir(COD)
(PMePh2)2]PF6 [16]. The catalyst was introduced into
polymer by dissolving both the polymer and catalyst
together in an organic solvent and then the organic solvent
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638
was removed by evacuation. However, the hydrogenation
reaction took a few days to obtain a desirable conversion.
This tedious method to introduce the catalyst into the
polymer is also not practical for a meaningful process. To
improve the catalyst diffusion in a solid polymer matrix,
Li et al. [17] studied the effect of supercritical CO2
on the bulk hydrogenation of NBR entrapped with the
Wilkinsons catalyst under various reaction times, reaction
temperatures, hydrogen pressures, and loadings of the
catalyst and the thicknesses of the polymer films. It was
found that CO2 could help in improving the transport
behavior of catalyst in the polymer matrices and a rela-
tively fast reaction rate was observed.
Here, we initially investigated the hydrogenation of
diene based polymers in bulk form by simply mixing dif-
ferent solid catalysts with the polymers. Different types of
catalysts and polymers were compared and it was found
that the Wilkinsons catalyst was the most effective cata-
lyst to achieve hydrogenation in a bulk polymer system.
Compared with previous methods, a high degree of
hydrogenation of the polymers was achieved in a short
time. Most notably, no organic solvent is required for the
reaction, and many pre/post-treatment procedures are no
longer necessary which makes this process very promising
and robust, but simple.
2 Experimental Section
NBR, containing 62 wt% butadiene (5 wt% 1,2 addition,
Mw = 200,000 g/mol) and SBR, containing 75 wt%
butadiene (50 wt% 1,2, addition, Mw = 300,000 g/mol)
were supplied by Lanxess Inc. Polybutadiene purchased
from Scientific Polymer Product (98 wt% 1,2 addition,
Mw = 200,000 g/mol) was used as received. Hydrogen
gas (99.999 %) was supplied by Praxair (Kitchener, Can-
ada). RhCl(PPh3)3, OsHCl(CO)(PCy3)2O2 and RuHCl(CO)
(PPh3)3 were synthesized according to the procedures
described by Osborn et al., Esteruelas et al. and Vaska
et al. [1820], respectively. Rhodium on carbon (Rh/C)
(5 wt%) and palladium acetate (98 %) were purchased
from Sigma-Aldrich. PdCl2(PPh3)2 (99.9 %Pd) and Pd(PPh3)4
(99.9?% Pd) were purchased from Strem Chemicals, Inc.
Triphenylphosphine (PPh)3 with a purity of 99 % was also
purchased from Strem Chemicals Inc.
The hydrogenation was carried out in an autoclave
system (Parr Instrument Co., IL, USA), comprised of a
300 mL high pressure vessel with a temperature controller
(1 C). Solid polymer was cut into particles with scissors
(the average diameter of polymer particles is about 1.5 mm
if not otherwise specified), and then the polymer particles
were mixed with the solid catalysts. The reactor vessel was
heated with an electrical heating mantle. To avoid the
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Top Catal (2012) 55:637643
direct contact of solid polymer particle/catalyst mixture
with the bottom or wall of the steel reactor that could
possibly result in overheating of the sample, the mixture
was located in a 5 mL vial and the vial was suspended in
the reactor. The reactor was degassed with nitrogen gas.
The temperature and pressure were then adjusted to the set
point for the reaction.
The hydrogenation degree (HD) of NBR, SBR was
analyzed by FT-IR (FTS-3000; Bio-Rad Laboratories,
Inc.). The hydrogenated polymer was dissolved in methyl
ethyl ketone (MEK) and samples for analysis were pre-
pared by casting a polymer film on a sodium chloride disk.
The HD was calculated as previously reported in the lit-
erature [21]. The HD of PB was determined by 1H-NMR
(Bruker 300 MHz Spectrometer). For NBR, the peak at
2,236 cm-1 belongs to the CN stretching vibration. The
intense peak shown at 970 cm-1 is characteristic of the
level of olefin by the proton vibration of the 1,4-trans
double bonds. The absorbance peak at 920 cm-1 is due to
the 1,2 vinyl terminal bonds. The peak at 723 cm-1 in the
hydrogenated NBR corresponds to the saturated [CH2]n
unit (n [ 4).
The relative viscosity (g*) of the hydrogenated products
was measured using an Ubbelohde capillary viscometer
