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Homogeneous Hydrogenation Art of

Nitrile Butadiene Rubber: A Review
a a a
Hui Wang , Lijuan Yang & Garry L. Rempel
a
Advanced Rubber Technology Lab, Department of Chemical
Engineering , University of Waterloo , Waterloo , Ontario , Canada
Published online: 18 Apr 2013.

To cite this article: Hui Wang , Lijuan Yang & Garry L. Rempel (2013) Homogeneous
Hydrogenation Art of Nitrile Butadiene Rubber: A Review, Polymer Reviews, 53:2, 192-239, DOI:
10.1080/15583724.2013.776586

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 Polymer Reviews, 53:192–239, 2013
Copyright © Taylor & Francis Group, LLC
ISSN: 1558-3724 print / 1558-3716 online
DOI: 10.1080/15583724.2013.776586

Homogeneous Hydrogenation Art of Nitrile

Butadiene Rubber: A Review

HUI WANG, LIJUAN YANG, AND GARRY L. REMPEL

Advanced Rubber Technology Lab, Department of Chemical Engineering,
University of Waterloo, Waterloo, Ontario, Canada

Hydrogenation of nitrile butadiene rubber (NBR) is an important research topic in the

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field of chemical modification of unsaturated polymers. This review provides an overview

of the fundamental data, challenges, and recent advances in the research area of ho-
mogeneous hydrogenation of NBR. Besides NBR and its hydrogenation product HNBR,
some other important elastomers such as styrene butadiene rubber (SBR), polybuta-
diene rubber (BR), polystyrene-b-polybutadiene-b-polystyrene (SBS block copolymer),
and natural rubber (NR) were also involved for the related hydrogenation reactions and
characterization. A brief comparison of hydrogenation catalysts including the hetero-
geneous and homogeneous catalysts was first conducted and the importance of rhodium
(Rh) complex catalysts for homogeneous hydrogenation of elastomers was addressed.
This article continued to discuss the reaction pathways for realization of the homoge-
neous hydrogenation of NBR. This was followed by an examination of the microstructures
and characterization techniques of NBR and HNBR. After that the recovery/recycle of
precious metal catalysts from the reaction substrate, which have been drawing much
attention from industrial manufacturers, was reviewed and highlighted in this article.
The applications of HNBR were then summarized. In the end, future research directions
were suggested.

Keywords homogeneous catalysis, hydrogenation, high performance elastomers,

rhodium catalyst, catalyst recovery

1. General Introduction
In 1930, Konrad and Tshunkur first synthesized acrylonitrile butadiene rubber (NBR)
employing free radical emulsion polymerization.1 Since then, NBR has been widely applied
as an oil-resistant rubber, adhesives, coatings, plastics modifiers and so forth because
of its high strength and excellent elastic properties.2–4 However, due to the presence of
olefinic double bonds, NBR has many drawbacks with respect to chemical, physical and
mechanical properties. The main disadvantage for NBR is its poor aging property, which
results in oxidative and ozonolytic degradation, and the lack of stability to resist extreme
weather conditions. Furthermore, these drawbacks will be aggravated when NBR is used
in manufacturing components of the oil drilling and automotive industries for utilization in
very harsh operation environments. These deficiencies led to the emergence and later on to
the rapid development of hydrogenation techniques for the production of HNBR.

Received July 22, 2012; accepted October 15, 2012.

Address correspondence to Garry L. Rempel, Advanced Rubber Technology Lab, Department
of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada. E-mail:
[email protected]

192
 Hydrogenation of Nitrile Butadiene Rubber 193
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Figure 1. From NBR to HNBR: selective hydrogenation and property improvements (Color figure
available online).

Hydrogenation constitutes an important process of chemical modification of polymers

as it not only provides a pertinent way to improve the mechanical, chemical, physical, and
thermal properties of unsaturated polymers, but also offers a convenient method to synthe-
size polymers with required microstructures and unique stereochemistries that are difficult
or too expensive to achieve by conventional polymerization of monomers.3–4 The selective
hydrogenation of the unsaturated olefinic groups (C C) in NBR is a successful commercial
process in industry since Bayer A. G. (now Lanxess Inc.) filed the first NBR hydrogenation
patent using Wilkinson’s catalyst, that is, RhCl(PPh3 )3 in monochlorobenzene (MCB) as
solvent in the 1970s (Scheme 1).5 The produced hydrogenated NBR (HNBR) maintains the
elastomeric properties of NBR and shows exceptional resistance against thermo-oxidative
degradation and notable improvements in mechanical properties characterized by tensile
strength, elongation, abrasion resistance, and hardness (Fig. 1).4 Ascribed to these superior
physicochemical properties, HNBR have found numerous of important uses in automotive,
oil-well, aerospace, and a great variety of performance-demanding applications. After the
rapid development over the years since 1977, it is indisputable up to the present time that
HNBR has been the most significant member among all the hydrogenated elastomers and
has acted as a workhorse in high performance elastomer applications.
The driving force behind the fast development of hydrogenation techniques pertains
to a progressively heightened demand for high performance oil-resistant elastomers. Cur-
rently, HNBR is mainly manufactured by two companies: Laxness Inc (HNBR brandname:
Therban R
) and Nippon Zeon Chemicals (HNBR brandname: Zetpol R
). The physicochem-
ical properties of HNBR were mainly governed by the level of bound acrylonitrile (AN)
and residual carbon-carbon double bonds (C C) remaining within HNBR (can be used
for vulcanization to further improve the performance of HNBR).6 These two key defining
factors thus determine the grades of produced HNBR.
 194 H. Wang et al.
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Scheme 1. Catalytic hydrogenation of acrylonitrile butadiene rubber (Color figure available online).

During the last two decades, several comprehensive reviews have provided a thorough
examination on the hydrogenation of elastomers.2–4 These reviews and many other studies
all illustrate that HNBR is a special important elastomer. However, there appears to be no
review particularly concentrating on the advances of the hydrogenation of NBR.
In the past decade a large number of important literature reports have appeared in the
field of hydrogenation of NBR. Many innovative hydrogenation processes were developed,
and perhaps the most striking progress is the development of catalytic hydrogenation of
NBR nanoparticles in the aqueous emulsion/latex media. In addition, a great variety
of robust efficient catalyst systems were designed and applied in the selective reduc-
tion of C C within NBR. Therefore, it is highly desirable to update the knowledge of the
hydrogenation of NBR. The objective of this review was thus to provide an overview of
recent progress towards the homogeneous hydrogenation of NBR.

2. Comparison of Hydrogenation Pathways

2.1 Diimide and Catalytic Routes

Generally, the hydrogenation process of unsaturated polymers can be achieved by means
of diimide hydrogenation and catalytic hydrogenation. Diimide hydrogenation is a non-
catalytic process, in which the hydrogenated polymers are formed through the reduction
reaction between the diimide and C C. The diimide is usually obtained from the reaction
between hydrazide and peroxide reagents. The diimide hydrogenation has been drawing
much attention since Wideman reported the first diimide hydrogenation of diene-based
 Hydrogenation of Nitrile Butadiene Rubber 195

polymers in 1984.7 The hydrogenation of diene polymers by diimide is an attractive alter-

native to the conventional catalytic hydrogenation due to the fact that it could circumvent the
requirements for specialized hydrogenation apparatus. However, the serious crosslinking of
produced HNBR has been the principal challenge in preventing the commercialization of
the diimide hydrogenation process. In addition, the stoichiometry of reactants and potential
side reactions in the diimide reduction reactions are not suitable for large scale processes.8
Considerable progress has been achieved towards reducing the extent of cross-linking in
the produced rubbers, especially for HNBR. Belt et al. reported that when boric acid was
added to play the role of being the alien catalyst, a higher degree of both the hydrogenation
and hydrogenation efficiency could be achieved and the cross-linking was decreased.9 A
similar observation was reported by Rempel and coworkers.10 Zhou et al. increased the
hydrogenation efficiency and reduced the gel formation through adding the hydrogen per-
oxide in a semibatch mode.11 Several chemicals including amines, hydroxylamine, imines,
azines, hydrazone, oximes,12 p-tert-butyl- pyrocatchecol, or antioxidants were reported
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to be efficient in reducing the gel formation occurring during the diimide hydrogena-
tion process.13 However, the cross-linking (gel formation) still cannot be circumvented
completely.
Catalytic hydrogenation is the most common method for the modification of elastomers,
and its research history can be traced up to seventy years ago.14,15 With respect to substrate
NBR, it has two types of important unsaturated functional groups represented by the olefin
group (C C) and nitrile group (C N) (Scheme 1). Therefore, the central challenge to
produce HNBR is to realize the selective hydrogenation of C C units while keeping
the nitrile group in the rubber intact. Any reduction of the polar nitrile group to imine
or amine would comprise the oil resistant properties for which the end-use application
is desired. Furthermore, such undesirable nitrile hydrogenation is suspected to promote
polymer cross-linking which reduces the processibility of elastomers.

2.2 Heterogeneous and Homogeneous Catalysts

The catalytic hydrogenation can be typically realized by the heterogeneous and homoge-
neous processes depending on the essence of catalysts. In heterogeneous hydrogenation,
the catalytically active species and the substrate polymer are not miscible and occur in two
phases. Heterogeneous catalysts are prepared by depositing metals represented by Ni, Pt,
Rh, Ru, and Pd onto supports such as activated carbon, silica and CaCO3 . Pd metal on car-
bon or silica is the main commercial used catalyst for NBR heterogeneous hydrogenation.
A typical method for heterogeneous hydrogenation is to dissolve the polymer into a suitable
solvent and then the polymer solution is contacted with the heterogeneous catalyst under a
hydrogen atmosphere. After the completion of the hydrogenation, a relatively simple post
treatment, that is, the filtration operation is applied for the recovery of the catalyst from the
reaction mixture. Therefore, the heterogeneous catalytic system is highly appraised for its
much easier handling of the catalyst recovery than a homogeneous one.
However, heterogeneous catalysis has several drawbacks. Ascribed to the limited con-
tact between the polymer solution and the catalyst induced by the high viscosity of the
polymer solution and the steric hindrances of the polymer chain caused, the hydrogenation
rate in a heterogeneous system suffers from severe mass transfer resistance. The catalyst
reactivity in the heterogeneous system decays gradually with the proceeding of the re-
action due to the occupation of the catalytic active centers by the hydrogenated polymer
molecues.3 Moreover, the heterogeneous catalytic system usually requires higher catalyst
 196 H. Wang et al.

