3 Polybenzoxazine
new generation phenolics

K.S. Santhosh Kumar and C.P. Reghunadhan Nair

Polymers and Special Chemicals Group, Vikram Sarabhai Space Centre, Thiruvananthapuram, India

O U T L I N E

Introduction 45 Blends/Composites of Polybenzoxazines 61

Synthesis of Benzoxazine Monomers (BZ) 46 Green Chemistry Approaches in PBZ 67
Ring-Opening Polymerization of Benzoxazines 47 Click Chemistry in PBZ 68
Regioselectivity and Cross-Linked Structure 47 Stability and Degradation 69
Inter/Intramolecular H-Bonding 49 Outlook 69
Kinetics of Thermal Cure 49 Acknowledgments 70
Structure-Property Relationships 51 References 70

Introduction 5. Low flammability.

Phenolic resins, a well-known class of materials in
the family of high-performance polymers, can poten-
tially find a myriad of applications in the aerospace,
defense, and structural fields. Their high char yield,
excellent thermo-structural stability, and chemical
inertness are superior to any other high temperature
polymer [1
4]. Although phenolics cannot be substi-
tutes for epoxies and polyimides in many engineering
areas, their composites still find a major market for
thermo-structural applications in the aerospace indus-
try due to good heat and flame resistance, excellent
ablative properties, and low cost. However, void for-
mation during the curing process is a major drawback
that hinders the processing of void-free composite
products from phenolic resins. In this backdrop, the
new polymer system, polybenzoxazines (PBz) from
the family of phenolic resins, assure many attractive
features, such as the following:
1. No catalyst required for curing.
2. No liberation of by-products.
3. No void formation.
4. Near zero volumetric expansion or shrinkage
on curing.
6. Low water absorption.
7. High UV and chemical stability.
8. High char yield.
9. Excellent static and dynamic mechanical
properties.
Comparative properties of PBz with respect to
other important high-temperature polymers are
given in Table 3.1. Due to their excellent thermoset
features, benzoxazine resins can be suitable substitute
materials for epoxy resins bismaleimides, cyanate
esters, and polyimides for many applications. Though
PBz has several advantages, it also has shortcomings
like high curing temperature (190°C and above). The
striking feature of cross-linked PBz is its strong inter
molecular H-bonding; these H-bonds may be
destroyed at higher cure temperature. Inherent brit-
tleness is also a concern for PBz. Hence, modifica-
tions are required to improve the ductility and to
lower the cure temperature for expanding its
applications.
Anchoring of additional polymerizable groups,
copolymerization, and blends and composites with
suitable polymer/reinforcement systems are some
of the routes attempted to achieve desirable

Handbook of Thermoset Plastics. DOI: http://dx.doi.org/10.1016/B978-1-4557-3107-7.00003-8

© 2014 Elsevier Inc. All rights reserved. 45
46 HANDBOOK OF THERMOSET PLASTICS

Table 3.1 Thermosetting Polymers and Their Relative Properties

Property Epoxy Phenolics Cyanate Ester PBz

Cure temperature (°C) RT
180 150
190 180
250 160
220
Maximum use temperature (°C) 180 200 150
200 130
280
Cure shrinkage .3 0.002 B3 B0
Tg (°C) 150
220 170 250
270 170
340
Tensile strength (MPa) 90
120 24
45 70
130 100
125
Tensile modulus (GPa) 3.1
3.8 3
5 3.1
3.4 3.8
4.5
Elongation (%) 3
4.3 0.3 2
4 2.3
2.9
Dielectric constant (1 MHz) 3.8
4.5 4
10 2.7
3.0 3
3.5
Degradation onset temperature (°C) 260
340 300
360 400
420 380
400

properties for the system [5]. New synthesis OH R

O N
approaches like green strategy, click chemistry,
and main chain polymerization, etc., gain equal
importance.
+ 4 HCHO + 2R-NH2

Synthesis of Benzoxazine
Monomers (BZ)
Several methods were adopted for the synthesis
of benzoxazine monomer (3,4-dihydro-2H-1,3-
benzoxazines). Typical methods reported are dehy-
dration of N-(2-hydroxybenzyl)-3-aminopropanoic
acid in the presence of sulphuric acid [6], conden-
sation between o-hydroxy benzylamine and an
aldehyde [7], reaction of primary amines with 1-
(bromomethyl)-2-(chloromethoxy) benzene [8],
and finally, but most importantly, Mannich con-
densation of phenol and a primary amine with
formaldehyde [9
11].
Mannich condensation is the best method among
these and is popularized by Ishida et al. and widely
employed for the preparation of a variety of ben-
zoxazine monomers [12
14]. Three components,
namely an active hydrogen-containing compound
(for example, phenols), primary amines, and form-
aldehyde are the precursors for the synthesis of
benzoxazine (Bz) monomer. The Bz monomer can
be synthesized with and without solvent. In general,
upon heating to about 100°C, the mixture of
these components produces benzoxazine monomer
and ring-opened benzoxazine oligomers in a sol-
ventless method. In a solvent method, solvents like
OH N O
R
Scheme 3.1 Synthesis of bifunctional benzoxazine
monomer (R 5 Phenyl (Bz-A), R 5 CH3 (Bz-m)).
1,4-dioxane can be used at around 120°C under
reflux conditions. Bz monomers along with ring-
opened oligomeric structures are produced. These
ring-opened structures can be removed by using
soft base wash to yield pure benzoxazine monomer.
But for various applications, ring-opened structures
are advantageous as they can catalyze the ring-
opening and further polymerization to occur at
lower temperatures. Mono-functional benzoxazines
with one oxazine ring yield linear polymers. Bi-
and polyfunctional Bz yields cross-linked polymers.
For composite applications, bifunctional benzoxa-
zines are important in that they provide good adhe-
sion to fillers and subsequently high modulus to
composites. Scheme 3.1 shows the synthesis of
benzoxazine monomer from bisphenol A, formalde-
hyde, and primary amine to form bifunctional ben-
zoxazine monomer.
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS 47

OH OH +
O + CH
H+B– 2 CH2
N N B–
N
H3C R R R

CH3 CH3

R
O N
R
R
O N N
H
O
CH3 –H +B– CH3
N +
HO R B–
CH3
N
R
CH3 OH

Scheme 3.2 Initiation mechanism proposed for curing of benzoxazines [17]. (Reproduced with permission
from Wiley-VCH, J. Polym. Sci. Part A: Polym. Chem, 1999, 37, 1913.)

A R
O N
+ + B
R R – R OH
O N O N OR
Δ + N
Ring-opening N Electrophilic R
R substitution
Ring-chain tautomerism
Mannich base

Scheme 3.3 Simplified mechanism of thermal curing of benzoxazines. (Reproduced with permission from
American Chemical Society, Macromolecules, 2010, 43, 4562.)

