Chapter 2
Catalytic Accelerated Polymerization
of Benzoxazines and Their Mechanistic
Considerations
C. Liu1 and Q.-Y. Chen
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China
1
Corresponding author: e-mail: chaoliu@sioc.ac.cn
Chapter Outline
1 Introduction
2 Benzoxazine Polymerization Mechanism Consideration
3 Catalysts for Accelerated Benzoxazine Polymerization
3.1 Acidic Catalysts
3.2 Basic Catalysts
1 INTRODUCTION
Benzoxazine resins have gained much interest and attention
because of their many useful properties associated with con-
ventional phenolics, such as excellent heat and chemical
resistance, flame retardance, low dielectric constant, good
dynamic mechanical properties, and relatively inexpensive
cost. They also possess other desirable properties including
near-zero shrinkage cure, low water absorption, good
dimensional stability, excellent FST (fire, smoke, toxicity)
properties, and super molecule-design flexibility [1]. These
properties offer high potential to substitute epoxy, bisma-
leiimide, phenolics, or other thermosetting resins in many
important applications. For example, commercial benzoxa-
zines are good candidates for formulating prepregs used for
aerospace compositions, and are currently utilized fre-
quently in the aerospace industry. It is estimated that 30%
weight savings may be obtained by replacing metal with
benzoxazine composites, which results in reduced fuel con-
sumption, and emissions. However, the high temperature
(typically > 180°C) and relatively long reaction time
(typically > 2 h) required for the complete polymerization
of benzoxazines indicates their poor reactivity, which is
one of the main drawbacks and has been a problem in their
practical applications. Although some novel benzoxazine
monomers with special functional groups exhibit good reac-
tivity and can polymerize at lower temperatures, it is gen-
erally not practical and economical to use them for
Advanced and Emerging Polybenzoxazine Science and Technology. http://dx.doi.org/10.1016/B978-0-12-804170-3.00002-0
Copyright © 2017 Elsevier Inc. All rights reserved.
9 4 Catalyst Effects on Polymerization Mechanism
9 and Network Structures 16
12 4.1 Pure Benzoxazines 16
13 4.2 Benzoxazine-Epoxy Blends 19
15 5 Conclusion 20
industrial applications because of the high cost of preparing
the benzoxazine monomer itself. As a result, use of an added
catalyst to accelerate the polymerization of benzoxazines
becomes a good alternative.
Much effort has been devoted to developing convenient
and efficient catalysts to accelerate the benzoxazine poly-
merization at lower temperatures and reduced reaction time,
but has met with limited success. To develop a good catalyst, it
is important to understand the benzoxazine polymerization
mechanism. This chapter focuses on the understanding of
benzoxazine polymerization mechanism and the catalysts
reported for accelerating polymerization rate of benzoxazines.
The influence of an added catalyst on the polymerization
mechanism and the network structure of the resulting polymer
is discussed as well.
2 BENZOXAZINE POLYMERIZATION
MECHANISM CONSIDERATION
The fundamental understanding of the benzoxazine poly-
merization mechanism is an important foundation to learn
how a catalyst influences and may influence the progress
and mechanism of benzoxazine polymerization, including
the development of networks and the final structure units
of polybenzoxazines. This only favors a good molecular
understanding of the structure-property relationships because
it is well known that the development of networks and the
9
10 PART I Synthesis and Properties of Benzoxazine Resins
final structure units of polybenzoxazines to a great degree
determine their various properties. This understanding can
also guide us to develop good catalysts to efficiently accel-
erate the benzoxazine polymerization and tailor the desired
structure for various practical applications. Although
impressive progress has been achieved, the polymerization
mechanism of benzoxazines remains elusive and is still under
investigation.
In 1965, Burke’s group reported the ring-opening
reaction of benzoxazine with various phenols [2]. It was
found that the aminoalkylation reaction occurred preferen-
tially at the ortho position of phenols with both free ortho
and para positions. McDongh and Smith in 1968 investi-
gated the ring-chain tautomerism phenomenon of benzoxa-
zines by nuclear magnetic resonance (NMR) analysis and
proposed that the protonated benzoxazine prefers to produce
iminium ions in strong acidic conditions [3]. Riess et al. pro-
posed in 1985 two mechanistic pathways for the reaction of
benzoxazine with various kinds of phenols [4]. They sug-
gested that the formation of an intermolecular hydrogen
bond of phenolic hydroxyl group with oxygen atoms of
oxazine ring resulted in the ortho reaction. The para reaction
resulted from the reaction of iminium species derived from
the ring opening of benzoxazine via protonation by the
phenol.
Ishida and coworkers have devoted great effort to the
study of polymerization mechanism of benzoxazines. They
propose that the polymerization of benzoxazines proceeds
through a cationic ring-opening mechanism based on the
detailed study of various reaction catalysts [5]. The for-
mation of the iminium ion intermediate by protonation of
oxygen atom of benzoxazine with a strong acid followed
by aromatic electrophilic substitution on another benzox-
azine molecule may induce the ring-opening polymeri-
zation of benzoxazines [6]. Alternatively, both the oxygen
and the nitrogen atom of benzoxazine can act as the
potential initiation sites. Their coordination with a cationic
catalyst results in the formation of a cyclic tertiary oxonium
or nitronium ion. The subsequent insertion of the benzox-
azine monomers through the reaction of the oxygen,
nitrogen, or the unoccupied benzene ortho position of ben-
zoxazine finishes the polymerization process, producing
phenolic or phenoxy (N,O-acetal) structure repeat units
depending on the polymerization conditions used [7]
(Scheme 1). The phenoxy structure can rearrange into the
corresponding phenolic structure upon further heating [8].
Ishida et al. recently investigated further the ring-opening
polymerization mechanism by the detailed and systematic
analysis of the crude products of various model benzoxazine
dimerization reaction with a large number of pure-model
compounds prepared based on the hypothesized initiation
mechanism [9]. It was found that the protonation initiation
can occur both on the oxygen and the nitrogen atom, but the
corresponding nitrogen-protonated species is more stable,
and the oxygen-protonated species is more reactive. In the
final polybenzoxazine structure, the phenolic structure unit
is less stable than the methylene bridge structure unit.
Yagci et al. investigated the photoinitiated cationic poly-
merization of benzoxazines at room temperature and found
that the structure of the polybenzoxazines was very compli-
cated because of different ring-opening polymerization pro-
cesses of the protonated oxygen or nitrogen species [10].
Ueda and colleagues proposed some possible polymeri-
zation pathways at the initial stage based on the study of
acid-initiated model condensation reactions of benzoxa-
zines with phenols [11].
On the basis of the literature mentioned previously and
the detailed NMR study of ring-opening polymerization
behavior of a model p-cresol-aniline-based benzoxazine,
Sebastián, Marquet, and coworkers proposed an improved
mechanistic scheme to explain various observed experi-
mental results, as shown in Scheme 2 [12]. The polymeri-
zation mechanism of benzoxazines is considered to
include three main steps: coordination ring-opening of
oxazine ring, electrophilic attack, and rearrangement. First,
the catalyst coordinates with an oxygen or nitrogen atom of
benzoxazine, and ring opening occurs to generate three pos-
sible cationic intermediates: A, B, and C, by different het-
erolysis patterns. The following electrophilic reactions of
each intermediate may involve O-attack, N-attack, and
Aryl-attack at another benzoxazine molecule, resulting in
the polymerization chain propagation. It is worth noticing
that the Aryl-attack of the active intermediates may occur
at various sites of benzene ring of benzoxazine including
the arylamine ring of benzoxazine with varying degrees
of reactivity, resulting in a more complex polymerization
mechanism [13–17]. The inner structure of the polymer
formed may contain various phenoxy structures and phe-
nolic structures. Upon further heating at an elevated temper-
ature or extended reaction time, phenoxy structures can
rearrange to corresponding phenolic structures.
Because the signals of CH2 units of the polybenzoxazine
in 1H NMR spectra are most characteristic and easily recog-
nized, the NMR analysis of various CH2 units in polyben-
zoxazine structure was performed to learn more about the
polymerization mechanism of benzoxazines. It should be
mentioned that using deuterated dimethyl sulfoxide
(DMSO) instead of deuterated chloroform as the NMR
solvent allows better resolution of signals in the 1H NMR
spectra. During the ring-opening polymerization of benzox-
azines, six different types of CH2 units can be formed:
ArO-CH2-OAr (a), -(Ph)N-CH2-N(Ph)- (b), ArO-CH2-N
(Ph)- (c), ArO-CH2-Ar (d), -(Ph)N-CH2-Ar (e) and
Ar-CH2-Ar (f) (Scheme 2). CH2(a–d) and CH2(e–f) are
phenoxy CH2 units and phenolic CH2 units, respectively.
Although it is very difficult to exactly distinguish the con-
tribution of every type of CH2 units on the signals in the 1H
NMR spectrum, the possible chemical shift ranges of
 Catalytic Accelerated Polymerization of Benzoxazines Chapter 2 11