concentration and longer reaction time as well as higher temperature and pressure, which
easily induces the degradation of the polymer and gelation of the reaction system.2
The past decade has witnessed increasing attention concentrated on the homogeneous
catalysts, particularly for their application in the reactions related to polymers. The appli-
cation of the homogeneous catalyst with clearly defined molecular structure allows for a
solid tracking of the catalytic reaction process and interpretation of the mechanism involved
into it, which contributes great favor for the realization of the quantitative hydrogenation,
as well as providing informative inputs for optimizing and controlling of a reaction pro-
cess.16 Homogeneous catalysis is defined as a catalytic system in which the hydrogenation
reaction of the polymer substrate and the catalyst component are brought together in one
phase, in particular the liquid phase. The universal operation of a polymer homogeneous
hydrogenation is similar with a heterogeneous one. First, the polymer, that is, the substrate
is dissolved into a matching organic solvent with abundant solvent power to form a homo-
geneous solution. For example, NBR is preferably dissolved in MCB, acetone, or methyl
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ethyl ketone (MEK) while the SBR solution is usually formed in toluene or cyclohexane.
After the substrate polymer solution is prepared, the catalyst in a solid or solution form is
mixed with the polymer solution under a hydrogen atmosphere. Following the completion
of the hydrogenation, subsequent steps include the recycle of the noble metal catalyst such
as Rh if desirable, precipitation, and isolation of the hydrogenated polymer.
Besides its feature of knowability at a molecular level, a homogeneous catalyst has
another two commonly recognized advantages, that is, high selectivity and reactivity. Cat-
alyst reactivity can be enhanced due to the effective dispersion of a homogeneous catalyst
or its derivatives in the substrate solution. Furthermore, homogeneous catalysis offers cat-
alytic mobility and hence circumvents the problem of orienting the long polymer chain on
an immobile active site in the heterogeneous systems.17–19 Although possessing all these
superior features, homogeneous catalytic processes are much less employed in industries
than their counterparts—the heterogeneous ones. The application of a homogeneous cata-
lyst is mostly impeded in the manufacture of products with high economic value. This is
generally blamed to the relatively high production cost of the homogeneous catalyst and
the difficulties encountered for the separation of the catalyst from the final product. The
residue of the expensive catalyst causes an addition of the production cost. Among the
investigated homogeneous catalysts, major concern has been focused on the homogeneous
Rh-based catalysts. Rh complexes representative with Wilkinson’s catalyst are well recog-
nized with their stability and excellent selectivity towards the olefinic C C double bonds in
the presence of the other functionalities. Together with their special properties required for
the unique applications, the recovery of Rh complexes from products is urgently demanded
at the same time. Rh is one of the extremely scarce metals in the earth and its price is
subject to be fluctuated dramatically over the past decade. The historical highest prices
of Rh was recorded as high as 10 000 US $/oz. Therefore, there exists a huge economic
drive for researchers to develop simple and effective methods in order to recover the metal
value after hydrogenation so as to save the high investment costs for purification of the
product with high grade quality, Many substantial improvements have been achieved in the
recovery of noble metal complexes, for example, the use of supercritical carbon dioxide
(scCO2 ) (see Section 5).
In addition to the precious metal based organometallic catalysts, Ziegler catalysts
are another type of homogeneous catalysts, which have been extensively investigated and
applied for catalytic hydrogenation of unsaturated polymers.
Metallocene catalyst involving positively charged Group III or IV metal ions con-
stitutes one type of Ziegler catalyst, which can be used for the polymer hydrogenation.
 Hydrogenation of Nitrile Butadiene Rubber 197

Metallocene catalysts are featured by a structure with metal ions sandwiched between
two planar rings of unsaturated carbon atoms that have five atoms apiece. Nevertheless,
metallocenes have a number of disadvantages with respect to the polymer hydrogenation.
They lack thermal stability, cannot be exposed to air, and are intolerant of polar func-
tionality.2 Moreover, the ligands are highly complex and are costly to synthesize. Another
type of Ziegler catalyst is characterized by comprising of a salt and a reducing agent as
effective and necessary constituents. The most used salts for this type of Ziegler catalysts
include organic acid and acetylacetone salts based on the metals of Ni, Co, Pd, Fe, and
Cr, while the two commonly employed co-catalysts are methylaluminoxane (MAO) and
triethylaluminium, (C2 H5 )3 Al.20–21 Compared to the organometallic catalysts comprised
of platinum group metals, Ziegler catalyst systems show the advantages with relatively
inexpensive manufacture cost in terms of the metals used. However, caution should be
taken in that Ziegler catalysts are not applicable for an NBR system attributed to the highly
coordinating nature of the polar nitrile functional group (C N), since the group III cations
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are usually extremely Lewis acidic and would be expected to bind irreversibly with the
nitrile functionality.
The history of homogeneous hydrogenation involving organometallic catalysts over
the past half of a century revealed that Rh-based complexes are the most effective and
widely used homogeneous catalysts for the selective hydrogenation of polyolefins, and
are particularly suitable for the commercial production of HNBR. A classic commercial
example is the Tornac R
rubber process, which was invented by Rempel and developed
with Polysar (later Lanxess), for the production of highly saturated acrylonitrile rubbers
using HRhCl(P(C6 H5 )3 )3 and RhCl(P(C6 H5 )3 )3 . The complex is most easily prepared by
treating RhCl3 ·3H2 O with triphenylphosphine (TPP) in ethanol.22–24 Wilkinson’s catalyst
has numerous advantages compared to other catalyst systems: (i) high selectivity toward
the olefin double bond; (ii) effective suppression of crosslinking problems; (iii) easy to
achieve high conversion and (iv) excellent air stability in the solid form.2
Besides the studies focusing on the recovery of Rh catalysts, a lot of effort has been
made by researchers to design and develop novel homogeneous catalysts based on the less
expensive metals, targeting at seeking proper catalysts for manufacture of high performance
HNBR with a reduced cost. These mainly include Ru-, Os-, Ir-, and Pd-based catalyst
systems. Nevertheless, some drawbacks were found when these catalysts are applied for
the homogeneous hydrogenation reactions (as listed in Table 1), which thus hinders the
wide application of these metal catalysts in industry.

3. Reaction Routes for Homogeneous Hydrogenation of NBR

Depending on the physical state of NBR in the reaction environment for the hydrogenation,
three techniques of hydrogenation characterized as solution hydrogenation, latex hydro-
genation, and bulk hydrogenation have been well established and continue to be developed
up to the present time. It is worth pointing out that the Rh-based catalyst has been an
indispensable component in realizing a successful homogeneous hydrogenation reaction
whether the NBR state is solution, latex or bulk.

3.1 Solution Hydrogenation

The hydrogenation of NBR in an appropriate organic solution has been a sophisticated
and widely used technique in industry since the first successful commercial example of
solution hydrogenation (NBR in MCB) patented by Bayer (now Lanxess) in 1977.5 At
 198 H. Wang et al.

Table 1
The drawbacks of noble metal based catalysts compared with Rh complexes in the homo-
geneous hydrogenation of olefinic unsaturated polymer

Metal Drawback compared with rhodium References

Ruthenium Degradation and crossing linking problems under 2,3
the high temperature and pressure;
isomerization of C C; form the inactive
Ru-CN species in NBR hydrogenation
Osmium Crosslinking problem occurring during the later 25
stages of hydrogenation
Iridium Low catalytic efficiency and the reaction 17, 18
conversion is not as high as Wilkinson’s catalyst
Palladium Degree of hydrogenation is hard to satisfy the 26, 27
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requirements of large-scale production

the present time, the solution hydrogenation process of HNBR is marketed by two major
companies in the world. Lanxess (formerly Polysar/Bayer) produces HNBR via a homoge-
neous hydrogenation process in Texas (US) and Leverkusen (Germany) while Nippon Zeon
manufactures HNBR using a heterogeneous hydrogenation process in Japan. However, the
solution hydrogenation process is known to bear several disadvantages, and the major con-
cern that has attracted considerable attention involves the usage of large amounts of organic
solvents which not only increases the cost of the process but also raises environmental
concerns.
In most cases for the solution hydrogenation of unsaturated polymers, in no way limited
to NBR, a fairly universal procedure is implemented (Fig. 2).2 First, the substrate polymer
is dissolved in a suitable solvent with a low concentration of ranging 2–10 wt% in order
to reduce the viscosity of polymer solution. MCB is a practical solvent and MEK is also
effective as the solvent under the mild reaction conditions such as ambient pressure and low
temperature (<100◦ C). After the polymer solution is ready, the hydrogen or an inert gas like
nitrogen was used to purge the reactor to remove air. The reaction system is subsequently
heated up to the desired temperature (preferred > 100◦ C) and then the hydrogen is charged
to reach a certain pressure (preferred > 2.7 MPa). Depending on the specific condition, the
catalyst can be purged into the reaction media before or after reaching the set up temperature
and pressure with or without addition of co-catalyst like TPP. Following the completion
of the hydrogenation, the catalyst and solvent are separated, recovered, and recycled. The
hydrogenated polymer is finally precipitated, dried, and baled.
Mohammadi and Rempel established the relationship between the quantitative hy-
drogen consumption and the reaction time without the influence of disturbance which
is inherent in normal sampling operations by using of a computer-controlled gas-uptake
equipment.28 The reaction experiments were investigated in three types of organic solvent
including MEK, MCB, and ethyl acetate (EtOAc) using Wilkinson’s catalyst under mild
conditions with moderate temperatures of over the range of 20–50◦ C and hydrogen pres-
sures below 1 atmosphere. Their results indicated that the selectivity of Wilkinson’s catalyst
for internal double bonds and terminal double bonds was greatly influenced by the nature
of the organic solvent used. In MEK and EtOAc, the catalyst showed nonselectivity for
the internal and terminal double bond. However, in the experiments of using MCB as the
 Hydrogenation of Nitrile Butadiene Rubber 199
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Figure 2. Schematic illustration of industrial process (i.e., solution hydrogenation) for the production
of HNBR.2 Reproduced from Rempel et al.2 with permission from Wiley.

solvent, the catalyst exhibited the distinct preference towards hydrogenation of the vinyl
groups. It is known that the polymerization of butadiene (BD) can yield three types of
C C, namely, trans, cis, and vinyl. The concentration and distribution of different types of
C C in the latex particles has a definite influence on the hydrogenation rate and reaction
kinetics since they have different reactivities. Generally, the order of the reactivity of these
three types of C C is vinyl > cis > trans using an Rh catalyst29 while the order changes to
vinyl > cis ≈ trans in the hydrazine/oxidant-induced diimide hydrogenation reaction.30–33
The vinyl-C C are more reactive towards chemical modification reactions than 1, 4 units
due to their lower steric hindrance.
More importantly, the authors found that the hydrogenation rate exhibited an apparent
first-order in the [Rh], [C C] of NBR, and [H2 ] at low hydrogen pressure, as expressed in
Eq. (1).34 Apparent activation energy (Ea ) of 87.28 kJ/mol was thus obtained.
 
k KK K1 [H2 ][Rh][C=C]
RH = × 100%
KK1 + K  [PPh3 ] + KK  [H2 ][PPh3 ] + KK  K1 [H2 ] + KK1 K5 [C≡N] + KK1 K2 K  [H2 ][C≡N]
(1)

where RH is the hydrogenation reaction rate; k  is the kinetic rate constant, and
K,K  ,K1 ,K2 ,K5 are the equilibrium constants.
In addition, an inverse dependence of reaction rate on the nitrile concentration [C N]
was observed. Based on these kinetic results and experimental observations a reaction
mechanism describing the hydrogenation of NBR using RhCl(PPh3 )3 was put forward as
shown in Scheme 2.28,34,35 It is worth noting that Scheme 2 can also be used to describe the
kinetics and mechanism of the hydrogenation reactions of BR and SBR, where K 2 and K 5
 200 H. Wang et al.
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Scheme 2. Mechanism of hydrogenation of NBR in the presence of Wilkinson’s catalyst,

RhCl(PPh3 )3 .34 Reproduced from Pan and Rempel34 with permission from ACS.

vanish. The kinetic constants and equilibrium parameters of several typical polymer/solvent
systems are presented in Table 2.
Bhattacharjee et al. extended Mohammadi and Rempel’s work28 to a higher reaction
temperature of 100◦ C and pressures up to 5.6 MPa in an effort to optimize the process and
characterize the final product.38 The method reported to obtain the data involved sampling
of the polymer solutions during the experimental runs at various time intervals, followed by
IR, NMR, and iodometric analyses to determine the degree of hydrogenation. The effect of
various reaction factors such as temperature, time, hydrogen pressure, catalyst concentra-
tion, and solvent were comprehensively examined. Under optimum reaction conditions a
100% hydrogenation degree was achieved at a catalyst concentration of 0.02 mmol, under
5.6 MPa hydrogen pressure at 100◦ C in MCB for 11 h. It was observed that the tempera-
ture plays a crucial role in the hydrogenation reaction. There was no conversion at room
temperature. However, the degree of hydrogenation increased with an increase in tempera-
ture, hydrogen pressure and RhCl(PPh3 )3 concentration. They showed that MCB is a better
solvent for the NBR solution hydrogenation using Wilkinson’s catalyst compared with
ODCB and monobromobenzene. Through the kinetic studies of the NBR hydrogenation,
the activation energy was calculated as 22 kJ/mol, dramatically smaller that the value of
87.3 kJ/mol reported by Mohammadi and Rempel28 and also not consistent with the normal
range of reaction activation energy as shown in Table 2. It probably was a result that the
hydrogenation reaction would became diffusion-controlled under the reaction conditions
employed in Bhattacharjee’s study.38 Some important physical properties of HNBR like
molecular weight, glass transition temperature (T g ) and stress-strain behavior were also
reported.
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Table 2
Kinetic constants and equilibrium parameters of several typical polymer/solvent systems.