Ring-Opening Polymerization
of Benzoxazines
Several groups have reported various mechan-
isms for the ring-opening and polymerization of
benzoxazine monomers. In 1968, McDonagh and
Smith proposed a mechanism that describes the
ring-opening of Bz through iminium ion formation
along the chain. This mechanism suggests the
migration of proton from the oxygen to nitrogen
atom and subsequent tautomerism [15]. Riess et al.
proposed a mechanism in which polymerization
pushes forward by condensation of amines with imi-
nium ions [16]. Later, in 1999, Ishida and Dunkers
proposed that the first step in the ring-opening of Bz
is the protonation of the oxygen atom to form an
iminium ion and in the second step the polymeriza-
tion occurs by the electrophilic aromatic substitution
reaction [17]. Scheme 3.2 shows the ring-opening
mechanism of Bz as proposed by Ishida et al.
This mechanism is more probable in view of the
basicity of oxygen and nitrogen of the oxazine ring
that may favor a cationic mechanism for the ring-
opening polymerization of benzoxazine monomers.
However, thermal polymerization without catalyst
is the most common method for the curing of ben-
zoxazine monomer to form cross-linked structures.
In this route, the mechanism can be envisaged as
(i) breaking of aO-CH2 bond, (ii) tautomerism,
and finally, (iii) electrophilic substitution, as
depicted in Scheme 3.3 [18]. As more phenolic
groups are produced during the polymerization, the
acidic phenolic groups enhance the polymerization
rate and create an autocatalytic curing process.
Regioselectivity and Cross-Linked
Structure
Regioselectivity is the most striking characteristic
of polymerization of benzoxazine. The thermal curing
occurs via the attack of iminium ions specifically on
the ortho positions of the phenolic part (Scheme 3.4).
48 HANDBOOK OF THERMOSET PLASTICS

R
R R
O N •• +
OH N

••
O OH O N

••
H2
+ CH2 C
N ••
N

R R

R
+
OH

••
O N ••
OH OH

••
H2 H
C H2
•• C
N ••
N N
R
R R

Scheme 3.4 Polymerization mechanism of PBz via ortho attack of iminium cation (mechanism of thermal
curing).

OH
Path C

OH OH N
Path A

N H3C
CH3 OH

N
N

OH CH3
N N H3C

OH OH
N
Path D
Path B
OH

Scheme 3.5 Major chemical bridge structures in polybenzoxazines. (Reproduced with permission from
American Chemical Society, Macromolecules, 2000, 33, 8149.)

If ortho positions of the phenolic structure of Bz
monomer are blocked, it is hard to undergo poly-
merization. Ishida and co-workers extensively stud-
ied the regioselectivity of polymerization on
difunctional PBz derived from bisphenol A with a
series of amines [19] and proposed the possibility
of formation of various chemical bridges in the
cross-linked structure. Phenolic Mannich bridge,
arylamine Mannich bridge, bisphenolic methylene
bridge, and aryl amine methylene bridge networks
are proposed depending upon the reactivity of ortho
sites and effect of substituents at meta and para
positions in the amine. If the benzoxazine poly-
merizes only at the ortho phenolic sites, the struc-
ture would be a phenolic Mannich bridge network
(Scheme 3.4). If no ortho positions are reacted (as
in the case of bisphenol A and m-methyl toluene-
based monomer), an arylamine Mannich bridge net-
work structure could form (Scheme 3.5).
The generally accepted cross-linked structure of
polybenzoxazine is depicted in Scheme 3.6. It is
characterized by Mannich bridge (CH2-N-CH2) and
an enormous amount of hydroxyl groups that are
inter- or intramolecularly H-bonded.
In some cases, the aryl amine ring can serve as
the site for formation of the methylene linkages,
in which case an aryl amine methylene bridge
network would result. Even though the major
structure is a phenolic Mannich bridge network,
other structures also contribute to the properties
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS
O N OH OH
N N
Heat H3C–C–CH3 H3C–C–CH3
H3C–C–CH3
N
OH N OH
O N
Scheme 3.6 Curing and cross-linked structure of
polybenzoxazine.
and the real structure will be a continuum of all
the structures. In general, the cross-linked structure
of PBz can be characterized by a Mannich base
bridge (CH2-NR-CH2) instead of the methylene
bridge structure associated with traditional phenolic
resins [20
24].
Inter/Intramolecular H-Bonding
A huge number of hydroxyl groups though are
present in the cross-linked structure of PBz; it pos-
sesses low moisture absorption and high water repel-
lence. This feature of PBz is attributed solely to
extensive inter/intramolecular H-bonding. Several
kinds of H-bonded species are identified in the PBz
structure. These are exemplified by examining vari-
ous Bz model dimers by assigning vibrational spectra
of these molecules [20,25]. Intermolecular H-bonding
such as aOH. . .O, intramolecular H-bonding like
aOH. . . .O and aOH. . . .N. were noticed. Further
studies on the H-bonding revealed that the hydrogen
bonding is strongly affected by the basicity of amine
functional group [26,27]. BA-m (derived from
bisphenol A and methylamine) showed mainly
aOH. . .N and aOa. . .H1N intramolecular hydro-
gen bonding, whereas Bz-A (derived from bisphenol
A and aniline) exhibited intermolecular hydrogen
bonding and relatively weak intramolecular hydrogen
bonding. Moreover, the distribution of H-bonding
varies with the symmetric and asymmetric structure
of amine counterpart. Possible H-bonding in symmet-
ric and asymmetric aniline dimers of benzoxazine is
shown in Scheme 3.7.
Two types of H-bonding are envisaged, viz., sta-
tistically distributed and chelated hydrogen bonds
in PBz structure. Temperature has a higher influ-
ence on the statistically distributed hydrogen
49
bonding than chelated H-bonds (low energy confor-
mation) [28]. The unexpected phenomenon of PBz
having high moduli and Tgs even with rather low
cross-link density is attributed to unique H-bonds
present in PBz [29]. The water absorption also
changes with the type of PBz; for instance, PBz-A
has 1.9 weight % water absorption whereas BA-m
possesses low water absorption of 1.3 weight %
after 600 days in water. These behaviors are estab-
lished partially by H-bonding. By computational
chemistry and NMR studies, the supramolecular
and helical structure of Bz oligomers were
described. The intramolecular hydrogen bonds were
identified as the driving force for ring-shape and
helical conformations of Bz oligomeric units
[30
32]. Many of the classical chemical properties
of the PBz materials are explained based on this
geometry, where the N. . . .H. . . .O and O. . . .H. . . .
O hydrogen bonds are protected in the inside of the
helix [33]. The physical and mechanical properties
of Bz were also deliberated on the grounds of exten-
sive H-bonding [34].
Kinetics of Thermal Cure
Benzoxazine monomers can undergo curing
either by thermal or photochemical means. Thermal
curing follows a cure schedule to achieve cross-
linked structure and generally the final cure temper-
ature is in the range of 200°C for 3
4 hours.
Depending upon Bz structure and autocatalysis, the
final cure temperature can vary. The sequence of
curing of PBz is identified as (i) monomer conver-
sion to low molecular weight oligomers, (ii) gela-
tion, and (iii) formation of a high molecular weight
cross-linked structure. The curing is autocatalytic in
nature due to the catalytic activity of phenolic
hydroxyl groups which generates on polymeriza-
tion; the overall reaction order is 2 [14, 35
43].
After vitrification, diffusion controls the kinetics.
The observed activation energy for total curing is
about 110 kJ/mol [14].
The kinetics of the thermal cross-linking poly-
merization of Bz-A monomer as a case study is
presented here. Rheological analyses were carried
out at different isothermal curing temperatures
which revealed the effect of autocatalysis [44]. The
S-shaped curve indicates the autocatalytic nature of
Bz polymerization and the high rate of reaction is
attributed to the presence of hydroxyl groups which
50 HANDBOOK OF THERMOSET PLASTICS

CH3
H3C
O
H
b) N
a) H3C N
H3C OH

CH3 H3C
c) d)
H3C O H O CH3
H
N
N N
H N
O H O CH3

H3C H3C

CH3

Asymmetric aniline dimers

CH3 CH3 CH3 CH3

HO
O O
H H
N b) N
a) H3C CH3 H3C CH3
O
H

CH3

c) H3C H3C

CH3 O
H N
O H O
N H H
O H3C

CH3 CH3

H3C

Symmetric aniline dimers

Scheme 3.7 Possible inter- and intramolecular hydrogen bonding in symmetric and asymmetric polybenzoxazine
analogs. (Reproduced with permission from American Chemical Society, Macromolecules, 2003, 36, 8320.)