(I)
O
(II) R
O N
N
δ+ M δ+ (III) (I,II)
δ+ δ+ R
R R R M δ– R
O N n
Δ O N O N δ– O N
δ– M Phenoxy structure
δ+ Electrophilic
Ring-opening δ+
substitution OH
M = Catalyst (III)
With reletively lower reactivity N
Active intermediates R
n
Phenolic structure
SCHEME 1 Proposed mechanism by Ishida and coworkers for benzoxazine ring-opening polymerization.

SCHEME 2 Improved mechanism for the ring-opening polymerization of benzoxazines. (Reproduced with permission from C. Liu, D. Shen,
€
R.M. Sebastián, J. Marquet, R. Schonfeld, Mechanistic studies on ring-opening polymerization of benzoxazines: A mechanistically based catalyst design,
Macromolcules 44 (2011) 4616–4622. Copyright (2010) American Chemical Society)

various CH2 units are estimated and indicated in Scheme 2
by using the chemical shifts of similar CH2 units in the
analogous known compound as the reference.
The structural changes during benzoxazine polymeri-
zation presented in Scheme 2 are further supported by the
1
H NMR spectra of a thermally cured mixture of model
p-cresol-aniline-based benzoxazine with 1 mol% lithium
iodide (LiI) at 150°C or 200°C for different time in
deuterated DMSO (Fig. 1). As can be seen in Fig. 1b, 1H
NMR spectrum of polymer P15min presents four main
signals caused by different types of CH2 units at d 5.5–
5.3, 4.7–4.5 parts per million (ppm) (I); 4.7–4.4 ppm (II);
4.4–4.0 ppm (III); 4.0–3.5 ppm (IV). Signal I, apart from
the peaks at 5.4 and 4.6 ppm caused by the starting
p-cresol-aniline-based benzoxazine, may be ascribed to
the residual oxazine rings in the structures formed by
12 PART I Synthesis and Properties of Benzoxazine Resins

FIG. 1 1H NMR spectra in deuterated DMSO of p-cresol-aniline-based benzoxazine monomer and various polymers obtained under different conditions.
The polymer P15min, P0.5h, P1h and P5h were obtained by heating p-cresol-aniline-based benzoxazine in the presence of 1 mol% LiI at 150°C for 15 min,
0.5 h, 1 h, and 5 h, respectively. The polymer P200 was obtained by heating polymer P5h at 200°C for 2 h. Note: Signal I ¼ CH2 (residual oxazine rings of
the structure formed by Aryl-attack of various intermediates, Scheme 2), Signal II ¼ CH2(a,b), Signal III ¼ CH2(c,d), Signal IV ¼ CH2(e,f). (Reproduced
€
with permission from C. Liu, D. Shen, R.M. Sebastián, J. Marquet, R. Schonfeld, Mechanistic studies on ring-opening polymerization of benzoxazines: A
mechanistically based catalyst design, Macromolcules 44 (2011) 4616–4622. Copyright (2010) American Chemical Society.)