Polymer Solvent K [mM−1] K 1 [mM] K’ [mM−1] K 2 [mM−1] K 5 [mM−1] k’ [mM−1·s−1] Ea [kJ/mol] References
NBR MCB ∞ 1.44 3.41 × 10−3 3.98 × 10−2 2.71 × 10−2 1.19 73.5 24
NBR
MEK ∞ 0.198 0.276 6.5 × 10−2 0 4.23 × 10−4 87.3 28
1,4-PB 1,2-Dichlorobenzene 0.60 4.45 0.59 0 0 1.28 × 10−4 98.5 36
(ODCB)
SBS ODCB 0.31 3.13 0.63 0 0 3.26 × 10−4 78.8 37
SBR Toluene 1.23 4.70 0.72 0 0 4.77 × 10−4 60.8 37

201
 202 H. Wang et al.

Table 3
Hydrogenation of NBR with cationic rhodium complexes.39

Hydrogenation Turnover rate,

conversion after mol·
Item Catalyst one hour (mol·Rh)−1·h−1
1 Rh(COD)(dppe)+ BF4 − 20 178
2 Rh(NBD)(dppe)+ BF4 − 22 196
3 Rh(COD)(dcpe)+ BF4 − 7 62
4 Rh(COD)(dppp)+ BF4 − 35 312
5 Rh(NBD)(dppp)+ BF4 − 40 356
6 Rh(COD)(dppb)+ BF4 − 91 810
7 Rh(NBD)(dppb)+ BF4 − 91 810
8 Rh(COD)(PPh3 )2 + PF6 − 97 863
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9 Rh(NBD) (PPh3 )2 + PF6 − 97 863

10 RhCl (PPh3 )3 99 881
dppe = bis(diphenylphosphino) ethane; dppp = bis(diphenylphosphino) propane;
dppb = bis(diphenylphosphino butane; dcpe = Bis(dicyclohexylphosphino) ethane.

Mao and Rempel reported a class of cationic rhodium catalysts with the form of
[Rh(diene)(L2 )]+ as shown in Table 3, where diene is norbornadiene (NBD) or 1,5-
cyclooctadiene (COD) and L is TPP or L2 is a chelating phosphine ligand, for the hy-
drogenation of NBR under 3.42 MPa hydrogen pressure at 140◦ C in MCB.39 As indicated
in Table 3, among the different types of ligands used, the activity of [Rh(diene)(PPh3 )2 ]+
is similar to RhCl (PPh3 )3 (Wilkinson’s catalyst), which showed that the catalytic activity
of the [Rh(diene)(L2 )]+ complexes is mainly dependent on the nature of phosphine. The
catalytic activity and a detailed kinetic study of this series of complexes were carried out
by screening groups of experiments. The reaction was monitored by periodically with-
drawing samples from the reactor and recording their IR spectra to determine the extent of
hydrogenation.
As shown in Table 3, Rh(NBD) (PPh3 )2 + showed a very high catalytic activity and
a near completion of hydrogenation. A mechanism was proposed to describe the kinetics
of hydrogenation of NBR using Rh(NBD) (PPh3 )2 + as the catalyst (Scheme 3). An Ea
calculated as 60.7 kJ/mol was acquired, which shows a satisfactory comparability with
the other values of Ea found for RhCl (PPh3 )3 (73.5 kJ/mol in MCB24 and 87.3 kJ/mol
in MEK28) and for RhH (PPh3 )4 (57.4 kJ/mol in MCB24). These data indicate that the
hydrogenation rate of these systems is controlled by the chemical reaction, rather than the
mass diffusion of the catalyst, polymer, or hydrogen, because the diffusion control reaction
generally requires Ea < 18 kJ/mol.
The role that TPP played in the hydrogenation of NBR using RhCl(TPP)3 (that is,
RhCl(PPh3 )3 ) in MCB was carefully examined by McManus and Rempel.40 The study
indicated that a side reaction occurred in parallel with the hydrogenation, which produces
benzene and HCl from the solvent of MCB. The by-products were likely generated by
the oxidative addition of the C Cl bond in MCB to a Rh intermediate complex during
the catalyst cycle for the hydrogenation (Scheme 2 of mechanism of hydrogenation using
RhCl(PPh3 )3 ), followed by reductive elimination of benzene in conjunction with hydrogen
addition to the Rh center. This reaction will result in the formation of a less active Rh
 Hydrogenation of Nitrile Butadiene Rubber 203
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Scheme 3. Mechanism of hydrogenation of NBR using [Rh(diene)(PPh3 )2 ]+ []. Reproduced from

Mao and Rempel39 with permission from Elsevier.

intermediate, which would induce rapid deterioration in catalyst activity. They reported
that excess free TPP could not only prevent a degradative side reaction of the active Rh
center, but act as a base to neutralize the HCl generated in the process. The relationship
between the addition of TPP and the hydrogenation degree is shown in Table 4. Parent
et al. also reported that addition of excess free TPP to the hydrogenation system under
elevated temperature and pressure could stabilize the Rh complex and prevent reduction of
RhCl(TPP)3 to Rh metal.24
McManus and Rempel proposed a mechanism to account for the formation of benzene
and HCl.40 The concentration of C C is considered to be the most important factor to affect
the amount of benzene produced during the hydrogenation process. Due to the neutralization

Table 4
The effect of TPP concentration on the degree of hydrogenation of NBR
using RhCl (TPP)3 .40

TPP, mM Hydrogenation degree,%

6.2 95.4
6.2 97.1
6.2 97.9
0.62 76.5
0.62 76.5
0.62 77.4
[C C]0 = 2.0 M, Temperature = 140◦ C, H2 pressure = 8.27 MPa, RhCl(TPP)3
= 0.081 mM, reaction time = 6 h.
 204 H. Wang et al.

reaction of TPP and HCl, alternate bases used as co-catalyst was added into the reaction
system to consume the HCl, by which the TPP consumption could be reduced and the overall
catalyst activities compared to the chosen concentration of RhCl(PPh3 )3 were improved. The
results showed that amines, especially primary amines and metal oxides such as MgO and
CaO, along with low levels of TPP could afford effective hydrogenation; however, these
co-catalysts are not effective without the presence of TPP.
Hsu et al. examined a bimetallic complex catalyst system (Rh-Ru) for NBR hydro-
genation and this bimetallic catalyst is designed to be comparable to the conventional single
Rh catalysts in activity and selectivity.41 Thus, the cost of Rh would be offset to a certain
extent by the relatively lower price of Ru. The bimetallic complex catalyst system is pre-
pared based on a combination of Rh and Ru with different mole ratios from 1:1 to 4:1. In
addition, the reaction is conducted by using a two-stage temperature reaction procedure. A
degree of hydrogenation of 96.3% was achieved when the amount of Rh and Ru is equal
at the two-stage temperature of 110◦ C for 2.5 h and 145◦ C for 1.5 h under 0.8 MPa H2
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pressure. When the ratio of Ru/Rh was increased to 4:1 (mol ratio), 99% hydrogenation
degree was obtained under the same experimental conditions. If only RuCl2 (PPh3 )3 is em-
ployed for the hydrogenation, gel formation is observed, which is not found when using
the bimetallic complex catalyst system (wherein Rh/Ru ≥ 1). The increase in the catalytic
activity of bimetallic catalyst system may be ascribed to a synergistic effect between two
metal complexes.

3.2 Latex Hydrogenation

Latex refers generically to a stable dispersion (emulsion) of small polymer particles in an
aqueous medium. Elastomer latices may be natural such as natural rubber (NR) or syn-
thetic including NBR, SBR, polychloroprene rubber (CR), acrylic polymers, vinyl acetate
polymers, vinyl acetate-ethylene polymers, vinyl chloride polymers, and copolymers of
polyisobutadiene and polyisoprene (butyl rubber, IIR). Latex products are used extensively
as alternatives to solvent based systems to produce adhesives, sealants, and coatings be-
cause of the concerns over environmental pollution and toxicity of solvents as well as for
practical reasons, such as ease of use.42
The current commercial process for the hydrogenation of unsaturated elastomers such
as NBR, SBR, and NR, etc., is the solution hydrogenation process, which typically involves
the following steps: (i) isolation and purification of the polymer from the parent emulsion;
(ii) dissolution of solid polymer into an abundant amount of organic solvent to form a
homogeneous solution; (iii) proceeding of the hydrogenation under certain temperature
and hydrogen pressure; (iv) recovery/recycle of both the catalyst and organic solvent after
one batch of hydrogenation. Nevertheless, this process raises environmental concerns and
increases the cost of production.
In order to avoid tedious hydrogenation steps involved in solution hydrogenation and
eliminate the need of large amounts of toxic organic solvents, the hydrogenation of unsat-
urated polymers in the latex or bulk form is thereby put forward and developed very fast.
These two forms of hydrogenation have appreciable advantages compared to the solution
hydrogenation, since they are not only an environmentally benign process, but an energy
efficient process. In addition, it will be highly desirable to hydrogenate the elastomers in
the emulsion phase when the hydrogenated product in emulsion is the demanded end use
product such as film formation, coating, and painting applications or only surface/gradient
hydrogenation of a product is required. More importantly, the direct hydrogenation oper-
ation of diene-based polymer latex can be potentially integrated into the polymerization
 Hydrogenation of Nitrile Butadiene Rubber 205
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Scheme 4. Schematic diagram illustrating the preparation and catalytic latex hydrogenation of diene-
based polymer nanoparticles. The latex hydrogenation using a catalyst pre-dispersion approach, which
consisted of three steps: the addition of catalyst (a-b), introduction of hydrogen gas (b-c), and selective
reduction of olefinic groups in nanoparticles (c-d).51 Reproduced from Wang et al.51 with permission
from Wiley (Color figure available online).

process for the parent polymer synthesis, as the conventional route for synthesis of diene-
based polymers is a semibatch emulsion polymerization process and its convenient products
are in latex form. The implementation of latex hydrogenation is not uniquely confined to
NBR and most unsaturated rubber latex can be hydrogenated directly in the latex form. On
the other hand, the recovery/recycle operation of the catalyst from the resultant hydrogena-
tion media will benefit greatly from the utilization of the latex hydrogenation,43–44 which
will be introduced in Section 3.2.3. Therefore, the commercialization of latex hydrogena-
tion is currently standing as the pursuit of rubber industry partners and representing an
important active research topic in academic community.3,4, 45–50
The uniqueness of the latex reduction process lies in that each latex particle functions
as an ideal reactor and the hydrogenation of NBR occurs inside each suspended particle
(Scheme 4).51 Latex hydrogenation could be classified into two categories according to the
nature of catalyst employed, namely an oil soluble catalyst and a water soluble catalyst. In
some cases, a suitable organic solvent is required to assist in dissolving the catalyst and
subsequently dispersing the organic solvent system in water.

3.2.1 Utilization of Oil Soluble Catalysts. The first example of NBR emulsion hy-
drogenation was reported by Weinstein in 1984 using Wilkinson’s catalyst. However,
the product was not HNBR, but another elastomer of being acrylonitrile-ethylethylene-
tetramethylene copolymer. The hydrogenation was carried out at 70–75◦ C and an initial
 206 H. Wang et al.