generate upon curing. The activation energies for first
order reaction and autocatalysis were 198 kJ/mol and
62 kJ/mol, respectively, and were deduced from fol-
lowing equation and curve fitting (Equation 3.1):
dα
5 ðk1 1 k2 αm Þð12αÞn
dt
Here, k1 and k2 are the first order and autocata-
lytic reaction rate constants, respectively. The low
activation energy derived from the empirical model
implies the prominence of autocatalysis in the
overall kinetics. The overall reaction order con-
formed to 1.6
1.8. The conversion rate obtained
from rheological profiles of Bz-A curing is shown
in Figure 3.1.
The availability of a huge number of aOH
groups formed during the polymerization is the ori-
(3.1)
gin of high autocatalytic behavior that was not as
seen in polyacrylonitrile and Alder-ene systems.
Different cross-linked structures are possible in
polybenzoxazine as stated in the previous sections
of this chapter. Whatever the structure, enormous
numbers of hydroxyl groups are easily accessible
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS 51

7.0⫻10–3
190 °C
6.0⫻10–3 195 °C
205 °C
210 °C
5.0⫻10–3

Rate of reaction 4.0⫻10–3

3.0⫻10–3

2.0⫻10–3

1.0⫻10–3

0.0
0 100 200 300 400 500 600
Time (min)

Figure 3.1 Conversion rate of Bz-A curing at different temperatures as a function of time. (Reproduced with
permission from Elsevier, Thermochimica Acta, 2006, 441, 150.)

H
O N OH
3HC–C–CH3 3HC–C–CH3
O N OH
H
Scheme 3.8 Hydrogen bonding and chelation in
polybenzoxazine. (Reproduced with permission from
Elsevier, Thermochimica Acta, 2006, 441, 150.)
and will cumulatively enhance the polymerization
rate. Very strong intramolecular H-bonding leads to
the chelation as depicted in Scheme 3.8. This struc-
ture contributes to increasing the stability of the
polymer, but the chelation is broken at high cure
temperature to release hydroxyl groups.
The kinetic parameter k2, which corresponds to
the autocatalytic reaction rate, showed one order
increase compared to the first-order rate constant
(k1) (Table 3.2).
Structure-Property Relationships
Benzoxazines Containing
Additional Curable Moieties
After the introduction of bisphenol A and
aniline-based benzoxazine monomer (traditional
benzoxazine, Bz-A) and their polymerization, a
vast number of Bz polymers equipped with addi-
tional cross-linkable groups were synthesized. Bz
monomer synthesis has several possibilities for
stitching curable groups into the Bz structure,
wherein the curable moieties can be anchored onto
either amine or bisphenol counterparts. High cure
temperature and brittleness are the two major nega-
tives of PBz thermoset, and this approach is benefi-
cial in obviating the shortcomings. The additional
curable groups also contribute to the enhancement
of the overall properties of the PBz structure.
Allyl groups are known to enhance the toughness
of bismaleimide polymers. In view of that, allyl
containing Bz was synthesized from allyl amine
and bisphenol A(B-ala), which manifested two
exotherms in calorimetric experiments correspond-
ing to allyl and oxazine polymerization
(Figure 3.2). Independent curing of allyl and oxa-
zine were established by IR studies. The attractive
feature of this PBz is its higher Tg at 322°C [45].
52 HANDBOOK OF THERMOSET PLASTICS

Table 3.2 Kinetic Parameters for Curing of Benzoxazine at Different Temperatures [44]

Temperature (°C) k1 3 104 (min21) k2 3 103 (min21) m n

190 2.0 7.64 0.68 0.57
195 3.2 10.20 0.61 0.58
205 11.0 12.67 0.71 0.63
210 15.4 15.71 0.71 0.78

0.8
Oxazine
0.7 Bz-A
0.6
O O 0.5
0.4

Heat flow (W/g)

0.3

N 0.2
N Oxazine
0.1
0.0
–0.1 Bz-allyl
B-ala –0.2
DABA
–0.3
–0.4
Figure 3.2 Chemical structure of B-ala.
50 100 150 200 250 300 350 400
Temperature (°C)

Figure 3.3 Differential scanning calorimetry profiles

of Bz-allyl, Bz-A, and diallyl bisphenol-A (DABA).
(Reproduced with permission from Elsevier,
European Polymer Journal, 2007, 43, 2504.)

OH N O

NH2
+ (CH2O)n +

O N
OH

Scheme 3.9 Synthesis of allyl-containing benzoxazine monomer (Bz-allyl).

In one of our studies, we incorporated allyl
groups into the ortho positions of bisphenol A to
identify the polymerization possibility of ortho site-
blocked benzoxazine monomers. Towards this, Bz
monomer was synthesized from o,o-diallyl bisphe-
nol A and aniline as presursors (Scheme 3.9). This
Bz also manifested a dual cure pattern in DSC due
to the independent polymerization of allyl and oxa-
zine groups, as observed in B-ala (Figure 3.3).
Here, the allyl polymerization occurred at relatively
higher temperature at 210°C and oxazine curing
was observed at a further high temperature of
273°C [46].
As the normal ortho sites are blocked, it is diffi-
cult to polymerize. But, surprisingly, the Bz under-
goes excellent curing to obtain good thermoset. The
curing mechanism was established by a pyrolysis
gas
chromatography technique by analyzing thermal
degradation products. A difference in aniline content
was noted during the evolved gas release of Bz-allyl
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS 53

Aniline 59%
200.0 200.0

159.9 159.9

119.8 PBz-a 119.8

m Volt Aniline 32%

m Volt

79.7 79.7
PBz-allyl

39.6 39.6

–5 –5
0 2.6 5.3 8 10.6 13.3 16 18.6 0 2.6 5.3 8 10.6 13.3 16

Figure 3.4 Pyrolysis-GC chromatogram of PBz-A and PBz-allyl. (Reproduced with permission from Elsevier,
European Polymer Journal, 2007, 43, 2504.)

against Bz-A. The released aniline content of

Bz-allyl was only 32% compared to 57% of Bz-A
(Figure 3.4). The rather poor release of aniline in Bz-
allyl implies the locking of the aniline moiety through
cross-linking. As the ortho positions are blocked,
polymerization occurred through the para position of
aniline, and aniline got locked in the cross-linked
structure (Figure 3.5). Hence, a different polymeriza-
tion mechanism, routed through the para position of
the aniline moiety, was proposed. The Bz-allyl pos-
sessed high Tg at 298°C and exhibited excellent ther-
mal stability as indicated from T5% at 395°C and
T10% at 425°C. The char yield of Bz-allyl (42%) was
also improved compared to Bz-A (32%).
Another cross-linkable group, maleimide, was
introduced into Bz by synthesizing benzoxazine
monomer with a maleimide pendant, [N-(4-hydro-
xyphenyl) maleimide]-benzoxazine (HPM-Ba). This
has shown good thermal stability with T5% at 330°C,
but only a lower Tg (,200°C) was offered by
this PBz [47]. Its flame retardancy in terms of a lim-
ited oxygen index (LOI) value also was not so Figure 3.5 Cross-linked structure of Bz-allyl.
high. But Bz derived from hydroxyphenylmaleimide aniline and amino phenyl propargyl ether-based mono-
and various amines (e.g. aniline, allylamine, and mers, the curing temperatures were reduced and poly-
amino phenyl propargyl ether) showed excellent merizations of benzoxazine monomers were faster
thermal features (Scheme 3.10) [48]. In the case of than those of maleimide groups. However, in the case
54 HANDBOOK OF THERMOSET PLASTICS

R
O O N

R- NH2 + HCHO Δ
OH + O

O
O

Mal-BZ

Mal-BZ-AI
R

O–CH2–C≡CH Mal-BZ-Pg

Scheme 3.10 Preparation and chemical structures of maleimido benzoxazine monomers.