(International Research Glassware) by dissolving
0.250 0.0015 g of polymer in 25 mL of methyl ethyl
ketone (MEK). Viscosity measurements were carried out at
35 C and reported as the elution time of the sample rel-
ative to that of pure MEK [22].
3 Results and Discussion
3.1 Solid NBR Polymer Hydrogenation Using
RhCl(PPh3)3
The RhCl(PPh3)3 catalyst has been found to be a very
active catalyst for conventional polymer hydrogenation.
Thus the initial investigation of NBR bulk hydrogenation
began with this catalyst. Apart from the previous tedious
method of mixing of the catalyst and polymer with a sol-
vent followed by evacuation of the solvent from the
polymer/catalyst solution [16], the catalyst and the solid
NBR particles were mechanically mixed in the investiga-
tion before carrying out the hydrogenation. It was found
that under a given reaction condition, NBR polymer could
be effectively hydrogenated using the RhCl(PPh3)3 cata-
lyst. Virtually complete hydrogenation of all of the olefin
(93.2 mol%) can be achieved within 10 h. FT-IR analysis
is consistent with this result (Fig. 1). From the resultant
HNBR, the intensity of peaks at 970 and 920 cm-1 are
considerably diminished while the peak at 723 cm-1
became very evident. This transformation indicates the
Top Catal (2012) 55:637643
C-H stretching aliphatic peaks
1,4 trans olefins (970 cm )
-1
C N stretch (2236 cm )
Intensity (a.u.)
a NBR
b HNBR
3500 3000 2500 2000
Wavem number (cm )
Fig. 1 Typical FT-IR spectra of NBR and hydrogenated NBR.
a NBR (0 mol% HD), b hydrogenated NBR (93.2 mol% HD)
(reaction condition as entry 1 from Table 2)
reduction of the unsaturated C=C bonds to saturated CC
bonds.
From the color of the HNBR, we could clearly see the
catalyst had diffused into the bulk of the polymer. Even
though the NBR is well above its glass transition temper-
ature (Tg) at the reaction temperature, the molecular motion
in the polymer is not sufficient to dissolve the catalyst
forming a solution at the interface. The mixing should
be mainly dependent on the diffusion of the catalyst within
Fig. 2 The morphology of NBR, RhCl(PPh3)3, PPh3 and resultant
HNBR during the bulk hydrogenation. a NBR particles,
b RhCl(PPh3)3, c PPh3, d RhCl(PPh3)3/PPh3 dispersed on the NBR
639
-1
1,2 vinyl olefins (917 cm ) the matrix. In polymer solution hydrogenation, it has been
reported that RhCl(PPh3)3 could easily dissociate one PPh3
-1
to form the catalytic active intermediate RhCl(PPh3)2
before entering the catalytic reaction cycle [23]. This dis-
C-C bending sociation still exists in the bulk system. The dissociated
PPh3 ligand promotes the diffusion of the catalytic inter-
mediate i.e., RhCl(PPh3)2 into the polymer. Thus, upon
initiation of the reaction, the dissociated catalyst ligand
itself becomes the solvent. To confirm it, a few experi-
ments were also conducted in the presence of added PPh3.
Saturated -(CH2)n-units
-1
Under identical reaction conditions, high conversions were
(723 cm )
achieved within a short reaction time. The color of the
resultant HNBR (Fig. 2f) is more uniform and the HD of
NBR from the surface of the solid particle is almost the
1500 1000 500 same as that from the center of the particle which also
-1
indicates that the catalyst is well diffused into the polymer
particles.
In addition to improving the transportation of the
catalytic active intermediate into the polymer bulk, the
effect of PPh3 to stablize the catalytic active species
should also be considered. It has been observed that the
presence of PPh3 could prevent dimerization of the cat-
alytic active intermediate to an inactive Rh2(PPh3)4Cl2
species in the polymer solution hydrogenation [23].
However, when the weight ratio of PPh3 to catalyst is
higher than 10, it has a marginal or even negative effect
on the hydrogenation rate. This is probably due to the fact
that the excess PPh3 shifts the equilibrium of the
RhCl(PPh3)3 dissociation which inhibits the formation of
the active intermediate.
particles, e HNBR using only RhCl(PPh3)3 (Table 2, entry 1),
f HNBR using RhCl(PPh3)3 and extra PPh3 (Table 2, entry 2)
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640 Top Catal (2012) 55:637643