Figure 3. The TEM of commercial NBR latex nanoparticles. This NBR latex has a solid content
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of ∼ 12 wt% and a mean diameter of about 70 nm (L); latex hydrogenation of commercial latex
particles. The hydrogenation temperature is set up as 145◦ C and hydrogen pressure is maintained
under 6.8 MPa (R).56 Reproduced from Wei et al.56 with permission from Wiley.

pressure of 240–275 kPa.52 Mahittikul et al. hydrogenated natural rubber latex (NRL)
using OsHCl(CO)(O2 )(PCy3 )2 53 or [Ir(cod)(PCy3 )(py)]PF6 54 as catalyst, respectively. A
higher conversion of greater than 95 mol% was achieved in both catalyst systems under
proper experimental conditions. The MCB was required in these two studies in order to
reach a desired degree of hydrogenation. Chemtob et al. studied the direct hydrogenation
of purely linear polybuta-1,4-diene (1,4-PB) latex in the presence of RuCl2 (PPh3 )3 and
complete hydrogenation was observed in 8 h using a catalyst loading around 10 wt% over
polymer substrate under 20 MPa hydrogen at 130◦ C.55 Rempel and coworkers developed
a NBR latex hydrogenation technique by which a NBR latex was directly hydrogenated
without requiring pretreatment before hydrogenation and no organic solvent was used.56
Wilkinson’s catalyst and TPP were used as a catalyst and co-catalyst ligand respectively.
In this study, the added excess TPP plays a crucial role to transport the catalyst into the
latex particles; thereby, no alien solvent was used. The hydrogenation of latex was carried
out at different pressures, temperatures and catalyst concentrations. More than 95 mol%
hydrogenation degree, without any cross-linking problem could be achieved at 145◦ C and
6.8 MPa. It should be noted that 95% conversion without gel formation is an important
criteria for the commercialized hydrogenation of NBR, because it is a critical level that
guarantees the outperformance of HNBR in miscellaneous applications and facilitates the
successive processibility of HNBR, for example, vulcanization. During the hydrogenation
reactions, the degree of hydrogenation increases with increasing catalyst concentration and
reaction time (Fig. 3). No coagulation was observed even under the running conditions of
longer reaction time of above 90 h. It is interesting to find that the particle diameter and
its distributions of original NBR latex particles are maintained consistent with HNBR after
hydrogenation. The major drawback of this study is that the hydrogenation rate is quite
slow (Fig. 3), which became the main obstacle limiting the further development of this
technique.
Very recently, Lanxess (Sarnia, Canada) filed a patent focusing on the latex hydro-
genation of NBR latex using in-situ synthesized RhCl(PPh3 )3 .57 The typical experimental
procedure was reported as: first mix 25 mL latex, 75 mL water, and a certain amount of
 Hydrogenation of Nitrile Butadiene Rubber 207
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Figure 4. Size and morphology of NBR nanoparticles observed by TEM imaging. (a) NBR nanopar-
ticles; (b) the hydrogenated NBR nanoparticles (HNBR) with the hydrogenation degree higher than
95 mol%. Figures 4a and 4b represent the same batch nanoparticles before and after hydrogenation.
Experimental conditions of synthesis: AN = 5 mL, BD = 15 mL, APS = 0.2 g, distilled water =
80 mL, T = 50◦ C, addition time = 200 min, aging time = 8 h, concentration of GS 12–3-12 is
50 mM. Experimental conditions of latex hydrogenation: RhCl(PPh3 )3 /NBR is 1 wt%, RhCl(PPh3 )3
/TPP is 10 wt%, 600 rpm of agitation, 130◦ C, 6.89 MPa of H2 .51 Reproduced from Wang et al.51 with
permission from Wiley (Color figure available online).

RhCl3 ·3H2 O and TPP. The mixture was then placed inside a 300 mL glass lined stainless
steel autoclave, degassed with nitrogen, and heated up to a setup temperature. The hydro-
genation embarked on when the hydrogen was charged. The RhCl3 ·3H2 O was pre-mixed
with TPP before contacting with NBR latex as well as one experiment without addition of
TPP was carried out. The results showed that when RhCl3 ·3H2 O was used in the absence
of TPP, gel was generated and the hydrogenation degree can only reach 23 mol% at 100◦ C
and 6.8 MPa hydrogen pressure after 4 h. In case of the presence of TPP, the hydrogenation
situation was greatly improved. 97 mol% degree of hydrogenation could be obtained at
160◦ C and 6.8 MPa with a TPP/RhCl3 ·3H2 O ratio of about 27 after 19 h and no gel was
observed. The catalyst was synthesized in-situ; therefore, no alien organic solvent was used
to transport the catalyst.
These studies mentioned above confirm that the central challenge inherent in the
field of latex hydrogenation is the optimal interplay of accelerating the hydrogenation rate,
decreasing the required quantity of catalyst, and eliminating the need for an organic solvent,
which is the key for success in this latex hydrogenation route. Rempel and coworkers have
met this challenge completely through integrating the advantages of polymer nanomaterials.
They found that the latex hydrogenation rate increased drastically with decreasing of the
particle size of the substrate particles.51 For the first time, they synthesized a type of NBR
nanoparticles with a size of less than 20 nm with narrow particle size distributions via a
semibatch microemulsion polymerization method using Gemini surfactant trimethylene-
1,3-bis (dodecyldimethylammonium bromide) (GS 12-3-12) as the surfactant (Fig. 4).
Through programming the concentration of surfactant, the particle size of NBR particles
can be controlled in the range from 17–54 nm. The prepared NBR nanoparticles were then
used as the substrates for the catalytic latex hydrogenation catalyzed by RhCl(PPh3 )3 . For
 208 H. Wang et al.
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Figure 5. The dependence of latex hydrogenation rate upon the particle size. Experimental conditions
of preparation: AN = 5 mL, BD = 15 mL, APS = 0.2 g, distilled water = 80 mL, T = 50◦ C, addition
time = 200 min, aging time = 8 h, concentration of surfactant is a variable. Experimental conditions of
latex hydrogenation: RhCl(PPh3 )3 /NBR is 1 wt%, RhCl(PPh3 )3 /TPP is 10 wt%, 600 rpm of agitation,
130◦ C, 6.89 MPa of H2 .51 Reproduced from Wang et al.51 with permission from Wiley (Color figure
available online).

the 17 nm NBR nanoparticles, the hydrogenation rate is maximized and a near completion
of hydrogenation was reached within 18 h using only 0.1 wt% RhCl(PPh3 )3 based on the
mass of NBR solid (Figs. 5 and 6). It is worth pointing out that no organic solvent was used
in the latex hydrogenation process and no gel formation was observed.
Furthermore, Rempel and coworkers prepared a type of PMMA-NBR core-shell struc-
tured nanoparticles using a two-stage semibatch microemulsion polymerization method
using GS 12-3-12 as the surfactant (Fig. 7).58 As shown in Fig. 7 the light domains corre-
spond to the NBR shell whereas the PMMA core exhibits dark regions. The size of PMMA
is 22.7 and PMMA-NBR is 30.6 nm (DLS data). In the second stage of their research, the
prepared PMMA-NBR nanoparticles were hydrogenated in latex form using RhCl(PPh3 )3
in the absence of organic solvent. It was found that the hydrogenation rate is very fast.
Without using organic solvent, the hydrogenation of NBR shell was near completed using
3 h with 0.9 wt% RhCl(PPh3 )3 at 130◦ C and hydrogen pressure of 6.89 MPa. Because the
NBR layer in the core-shell nanoparticles is very thin with a thickness of around 5 nm,
which provides a considerable benefit for the mass diffusion of the catalyst into the NBR
polymer layer. In contrast, the commercial NBR nanoparticles with a larger particle size
(∼ 70 nm) (Fig. 3) showed a very slow rate of reaction as a result of severe mass transfer
limitation of catalyst inside the particles.
The synthesis and following green hydrogenation process of NBR nanoparticles and
PMMA-NBR core-shell nanoparticles provided by Rempel and coworkers can be extended
to the other latices made from semibatch microemulsion polymerizations containing other
unsaturated polymers such as SBR and BR. These two studies confirm the significance in
 Hydrogenation of Nitrile Butadiene Rubber 209
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Figure 6. Effect of Wilkinson’s catalyst amount on the latex hydrogenation rate. Experimental
conditions of preparation: AN = 5 mL, BD = 15 mL, APS = 0.2 g, distilled water = 80 mL, T =
50◦ C, addition time = 200 min, aging time = 8 h, concentration of surfactant is 50 mM. Experimental
conditions of latex hydrogenation: RhCl(PPh3 )3 /TPP is 10 wt%, 600 rpm of agitation, 130◦ C, 6.89
MPa of H2 .51 Reproduced from Wang et al.51 with permission from Wiley (Color figure available
online).

Figure 7. TEM imaging and 1H NMR spectra of PMMA-NBR and PMMA-HNBR core-shell
nanoparticles. Hydrogenation conditions: RhCl(PPh3 )3 /NBR shell is 0.9 wt%, RhCl(PPh3 )3 /TPP
is 10 wt%, 600 rpm of agitation, 130◦ C, 6.89 MPa of H2 , reaction time = 3 h. Reproduced from
Wang et al.58 with permission from Wiley (Color figure available online).
 210 H. Wang et al.

designing and synthesizing the nanoscale polymeric materials and show great promise in
the large scale production of green hydrogenation of NBR in the latex form.

3.2.2. TPP’s Role as a Catalyst Carrier. The unique role of TPP in the typical solution
hydrogenation process pertains to the maintenance of the superior catalytic efficiency of
RhCl(PPh3 )3 . With respect to the latex hydrogenation, the free ligand TPP bears an ex-
tended important role: being a carrier to deliver the oil miscible RhCl(PPh3 )3 molecules
from the aqueous regime to the polymer regime (particles). This phase-transfer process was
described in Scheme 5. In a typical run for catalytic latex hydrogenation, the RhCl(PPh3 )3
and TPP with a ratio of 10:1 (w/w) were first added into the latex (Scheme 5a) before
charging H2 gas. Under elevated reaction temperatures (generally above 90 ◦ C), TPP (m.p.
∼80 ◦ C) will be melted and then form numerous liquid droplets, which will act as a con-
tinuous phase to dissolve the catalyst to form a homogeneous mixture solution (Scheme
5b). This mixture will be stabilized and suspended in the latex system by the surfactant
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molecules (Scheme 5c). In a latex system, the surfactants are moving in a dynamic assem-
bling state and the surfactant molecules are actively being assembled onto the particles
and departed from them. These surfactant molecules will bring the TPP-catalyst mixture
droplets into the latex particles (Scheme 5d). The liquid state TPP is miscible with the
polymers like NBR and HNBR. Therefore, when RhCl(PPh3 )3 and TPP are transferred
into polymer phase, the compatibility between the catalyst and polymer phase is promoted
by TPP and finally, RhCl(PPh3 )3 is dispersed inside the polymer matrix. Form the view-
point of this mass transfer mechanism, these three components TPP, catalyst, and polymer
substrate are considered to form a homogeneous mixture under the proper experiential
conditions. It can be stated that the latex hydrogenation described here can be regarded as
“mini-bulk” hydrogenation, i.e., each latex nanoparticle is the location for the solid bulk
hydrogenation.