O N

N
N O
O

O
P-a HPM-Ba

O O O

N OH N COOH N

O O O

MI-OH MI-COOH MI-H

Scheme 3.11 Chemical structures of benzoxazine and maleimide compounds.

of the allyl amine system, curing of benzoxazine was
delayed slightly. The allyl amine-based PBz (Mal-BZ-
Al) has shown Tg at 299°C, whereas propargyl amine-
based PBz (Mal-BZ-Pg) showed a very high Tg at
355°C (due to the contribution of propargyl curing).
Another study investigated the catalytic nature of
maleimide groups in benzoxazine curing [49]. Acids
can catalyze the polymerization of benzoxazine, and it
is reflected in the polymerization P-a (phenol and ani-
line based Bz) when mixed with maleimido phenol.
The curing temperature got reduced due to the cata-
lytic effect of maleimidophenol [49]. The acidic MI-
OH promoted the polymerization of P-a (Scheme
3.11). This is further established by mixing maleimi-
dobenzoic acid (MI-COOH) with P-a, which showed a
very low curing temperature. Another observation is
that the presence of benzoxazine compounds might
also catalyze the reaction of maleimide groups of MI-
OH. Similarly, we also reported the catalysis of ben-
zoxazine by imide groups in a co-reactive blend study
(vide infra).
As propargyl groups can polymerize indepen-
dently to generate cross-linked structures, Bz func-
tionalized with a propargyl group can increase
high-temperature properties of PBz (Scheme 3.12).
Difunctional (bisphenol A and propargylamine,
B-appe) propargyl benzoxazine monomer has shown
only one exotherm in DSC, implying the simulta-
neous polymerization of both propargyl and oxazine
groups. Though the cure maximum observed at
249°C was relatively higher temperature, it pos-
sessed high Tg of 318°C and good char yield of 61%
[50]. In addition, oxazine groups were also intro-
duced as side groups into propargyl main chain
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS
O O
N N
HC
B-appe
C C
O O
Scheme 3.12 Chemical structures of propargyl and furan-functionalized benzoxazine monomers.
O O
N N
C C C C
CH CH
BA-apa
O N
Ph-apa
Scheme 3.13 Acetylene-functionalized benzoxazine monomers.
polymers (polyacetylenes), which resulted in high
char yielding PBz [51]. Furfural units are interesting
due to their capability to withstand high temperature.
From furfurylamine and bisphenol A, Bz was pre-
pared which has a high cure exotherm of 247°C [52].
This high cure temperature is due to the steric hin-
drance from furfural moieties. It possesses Tg at
308°C, and lower CTE values of 37 ppm compared to
56 ppm of Bz-A, which are advantages of these PBz.
Thermally curable acetylene-containing PBz has
superior char yield ranging from 71
81°C [53].
The T10% values were in the range of 520
600°C.
These polymers also have superior solvent resis-
tance. These polybenzoxazines, BA-apa, BPFP-apa,
and Ph-apa monomers (Scheme 3.13), showed Tg
values starting from 330
368°C, which were
55
O O
N N
CH
O O
BA-af
CF3
O O
CF3
N N
CH CH
BPFP-apa
C
CH
significantly higher than those of the analogous
Bz-A, and much higher than their polymerization
temperature (190°C). These excellent thermal fea-
tures are attributed to the acetylene curing.
Phthalonitrile groups incorporated in PBz showed
relatively higher cure temperature (250°C), high Tg
(275
300°C), and char yield of 65
70% at 800°C
as a result of polymerization of nitrile groups along
with oxazine curing [54]. Similarly, the phenylni-
trile cross-linking sites containing polymers showed
excellent thermal properties and improved mechani-
cal properties (Scheme 3.14) [55]. However, the
nitrile functionalities don’t offer any specific pro-
cessing advantages as the nitrile curing warrants
high temperature and long duration. Major features
of functionalized PBz are shown in Table 3.3.
56 HANDBOOK OF THERMOSET PLASTICS

C N
C N
C N
C N

N N
CH3
O
O C O
O C O
CH3
N
N

C N
C N
C N
C N

Phthalonitrile benzoxazines

O O
N O N

NC CN

Phenylnitrile benzoxazine

Scheme 3.14 Phthalonitrile and phenyl nitrile benzoxazines.

Table 3.3 Major Features of Functionalized Polybenzoxazines

Type of Additional Curable Groups Special Features

Allyl High Tmax, TgB300°C, low char yield
Maleimide Low/High Tg (highly dependent on structure)
Propargyl Tg . 300°C, high char yield
Acetylene High char yield (70
80%) and Tg (B330
360°C)
Phthalonitrile Moderate Tg and high char yield
Furfural TgB300°C, Low CTE

In addition, the effects of various functional
groups on traditional polybenzoxazine are compiled
in Table 3.4.
Unfunctionalized
Polybenzoxazines
Without any additional curable groups, a variety
of Bz was reported by changing only the structure of
the amine and phenolic part. Bz derived from dicy-
clopentadiene phenol adduct (DCPD) exhibited a low
dielectric constant of 2.94, which was better than that
of polymers derived from Bz-A (3.31), and traditional
phenolic resin (3.9
4.0, Figure 3.6) [56]. This is
attributed to less efficient chain packing and an
increase in the free volume of the polymer due to the
non-planar structure of DCPD.
By varying the bisphenolic structure, 8,80 -bis(3,4-
dihydro-3-phenyl-2H-1,3-benzoxazine) (22P-a) and
6,60 -bis(2,3-dihydro-3-phenyl-4H-1,3-benzoxazinyl)
ketone (44O-a) were prepared (Figure 3.7) [57]. The
Tg of 22 P-a and 44O-a were 200°C and 365°C,
respectively. Due to the high cross-linking of 44O-a
PBz, Tg was much higher than Tmax (290°C).
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS 57

Table 3.4 Effect of Cross-Linkable Groups on Tg and Thermal Properties of Polybenzoxazine

Functional Benzoxazine Tg (°C) T5% (°C) Char Yield 800°C (%)


180
205 275 28

O O

No additional cross-linkable groups (traditional PBz)

322 343 28
O O

N N

298 393 42

O O

N N

C N 330 423 68
C N

N
CH3

O C O

CH3
N

C N

C N

(Continued )
58 HANDBOOK OF THERMOSET PLASTICS

Table 3.4 (Continued)

Functional Benzoxazine Tg (°C) T5% (°C) Char Yield 800°C (%)

350 462 73
O O

N N

C C
CH CH
B-aa

318 352 62
O O

N N

HC CH

C C

O O
B-appe

315 347 47
O O

N N

O O


Reported by different groups.