Table 1 Relative viscosity of

Entry WCat./WaNBR WPPh3/WbCat. T (C) P (psig) t (h) HD (mol%) g*c
HNBR product
Blank (NBR) 0 2.65 0.02
NBR with PPh3 0 2.66 0.05
1 0.0050 10.0 160 500 4 99.1 3.70 0.05
a
Weight ratio of catalyst to 2 0.0050 10.0 145 500 6 97.9 3.65 0.10
NBR; bWeight ratio of PPh3 to 3 0.0050 0 160 500 7 96.5 4.20 0.15
catalyst; cRelative viscosity to 4 0.0050 0 145 500 10 93.2 4.14 0.10
MEK

Table 2 Selected catalysts for

Entry Catalyst WCat/WaNBR WPPh3/WbCat T (C) P (psig) t (h) HD (mol%)
the hydrogenation of bulk NBR
1 RhCl(PPh3)3 0.0050 0 145 500 10 93.2c
2 RhCl(PPh3)3 0.0050 10.0 145 500 6 97.9
3 Rh/C (5 wt %) 0.011 0 160 500 5 0
4 OsHCl(CO)(PCy3)2O2 0.0046 0 160 2,000 0.8 \20
5 OsHCl(CO)(PCy3)2O2 0.0050 10.0 160 500 1 \5
6 RuHCl(CO)(PPh3)3 0.0083 0 160 2,000 1 \30
1 g of solid NBR particles was 7 RuHCl(CO)(PPh3)3 0.0050 10.3 160 500 1 \20
used in each experiment 8 (Pd (OAc)2)3 0.017 0 70 1,000 4 0
a
Weight ratio of catalyst to 9 PdCl2(PPh3)2 0.050 2.5 145 500 3 0
NBR; bWeight ratio of PPh3 to 10 Pd(PPh3)4 0.050 2.5 145 500 3 0
catalyst; cAverage HD