3.2.3. Utilization of Water Soluble Catalysts. The use of hydrophilic analogues of Wilkin-
son’s catalyst have been attracting attention over the past few years in the area of the
biphasic hydrogenation of olefinic unsaturated polymers since it provides a chance to
separate the end-product from the catalyst in the homogeneous catalytic systems. In
addition, water is used as the bulk reaction solvent instead of organic solvents, which
thereby offers a safer, cheaper, and environmentally benign alternative for current industrial
processes.59–61
Kuntz introduced the idea of biphasic catalysis in water and the first industrial appli-
cation of biphasic hydroformylation promoted the interest in such water-soluble organo-
metallic systems.62 Nomura has summarized transition metal catalyzed hydrogenation in
water.63 Amongst, the most important and efficient water-soluble catalysts is RhCl(TPPTS)3
(TPPTS = trisulphonated-triphenylphosphine, P(C6 H4 -m-SO3 Na)3 ).64 Following this suc-
cess, many water-soluble ligands and catalysts were studied for the biphasic reaction with
a polymeric substrate.
The first water soluble catalyst that applied for catalytic hydrogenation of NBR la-
tex is RhCl(DPM)3 65 (DPM = diphenyl phosphino benzene m-sulphonat, prepared by
Kalck and Montail66), which was synthesized and examined on its performance by Sivaram
and coworkers. A large range of operational conditions including pressure, temperature,
and catalyst concentration were investigated with respect to their influence on the cat-
alytic hydrogenation process of the NBR latex via RhCl(DPM)3 . More than 60% con-
version could be achieved with 0.5 mol% catalyst in 12 h at 75◦ C under atmospheric
 Hydrogenation of Nitrile Butadiene Rubber 211
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Scheme 5. Mass transfer of catalyst using TPP as the catalyst carrier from aqueous phase to bulk
polymer phase (Color figure available online).

H2 pressure. The latex was found to remain stable during the process of catalytic reac-
tion, accompanied by an increase in gel content but no coagulation of the latex. Accord-
ingly, the average diameter of the NBR particle in the latex was maintained at a simi-
lar level throughout the hydrogenation, but the particle size distribution showed a slight
broadening compared with the original latex. Elevating temperature and H2 pressure was
found to be effective for increasing the conversion of C C at no cost of increasing gel
content.
The catalytic reaction rate in such systems is largely determined by the phase contacting
rate of the catalyst and the substrate molecules which are soluble in separate phases and are
scarcely miscible with each other. Therefore, the catalytic reaction rate becomes extremely
slow due to the phase transfer limitations.61
 212 H. Wang et al.

In order to speed up the phase transfer rate of the catalyst or the polymer molecules
through the W/O interface, several attempts were made to meet this goal. Mudalige et al.
examined the catalytic activity of two water soluble Rh complexes for hydrogenation
of various polymers involving BR, SBR, and NBR in an aqueous/organic biphasic sys-
tem at 100◦ C and 5.5 MPa H2 .61 Instead of the usage of the polymer latexes as re-
action media, polymer emulsions were prepared by suspending polymer solutions (in
toluene) directly into distilled water and applied as a W/O biphasic system. The re-
sults were compared between two catalysts named [RhCl(HEXNa)2 ]2 (HEXNa = Ph2 P-
(CH2 )5 CO2 Na) and RhCl(TPPMS)3 (TPPMS = monosulphonated-triphenylphosphine,
PPh2 (C6 H4 -m-SO3 Na)). Both complexes showed a reasonable catalyst activity toward poly-
mer hydrogenation in a W/O biphasic media. The hydrogenation conversion of NBR latex
obtained after 6 h was 53% at 100◦ C and 5.5MPa. Nevertheless, the catalyst was found to
leach into the organic phase with proceeding of the reaction.
Yasuhiko et al. used another water soluble complex Rh-TPPTS for catalytic hydro-
genation of NBR latex.67 The produced latex after the hydrogenation reaction was stable
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and the hydrogenation conversion was 56% after 24 h at 60◦ C and under 0.8 MPa H2 .
Lanxess (Sarnia, Canada) disclosed a patent concentrating on using the water-soluble
catalyst RhCl(TPPMS)3 for hydrogenation of NBR latex with addition of a water-insoluble
co-catalyst TPP in the absence of any organic solvent.68 The experimental procedures are
similar with those previously described in another patent claimed by Lanxess except for
the replacement of RhCl3 ·3H2 O by RhCl(TPPMS)3 .57 The addition of TPP was found
to be important as for suppressing the cross-linking and improving the final degree of
hydrogenation. The results showed that only 43 mol% degree of hydrogenation was obtained
after 21 h at 160◦ C under 6.8 MPa H2 and gel was generated without the presence of TPP.
However, after the addition of TPP (around ten times over catalyst in mass), a 92 mol%
degree of hydrogenation was achieved under the same experimental conditions and no gel
was generated under the same experimental conditions.
Wei et al. studied another biphasic catalytic system comprised of a polyether modified
ammonium salt ionic liquids and organic solvent as reaction media regarding its applica-
tion of hydrogenation of block copolymers SBS using Ru/TPPTS complex.69 They found
that the addition of TPP worked effectively as for the particular improvement of the hy-
drogenation degree of SBS. A high hydrogenation degree of 89 mol% was reported for
the polybutadiene segments of SBS under the optimized conditions of Ru/TPPTS/TPP
= 1: 5: 2 at 150◦ C under 5.0 MPa H2 . The immobilization of the Ru catalyst in the
ionic liquid greatly promoted the recycle of the catalyst by phase separation. However,
more work should be conducted towards enhancing the hydrogenation degree, increas-
ing the hydrogenation rate, and improving catalyst-recycling efficiency. The catalyst of
RhCl(TPPTS)3 was also investigated for its efficiency in catalytic hydrogenation of several
polymers involving BR, NBR and SBR in a ionic liquid biphasic system of toluene/N,N -
butylmethylimidazolium tetrafluoroborate system at 100◦ C and 3.1 MPa.70 The activity
of the catalyst in the ionic liquid differs among polymer substrates. BR can be some-
how hydrogenated directly via the catalyst, whereas co-solvent water has to be added for
enhancing the solubility of the catalyst in the ionic liquid for the substrate of NBR and
SBR.
Very recently, Papadogianakis and coworkers studied the latex hydrogenation of BR
using a water-soluble complex RhCl(TPPTS)3 .71 The authors reported that RhCl(TPPTS)3
is very active for the BR hydrogenation under the studied mild reaction conditions. The
turnover frequency (TOF) can reach 1245 h−1 through adjusting the experimental conditions
 Hydrogenation of Nitrile Butadiene Rubber 213

and a conversion of 83 mol% was obtained at this TOF. Different types of surfactants and
surfactant combinations were used to emulsify the n-hexane-PB solution for the purpose
of investigating the effects of added surfactant on the catalytic activity of RhCl(TPPTS)3 .
These emulsified systems include single cationic surfactant dodecyltrimethylammonium
chloride (DTAC) or cetyltrimethylammonium chloride (CTAC), combination of non-ionic
Brij type surfactants with DTAC or CTAC, and mixed surfactants comprising of anionic
surfactant sodium dodecylsulfate (SDS) and DTAC. It was found that the types of surfactant
imposed a significant effect on the activity of the catalyst and thereby the hydrogenation
rate. The authors attributed the influence of the nature of different surfactant systems on
the catalytic activity of Rh/TPPTS to the pronounced effect of the hydrophilic-lipophilic
balance (HLB value) on the distribution of catalytically active Rh of RhCl(TPPTS)3 inside
the latex particles. They proposed a schematic model to illustrate the location of catalyst
in the latex particles, as shown in Scheme 6. Therefore, it is not hard to understand
that the pH of the reaction media should induce a sound effect on the activity of the
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catalyst. It was reported that high TOFs were achieved under neutral conditions whereas
the acidic or basic conditions would render negative effect on the catalytic activity. In
another report of Papadogianakis and coworkers, they examined the latex hydrogenation of
diblock copolymers polybutadiene-1,4-b-poly(ethylene oxide) (PB-b-PEO) using the same
water-soluble catalyst RhCl(TPPTS)3 . Different from their previous report using BR as
the substrate,71 the substrate PB-b-PEO itself is amphiphilic copolymer and can assemble
into micellar particles. However, in this PB-b-PEO emulsion system, the catalytic activity
is pretty low (TOF < 10 h−1) and the degree of hydrogenation that can be reached was
only 30 mol%. In contrast, the addition of cationic surfactant DTAC can increase the
hydrogenation rate drastically and a 100 mol% conversion was reached with a TOF =
32 h−1. This phenomenon can be explained that the added cationic DTAC has a pronounced
attraction force with the negatively charged RhCl(TPPTS)3 complex ions, which thus
will increase the concentration of Rh in the particles. Meanwhile, the existence of DTAC
created a smaller mixed emulsification system along with PB-b-PEO (hydrodynamic radius
= 41 nm), compared with the single micelle system formed by PB-b-PEO (hydrodynamic
radius = 58 nm). Finally, the authors pointed out the homogeneous essence of the latex
hydrogenation reaction using RhCl(TPPTS)3 .

3.3 Bulk Hydrogenation

The pioneer work on bulk hydrogenation of olefinic polymers can be traced to Gilliom
and co-worker’s initial reports.17,18 In their studies, 1,2-polybutadiene (1,2-PB) and
SBS were hydrogenated in bulk form using the entrapped catalysts Rh(PPh3 )3 Cl or
[Ir(COD)(PMePh2 )2 ]PF6 . The catalysts were distributed into the butadiene-derived elas-
tomers by dissolving these two materials in a suitable solvent and then removing the solvent
to yield a solid polymer with a well dispersed catalyst starting mixture. The degree of hydro-
genation could reach 90% for SBS and 94% for 1,2-PB catalyzed by Wilkinson’s catalyst.
The higher conversion of unsaturated polymer free of solvent indicated that the catalytically
active species is homogeneously dispersed within the polymer matrix. The fundamental
principle for the successful bulk hydrogenation is that the homogeneous catalyst such as
Wilkinson’s catalyst could diffuse into the substrate polymer. The study of Gilliom pro-
vided strong evidence for this principle. They demonstrated that the hydrogenation can be
realized in the unsaturated polymer matrix without the presence of added organic solvent
and verified the homogeneous nature of the catalysis during the course of hydrogenation.
 214 H. Wang et al.
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Scheme 6. Schematic representation of latex hydrogenation of BR particles emulsified by cationic

surfactant alkyltrimethylammonium (e.g., DTAC) and non-ionic surfactant Brij (e.g., Brij-35) based
on the electrical double layer theory. The catalyst molecules Rh/TPPTS are encapsulated inside
the particles (doted part, core of the particles). X stands for the counter ions. Reproduced from
Kotzabasakis et al.71 with permission from Elsevier.

However, relevant studies on bulk hydrogenation appear rare since Gilliom and co-
worker’s work, probably due to the difficulties resulting from the mass transfer and heat
transfer involved in the reactions.
Rempel et al. attempted to facilitate the transport of the catalyst inside the polymer
matrix through decreasing the dimensions of the substrate.73 In their experiments, NBR
solid was cut into small pieces with scissors (the average diameter of the NBR particles
being about 1 cm), and then the polymer pieces were physically mixed with the solid
RhCl(PPh3 )3 and TPP. The mixture was then transferred into a 5 mL flask that suspended
in a Parr high pressure reactor so that any possible overheating of sample could be avoided.
After the reactor was purged with hydrogen gas, the temperature and pressure were then
adjusted to 145◦ C and 3.45 MPa, respectively. The results showed that the NBR bulk could
be hydrogenated up to 95% conversion in 5 h.
Rempel and coworkers reported the bulk hydrogenation of NBR by taking advantage
of a supercritical fluid (SCF).74 The influence of scCO2 on the hydrogenation of NBR
entrapped with Wilkinson’s catalyst was studied in detail under various reaction conditions
characterized by reaction time, temperature, hydrogen pressure, loading level of catalyst,
and thickness of the polymer film. An 88.5% hydrogenation degree for a bulk NBR film
with a thickness of 0.0637 cm2/mg could be obtained at a RhCl(PPh3 )3 concentration of
0.046 wt% under a pressure of H2 and CO2 of 5.52 and 6.89 MPa, respectively, at 140◦ C
 Hydrogenation of Nitrile Butadiene Rubber 215

for 3 h. It was observed that scCO2 has a strong swelling capacity for NBR and moves the
catalyst into or out of the NBR substrate effectively. Based on this phenomenon, the dis-
solution extent of RhCl(PPh3 )3 in scCO2 was estimated. It is found that high temperatures
and scCO2 densities, as well as in the presence of a co-solvent like acetone will enhance
the apparent solubility of catalyst. However, much more work, for example, the determi-
nation of the apparent solubility data of catalyst in scCO2 , is required in the upcoming
research.