Inorganic atoms-embedded polymers are known

for high-temperature stability. A benzoxazine
N O O N (dopot-m, Figure 3.8) from a phosphorus-
containing triphenol (dopotriol) was synthesized
and then copolymerized with DGEBA (diglycidyl
ether bisphenol A), which resulted in a Tg of 252°C
[58]. Thermal properties were increased with
dopot-m content and the T5% value was increased
DCPDBZ
slightly from 323 to 351°C.
Figure 3.6 Structure of dicyclopentadienephenol By incorporating the trifluoromethyl groups,
benzoxazine. fluorine-containing benzoxazine (F-1) was synthe-
sized (Scheme 3.15) [59]. The Tg of the copolymer
of F-1 and Bz-A increased and registered a value of
283°C. This increase in Tg is due to the high inter-
molecular interactions. Due to the hydrophobic
O
nature of the fluorine units, the copolymers exhib-
O O ited good water repellency also.
Cyclohexyl moieties were incorporated into the
N N PBz structure to get good processability and flexi-
ble PBz [60]. The synthesis scheme and structures
Figure 3.7 Structure of 44O-a. are given in Scheme 3.16. All of the cyclohexyl
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS 59

PBz possessed a good processing window and

lower cure temperature. The Tg values varied from
170 to 206°C. The low Tg of the polybenzoxazines
are due to the flexibility of cyclohexyl units and in
O P O cardanol PBz (R 5 C15H31), it is attributed to C15
aliphatic chain also.
O O
However, higher cross-link density vis-à-vis the
PBz-A was noted in cyclohexyl based PBz. The
N N cardanol-based cyclohexyl PBz has cross-link den-
sity of 4390 mol/m3, whereas that of PBz-A was
CH3 CH3 2900 mol/m3. DMA characteristics of cyclohexanol
PBz are shown in Table 3.5.
N O Though the Tg of cyclochexyl polymers were
H3C less than PBz-A, thermal stability of all cyclohexyl
systems were higher than PBz-A. The T5% of
Dopot-m
cardanol-based cyclohexyl PBz was 338°C against
Figure 3.8 Structure of Dopot-m benzoxazine 275°C of PBz-A. This is due to the higher cross-
derived from dopotriol. link density of these systems as already mentioned.
Meanwhile, low char yield was observed for all
cyclohexyl PBz; this is attributed to the low aro-

CF3 CF3

O N O N OH OH
N N

m CH3 CH3 + n CF3 CF3 H3C CH3 F3C CF3

N N
O N O N OH OH
p q
CF3
CF3

Bz-A F1 Bz-A-co-F1

Scheme 3.15 Polymerization of Bz-A with F1 (Bz-A-co-F1). (Reproduced with permission from Elsevier,
Polymer, 2003, 44, 7989.)

HO OH N N
NH2
O O
+ 4 HCHO +

R = -H (PBz-CH), -C15H31(PBz-PD-CH), (PBz-PHC-CH)

Scheme 3.16 Synthesis of cyclohexyl benzoxazine monomers.

60 HANDBOOK OF THERMOSET PLASTICS

Table 3.5 DMTA Characteristics of Cured Monomers

Cured Monomers Tg (°C) Cross-Link Density (mol/m3)

BZ-PD-CH 170 4390
BZ-CH 191 4760
BZ-PHC-CH 206 7590
Bz-A 215 2900

Table 3.6 Thermal Stability and Hydrophobicity of Cylohexyl Polybenzoxazines

Cured Monomers T5% (°C) T10% (°C) Char Yield at Water Contact
800°C (%) Angle ( 6 1°)
BZ-CH 290 324 17 98
BZ-PD-CH 338 366 05 105
BZ-PHC-CH 313 343 16 112
Bz-A 275 335 35 102
T5%: Temperature at 5% mass loss; T10%: Temperature at 10% mass loss.

CH3 CH3

C C

CH3 CH3
NH2 (CH2)6 N N (CH2)6 N
OH
O O n O

Figure 3.9 A main-chain benzoxazine polymer. (Reproduced with permission from Elsevier, Polymer 2006, 47,
7664.)

matic content of polymers. The cardanol derived
cylcohexyl PBz has very low char yield of 5% and
this is due to the fast decomposition of pentadeci-
nyl cyclohexyl moiety from the network structure.
These polybenzoxazines showed improved surface
de-wetting properties. The cardanol PBZ showed
contact angle of 105°. The TGA results are com-
piled in Table 3.6.
Main Chain Polybenzoxazines
By organizing oxazine units in the main chain,
new polymers with extraordinary properties can be
realized. From the simple benzoxazine chemistry to
the preparation of main chain PBz, they paved the
way for designing new functional and easily process-
able polybenzoxazines. The majority of main chain
PBz are thermoplastic and can form excellent films.
Linear PBz can be easily prepared by a main chain
benzoxazine synthesis method [61]. A main chain Bz
is shown in Figure 3.9. Two exotherms manifested in
DSC imply the polymerization of methylol groups
(161°C) and oxazine (242°C) curing, respectively. It
forms films, but thermal stability is poor.
Polyether esters containing benzoxazine units in
the main chain exhibited better film-forming proper-
ties, but thermal stability is not improved compared
to PBz-A [62]. High water absorption is a demerit
of this PBz system, though toughness was imparted
by a soft ether-ester group. Synthesizing Bz from
polyamine (poly(ether diamine)) as the starting
compound leads to main chain type benzoxazine
with low viscosity. These materials are easily pro-
cessable and are of a thermoplastic/thermoset type.
By changing polyamine chain length, cross-link
density, and consequently thermal stability, could be
increased. These materials have T5% from 280 to
350°C with various chain lengths [63].
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS
O N OH
N O OH
Scheme 3.17 Copolymerization of benzoxazine with epoxy.
Sonogashira coupling reaction between iodo
functional bis-benzoxazine (DIBB) and diacetylene
bisether (DABE) or diacetylene bis-benzoxazine
(DABB) yields the novel main chain copolybenzox-
azine precursors. Copolymers DIBB-co-DABE
(polymer A) and DIBB-co-DABB (Polymer B) have
higher thermal stabilities than DIBB/DABB due to
the incorporation of the oxazine structure. They
have high char yield of 58 and 61% for Polymer A
and B, respectively [64]. A low dielectric PBz
(dielectric constant is 2.20) was prepared from
highly fluorinated diamine and polyfluorinated
bisphenol A [65]. These are some of the main chain
PBz which resulted in remarkable properties.
Blends/Composites of
Polybenzoxazines
Blends of polybenzoxazine with other commer-
cially important polymers such as epoxy resins,
polyimides, bismaleimides, and cyanate esters have
been investigated. Some of them have shown a co-
reactive nature, and others resulted in simple blends
or interpenetrating polymer systems.
Co-Reactive and Non-Reactive
Blends
The PBz-epoxy copolymers showed co-reaction
between phenolic hydroxyl groups and epoxy groups.
The phenolic hydroxyl groups catalyzed the epoxide
ring-opening to form copolymers (Scheme 3.17).
The mechanical properties and Tg were optimized at
61
OH
R O H2C HC CH2
O
O
HC CH2
R O CH2
O
R O H2C HC CH2
OH
45% of epoxy content [66]. Though a synergism in
Tg was noted in the blends (Tg higher than Tg of
hompolymers), the char yields of the copolymers
were lower than pure polybenzoxazine. By introduc-
ing phenolic resin to the PBz-epoxy binary system,
the cure temperature got reduced as phenolic resin
acts as initiator for polymerization [67]. In another
study, benzoxazine units incorporated into novolac
resin showed improved high-temperature perfor-
mance [68]. Maleimide-functionalized benzoxazine,
on copolymerization with diglycidyl ether bisphenol-A
(DGEBA), showed three polymerization reactions
corresponding to epoxy, oxazine, and maleimide cur-
ing [69]. In the high content of epoxy, benzoxazine
polymerization was less affected whereas maliemide
polymerization was hindered by high content of
epoxy. A Tg at 278°C was observed at 10 mol% of
DGEBA. The flexural modulus was approximately
5.0 GPa for this composition.
In the presence of poly(imide-siloxane)s, Bz-A cur-
ing initiated at 130
140°C compared to 190
200°C
for pristine Bz-A [70]. The toughness and thermal
stability of PBz-A were enhanced by the addition of
poly(imide-siloxane). Polymer alloys of polybenzoxa-
zine (Bz-A) and soluble polyimide (PI) formed a
semi-interpenetrating network (IPN) structure whereas
PBz-A-poly(amide acid) (PAA) resulted in a complex
cross-linked structure [71]. The imidization of PAA
and ROP of Bz-A occurred simultaneously. An inter-
esting reaction between phenolic OH of PBz-A and
carboxylic acid of PAA generated an AB cross-linked
structure. However, both PBz-API and PBz-A/PAA
showed only one Tg. The Tg and thermal stabilities
increased remarkably with the PI content. Meanwhile,
62 HANDBOOK OF THERMOSET PLASTICS

(a) 21 (b)

Transmittance (%)

Transmittance (%)
26 18
1687

15

25 1702
1714
1719 12
1700 1680 1710
Wave number (cm–1) Wave number (cm–1)

Figure 3.10 FTIR spectra of carbonyl region of (a) Cured blend of Bz-A/BMI (1/1), (b) Cured BMI.
(Reproduced with permission from Santhosh Kumar KS, Reghunadhan Nair CP, Sadhana R, Ninan KN. Eur
Polym J 2007;43:5084.)