Aryl-attack of intermediates A, B, or C (Scheme 2). Signal
II can be the result of phenoxy CH2 units CH2(a,b). Signal
III probably indicates the presence of phenoxy CH2 units
CH2 (c,d). Signal IV may be the result of phenolic CH2
units CH2 (e,f). The coordination ring-opening step is indi-
cated by the disappearance of signal (I) (Fig. 1b and c).
After complete ring opening and the following electrophilic
attack steps, various CH2 units in the polybenzoxazine are
formed, which is shown by signals (II, III, and IV) in
Fig. 1c. The rearrangement of phenoxy CH2 units CH2(a,b)
into phenoxy CH2 units CH2(d) and phenolic CH2 units
CH2(e), respectively, and the transformation of phenoxy
CH2 units CH2 (c,d) into phenolic CH2 units CH2(e,f) by
rearrangement are demonstrated by the gradual disap-
pearance of signals (II and III) in Fig. 1d, e, and f. These
results suggest that coordination of ring-opening steps
occurs easily in benzoxazine polymerization process, and
that rearrangement in labile phenoxy structure units to the
final stable phenolic structure units is relatively difficult.
3 CATALYSTS FOR ACCELERATED
BENZOXAZINE POLYMERIZATION
In light of this understanding of the benzoxazine polymer-
ization mechanism, a catalyst accelerates the benzoxazine
polymerization by inducing fast ring opening of benzox-
azine monomer. The benzoxazine polymerization is an
autocatalyzed reaction until vitrification is reached and dif-
fusion begins to control the curing process afterwards
[18–20]. A good catalyst should be able to effectively coor-
dinate with oxygen or nitrogen atoms to produce active
 Catalytic Accelerated Polymerization of Benzoxazines Chapter 2
δ+ δ+
A δ–
Acidic catalysts [A] O N
R R
O N
δ–
B Benxoazine
R Nucleophilic
Basic catalysts [B] δ– O
δ+ N
SCHEME 3 Proposed two types of ring-opening patterns with different catalysts.
iminium cation intermediates and greatly promote the rear-
rangement step to obtain higher percentage of stable phe-
nolic structure, especially Mannich phenolic structure.
As shown in Scheme 3, most reported effective catalysts
are acidic compounds and prefer to accelerate the benzox-
azine polymerization by a typical cationic ring-opening
pattern. However, basic compounds are also able to accel-
erate the benzoxazine polymerization by a nucleophilic
ring-opening pattern, although they are not much studied.
It should be mentioned that in many cases the two types
of ring-opening patterns may exist simultaneously. In other
words, the cationic part of a catalyst coordinates with
oxygen or nitrogen atoms of benzoxazine to accelerate
ring-opening of benzoxazine, and the anionic part may play
a nucleophilic role meanwhile, more or less to facilitate the
ring-opening step. It is expected that a highly effective cat-
alyst would consist of a cationic part with a high affinity
towards oxygen and/or nitrogen atoms and an anionic part
with both strong nucleophilic ability and good leaving-
group properties.
3.1 Acidic Catalysts
The majority of effective catalysts reported for accelerating
benzoxazine polymerization rate are acidic catalysts, proba-
bly because of the nature of cationic ring-opening polymeri-
zation. Some representative acidic catalysts presented in the
literature are shown in Fig. 2.
Ishida et al. investigated in detail the effect of many
potential catalysts on benzoxazine polymerization. On the
basis of comprehensive survey and studies of various cat-
ionic, anionic, and radical catalysts, they proposed a cationic
ring-opening mechanism for benzoxazine polymerization
[5]. In general, an acidic catalyst is more effective. Many
Lewis acids, such as PCl5, PCl3, POCl3, TiCl4, AlCl3, and
MeOTf were shown to be effective for the benzoxazine
polymerization at moderate temperatures. Interestingly, it
was found that the BF3 Et2O complex was not an effective
catalyst for the polymerization reaction of benzoxazine in
methylene chloride solution, while BF3 2H2O complex
13
Benxoazine
R Cationic OA
monomer
ring-opening + Polybenzoxazine
N
–
O
monomer
ring-opening +
Polybenzoxazine
N B
R
exhibits good catalytic activity, which might be to the result
of the formation of free protons derived from the reaction of
BF3 with more basic water [21]. Recently, it was demon-
strated by Ronda and coworkers that BF3 Et2O in combi-
nation with alcoholic solvents is an efficient catalyst
system for the benzoxazine polymerization in solution
under mild conditions [22]. It was proposed that the benzox-
azine polymerization proceeds through an intermediate
hemiaminal ether that leads mainly to the formation of diphe-
nylmethane bridges, and not only the classic Mannich-type
bridges. All these results suggest that exploring a wide range
of metallic compounds would be a good way to develop
highly efficient catalyst for accelerated rate benzoxazine
ring-opening polymerization. Moreover, it is also advanta-
geous that the catalytic activity of a metallic compound can
be conveniently tuned by combination of center metals with
appropriate ligands. Various phenolic structures derived
from the ring-opening of the oxazine ring or dimers and
higher oligomers in the benzoxazine monomers can actually
act as catalysts for further ring-opening polymerization
reactions, resulting in the autocatalyzed nature of benzox-
azine polymerization [20]. Some phenols have been shown
to exhibit a good catalytic effect on the benzoxazine poly-
merization (Fig. 2). Benzoxazine polymerization with a
strong carboxylic acid such as trifluoroacetic acid as the cat-
alyst was found to proceed with no lag between the ring-
opening and aromatic electrophilic substitution steps by
an iminium cation intermediate. [6] By comparison, amino-
methyl ester species are initially generated when a weak car-
boxylic acid, such as adipic acid, is used as catalyst for the
benzoxazine polymerization. While the dielectic constant
increases, they are transformed into the iminium ion form
of the reactive intermediate and the following electrophilic
attack reactions occur. In general, weak carboxylic acids
show better performance on the benzoxazine polymeri-
zation (Fig. 2).
Yagci’s group studied the photoinitiated ring-opening cat-
ionic polymerization of a monofunctional benzoxazine with
onium salts such as diphenyliodonium hexafluorophosphate
(Ph2I+PF6-) and triphenylsulfonium hexafluorophosphate
14 PART I Synthesis and Properties of Benzoxazine Resins
FIG. 2 Representative acidic catalysts used for accelerated benzoxazine polymerization.
(Ph3S+ PF6-) [10]. Irradiation of the catalyst results in the for-
mation of protons. The subsequent protonation of benzoxazine
can possibly occur either at oxygen or nitrogen atoms. The
structure of the polymers formed is complex and suggests a
complicated polymerization mechanism.
Endo and coworkers developed several active catalyst
systems for accelerating benzoxazine polymerization.
(1) Electron-deficient hexafluoroacetylacetonato (F6-acac)
complexes of manganese and iron were found to be highly
active catalysts for benzoxazine polymerization, which are
moisture tolerant and harmless to the thermal stability of
the resulting polybenzoxazine [23]. (2) They first reported
the use of metal free and neutral aromatic urethanes
derived from the phenolic compounds such as resorcinol
and phenyl isocyanate as efficient catalysts for the poly-
merization of benzoxazines in [24]; the possible catalytic
mechanism is presented in Scheme 4. Thermal dissociation
of these urethanes may result in the formation of real active
species, resorcinol and phenyl isocyanate, which facilitate
the rapid induction of the ring-opening polymerization of ben-
zoxazine and finally are incorporated into the resulting poly-
benzoxazine. (3) Cyclohexyl p-toluenesulfonate (TsOCH)
and neophenyl p-toluenesulfonate (TsONP) were estimated
as metal free and highly efficient thermally latent catalysts
for the benzoxazine ring-opening polymerization [25]. They
do not catalyze the polymerization below 100°C while
inducing the polymerization at elevated temperatures. The
possible mechanism may involve the thermal dissociation of
these sulfonate to afford the real active species alkyl cations
and/or p-toluene sulfonic acid (PTS). It is worth noticing that
Ishida’s group reported in 1999 that TsOCH showed good
catalytic activity on cationic ring-opening polymerization of
benzoxazines [26]. (4) It was further found that more efficient
ring-opening polymerization of benzoxazine was achieved by
using a dual system composed of 2-ethyl-4-methylimidazole
(EMI) and PTS [8], which can also be considered a latent cat-
alyst system, with PTS providing active protons to coordinate
with oxygen or nitrogen atoms of benzoxazine, and EMI as the
nucleophile to facilitate the ring opening and the following
rearrangement steps. (5) Recently, they demonstrated the
ability of simple thiophenols as catalysts for the ring-opening
polymerization of benzoxazines, which was designed based
on the reversible nature of the reaction of benzoxazines with
thiols (Scheme 5) [27]. It should be noted that Gorodisher
and coworkers reported in 2011 the detailed study on the reac-
tions of various thiols with benzoxazines [28].
Based on the NMR study on the ring-opening polymer-
ization behavior of a model p-cresol-aniline-based benzox-
azine under various conditions, Sebastián, Marquet, and
coworkers further examined the mechanistic process of ben-
zoxazine polymerization and designed and studied several
bifunctional catalysts. Lil was found to be an extremely
active and effective catalyst [12]. To our knowledge, it is
one of the most effective catalysts yet reported for the
 Catalytic Accelerated Polymerization of Benzoxazines Chapter 2 15