4. Characterization of Hydrogenation of NBR

Characterization and understanding of the microstructure of HNBR becomes important
after hydrogenation of the olefinic nitrile rubber since the amount and distribution of the
residual double bonds as well as the nitrile group greatly influence the properties of modified
rubber. Conventional analytical tools have been used to characterize the elastomers.
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4.1 Infrared (IR) Spectroscopy

The degree of hydrogenation in the hydrogenated NBR is defined as Eq. (2):
[C=C]0 − [C=C]
Hydrogenation Degree (%) = × 100% (2)
[C=C]0
where [C = C]0 is the initial carbon-carbon double bonds in NBR and [C = C] is the
residual carbon-carbon double bonds in HNBR.
Brück first developed an infrared (IR) spectrophotometric method for determination
of the properties of AN, BD, and hydrogenated BD in hydrogenated NBR of unknown
composition.75,76 All the characteristic peak assignments for NBR and HNBR are listed
in Table 5.3 The degree of hydrogenation was calculated using an absorption constant (k)
based on the strength of three characteristic peaks at 2236, 970, and 723 cm−1 from the
IR spectrum.38 The 2236 cm−1 peak is the cyano group (C N). The 970 cm−1 peak is the
C C (1,4-trans). The 723 cm−1 is a new peak assigned to the (CH2 )n , n > 4. The detailed
calculation procedures are presented below:38,75,76

Let Ā(723) = A(723) /A(2236) and Ā(970) = A(970) /A(2236) (3)

F = 1 + Ā(723) /K(723) + Ā(970) /K(970) (4)

where K (723) = 0.255 and K (970) = 2.3 are constants specific to the HNBR polymer.
Then, the relative amount of C C remaining in HNBR is:

C(BR) = Ā(970) /[K(970) F ] (5)

and the relative amount of methylene groups formed through hydrogenation of C C in

NBR is:

C(HBR) = Ā(723) /[K(723) F ] (6)

Finally, the degree of hydrogenation can be calculated as:

Degreeofhydrogenation (mol%) = 100 − C(BR)/[C(BR) + C(HBR)] × 100 (7)

 216 H. Wang et al.

Table 5
Characteristic peaks for NBR and HNBR FTIR spectrum.3

Wave number Peak Absorption Strength

(cm−1) assignment factor (k) changes
Around 3500 Primary or secondary — Peaks appear if the
amines C N group is
reduced by H2
2236 ν ( C N) 1.00 This peak is used as the
internal standard for
the calculation of
hydrogenation degree
970 wagging of CH in 2.3 This peak decreases in
1,4-trans unit, strength and
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CH CH disappears during the

hydrogenation
920 wagging of CH2 in 1,2 2.24 This peak decreases in
unit, CH CH2 strength and
disappears during the
hydrogenation
750 wagging of CH in 1,4-cis 0.36 This peak decreases in
unit, CH CH strength and
disappears during the
hydrogenation
723 rocking of CH2 vibration 0.25 This peak appears and
in saturated–[CH2 ]n – increases in strength
group (n > 4) during the
hydrogenation

Figure 8 shows a typical hydrogenation process of NBR determined via FT-IR spectra.51
The peak intensity due to the olefinic double bonds at both 970 cm−1 and 917 cm−1
decreases gradually with the proceeding of the hydrogenation reaction. There is a new peak
at 723 cm−1 assigned to the (CH2 )n , n > 4, which is attributed to the oscillating H attached
to the saturated backbone CH2 CH2 . It can be seen in Fig. 8 that both the 970 cm−1
and 917 cm−1 peaks almost disappear after the hydrogenation reaction is completed.

4.2 Nuclear Magnetic Resonance (NMR) Spectroscopy

NMR is an accurate and convenient method to determine the composition of polymers,
which is pervasively employed to investigate the microstructure and indentify the extent of
hydrogenation of hydrogenated elastomers.77–80
The degree of hydrogenation can be calculated using the following equation:3
  
[8 − 5C(AN )] [2 + 4(A/B)]
Hydrogenation Degree (%) = 1− × A/B × 100%
1 − C(AN)
(8)
 Hydrogenation of Nitrile Butadiene Rubber 217
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Figure 8. A set of representative FT-IR spectra of 26 nm NBR nanoparticles with different extent of
hydrogenation. Experimental conditions of preparation of 26 nm NBR nanoparticles: AN = 5 mL,
BD = 15 mL, APS = 0.2 g, distilled water = 80 mL, T = 50◦ C, addition time = 200 min, aging
time = 8 h, concentration of surfactant is 40 mM. Experimental conditions of latex hydrogenation:
RhCl(PPh3 )3 /NBR is 1 wt%, RhCl(PPh3 )3 /TPP is 10 wt%, 600 rpm of agitation, 130◦ C, 6.89 MPa
of H2 . Reproduced from Wang et al.51 with permission from Wiley (Color figure available online).

where C(AN) = mole fraction of AN in HNBR, A = integral of peaks representing protons

of the residual olefinic units in HNBR, and B = integral of peaks of protons in methylene
chains in NBR.
The polymerization of BD usually gives rise to products which have a mixture of 1,4
and 1,2 olefinic units, and the 1,4 addition products consist of trans and cis isomers, whereas
1,2 addition may result in isomers with isotactic, syndiotactic, and atactic structural units.
Table 6 presents the chemical shifts of the proton in different microstructures of NBR and
HNBR, respectively.3 Figures 9 and 10 show the 1H NMR and 13C NMR spectra of NBR
and HNBR, respectively.28

4.3 Iodometric Analyses

In addition to the IR and proton NMR, Iodine values for nitrile and hydrogenated nitrile
rubbers were also measured in order to evaluate the extent of hydrogenation.3,38 The iodine
 218 H. Wang et al.
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Figure 9. 1H NMR spectra of acrylonitrile-butadiene copolymer (a) and hydrogenated acrylonitrile-

butadiene copolymer (b) (polymer solution in chloroform-d1 ).28 Reproduced from Mohammadi and
Rempel28 with permission from ACS.
 Hydrogenation of Nitrile Butadiene Rubber 219

Table 6
Chemical shifts of protons of different microstructures of NBR and HNBR.3

Hydrogenation status Microstructure Type of Protons δ (ppm)

NBR 1,4 Unit CH 5.50 (1,4 Unit)
CH2 2.15
CH(CN) 2.65
CH2 CH(CN) 1.70
NBR 1,2 Unit CH & CH2 4.90–5.10
HNBR CH3 0.90
CH2 1.30
CH(CN) 2.60
CH2 CH(CN) 1.50
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values were lowered with the reduction of the C C in the polymer backbone. The degree
of hydrogenation calculated from all three methods, IR, NMR, and iodometric analyses,
were comparable. Table 7 represents the degree of hydrogenation and corresponding iodine
values of the rubber samples.38

Table 7
Iodine value and degree of hydrogenation of nitrile rubber with different levels of bound
AN.38

Hydrogenation
Samples AN content, % I2 value degree, %
NBR 40 300 0
HNBR 40 156 48
HNBR 40 126 58
HNBR 40 90 70
HNBR 40 87 71
HNBR 40 72 76
HNBR 40 48 84
HNBR 40 42 86
HNBR 40 39 87
HNBR 40 15 95
HNBR 40 4 99
NBR 33 303 0
HNBR 33 25 92
NBR 51 295 0
HNBR 51 5 99
XNBR 34 308 0
HXNBR 34 35 89
BR 0 320 0
HBR 0 74 77
 220 H. Wang et al.
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Figure 10. 13C NMR spectra of acrylonitrile-butadiene copolymer (a) and hydrogenated acrylonitrile-
butadiene copolymer (b) (polymer solution in chloroform-d1 ). Reproduced from Mohammadi and
Rempel28 with permission from ACS.

4.4 Differential Scanning Calorimetry (DSC)

The glass transition temperature (T g ) is an important characteristic of rubbers as it deter-
mines the range of temperatures for processing and applications. The values of T g were
 Hydrogenation of Nitrile Butadiene Rubber 221

commonly estimated as the temperature at the midpoint of the transition region from glassy
to rubbery, which were usually given by differential scanning calorimetry (DSC).
The superior flexibility retained by HNBR at low-temperatures is highly demanded
by the rubber parts that applied under rigorous working environment. The flexibility and
T g of HNBR are considered to be subject to the effects of both the level of bound AN
units and the length of the tetramethylene sequence in a polymer chain of HNBR.81–83 For
NBR without tetramethylene units, its T g was reported to increase linearly with an increase
of the molar fraction of AN units in a polymer chain, and thereby the flexibility and T g
of NBR can be very well controlled by the means of regulation of the levels of bound
AN of NBR. However, the same regulation practice is not effective for the production
of HNBR with the presence of tetramethylene units produced by the hydrogenation of
the BD of NBR, the crystallization of which leads to HNBR of poor flexibility in spite
of a low AN content.81 Some research work was carried out to explore the relationship
between the low-temperature flexibility of HNBR and the content of the chemical groups
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excluding AN. Arsenault et al. investigated the relationship between the low-temperature
flexibility of HNBR and the molar ratio of ethylene units in it.82 Kobatake studied the
effects of the polymer structure of HNBR on its low-temperature flexibility, involving the
distribution of the monomer unit along a polymer chain and a higher order structure83
They reported that the length of the tetramethylene sequence contained in HNBR is the
key factor that governs the low-temperature flexibility of HNBR. Tetramethylene sequences
with more than five continuously linked tetramethylenes (TM-5) render crystallization upon
stretching, which results in the poor low-temperature flexibility of HNBR. Two effective
methods were proposed by Kobatake to reduce the TM-5 content so as to depress its
hydrogenated counterpart’s T g , as well as to improve its low-temperature flexibility. These
two modification methods were not directly used upon HNBR, but practiced in the stage
of NBR polymerization. The first approach is to copolymerize with a third monomer and
second one is to add mercaptans.83
The T g of HNBR is usually decreased with the increasing level of hydrogenation. T g
of the pure and hydrogenated nitrile rubbers are given in Table 8.38,83 T g of hydrogenated
rubber is lower than that of the pure polymer. The higher the degree of hydrogenation, the

Table 8
T g values of NBR and HNBR with different degree of hydrogenation and nitrile content.38,83

Hydrogenation
Elastomers AN content, % degree, % T g, ◦C
NBR 40 0 −18
HNBR 40 58 −19
HNBR 40 71 −20
HNBR 40 100 −24
NBR 33 0 −25
HNBR 33 92 −26
NBR 51 0 −11
HNBR 51 99 −18
Carboxylated nitrile (XNBR) 34 0 −23
HXNBR 34 89 −25
 222 H. Wang et al.

Figure 11. WAXS pattern for HNBR stretched at 600% elongation: (a) HNBR-1 (49.9% ACN), (b)
HNBR-8 (42% ACN), and (c) HNBR-7 (16.35% ACN). Reproduced from Severe and White81 with
permission from Hüthig GmbH.
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lower is the T g . This might be due to the chain flexibility upon the hydrogenation of C C
units. Hence, low temperature resistance improves on hydrogenation.
Severe and White investigated the phase transition behavior of HNBR and its tendency
to crystallize in the quiescent and stretched mode.81 It was found that the crystallinity can
be developed in HNBR through annealing and stretching NBR samples. The crystallinity at
high level of bound AN in HNBR was attributed to the alternating sequence of hydrogenated
BD and AN. With respect to the HNBR with low AN content, it was due to long sequences
of tetramethylene units. Severe and White confirmed the existence of crystallinity in HNBR
by using Wide-angle X-ray scattering (WAXS) pattern for three types of HNBR (Fig. 11).
Stretched HNBR with high level of bound AN such as 42% or 49.9 gives rise to the patterns
that contained diffused halo and three sharp reflections, which indicate that these samples
crystallized and oriented along the stretching direction (Fig. 11a and 11b). The diffraction
pattern for the stretched low AN content HNBR was diffused with no distinctive spot or
arc (Fig. 11c).