Hydrogen bonding of carbonyl moiety

H
the modulus of the alloy films increased with Bz-A O O
with free hydroxyl group
content. Polysiloxane-block-polyimide (SPI) has a
number of attractive characteristics such as excellent N

thermal stability and low moisture absorption. In

another work, the Bz-ASPI blends showed excellent O
stability with T10% at 450°C. The flexibility got
enhanced significantly compared to PBz-A but Tg was
not affected [72].
In the blend of PBz-A/BMI (bismaleimide (2,2-
bis[4(4-maleimidophenoxy) phenyl] propane, the
curing temperature of BMI was reduced due to the
O O
catalysis of maleimide polymerization by benzoxa- O H
zine groups. In one of our studies, the peak cure H H

temperature of the blend got reduced to 211°C vis- O

H-bonding of carbonyl moiety with
à-vis of BMI (270°C) and PBz-A (218°C) [73]. No intermolecular H-bond hydroxyl group
N
strong catalysis in Bz polymerization was noted in
this work. But BMI polymerization was affected
significantly. H-bonding between the carbonyl group O

of BMI and the aOH group of polybenzoxazine

played a crucial role in determining the cross-linked Figure 3.11 H-bonding in Bz-A/BMI (1/1 molar)
matrix structure. Two different types of H-bondings blend. (Reproduced with permission from Santhosh
were revealed by IR between the free hydroxyl Kumar KS, Reghunadhan Nair CP, Sadhana R,
group and aCO of BMI, and the intermolecular Ninan KN. Eur Polym J 2007;43:5084.)
H-bonded aOH and aCO of BMI (Figures 3.10
and 3.11). This extensive H-bonding facilitates a mechanism is shown in Figure 3.12 [74]. However,
homogeneous phase in the PBz-ABMI matrix. in DMA, two Tg values were noted at 145°C and
A mutual catalytic mechanism was proposed for 267°C due to microphase separation. In support of
the curing of the total system. The electron- the DMTA observation, dual-phase morphology due
deficient maleimide groups and electron-rich ben- to microphase separation was noted in Bz-A/BMI
zoxazine groups may undergo nπ-pπ interaction blends by SEM analysis (Figure 3.13). But, the min-
(between amino group of benzoxazine and unsatu- ute and undefined domains reveal strong phase con-
rated group of maleimide) to weaken the O-CH2-N tinuity. This high-level miscibility is attributed to the
bond, which makes the cleavage easier. The catalytic H-bonding between polymers.
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS
O Bz-allyl/BMI showed two exotherms at 228°C and
Weakening of-C-O bond
N O
N 269°C is due to the ROP of benzoxazine. An
O The heat of reaction of the blend was 190 J/g,
Figure 3.12 Weakening of aC-O bond of oxazine
group by nπ-pπ interaction in the Bz-A/BMI blend.
(Reproduced with permission from Santhosh Kumar
KS, Reghunadhan Nair CP, Sadhana R, Ninan KN.
Eur Polym J 2007;43:5084.)
Figure 3.13 (a) Homogeneous morphology of cured
Bz-allyl/BMI blend (1/1), and (b) Minute level
microphase separation in cured Bz-A/BMI blend (1/1).
(Reproduced with permission from Santhosh Kumar
KS, Reghunadhan Nair CP, Sadhana R, Ninan KN.
Eur Polym J 2007;43:5084.)
63
Another work describes the co-reactions in allyl-
containing Bz (Bz-allyl) and BMI. The blend of
269°C, respectively. The first exotherm is attributed
to the co-curing of Bz-allyl-BMI, and exotherm at
important observation in this blend concerns the
heat of reaction of the blend (1/1 by molar ratio).
whereas the heat of reaction for independent curing
of Bz-allyl is 40 J/g and for BMI is 130 J/g. This
strongly suggests a change in mechanism of cure.
A mechanism is proposed which invokes an Alder-
ene reaction followed by ROP of Bz-allyl (Scheme
3.18). The Bz-allyl/BMI co-reacted network exhib-
ited a single Tg at 274°C. However, polymer alloys
of 1,10 -(methylene-di-4,1-phenylene)-bismaleimide
(BMI) and Bz-A showed improved toughness and
Tg of 268°C at 76% of BMI content [75].
Cyanate ester, an important polymer for the
aerospace/electronic industry, has been incorporated
in PBz-A. The PBz-A/BACY (cyanate ester) blend
showed the trimerization of cyanate groups and
ROP of benzoxazine that occur almost simulta-
neously (in a mutually catalyzed manner) [76]. The
OH groups resulting from ROP of oxazine react
with cyanate groups to form triazine networks at
the end of co-reactions. The cross-linked structure
is proposed in Figure 3.14.
A very significant inference from the PBz/
BACY reactive blend is a multifold increase in the
glassy modulus at 30°C of the blend compared to
homopolymers (Figure 3.15). The glassy modulus
of PBz-A was ,1 GPa, BACY was ca. 2.2 GPa,
but the 1/1 molar blend exhibited a glassy modulus
of about 7.5 GPa. This enormous increase is due to
the co-reactions which resulted in a new matrix
containing both cyanate ester and polybenzoxazine.
Non-reactive blends also offered equally good
properties due to secondary interactions like hydro-
gen bonding. Significant hydrogen bonding interac-
tions were noticed in the non-reactive blends of PBz-A
and poly(3-caprolactone) (PCL) upon curing. The Tg
of the blends got optimized at 33 wt.% of PCL
[77
80], and no reactions were noticed in this system.
But it is also reported that the ROP and curing of Bz
was hindered by polycaprolcatone (PC) [81,82]. The
hydrogen-bonding was observed between aOH and
aCO groups, and due to the H-bonding, the PBz/PC
blend showed enhanced miscibility [83]. Rubber-
modified polybenzoxazine-PCL blend featured low
64 HANDBOOK OF THERMOSET PLASTICS

thermal properties [84]. Similarly, PBz/poly(N-vinyl-
2-pyrrolidone) exhibited strong hydrogen bonding
interactions between PBz-A and polyvinyl pyrrolidone
segments [85]. Poly(urethane-benzoxazine) films
showed no phase separation due to in situ polymeriza-
tion [86]. Up to 15% Bz-A, content good elastic
behavior was observed, but a plastic nature was
observed for more than 20% of Bz-A-containing com-
positions. The properties of blends of bisphenol A-
based polybenzoxazine and different bisphenol A-
based thermosetting polymers (1:1 molar ratio sys-
tems) are compared in Table 3.7.