H H
N HO OH O
Ph O O N C
Ph
+ Ph N
O O
Me Me
O N O N

Me Me

+ O
H Me C
O N +
Ph N –
Me
–
O N
O OH

Me
Me

O
–
OH OH N O
+
N Ph
N
Me Me
HO
Me Me
SCHEME 4 Plausible mechanism for the catalytic effect of urethanes on the benzoxazine polymerization.

SCHEME 5 Reversible reaction of benzoxa- –

zines with thiols. RS
+
Ph H Ph
O N O N OH OH
+
R-SH –
N SR N
RS
Me Me

Me Me Me Me

ring-opening polymerization of benzoxazines. They further
established the catalytic activities of a number of different
catalysts and their effects on the structure of the final
polymer by dynamic differential scanning calorimetry
(DSC) and NMR analysis [29].
3.2 Basic Catalysts
Compared with numerous acidic catalysts reported for accel-
erating benzoxazine polymerization rate, basic catalysts have
not drawn much attention, although some amines and imid-
azoles were demonstrated to show good catalytic effect
onbenzoxazine polymerization in some Japanese patents
[30,31].
We chose several typical basic catalysts including
EMI, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 4-
dimethylaminopyridine (DMAP), triphenylphosphine
(PPh3), and tributylphosphane (PBu3) to investigate and
compare their catalytic activities on ring-opening polymer-
ization of the model p-cresol-aniline-based benzoxazine by
DSC analysis. The corresponding mixtures of p-cresol-
aniline-based benzoxazine with various basic catalysts were
placed in a DSC and heated with a rate of 10°C/min. Fig. 3
shows the plots and data obtained by the DSC. Pure p-
cresol-aniline-based benzoxazine reacts with an onset tem-
perature of 261°C and a maximum temperature of 268°C,
showing its poor reactivity. All of the basic catalysts studied
exhibit catalytic effects, more or less. In cases of DBU,
PBu3, and DMAP, the heat-evolution profiles are signifi-
cantly shifted toward a low temperature field, and the cor-
responding onset and maximum temperatures decrease by
61°C and 44°C, respectively, demonstrating their obvious
catalytic effects. By comparison, EMI shows lower catalytic
activity with onset and maximum temperatures at 221°C
and 237°C, respectively. When PPh3 is used, the onset
and maximum temperatures are just slightly lower than that
observed with pure p-cresol-aniline-based benzoxazine,
which might be the result of its lower nucleophilic ability.
These results also suggest that basic catalysts are not as effi-
cient as acidic catalysts. However, considering the different
16 PART I Synthesis and Properties of Benzoxazine Resins

6 FIG. 3 DSC plots and data of pure p-cresol-

Catalysts Tonset (°C) Tmax (°C) ΔH (KJ/mol) Exo Up
Pure monomer aniline-based benzoxazine and its mixtures
No catalyst 261 268 345 with 5 mol% of various basic catalysts.
EMI 221 237 321
4 DBU 200 226 355 PPh3
DMAP 212 224 353
PPh3 257 265 301
Heat flow (W/g)

PBu3 209 227 372 DMAP EMI

2
PBu3

DBU
0

–2

–4
0 50 100 150 200 250 300
Temperatures (°C)

catalytic patterns (Scheme 3), basic catalysts might have
unique catalytic effects and result in special and valuable
inner structures in the final polymer. Moreover, they may
be used in combination with an acidic catalyst to form a dual
catalyst system to facilitate the accelerated benzoxazine
polymerization.
4 CATALYST EFFECTS ON
POLYMERIZATION MECHANISM
AND NETWORK STRUCTURES
4.1 Pure Benzoxazines
Benzoxazines, especially with high purity, have compara-
tively poor reactivity in the absence of catalysts, which
may hinder their widespread applications. The catalyst
has the greatest impact on the ring-opening step and induces
a faster benzoxazine polymerization, but it does not affect
the later processes associated with cross-linking to the same
degree [18–20]. In the middle to later stages, the catalyst-
acceleration effect is decelerated significantly, which might
be caused by decreased freedom in motion of the polymer in
solid state in part caused by the development of a hydrogen-
bonding network. On the other hand, the inherently difficult
transformation of a relatively labile phenoxy structure into a
final stable phenolic structure by rearrangement may be
another reason (Fig. 1) [8,12]. However, the nature of the
catalyst has a profound influence on the progress and termi-
nation mechanism of the benzoxazine polymerization. As a
result, different final network structures and cross-link
density may be generated with different catalysts, which
may allow, in principle, the tailoring of a particular structure
and, therefore, the final properties of the polymer.
A dual catalyst system composed of PTS and EMI was
proposed for efficient catalysis of ring-opening polymeri-
zation of benzoxazines (Scheme 6) [8]. PTS is advantageous
for C-O dissociation of benzoxazines, and EMI serves as a
nucleophile to facilitate the C-O dissociation and to prevent