4.5 Pyrolysis Gas Chromatography/Mass Spectrometry (Py-GC/MS)

Pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) arises as an efficacious in-
strumental solution for a reproducible characterization of the ill-defined materials such as
involatile macromolecular and bio-mass.85–93 In a conventional GC/MS system, the sample
is prepared by dissolving in an organic solvent followed by introducing into the GC/MS
system. The different components in a sample are separated though the GC column and
characterized by MS. When a pyrolysis unit is incorporated into the conventional GC/MS
system, the sample is enabled to be introduced directly first into the pyrolysis section and
is thermally degraded into a suit of featured small chemical molecules containing useful
information related to the functionalities and structure of the ill defined system. In some
pyrolysis processes, chemical reagent will be added to assist the thermal degradation of the
macromolecules so as to result in the specific split in preferential domains. This special
pyrolysis process is also known as thermally assisted chemolysis. Tetramethylammonium
hydroxide (TMAH) and trimethylsufonium hydroxide (TMSH) are typically used for pref-
erential cleavage of ester domains.85–93 The utilization of Py-GC/MS to determine the
structure of rubbers that are made from copolymer, for example, NBR is more difficult
compared to other rubbers such as NR and CR. Because the characteristic of generating
 Hydrogenation of Nitrile Butadiene Rubber 223
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Scheme 7. Characteristic fragments of pyrolytic degradation for a segment of NBR chain with
adjoining AN and BD molecules after pyrolytic degradation. Reproduced from Hiltz87 with permission
from Elsevier.

degradation products comprising ethenylcyclohexene (the dimer of BD) and AN are shared
by all poly(butadiene-acrylonitrile) rubbers, but not exclusively by NBR.
Several studies have been reported for the purpose of the unambiguous identification of
NBR and HNBR. Alekseeva reported that the presence of AN, BD and ethenylcyclohexene
in the pyrolysis products can be considered as identification of NBR elastomer.91 Choi and
Han studied the pyrolysis behaviors of NBR with different levels of bound AN.86 Different
temperatures were practiced to pyrolyze NBRs with different AN contents: the temperatures
of 750, 670, 830, and 780◦ C were applied on the AN contents of 20.0, 33.4, 40.5, and
41.5 wt%, respectively. According to Choi and Han’s report, the characteristic pyrolysis
products of NBR involve BD, AN, benzene, cyclohexa-1,4-diene, 4-vinyl-1-cyclohexene,
cyclopent-3-ene-1-carbonitrile, cyanobenzene, and cyclohex-3-ene-1-carbonitrile.86 Hiltz
performed an extensive analysis focused on the pyrolytic degradation products related to
areas of NBR with adjoining AN and BD units (Scheme 7).87 By combining the pyrograms
of NBR, Hiltz summarized that the characteristic pyrolysate of NBR comprised of five
compounds with molecular weights of 93, 103 (cyanobenzene), 107, 119, and 160, which
can be employed to identify the NBR rubbers.
Kondo et al. investigated the microstructures of HNBRs with various degrees of hy-
drogenation by PyGC.93 They summarized the characteristic thermal degradation products
observed on the pyrolysates of NBR and hydrogenated NBR (Table 9). Typical mass spectral
data of the characteristic degradation products are shown in Table 10.93
 224 H. Wang et al.

Table 9
Characteristic degradation products from hydrogenated NBR.93

Compound class Structure Sequencea

Butadiene B
Butadiene dimer (4- BB
vinylcyclohexene)

Acrylonitrile A
Hydrocarbons

Mononitriles
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EAE

BA

Dinitriles AEA
AEA

a
B = 1,4-butadiene unit; A = acrylonitrile; E = hydrogenated 1, 4-butadiene unit.

5. Recovery of Catalyst

5.1 Catalyst Recovery from Polymer Solution

5.1.1 Precipitation. The catalyst retained in a polymer solution can be precipitated and
separated from the polymer solution by means of chemical reaction with various addi-
tives including acid/base and/or oxidant. The applied acids/base can present a variety of
forms involving aqueous solution of acids/base,97,98 ion exchange resins having acidic/basic
functionalities,95 and amphoteric hydrate of alumina.94 Acids can be used together with
oxygen/nitrogen as oxidant to deal with the polymerization solution for precipitation of the
catalyst.96 The precipitation of the catalyst was also reported by the means of contacting
the polymer solution with an aqueous solution of weak acid followed by contacting with
an weak base.98

5.1.2 Adsorption. Adsorption via solid materials probably is the most common practice
for recovery of organometallic catalysts from polymer solutions. A wide spectrum of
materials can be used as absorbents including silica, cross-linked polymers, inorganic
porous material, and hybrid materials of two or three of them. Generally, the process
involves passing the polymer solution through a column packed with the absorbent or
 Hydrogenation of Nitrile Butadiene Rubber 225

Table 10
Typical mass spectral data of characteristic degradation products from hydrogenated NBR.93

Major ion by electron

Notation MWa impact (EI)b Structure
C7 -MN(A) 109 41(100),55(30),54
(unsaturated) (20),68(14),
69(14),80(14)
C11 -MN(A) 165 41(100),55(86),122
(unsaturated) (38),39(34),136
(30),69(28)
C10 -MN(A) 153 41(100),43(74),96
(saturated) (59),82(54),110
(54),55(45)
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C7 -MN(B) 109 68(100),43(80),41

(70),67(57),42
(42),39(34)
C11 -MN(B) 165 41(100),43(82),57
(47),108(45),94
(35),122(35)
C11 -MN(C) 165 41(100),94(60),109
(55),108(38),55
(35),54(33)
C7 -MN(D) 107 41(100),92(55),79
(49),80(49),107
(49),52(43)
C9 -DN 150 41(100),92(55),79
(49),80(49),107
(49),52(43)
C10 -DN 162 41(100),55(99),94
(55),39(47),54
(37),68(36)
a
Determined by chemical ionization (CI) mass spectra. bThe relative intensities of major peaks in
the mass spectra are given in parentheses.

mixing the absorbent with the solution followed by filtration or decanting. Panster et al.
used organo siloxane copolycondensates as absorbent for recovery of Rh and Ru catalysts
from HNBR solutions.99 A residue of Rh less than 5 ppm was reported by Panster et al.
with using the aforementioned absorbent. Additionally, ion-exchange resins modified with
different functional groups like thiourea were also reported with efficiency for recovery of
Rh catalysts from HNBR solution.100

5.1.3 Problems in Current Technology. Precipitation and adsorption as two principal cat-
alyst recovery techniques that employed in solution hydrogenation process suffer from
their respective drawbacks. The precipitation process carries high risk to contaminate the
final product if the additives that used for precipitation of the catalyst were not completely
removed, particularly for a process involving HNBR solution of high viscosity.99 The
 226 H. Wang et al.

adsorption process involves a large amount of resin and related recycle/regeneration oper-
ation, which extends the time of a whole process and causes an increase of the expense.100
Furthermore, at the end of its recycle times, the resin is generally buried or dumped in an
open air, which becomes an environmental concern.
The technique of homogeneous catalyst recycle has made tremendous progress in the
past decade with the efforts from many chemists and engineers. Driven by the prominent
advantage of homogeneous catalyst in producing fine chemical products, a wide range of
creative solutions were proposed and investigated in their effectively and stably applications
for separation of homogeneous catalysts from products.101–107 These processes are still in
the stage of development and can be principally divided into two categories: (i) single-site
heterogenization of homogeneous catalyst, in which the catalyst was anchored on insoluble
or soluble macromolecules or supports to facilitate its separation by filtration in the end of
reaction; (ii) biphasic catalytic systems with exploitation of some versatile solvents such
as fluorous compounds, ionic liquids, and supercritical fluids, in which the transform of
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the phase behavior of the reaction systems can be triggered by a series of factors, e.g.
temperature, pressure and small molecules etc. Although these processes showed certain
efficiency in recycling of homogeneous catalyst, none of them are fully developed for
industrial application as a stable process. The major challenges include the expensive
catalyst, ligand, solvent and the high catalyst leaching.

5.2 Catalyst Separation in Latex System

Hydrogenation of NBR in the latex form creatively abstains many cumbersome operations
involved in the conventional NBR hydrogenation process and however confronts the recycle
of catalyst with new challenges. Several fundamentally different approaches have been
reported to address the catalyst separation problem.108,109 Among these approaches, water-
soluble chelating agent and super critical CO2 (scCO2 ) were found promising for realizing
the catalyst separation, as the water-soluble chelating agent can transfer the catalyst from
reaction phase to water phase while scCO2 is able to assist the reaction and separation.
Weiss and Creutz used a complexing agent to absorb the Ni colloidal catalyst remaining
in the HNBR particles after the completion of the hydrogenation reaction in order to separate
the catalyst.110 However, the complexing agent caused the coagulation of the HNBR latex
and the metal retained as the metal salt in the latex after the operation. Water/scCO2 biphasic
catalytic systems were also developed to immobilize the catalyst in a separate phase from
the reaction phase so as to facilitate the recycle of the catalyst. In the biphasic systems
(water/scCO2 ) that were applied to the hydrogenation reactions, catalysts were generally
immobilized in the water phase due to the non-polarity of the reactants.111,112 Enhanced
catalyst reactivity and separations were reported by employing the water/scCO2 emulsion
or micro-emulsions.113,114 Moreover, the water/scCO2 emulsion can be conveniently broken
by depressurization of the system to allow the precipitation and separation of the products
from the catalyst, which demonstrates distinct advantage over common W/O emulsions.
For the polar reactants, an inverted biphasic catalysis system was reported, which consisted
of scCO2 as the stationary catalyst phase and water as the continuous phase.115
Catalytic hydrogenation of NBR in emulsion form results in more difficulties in the re-
covery of Wilkinson’s catalyst since the substrate that RhCl(PPh3 )3 has to be separated from
is the nanoparticles. A polymer matrix of HNBR provides more severe mass transfer resis-
tance that has to be overcome in order for a successful separation of the catalyst. Yang et al.
developed effective separation techniques by using CO2 -expanded liquids and chelating
ligand N,N,N’,N’,N”-pentamethyldiethylenetri- amine (PMDETA).116,117 The presence of
CO2 in the polymer phase can greatly assist in the extraction process by depressing HNBR’s
 Hydrogenation of Nitrile Butadiene Rubber 227
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Figure 12. Reactions involved in the extraction process for separation of RhCl(PPh3 )3 from
HNBR by the means of CO2 -expanded methanol and N,N,N ,N ,N -pentamethyldiethylenetriamine
(PMDETA). Reproduced from Yang et al.116 with permission from Elsevier (Color figure available
online).

viscosity and increasing its permeability. The mass transfer resistance within HNBR was
thereby greatly reduced and most of the extraction was found to be completed within one
hour.116,117 After 9 h of operation at 80◦ C and 60 bar, only 59 ppm Rh remained in the
HNBR particles coagulated from the HNBR latex. Yang et al. indicated that the extraction
equilibrium was chemically determined.116 They reported that Wilkinson’s catalyst under-
goes dissociation of its TPP ligand at elevated temperatures and the CN group of HNBR
has a strong coordination interaction with these Wilkinson’s complexes RhCl(TPP)n (n ≤
2), which constitutes the central challenge involved in separation of catalyst from HNBR-
catalyst matrix. The extraction process and the challenges involved are elaborately illus-
trated in Fig. 12.116 Moreover, they pointed out that the existence of excessive TPP ligand
inside of HNBR plays a crucial role in releasing the Rh complexes from the CN group and
thus ensures their free diffusion within HNBR.
The application of CO2 expanded liquid technology in the recovery of organometallic
catalysts, that is, Wilkinson’s catalyst from polymers, that is, HNBR is still very promis-
ing, since this technology incorporates many advantages of the application of compressed
CO2 for polymer processing and homogeneous catalysis. As illustrated in Fig. 13, the
plasticization of the polymer by addition of scCO2 greatly improves the extraction pro-
cess by speeding up the overall mass transfer process at mild temperature and pressure.117
Meanwhile, CO2 expanded liquids can dissolve the objective organometallic catalysts at
mild temperature and pressure. CO2 expanded liquids are excellent solvents with tunable
solvation ability through manipulating the operational temperature and pressure, which fa-
cilitates the separation and purification for the recovery organometallic catalysts. Moreover,
with a large amount of replacement of organic solvents by environmentally benign CO2
provides this technology with green potential.