Ene adduct

Wagner-Jauregg
Alder-ene

Further cross-linking

Scheme 3.18 Cure reaction in Bz-allyl and BMI blends. (Reproduced with permission from Santhosh Kumar KS,
Reghunadhan Nair CP, Sadhana R, Ninan KN. Eur Polym J 2007;43:5084.)
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS 65

Fiber and Micro Composites
Glass/silica/carbon fibers and microballons were
used as filler for PBz composites. Silane-treated
and untreated glass fibers strongly influenced the
ILSS (inter laminar shear strength) of PBz compo-
sites. Untreated glass fiber-PBz composite reduced
the ILSS to about half, whereas the silane-treated
RO N OR RO
N N
O O
N N
Figure 3.14 Postulated co-reacted network in Bz-A
and BACY blend. (Reproduced with permission from
Santhosh Kumar KS, Reghunadhan Nair CP, Ninan
KN. Eur Polym J 2009;45:494.)
8 PBZ was reduced by adding silica fiber with micro-
1/1
7
Storage modulus (GPa)
one retained the strength [87]. Carbon fiber compo-
sites of Pbz showed excellent properties with
respect to change in length of fiber [88]. Tensile
strength was doubled by carbon fiber reinforcement
due to an increase in contact area of fiber with
polymer which renders the interface strong. About
2.5 times increase in flexural strength was noted in
these composites. Variation of tensile strength with
carbon fiber length is shown in Figure 3.16. The
N OR mechanical properties of PBz-carbon fiber with
N N
fiber length are collected in Table 3.8.
Lightweight materials like syntactic foams are
attractive, and can be made by dispersion of hollow
N microspheres/microballoons in precursors and sub-
sequent curing. They find wide applications in
structural fields. Syntactic foams of PBz showed
moderate strength with low density [89]. The ten-
sile and compressive strengths were optimized at
40% by weight (68% by volume). The failure
mechanism occurs by the fracture of microballoons.
A noted point is the accumulation of air voids as
observed in SEM.
The coefficient of thermal expansion (CTE) of
ballons [90]. The CTE of neat PBz was
50
60 ppm/°C. The CTE of silica fiber-filled Pbz

4 160
Tensile strength (MPa)

3
BACY
2 120
1

0 Bz-A
80
–1
0 100 200 300 400
T(°C) 40

Figure 3.15 Storage modulus profiles of

0 7 12 17 22 27
homopolymers and polybenzoxazine
cyanate ester
Fibre length (mm)
blends. (Reproduced with permission from Santhosh
Kumar KS, Reghunadhan Nair CP,Ninan KN. Eur Figure 3.16 Variation of tensile strength with fiber
Polym J 2009;45:494.) length.

Table 3.7 Relative Properties of Blends of Bisphenol A-based PBz-A and Other Bisphenol A-Based Thermosets

Blends Cure Initiation (Ti) °C Tg (°C) T5% (°C) Phases

PBz/Cyanate ester B125 230 290 Homogenous
PBz/Bismaleimide 142 145, 267°C 335 Microphase separation
PBz/Epoxy resin B150 B150 B280 Homogenous
66
Table 3.8 Modulus of Composites with Carbon Fiber Length
References Tensile Modulus
(GPa)
PBZ 3.0 (ca.)
BC-7 4.3 6 0.6
BC-12 4.8 6 0.8
BC-17 6.2 6 0.8
BC-22 3.7 6 0.1
BC-27 2.3 6 0.3

Approximate values.
Note: The number associated with the References column indicates the length of carbon fiber (millimeters) used for composite preparation.
was in the 15
50 ppm/°C range. Meanwhile, the
CTE of silica-filled syntactic foams was still lower,
about 4.7 ppm/°C, and showed no change with
microballoon incorporation. These results show that
the fiber-embedded PBz syntactic foams have better
dimensional stability under thermal stress condi-
tions than the corresponding fiber-incorporated
PBz. Such synthetic foams could serve as excellent
thermal insulators and ablatives with potential
applications in satellite and launch vehicles.
Nanocomposites of PBZ
Nanomaterials of PBz were investigated, and a
few works have reported on PBz-based nanocom-
posites. These nanocomposites can show improved
toughness, increased tensile properties, and flam-
mability features, etc. Nano-clays and POSS nano-
particles are the two major nanomaterials
incorporated into PBz. Organically modified mont-
morillonite (OMMT) spedup the ROP of Bz-A to
occur at 180°C compared to 223°C of Bz-A
[91,92]. The acidic protons on the OMMT surface
catalyzed the ROP of Bz-A. Depending upon the
loading of OMMT, exfoliation and intercalation
occurred in PBz-PU/OMMT hybrid nanocomposites
[93]. Exfoliation occurred in composites with less
than 5% OMMT, and above that a mixed nature
was observed. The curing temperature was reduced
due to the catalytic effect of the clay surface that
enabled the complete cure of Bz without thermally
decomposing the polyurethane part. Fluid benzoxa-
zine, 3-pentyl-5-ol-3, 4-dihydro-1,3-benzoxazine,
was used to make nanocomposites with clays, which
HANDBOOK OF THERMOSET PLASTICS
Flexural Modulus Compressive Modulus
(GPa) (GPa)
4.0

32.0 6 2.4 2.6 6 0.2
30.8 6 2.8 3.4 6 0.2
30.1 6 0.6 3.3 6 0.1
27.5 6 0.9 2.8 6 0.1
24.4 6 2.0 2.7 6 0.1
increased the diffusion of Bz to the clay layer.
Polymerization of Bz occurred through the gallery
of nanoclay layers. However, the thermal properties
did not show significant improvement [94].
The octa(propylglycidyl ether) polyhedral oligo-
meric silsesquioxane (OpePOSS) and octa-
aminophenyl polyhedral oligomeric silsesquioxane
(OAPS) were incorporated into PBz. OpePOSS-
PBZ showed reaction between epoxide groups and
OH of PBz. The properties enhanced slightly with
nano reinforcement [95,96]. Methyl methacrylate
POSS was incorporated into furfural functionalized
benzoxazine by a Diels-Alder reaction (Scheme
3.19). They could undergo simultaneously ther-
mally induced cross-linking reactions between
200
240°C. Due to the lack of macrophase separa-
tions, transparent samples were obtained. The
dielectric constant of pristine benzoxazine was
about 3.4, which drastically reduced to 2 by incor-
porating MMA-POSS [97].
In PBz and carboxyl MWCNT nanocomposites,
carboxyl groups catalyzed the ROP of Bz and
decreased the curing temperature [98]. In PBZ-
isocyanate MWCNT, the isocyanate groups reacted
with the phenolic hydroxyl groups resulting in
increased adhesion of PBz with MWCNT. The
well-known Diels-Alder chemistry was used to pre-
pare CNT
PBz composites in another work
(Scheme 3.20). Here, furan-containing Bz was used
as the diene [99]. PFBz chains could graft onto
MWCNT and addition of only 0.5 wt% of
MWCNT significantly increased the electrical con-
ductivity of the nanocomposite to 5 3 1027 S cm21
at 0.1 Hz. The most important result is the
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS 67

O
O + O
O O
O
8 N
MMA-Poss O
O
N

O
O

O
O
O O
Si Si O
O
Si O O
O Si
O O
O O
O O
Si
O
O Si O
O Si O
Si O
O
O O
O
O O O

8= MMA-Poss

Scheme 3.19 Diels-Alder reaction between methyl methacrylate POSS and benzoxazine. (Reproduced with
permission from Elsevier, Polymer 2010, 51, 5567.)