SCHEME 6 Proposed catalytic rearrangement model of the dual catalyst system comprising of PTS and EMI.
 Catalytic Accelerated Polymerization of Benzoxazines Chapter 2
its recombination. This dual catalyst system is particularly
efficient for successful main-chain rearrangement of
phenoxy into phenolic structure, because it significantly sup-
presses the recombination of the iminium species into the
original phenoxy structure. This process allows the iminium
species time to move to the position for the Mannich reaction
with the ortho position of the phenol moiety.
LiI was designed and found to be a highly active difunc-
tional catalyst for the ring-opening polymerization of
benzoxazines (Scheme 7). Lithium cation effectively coor-
dinates with oxygen or nitrogen atoms and accelerates ring-
opening of benzoxazines. Iodide ion is the nucleophilic
anionic part with good leaving ability and can react with
the ring-opened iminium intermediates to prevent its rapid
recombination with the phenolate (Scheme 7) [12]. This
synergistic effect is also highly efficient for the rearran-
gement of phenoxy into phenolic structures.
The effect of various catalysts on the ring-opening poly-
merization and structure of a simple-model p-cresol-aniline-
based benzoxazine was further investigated by qualitatively
analyzing the shape of signal at 4.0–3.5 ppm in 1H NMR
spectra caused by phenolic CH2 units of the final polymer
[29]. Several typical catalysts were chosen to study how a
catalyst can affect the structure of the final polymer
structure. The polymerization of p-cresol-aniline-based
benzoxazine were carried out in the presence of 1 mol%
of various catalysts at 180°C for 2 h, and the structure of
the phenolic polymer was compared by analyzing their 1H
NMR spectra in DMSO-d6. As can been seen in Fig. 4,
except for the Mannich phenolic CH2 units, more complex
types of phenolic CH2 units such as arylamine Mannich phe-
nolic CH2 units, general phenolic CH2 units, and arylamine
general phenolic CH2 units, may exist with different cata-
lysts. As a result, the amounts and type of phenolic CH2
units might be adjusted by using an appropriate catalyst.
It was reported in 2012 that in the presence of FeCl3,
ring-opening polymerization of benzoxazines proceeds
effectively to generate the arylamine Mannich phenolic
structure in the polybenzoxazine because the coordination
of Fe3+ with the oxygen atom decreases reactivity of phenol
ring and makes the cross-linking reactions occur on the
paraposition of aniline [17]. This arylamine Mannich
structure can delay degradation of the aniline moiety and
improve the thermal properties of polybenzoxazine. On
Nucleophile
I
δ+
R Li δ– δ+ R
O N O N
LiI
Coordination
Leaving group
SCHEME 7 Possible mechanism for LiI-catalyzed ring-opening polymerization of benzoxazines.
17
the other hand, the coordination of Fe3+ with the oxygen
and nitrogen atom in the polybenzoxazine may increase
the cross-link density and anchor the potentially weak moi-
eties, therefore improving the thermal properties of the
polymer.
Recently, the catalytic effect on the ring-opening poly-
merization of benzoxazines was compared in detail using
two representative acidic catalysts, 3,30 -thiodiphenol
(TDP) and 3,3’-thiodipropionic acid (TDA), at a variety
of loadings [32]. The nature of the catalyst has an obvious
influence on the progress and termination mechanism of the
polymerization reaction and therefore the network archi-
tecture and final properties of the polybenzoxazines. It
was found that TDA better reduces the onset of polymeri-
zation and improves cross-link density and thermal prop-
erties (Tg and thermal stability) of the polybenzoxazine.
Because TDA (pKa ¼ 4.1) is a stronger acid than TDP
(pKa ¼ 6.6), it is reasonable that TDA shows higher catalytic
activity on the benzoxazine polymerization and induces a
faster ring opening of benzoxazine. On the basis of vibra-
tional spectroscopic analysis, the thermal polymerization
and TDP-catalyzed polymerization of benzoxazines
conform to a similar polymerization mechanism, and the
resulting polymer network has similar cross-link density
and glass transition temperatures. By comparison, the
ring-opening polymerization of benzoxazine with TDA pro-
gresses via a different mechanism. After faster ring opening
of more benzoxazine monomers, the chain propagation is
more cluster-like (less linear) before cross-linking, leading
to more reaction sites and a higher cross-link density and a
subsequently higher Tg. In addition, we propose that the
higher acidity of TDA might result in deactivation of the
phenol ring of benzoxazine toward active cationic interme-
diates and, consequently, more reactions of the active inter-
mediates on the arylamine ring of benzoxazine. This change
of reaction path further increases the cross-link density and,
therefore, the thermal properties of the polybenzoxazine.
The effect of catalyst loading is initially really obvious
but reaches on apparent plateau at 10–15 mol%, and the
addition of >15 mol% of catalyst had a negative effect on
the cross-link density, Tg and thermal stability of the
polymer. Although the conclusion was made on the basis
of the experimental results without any plausible expla-
nation, we suppose that the catalyst added may act, in part,
OLi Benzoxazine
monomer
Polybenzoxazine
N I
R
18 PART I Synthesis and Properties of Benzoxazine Resins

OH OH
I
N

Me Me I : Mannich phenolic CH2 units

OH
IV II II: Arylamine Mannich phenolic CH2 units
N
III: General phenolic CH2 units
OH IV: Arylamine general phenolic CH2 units
Me III
Me
OH

Me

CH2(I,II)
(a) Standarda

(b) PTS

(c) EMI
CH2(III,IV)
(d) LiI
CH2(III,IV)
(e) LiBr
CH2(III,IV)
(f) LiOTf
CH2(III,IV)
(g) Al(OTf)3