6. Applications of HNBR
Among the numerous hydrogenated elastomers, HNBR is a high performance specialty elas-
tomer which has excellent aging resistance and fluidic tolerance at high temperature.118–121
 228 H. Wang et al.
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Figure 13. Extraction process for recovering Wilkinson’s catalyst from HNBR-catalyst matrix via
CO2 -expanded methanol and N,N,N ,N ,N -pentamethyldiethylenetriamine (PMDETA). (a) extrac-
tion vessel; (b) one single polymer strip selected for the mass transfer investigation; (c) methanol
expanded by CO2 ; polymer plasticized by CO2 ; PMDETA absorbs on the surfaces of the polymer and
reacts with Wilkinson’s catalyst distributed on the polymer surfaces; (d) Wilkinson’s catalyst diffus-
ing from the interior of the polymer towards its surfaces; (e) Wilkinson’s catalyst coordinates with the
functional groups of the polymer and is retained in the polymer matrix; (f) separation of Wilkinson’s
catalyst terminated and the volume of polymer recovered after the CO2 release. Reproduced from
Yang et al.117 with permission from Elsevier (Color figure available online).

Figure 14. Classification of elastomers by the Committee on Automotive Rubber Specifications

(CARS) in the Society of Automotive Engineers (SAE). Reproduced from Hayashi121 with permission
from Marcel Dekker.
 Hydrogenation of Nitrile Butadiene Rubber 229
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Figure 15. Sour environment test for tensile strength in liquid phase. Tensile strength in liquid phase
conditions: gas (H2 S 5%; CO2 20%; CH4 75%) and liquid (oil 95%; H2 O 4%; Amine B 1%) at 150◦ C
and 6.9 MPa. Reproduced from Hayashi121 with permission from Marcel Dekker.

Figure 14 provides the classification of elastomers by the Committee on Automotive Rub-

ber Specifications (CARS) and NBR is classified BF, BG, BK at 100◦ C application and CH
at 125◦ C, and HNBR is classified as DK.121
HNBR offers a balance of properties which are not easily attainable with more ex-
pensive elastomers. HBNR has very high tensile strength and equalled only by chlorinated
polyethylene (CM). The HNBR polymer has very good low temperature properties in terms
of both brittle point and Gehman torsional stiffness. HNBR has much superior low tem-
perature performance to the ACM (polyacrylate rubbers), AEM (ethylene acrylate rubber),
CM (chlorinated polyethylene), and FKM (flouroelastomers). However, VMQ (silicone
rubber) and ECO (ethylene epichlorohydrin rubber) are completely destroyed upon heat
aging. VMQ and FKM compounds are virtually unaffected by heat aging. HNBR is quite
comparable with acrylate polymers in terms of hardness increase and elongation change
under severe conditions.3 The fluid resistance of high performance elastomers has been
characterized by tensile strength retention and volume change after aging in different types
of oil for 168 h at 150◦ C.121 As shown in Fig. 15, HNBR demonstrates good resistance to
sulfide mixtures.
After hydrogenation of NBR, the structure of HNBR is primarily composed of three
types of functional groups (Fig. 16), which determine the major physicochemical properties
as well as its use in various important applications. Many of the applications of HNBR
are shown in Table 11.3,118–126 HNBR is largely employed for manufacturing of dynamic
and static seals, hoses, and belts that are used in automobiles, which constitutes one of
the largest consumers of HNBR based on volume criteria.120–123Apart from this, HNBR is
also an important material for fabrication of components and accessories serving industrial
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230
Table 11
Common applications for HNBR.3, 118–126

Bulk

Automotive Industrial Specialized Latex

Engine seals, grommets Blow-out preventors, drill well Seals and cable jackets in atomic Advanced adhesives with resistance to
and gaskets protectors energy industry heat, fluid, ozone, UV, oxygen and
abrasion
Fuel system seals and Chevron seals High performance shoe soles Gaskets and paints to metal, ceramics, and
hoses textiles
Power transition belts Heat exchanger gaskets Rocket fuel bladders High-temperature binding
Serpentine (multi-V) Oil field packers Navy cable Films and protective coatings
belts
Transmission system Paper mill rolls Tank pads Resorcinol/Formaldehyde/Latex (RFL)
bonded piston seals dip
Synchronous (timing) Rotary shaft seals Heat-shielding materials Injection-molding applications
belts
A/C Seals and hoses Steel mill rolls
Suspension seals O-rings
Flexible oil pipes
Oil pump and valve linings
 Hydrogenation of Nitrile Butadiene Rubber 231
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Figure 16. Major functional groups and their corresponding applications of HNBR.

applications. The seals made of HNBR are high demanded by oil field exploration and
processing under extreme high or low temperature and pressure conditions. The superior
mechanical properties at high temperature make HNBR also a dispensable material for
production of rolls for steel and paper mills.

7. Conclusions
Hydrogenation of unsaturated polymers to prepare the high performance specialty elas-
tomers and thermoplastics has been an important and interesting research area for both
industry partners and academic community. This article reviewed the fundamental knowl-
edge related to the hydrogenation of unsaturated rubbers and presented an overview of
the general features of catalysts that have been employed to hydrogenate NBR. Rh-based
complexes are the most important homogeneous catalysts for the highly efficient selec-
tive hydrogenation of polyolefins, and are particularly suitable for the hydrogenation of
NBR. Three reaction routes represented by the solution, latex, and bulk hydrogenations
were established to realize the selective hydrogenation of NBR. Comprehensive analysis
of the kinetics and mechanism of these three processes was provided. The conventional
techniques used for the characterization and analysis of NBR and HNBR microstructures
were well examined. Recent advances for catalyst recovery from polymer solutions and
latex systems were extensively discussed.

8. Future Outlook
(i) With respect to solution hydrogenation, some further work is suggested in or-
der to improve the productivity of the hydrogenation operation and to reduce the
production cost. In the cases of BR, SBR, SBS, and NBR, etc., hydrogenation
operation, it would be very important to develop a highly efficient reactor, which
can deal with highly viscous polymer fluids with superior transport capacity with
respect to increasing C C loading level in order to gain productivity. Enhancing
the transport behavior of a reactor for operation with high polymer concentration
 232 H. Wang et al.

is a challenging subject. So some novel reactors with superior transport behavior

are required. For NBR hydrogenation, the effect is not very significant with respect
to increasing the C C loading level on the productivity unless the coordination
of the CN groups to the catalytic sites could be eliminated by the design of a
more selective catalyst. In addition, the rheological behavior of the diene-based
polymer solutions under different degrees of hydrogenation and different polymer
concentrations needs to be measured. The relationship of the transport behavior in
hydrogenation reactors over a wide range of operation conditions and fluid proper-
ties also needs to be established for the direct design of an optimal hydrogenation
process.
(ii) Green latex hydrogenation is drawing much attention from both academia and
industry. However, latex hydrogenation of NBR nanoparticles is a complex re-
action system. In order to facilitate the progress of commercialization of latex
hydrogenation, it would require a comprehensive fundamental understanding of
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the latex hydrogenations process and the mechanism of transport of hydrogen and
catalyst across the interphase in the reaction system. Meanwhile, the exploration
of a highly efficient catalyst is demanded, in which a water soluble catalyst and
an in-situ activated catalyst provide promising research directions.
(iii) Another worthy pursuit involves a bulk hydrogenation operation assisted by super-
critical fluids, which would eliminate the impregnation operation of catalysts by
organic solvent and enhance mass transfer performance. In addition, considerable
insight into the kinetics and mechanism of bulk polymer hydrogenations should
be carried out, such as catalyst dissolution/diffusion in the polymer matrix.
(iv) It is very important to design and develop novel and efficient catalyst systems which
have high catalytic activities and production, as well as feasible and are economical
for recovery/recycle. Development of new heterogenization techniques for single-
site anchoring homogeneous catalyst is still promising for Wilkinson’s catalyst
recovery/recycle.
(v) Arising from the green hydrogenation processes based on latex form and bulk
form, the recovery of catalysts including both the oil soluble and water soluble
ones from the hydrogenated products with the aid of compressed CO2 holds great
potential to meet the requirements of industry.
(vi) It is highly desirable to extend new applications for hydrogenated polymers.

Acknowledgements
The authors gratefully acknowledge the support of Waterloo Institute for Nanotechnology
(WIN) and the NSERC Industrial Research Chair Program for the corresponding author
(G. L. Rempel).

Nomenclature
ACM Polyacrylate rubbers
AN Acrylonitrile
AEM Ethylene acrylate rubber
BD Butadiene
BR Polybutadiene rubber
CM Chlorinated polyethylene
CR Chloroprene rubber
 Hydrogenation of Nitrile Butadiene Rubber 233

DSC Differential scanning calorimetry

DTAC Dodecyltrimethylammonium chloride
ECO Ethylene oxide and epichlorohydrin copolymer
EPDM Terpolymer of ethylene, propylene, and diene
EFTEM Energy Filtered Transmission Electron Microscopy
EtOAc Ethyl acetate
FKM/FPM Flouroelastomers
VMQ Silicone rubber having fluorine, methyl, vinyl substituents on the
polymer chains
GC Gas chromatographic
GPO Copolymer of propylene oxide and allyl glycidyl ether
GS 12–3-12 Gemini surfactant trimethylene-1,3-bis (dodecyldimethylammo-
nium bromide)
HNBR Hydrogenated nitrile butadiene rubber
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HXNBR Hydrogenated carboxylated nitrile-butadiene rubber

IIR Isobutene-isoprene copolymers (butyl rubber)
MAO Methylaluminoxane
MCB Monochlorobenzene
MEK Methyl ethyl ketone
MS Mass spectrometry
NBR Poly(butadiene-co-acrylonitrile)/nitrile butadiene rubber
NR Natural rubber
ODCB 1,2-Dichlorobenzene
PEO Poly(ethylene oxide)
PMDETA N,N,N ,N ,N -pentamethyldiethylenetriamine
PMMA Poly(methyl methacrylate)
PMQ Silicone rubber having phenyl and methyl substituents on the poly-
mer chain
Py Pyrolysis
SBR Poly(styrene-co-butadiene)/styrene butadiene rubber
SBS Polystyrene-b-polybutadiene-b-polystyrene block copolymer
scCO2 Supercritical carbon dioxide
SCF Supercritical fluid
Tg Glass transition temperature
TOF Turn over frequency, h−1
TPE (TFE/P) Thermoplastic elastomer
TPP Triphenylphosphine
TPPMS Monosulphonated-triphenylphosphine, PPh2 (C6 H4 -m-SO3 Na)
TPPTS Trisulphonated-triphenylphosphine, P(C6 H4 -m-SO3 Na)3
VMQ Silicone rubber having both methylvinyl and vinyl substituent
groups on the polymer chain
Wilkinson’s catalyst RhCl(PPh3 )3 , RhCl(P(C6 H5 )3 )3 , or RhCl(TPP)3
WAXS Wide-angle X-ray scattering
XNBR Carboxylated nitrile-butadiene rubber

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