3.2 The Analysis of HNBR
An important factor, the selectivity (e.g., reduction of C=C
or C:N bonds) of this hydrogenation was also monitored.
It has been previously shown that secondary amines that
are produced by an addition of a fully saturated nitrile to an
imine intermediate inhibits crosslinking of the polymer [2].
The characteristic signals for primary amines (two bands
from 3,250 to 3,400 cm-1) or secondary amines (one band
from 3,310 to 3,350 cm-1) did not appear in the spectra
indicating the hydrogenation was completely selective
towards the C=C bond in the bulk polymer system.
The changes in the polymer structure such as degrada-
tion (molecular weight reduction) and cross-linking
(molecular weight growth) during the reaction are very
important because they can have a great impact on the
physical properties (e.g., viscosity) of the HNBR product
which further affects its processability.
The existence of a visible gel in the HNBR could be
simply detected by dissolving it in mono-chlorobenzene
(MCB). Although all of the HNBR was soluble in MCB,
the dissolution requires a different period of time. The
HNBR produced from RhCl(PPh3)3 with the addition of
PPh3 dissolved quickly while those using rhodium catalyst
alone took a much longer time, indicating the microstruc-
ture of these two HNBRs were different. Therefore,
viscosity measurements were used to quantitatively assess
the shifts in molecular weight. The results in Table 1 show
that in the presence of PPh3 during the hydrogenation
(Entry 1 and 2), the relative viscosity of HNBR was lower
than those without PPh3 (3.70 vs. 4.20). Nevertheless, the
quality of HNBR produced here is still much superior to
those produced using other catalysts (e.g. Os, Ru catalyst).
3.3 Effect of Other Types of Catalyst on the Bulk NBR
Polymer Hydrogenation
Some ruthenium, osmium, and palladium catalysts have
been found to be active for the catalytic hydrogenation of
diene-based polymers [24]. Therefore, these catalysts were
also examined for the bulk hydrogenation process. Exper-
imental conditions and results are shown in Table 2.
No bulk hydrogenation was observed with the rhodium
on carbon (Rh/C, 5 wt%) catalyst. The resultant polymer
was still soluble in MCB and possessed a similar viscosity
like virgin NBR, indicating that no reaction had occurred.
The possible reason could be that this heterogeneous rho-
dium catalyst could not diffuse into the NBR matrix. It has
been described in Collmans [25] research work that
homogeneous and heterogeneous catalysts behaved inver-
sely on catalytic reactions of both polymer- and network-
supported olefins.
When OsHCl(CO)(PCy3)2O2 and RuHCl(CO)(PPh3)3
were used as catalysts, the hydrogenation reaction was
observed, however, severe gel formation of the polymer
was found in the product which was only partially soluble
in MCB. The HD of the soluble part was less than
20 mol%. It has been reported by Parent et. al. [26] that