(h) NH4I

(i) ZnCl2

9 8 7 6 5 4 3 2 PPM
FIG. 4 1H NMR spectra in DMSO-d6 of thermally cured mixtures of p-cresol-aniline-based benzoxazine with 1 mol% various catalysts at 180°C for 2 h.
a
Polymer obtained by thermal polymerization of p-cresol-aniline-based benzoxazine at 20°C for 4 h. (Reproduced with permission from C. Liu, D. Shen,
€
R.M. Sebastián, J. Marquet, R. Schonfeld, Catalyst effects on the ring-opening polymerization of 1,3-benzoxazine and on the polymer structure, Polymer
54 (2013) 2873–2878.

as a terminator by its own reaction with the active interme-
diates. When its loading is too high (>15 mol%) in the
system, the chain propagation process may be disturbed
or even prevented, which decreases the cross-link density
and consequently reduces the Tg and thermal stability of
the resulting polymer. Moreover, too much loading amount
of the catalyst may result in the polymer degradation issue.
Decreasing the benzoxazine polymerization temperature
is highly desirable and, by using various catalysts, different
degrees of success have been achieved. However, in view of
the previous discussion, polymerization temperature is still
an important factor for obtaining polybenzoxazine with
good properties. Although benzoxazines can polymerize
under lower temperatures with extended reaction time by
using a catalyst, the corresponding polymers may possess
different inner structure and poor properties. As shown in
Scheme 8, (1) the ring-opening polymerization of benzoxa-
zines performed at lower temperatures (typically < 160°C)
under a catalyst provides polybenzoxazine with more
complex inner structures because at lower temperatures
and in the presence of a catalyst, more ring-opening patterns
seem to be available, resulting in three main intermediates:
A, B and C. The following aromatic electrophilic substi-
tution reactions of these active intermediates operate by
O-attack, N-attack, and Aryl-attack patterns with low selec-
tivity, affording various phenoxy or phenolic structures. The
polybenzoxazine obtained commonly possesses relatively
poor properties because of less Mannich phenolic structure
units generated, which is thought to account for many
unusual properties of polybenzoxazine by forming the very
 Catalytic Accelerated Polymerization of Benzoxazines Chapter 2
SCHEME 8 Proposed polymerization temperature and catalyst effect on benzoxazine polymerization mechanism and inner structure of polybenzoxazine.
stable six-membered hydrogen bond [33,34]. More impor-
tantly, the chain propagation process possibly faces more
difficulty at lower temperatures because of the competing
intramolecular six-membered ring hydrogen bonding for-
mation [35,36]. Monofunctional benzoxazines cannot
provide a large molecular-weight linear polybenzoxazine.
(2) However, when the benzoxazine polymerization is
carried out at higher temperatures (typically > 180°C),
O-CH2 bonds of the benzoxazine monomers may be in com-
plete or partial dissociation state, and ring opening of the
benzoxazines selectively generates the thermodynamically
more stable intermediate A. The following aromatic electro-
philic substitution reactions of intermediate A mainly are O-
attack or Aryl-attack type electrophilic reactions, providing
only Mannich phenoxy and Mannich phenolic structures.
The subsequent fast rearrangement of Mannich phenoxy
structure into Mannich phenolic structure proceeds at higher
temperatures. Moreover, the chain propagation process goes
smoothly at higher temperatures as well. As a result, the final
polybenzoxazine has larger amounts of Mannich phenolic
structure with better network development and therefore
might possess better properties. Notably, too high polymeri-
zation temperature may destroy the inner hydrogen-bonding
interaction and lead to polymer degradation. In brief, when
conducting the polymerization of benzoxazines in practical
applications, we should appropriately choose the polymeri-
zation temperature, polymerization time, and catalyst to
achieve the best cost/performance ratio.
4.2 Benzoxazine-Epoxy Blends
Despite their excellent properties, polybenzoxazines possess
surprisingly low chemical cross-link density in comparison
with the ordinary thermosetting resins, and the molecular
origin of their unusual properties originate from large
amounts of complex hydrogen bonds [33,34] that act as
19
physical cross-link points. To further improve the pro-
cessing and properties of polybenzoxazine, it has been
reported that copolymerization of benzoxazines with
epoxies may improve the cross-link density and inner
structure of polybenzoxazines by the reaction of the phe-
nolic hydroxyl groups from the ring opening of benzoxazine
monomers with epoxy groups, and therefore enhance
thermal and mechanical properties [37]. Investigation of
the polymerization behavior of a benzoxazine-epoxy blend
suggests that the copolymerization of benzoxazine and
epoxy resins occurs at high temperatures after the polymer-
ization reaction of benzoxazines [38]. Thus it is valuable for
practical applications to use catalysts to accelerate the copo-
lymerization reaction rate at lower temperatures and reduce
the copolymerization time. Notably, the catalysts effective
for the benzoxazine polymerization, especially acidic cata-
lysts, commonly show weakened catalytic effects on the
benzoxazine-epoxy blend, because they may be deactivated
because of their coordination with epoxy groups.
During the polymerization of a benzoxazine-epoxy
blend in the presence of a catalyst, three types of reactions
may occur including benzoxazine homopolymerization,
epoxy homopolymerization ,and benzoxazine-epoxy copo-
lymerization (Scheme 9). Different catalysts can be used to
selectively polymerize the blend components, to control the
polymerization kinetics of the individual components in the
benzoxazine-epoxy blend to a degree by choosing the appro-
priate catalyst. Depending on the catalyst and the blend com-
position, the inner structure of the resulting polymer can be
varied, and a predominantly interpenetrating network of
homopolymers or grafted copolymer structure may be gen-
erated, which allows the final properties to be tailored as
desired [39].
The copolymerization of a bisphenol A-based
benzoxazine-epoxy blend in the presence of a thermolatent
catalyst (the salts of p-toluenesulfonic acid and amines) was
20 PART I Synthesis and Properties of Benzoxazine Resins
R SCHEME 9 Three types of polymerization
OH
O N
Δ or Catalyst N presence of a catalyst.
n
(1) R
Benzoxazine homopolymerization
O Catalyst O H
n
(2) CH2R
CH2R
Epoxy homopolymerization
R
OH
O N
Δ or Catalyst N
Epoxy
(3) n Δ or Catalyst
R R
Benzoxazine-epoxy copolymerization
found to occur more rapidly and led to a resulting polymer
with superior mechanical properties than those from
benzoxazine-epoxy blend without a catalyst. This was the
result of a higher cross-link density [40]. Nevertheless,
study of the copolymerization of benzoxazine-epoxy blend
in the presence of EMI suggests that EMI-catalyzed homo-
polymerization of the epoxy occurs at lower temperatures,
and the copolymerization of the residual epoxy with ben-
zoxazine occurs at elevated temperatures. On the other
hand, during the polymerization process of benzoxazine-
epoxy blend, the three types of polymerization reactions
show different sensitivity to the polymerization tempera-
tures. Their sequences can be changed by different initial
polymerization temperatures, which affects the inner struc-
tures and final properties of the resulting polymer [41].
5 CONCLUSION
Benzoxazines have a slow rate of polymerization compared
with other thermosetting materials such as epoxy resins; for
many applications, a faster rate is desirable. The effort to
develop a variety of catalysts, including acidic and basic
catalysts, to efficiently accelerate benzoxazine polymeri-
zation rate at lower temperatures and reduced reaction time
has been the focus of many studies with different degrees
of success. Understanding benzoxazine polymerization
mechanism is helpful to know how catalysts influence the
development of networks and inner structures of polyben-
zoxazines. This knowledge can guide the search for efficient
catalysts for accelerated benzoxazine polymerization. The
catalyst accelerates the benzoxazine polymerization by
smoothly initiating a fast ring opening of benzoxazines at
the initial stage, and does not affect the later process to
the same degree. However, the nature of the catalyst is
important in the progress and mechanism of the benzox-
azine polymerization, and affects the network architecture
and therefore the final inner structure and properties of
the polybenzoxazines. There is still further territory to
explore in understanding the polymerization mechanism
reactions in a benzoxazine-epoxy blend in the
H
m
O CH2R
O
N
n
of benzoxazines and how a catalyst influences the devel-
opment of networks and inner structure of the resulting
polymer. This understanding will help to find desired cata-
lysts that can provide polybenzoxazines with good prop-
erties at lower temperatures and reduced reaction time.
REFERENCES
[1] H. Ishida, T. Agag (Eds.), Handbook of Polybenzoxazine Resins,
Elsevier, New York, 2011.
[2] W.J. Burke, J.L. Bishop, E.L. Mortensen Glennie, W.N. Bauer Jr.,
A new aminoalkylation reaction. condensation of phenols with
dihydro-1,3-aroxazines, J. Org. Chem. 30 (1965) 3423–3427.
[3] A.F. McDonagh, H.E. Smith, Ring-chain tautomerism of derivatives
of o-hydroxybenzylamine with aldehydes and ketones. Nuclearmag-
netic resonance spectra of immonium ions, J. Org. Chem. 33 (1968)
8–12.
[4] G. Riess, M. Schwob, G. Guth, M. Roche, B. Lande, B.M. Culbertson,
J.E. McGrath (Eds.), Advances in Polymer Synthesis, Plenum,
New York, 1985.
[5] Y.X. Wang, H. Ishida, Cationic ring-opening polymerization of ben-
zoxazines, Polymer 40 (1999) 4563–4570.
[6] J. Dunkers, H. Ishida, Reaction of benzoxazine-based phenolic resins
with strong and weak carboxylic acids and phenols as catalysts,
J. Polym. Sci. A Polym. Chem. 37 (1999) 1913–1921.
[7] Y.X. Wang, H. Ishida, Synthesis and properties of new thermoplastic
polymers from substituted 3,4-dihydro-2H-1,3-benzoxazines, Macro-
molecules 33 (2000) 2839–2847.
[8] A. Sudo, R. Kudoh, H. Nakayama, K. Arima, T. Endo, Selective for-
mation of poly(N, O-acetal) by polymerization of 1,3-benzoxazine
and its main chain rearrangement, Macromolecules 41 (2008)
9030–9034.
[9] P. Chutayothin, H. Ishida, Cationic ring-opening polymerization of
1,3-benzoxazines: mechanistic study using model compounds, Mac-
romolecules 43 (2010) 4562–4572.
[10] F. Kasapoglu, I. Cianga, Y. Yagci, T. Takeichi, Photoinitiated cat-
ionic polymerization of monofunctional benzoxazine, J. Polym.
Sci., Part A: Polym. Chem 41 (2003).
[11] T. Hayakawa, Y. Osanai, K. Niizeki, O. Haba, M. Ueda, The curing
reaction of 3-aryl substituted benzoxazine, High Perform. Polym.
12 (2000) 237–246.
 Catalytic Accelerated Polymerization of Benzoxazines Chapter 2
[12] C. Liu, D. Shen, R.M. Sebastián, J. Marquet, R. Sch€onfeld, Mecha-
nistic studies on ring-opening polymerization of benzoxazines: A
mechanistically based catalyst design, Macromolcules 44 (2011)
4616–4622.
[13] H. Ishida, D.P. Sanders, Regioselectivity and network structure of
difunctional alkyl-Substituted aromatic amine-based polybenzoxa-
zines, Macromolcules 33 (2000) 8149–8157.
[14] H. Ishida, D.P. Sanders, Regioselectivity of the ring-opening poly-