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these catalysts tend to cause crosslinking in the solution
hydrogenation of NBR. The situation becomes even worse
for the hydrogenation of bulk NBR as the local catalyst
concentration in the bulk polymer matrix is much higher.
With addition of PPh3 to the reaction system, the diffusion
of the catalyst in the bulk system was greatly improved,
however, no high conversion was observed. Due to the high
PPh3 local concentration and its stronger affinity, the PPh3
could easily exchange with the PCy3 ligand from the Ru
and Os catalysts mentioned above thus destroying their
hydrogenation activity.
Palladium acetate, [Pd(OAc)2]3, works well for the
hydrogenation of NBR in a solvent [27]; however, no
conversion was observed for the hydrogenation of NBR in
bulk form. Although the potential involvement of small
metal colloids i.e., Pd(0) formed from Pd(OAc)2 reduction
could not be ruled out, effective hydrogenation of polymers
requires a soluble catalyst. Two other types of palladium
complexes, Pd(PPh3)4 and PdCl2(PPh3)2, that have the
same phosphine ligands as in RhCl(PPh3)3, were also
investigated for the bulk hydrogenation. No hydrogenation
was observed with either of these two catalysts showing
that the Pd catalysts are not effective for bulk polymer
hydrogenation.
3.4 Effects of Operational Conditions on the NBR
Hydrogenation Using the RhCl(PPh3)3 Catalyst
Before investigation of different parameters affecting bulk
hydrogenation, the mass transfer in this process was first
considered. Previous kinetic studies have shown that the
hydrogenation of NBR with the RhCl(PPh3)3 catalyst in
homogenous solution fits a pseudo first order reaction with
respect to the concentration of C=C and a hydride path was
proposed for the hydrogenation mechanism [28]. The
hydrogenation of NBR with Wilkinsons catalyst in bulk form
would be expected to follow the same mechanism as that in
the homogeneous hydrogenation. However, from Fig. 3a
(filled triangle), the conversion versus time profile deviates
from a first order reaction curve that we believe is the result of
a mass transfer issue. To alleviate the mass transfer limita-
tions, finer NBR particles were prepared by dissolution of
NBR in a solvent to cast a thin film on a plate; the thickness of
the film was about 0.1 mm. The film was cut into small pieces
after being dried under vacuum. The average thickness is only
0.1 mm which is 1/15 of the previous ones. Meanwhile, the
solid NBR particle were pre-mixed with catalyst and PPh3 at
elevated temperature (100 C) under a N2 atmosphere for half
an hour before commencing the hydrogenation reaction.
About 96 mol% HD was achieved within 3 h for these fine
NBR particles (0.1 mm 9 1 mm 9 1 mm). The results
imply that the mass transfer limitation within the finer parti-
cles is much suppressed.
641
The effect of the reaction pressure, temperature, and the
catalyst loading are important factors which have been
commonly analyzed in NBR solution hydrogenation [29].
Here, these factors were investigated with respect to the
extent of hydrogenation conversion for bulk NBR hydro-
genation and the results are summarized in Fig. 3.
The influence of hydrogen pressure was also examined
here and the results are shown in Fig. 3b. A first- to zero-
order dependence on hydrogen as the system pressure
increased was observed for the bulk polymer reaction
system using RhCl(PPh3)3 as catalyst. As the hydrogen
pressure was varied over the range of 100500 psig, it was
found that the hydrogenation rate increased with increasing
hydrogen pressure. However, no significant effect on the
catalytic performance was observed at higher hydrogen
pressures ([500 psig).
As shown in Fig. 3c, higher HDs were obtained under
higher reaction temperatures, which is consistent with
previous research. In the present bulk polymer system,
mass transfer of the catalyst into polymer is likely the rate
controlling step for the reaction. When the temperature
increases, both the intrinsic chemical reaction and the mass
transfer of the catalyst into the NBR matrix are improved.
The effect of the catalyst amount on the hydrogenation
was also investigated and the results are shown in Fig. 3d.
A high catalyst loading resulted in a fast reaction. When
the weight ratio of the catalyst to NBR was lower than
1/600, the hydrogenation degree was more sensitive to the
amount of catalyst and the conversion dropped sharply
when the amount of catalyst was further reduced.
3.5 Hydrogenation of Other Bulk Diene-Based
Polymers
Finally, a comparison of hydrogenation of bulk NBR, SBR,
and PB is shown in Table 3. The 1H NMR spectrum of the
hydrogenated PB product showed near-complete removal
of the peaks attributed to olefinic protons. Meanwhile, the
infrared spectra of the hydrogenated SBR product also
indicated that substantial hydrogenation had occurred. Both
of these polymers undergo faster bulk hydrogenation (more
than 95 mol% HD in less than 3 h) with RhCl(PPh3)3 as
catalyst than that achieved with NBR. The slower reaction
observed for NBR hydrogenation is attributed to the
inhibiting effect of the nitrile unsaturation on the olefin
hydrogenation rate. A similar inhibition by nitrile is
reported by Schrock et al. [30] who identified a strong
coordination of acetonitrile as being responsible for less-
ening the catalytic activity of a cationic rhodium complex.
In addition, some preliminary research on catalyst sep-
aration from the bulk polymer was also carried out and the
results showed that most of the added rhodium catalyst
could be removed from the polymer by swelling the
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642 Top Catal (2012) 55:637643

Fig. 3 Bulk hydrogenation of

NBR using RhCl(PPh3)3 and
PPh3. a WCat/WNBR = 1/200,
WCat/WPPh3 = 1/10, P = 500
psig, T = 145 C, b WCat/
WNBR = 1/200, WCat/
WPPh3 = 1/10, T = 160 C,
t = 1 h, c WCat/WNBR = 1/200,
WCat/WPPh3 = 1/10,
P = 500 psig, t = 1 h, d WCat/
WPPh3 = 1/10, T = 145 C,
P = 500 psig, t = 1 h. Filled
square fine particles,
0.1 mm 9 1 mm 9 1 mm,
filled triangle solid NBR
particles with average diameter
of 1.5 mm

Table 3 Comparison of bulk hydrogenation of NBR, SBR and PB Acknowledgments We thank the Natural Science and Engineering
Research Council of Canada (NSERC) and Lanxess Inc.for financial
Entry WCat./WNBR WPPh3/WCat. t (h) HD (mol%) support.

NBR 0.0050 10.0 6 97.9

SBR 0.0061 10.0 3 98.9
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