merization of monofunctional alkyl-substituted aromatic amine-based
benzoxazines, Polymer 42 (2001) 3115–3125.
[15] A. Van, K. Chiou, H. Ishida, Use of renewable resource vanillin for
the preparation of benzoxazine resin and reactive monomeric sur-
factant containing oxazine ring, Polymer 55 (2014) 1443–1451.
[16] M.W. Wang, R.J. Jeng, C.H. Lin, Study on the ring-opening polymer-
ization of benzoxazine through multisubstituted polybenzoxazine pre-
cursors, Macromolecules 48 (2015) 530–535.
[17] Q.C. Ran, D.X. Zhang, R.Q. Zhu, Y. Gu, The structural transfor-
mation during polymerization of benzoxazine/FeCl3 and the effect
on the thermal stability, Polymer 53 (2012) 4119–4127.
[18] H. Ishida, Y. Rodriguez, Curing kinetics of a new benzoxazine-based
phenolic resin by differential calorimetry, Polymer 36 (1995)
3151–3158.
[19] J. Jang, S. Shin, Cure studies of a benzoxazine-based phenolic resin by
isothermal experiment, Polymer J. 27 (1995) 601–606.
[20] H. Ishida, Y. Rodriguez, Catalyzing the curing reaction of a new
benzoxazine-based phenolic resin, J. Appl. Polym. Sci. 58 (1995)
1751–1760.
[21] J.A. Cid, Y.X. Wang, H. Ishida, Cationic polymerization of benzox-
azine monomers by boron trifluoride complex, Polym. Polym. Comp.
7 (1999) 409–420.
[22] R. Andreu, M. Gàli, V. Cádiz, G. Lligadas, J.A. Reina, J.C. Ronda,
BF3 OEt2 in alcoholic media, an efficient initiator in the cationic
polymerization of phenyl-1,3-benzoxazines, J. Polym. Sci. A Polym.
Chem. 51 (2013) 5075–5084.
[23] A. Sudo, S. Hirayama, T. Endo, Highly efficient catalysts-
acetylacetonato cmplexes of tansition metals in the 4th period for
ring-opening polymerization of 1,3-benzoxazine, J. Polym. Sci. A
Polym. Chem. 48 (2010) 479–484.
[24] A. Sudo, A. Mori, T. Endo, Promoting effects of urethane derivatives
of phenols on the ring-opening polymerization of 1,3-benzoxazines, J.
Polym. Sci. A Polym. Chem. 49 (2011) 2183–2190.
[25] A. Sudo, H. Yamashita, T. Endo, Ring-opening polymerization of 1,3-
benzoxazines by p-toluenesulfonates as thermally latent initiators, J.
Polym. Sci. A Polym. Chem. 49 (2011) 3631–3636.
[26] Y. Wang, H. Ishida, Methyl p-toluenesulfonate-initiated cationic
polymerization of benzoxazine resin, Polym. Mat. Sci. Eng., ACS
81 (1999) 114.
[27] A.W. Kawaguchi, A. Sudo, T. Endo, Promoting effect of thiophenols
on the ring-opeing polymerization of 1,3-benzoxazine, J. Polym. Sci.
A Polym. Chem. 52 (2014) 2523–2527.
[28] I. Gorodisher, R.J. DeVoe, R.J. Webb, Catalytic opening of lateral
benzoxazine rings by thiols, in: H. Ishida, T. Agag (Eds.),
Handbook of Benzoxazine Resins, Elsevier, Amsterdam, 2011,
pp. 211–234.
21
[29] C. Liu, D. Shen, R.M. Sebastián, J. Marquet, R. Sch€onfeld, Catalyst
effects on the ring-opening polymerization of 1,3-benzoxazine and on
the polymer structure, Polymer 54 (2013) 2873–2878.
[30] S. Miura, N. Kano, (Shikoku Chemicals Corp.), Thermosetting resin
composition, Jpn. Kokai Tokkyo Koho Patent JP2000178332A, Jun.
27, 2000.
[31] Sumitomo Bakelite Co., Ltd., Thermosetting resin composition, Jpn.
Kokai Tokkyo Koho Patent JP200086863A, Mar. 28, 2000.
[32] I. Hamerton, L.T. McNamara, B.J. Howlin, P.A. Smith, P. Cross,
Examining the initiation of the polymerization mechanism and
network development in aromatic polybenzoxazines, Macromole-
cules 46 (2013) 5117–5132.
[33] S. Wirasate, S. Dhumrongvaraporn, D.J. Allen, H. Ishida, Molecular
origin of unusual physical and mechanical properties in novel phe-
nolic materials based on benzoxazine chemistry, J. Appl. Polym.
Sci. 70 (1998) 1299–1306.
[34] H.D. Kim, H. Ishida, A study on hydrogen-bonded network structure
of polybenzoxazines, J. Phys. Chem. A 106 (2002) 3271–3280.
[35] A. Laobuthee, S. Chirachanchai, H. Ishida, K. Tashiro, Asymmetric
mono-oxazine: an inevitable product from mannich reaction of ben-
zoxazine dimers, J. Am. Chem. Soc. 123 (2001) 9947–9955.
[36] S. Chirachanchai, A. Laobuthee, S. Phongtamrug, Self termination of
ring opening reaction of p-substituted phenol-based benzoxazines: an
obstructive effect via intramolecular hydrogen bond, J. Heterocycl.
Chem. 46 (2009) 714–721.
[37] H. Ishida, D.J. Allen, Mechanical characterization of copolymers
based on benzoxazine and epoxy, Polymer 37 (1996) 4487–4495.
[38] C. Jubsilp, K. Punson, T. Takeichi, S. Rimdusit, Curing kinetics of
benzoxazine-epoxy copolymer investigated by non-isothermal differ-
ential scanning calorimetry, Polym. Degrad. Stabil 95 (2010)
918–924.
[39] T. Endo, A. Sudo, H. Yamashita, J. Nishida, T. Huver, R. Sch€onfeld
et al., Copolymerization method, WO2009115488A1, Sep. 24, 2009.
[40] H. Kimura, A. Matsumoto, K. Ohtsuka, Studies on new type of phe-
nolic resin—curing reaction of bisphenol-A-based benzoxazine with
epoxy resin using latent curing agent and the properties of the cured
resin, J. Appl. Polym. Sci. 109 (2008) 1248–1256.
[41] H. Wang, P. Zhao, H. Ling, Q. Ran, Y. Gu, The effect of curing cycles
on curing reactions and properties of a ternary system based on ben-
zoxazine, epoxy resin, and imidazole, J. App. Polym. Sic. 127 (2013)
2169–2175.
[42] M.A. Espinosa, V.C.M. Galiá, Synthesis and characterization of
benzoxazine-based phenolic resins: crosslinking study, J. Appl.
Polym. Sci. 90 (2003) 470–481.
[43] A.A. Gallo, Method for preparing polybenzoxazine, US 6,376,080
B1, Apr. 23, 2002.
[44] S. Miura, (Shikoku Chemicals Corp.), Thermosetting resin compo-
sition, Jpn. Kokai Tokkyo Koho Patent JP2003082099A, March 19,
2003.
[45] I. Gorodisher, (3 M Inovative Properties Company), Polybenzoxazine
composition, WO 2011/025652 A1, Mar. 3, 2011.
[46] I. Hamerton, B.J. Howlin, P. Mhlanga, W.A.W. Hassan, Using QSPR
techniques to predict char yield arising from the thermal degradation
of polybenzoxazines, Polym. Degrad. Stab. 98 (2013) 446–452.