O O
O O O
O H
+ N CH3 N + N C N
C
H
CH3 O O
MWCNT BPA-FBz BMI
DMF 80°C, 120 h

O O
H
O O O N C N O
N CH3 N H
C O O
CH3 n
MWCNT-PFBz

Scheme 3.20 Grafting of PFBz onto MWCNT by Diels-Alder chemistry. (Reproduced with permission from
Elsevier, Polymer 2012, 53, 106).

achievement of electrical conductivity of preparation of their monomers from renewable

1025 S cm21 for the composites with the addition
of 2.5 wt% of MWCNT-FBz.
Green Chemistry Approaches
in PBZ
Renewable materials are always a key subject of
interest to researchers due to the alarming rate of
depletion of petroleum-based products. Apart from
traditional PBz, polybenzoxazines are also synthe-
sised from bio-based products and mixed with bio-
materials to enhance the utilization of natural
resources and properties of PBz. Polybenzoxazine
chemistry is now finding a breakthrough through the
active hydrogen-containing compounds. For
instance, benzoxazine derived from cardanol (which
is a phenolic compound from cashew nutshell liquid
(CNSL)) offers high flexibility to polybenzoxazine
films. However, cardanol moieties hampered the
polymerization of Bz due to steric hindrance.
Furfural-based (produced from vegetable waste)
PBz endowed with high thermal stability and furan
groups decreased the curing temperature of PBz.
Recently, another bio-based compound, viz.,
diphenolic acid (DPA), which is obtained as a con-
densation product of phenol and levulinic acid, is
used for the preparation of polybenzoxazine.
Methyl diphenolic acid-based benzoxazine (MDP-
Bz, Figure 3.17) was synthesized by the reaction of
68 HANDBOOK OF THERMOSET PLASTICS

CH3
CH3 O C O
O C O
N CH2 N
N CH2 N CH2
CH2 COOH
COOCH3 DPA-Bz
MDP-Bz

Figure 3.17 Chemical structures of methyl diphenolic acid and diphenolic acid-based benzoxazines.

n m O CuBr, 2,2-dipyridyl n m
+
N THF, rt, 24h O

O N N
N3 CH N N

Scheme 3.21 Thermally curable polystyrene via click chemistry of benzoxazines. (Reproduced with permission
from American Chemical Society, Macromolecules, 2007, 40, 4724.)

diphenolic acid methyl ester (MDP, which is syn-
thesized from diphenolic acid), 1,3,5-triphenylhexa-
hydro-1,3,5-triazine, and formaldehyde. MDP-Bz
evinced a peak cure temperature at 261°C, which is
quite high, and is a major drawback of this benzoxa-
zine. It is well known that acid catalysts can enhance
the polymerization rate and reduce the curing temper-
ature. Towards this end, DPA was added to the
MDP-Bz system. A shifting of the polymerization
exotherm to lower temperatures was noted with dif-
ferent DPA content. Curing temperature was reduced
to 179°C (from 249°C of neat Bz) by adding 25 wt.%
of DPA to MDP-Bz. Though the thermal stability of
the system is satisfactory, the Tg goes down to 179°C
from the 301°C of MDP-Bz [100].
The diphenolic acid-based benzoxazine (DPA-
Bz) is an excellent rigid foam material due to its
inherent chemical structure and subsequent decom-
position. The decarboxylation of DPA-Bz was
exploited here to realize benzoxazine foam. The foam
properties can be varied by changing the decomposi-
tion temperature to around 200°C. The obtained
low-density foams exhibit high glass transition tem-
perature (207°C) with heterogeneous open-cell
morphology [101].
By the sol-gel route, cardanol-based benzoxazine
(CBz)/SiO2 hybrid films were prepared and hydro-
gen bonding between CBz and SiO2 particles were
noted [102]. Cashew nut shell liquid was used for
the preparation of benzoxazine, and it possessed
high processability due to internal plasticization.
But a poor Tg of 85°C reduces its application in
many fields. Green composite can be prepared by
using wood flour as filler [103]. As lignin, a renew-
able natural resource with a structure similar to phe-
nolic resins, possesses aliphatic and phenolic aOH
groups, it can act in dual ways as a catalyst as well
as for functionalization. Self-extinguishable and
high LOI were observed with this PBz system [104].
Click Chemistry in PBZ
Click chemistry using an azide/alkyne reaction is
a good strategy for preparing tailor-made polymer
compositions with unusual properties. A few
reports were published on the use of click chemis-
try in polybenzoxazines. Room temperature curable
polystyrene was prepared by attaching Bz as a side
chain through click chemistry (Scheme 3.21). In a
comparison, the char yield of the thermally cured
polystyrene was 36.5% and much higher than
chloromethyl silane-cured styrene (11.5%) and divi-
nyl benzene-cured styrene (0.0) [105]. Linear
benzoxazine-containing polymers were also suc-
cessfully synthesized through click reaction [106].
By combining cellulose to Bz through click
chemistry, char yield of cellulose was increased
3: POLYBENZOXAZINE
NEW GENERATION PHENOLICS 69

O Bz-A is stable in the presence of acids, whereas

O S CH3 BA-m is not, and BA-m fragmented into powder
O OH
O HO O
form in the carboxylic acid treatment. Generally, the
O
O decomposition of PBz mainly consist of three steps:
HO OH O
O S (i) loss of amine moieties, (ii) degradation of
O CH3 Mannich bridges, and (iii) main chain degradation
DMF NaN3 [54]. As the initial decomposition is the loss of amine
N3 fragments, one way to increase the thermal stability
OH is to allow the amine part to react to form a cross-
O HO O
O
O linked network [110]. Additional cross-linking sites
HO OH
N3 to amines can be incorporated by allyl, acetylene,
DMSO O propargyl, and maleimide groups, etc. This strategy
Cul pyridine N established that the thermal stability of polybenzoxa-
zines can be enhanced by further cross-linking
H3C O
through these reactive amines [111,112].
N The decomposition products of PBz were identi-
N N
NH fied by TGA and gas chromatography
mass spec-
troscopy (GC-MS) analysis. Several degradation
OH
O HO O
products were identified [113,114]. Direct decom-
O
O position products and recombination of decom-
HO OH
posed gases also contributed. Mainly, benzene
HN derivatives, amines, phenolic compounds, and
N N N
O Mannich base were emerged directly from the poly-
mer. Biphenyl compounds from the recombination
of phenyl radicals, secondary degradation of phe-
H3C nols to benzofuran, isoquinoline, and phenathridine
derivatives by loss of OH groups and dehydrogena-
Scheme 3.22 Benzoxazine functional cellulose; a tion were the some of the decomposition products
combination of click reaction and green chemistry. detected. The overall degradation of polybenzoxa-
(Reproduced with permission from Wiley-VCH, Journal zine is shown in Scheme 3.23.
of Applied Polymer Science, 2012, 125, 1346.) Under UV light, PBz undergoes oxidation at iso-
propylidene linkage (in PBz-A polymer) and further
from 4% to 44% at 800°C. Lowering of curing photooxidation to form 2,6-di-substituted benzoqui-
temperature and improved decomposition character- none [115,116]. The major structure of PBz is
istics are other benefits of PBz derived by this route Mannich bridge, which is highly resistant to photo-
(Scheme 3.22) [107]. oxidation. Minute quantities of Schiff bases were
Low surface energy materials were prepared by identified, which may be due to non-oxidative
click chemistry on POSS nanocomposites with ben- cleavage of the Mannich bridge.
zoxazine groups [108]. They could be cured at 120°
C. Very low surface energy materials (14.6 mJ/m2),
lower than that of PTFE (22 mJ/m2), were prepared Outlook
from PBz/POSS nanocomposites.
Polybenzoxazine chemistry is incredibly attrac-
tive in the milieu of high-temperature polymers due
Stability and Degradation to many superior aspects. It is poised to outshine
the phenolic resins market in terms of processabil-
The basic amine groups in a polybenzoxazine net- ity and thermal and mechanical properties. This
work are vulnerable to acids [109]. In the presence of chapter throws some light on the fundamental
acids, BA-m polymer is less stable and weight loss aspects and developments in the field of benzoxa-
was observed below 250°C. The susceptibility of zine polymers. The inter- and intramolecular hydro-
PBz to acids varies with the final network structure. gen bonding in the polymer is the origin of
70 HANDBOOK OF THERMOSET PLASTICS

OH
OH OH
N N
N

C
C

OH HO
Primary decomposition Products

NH2 OH OH
N

NH2 OH

Mannich base
Benzene Amines Phenilic compounds
derivatives compounds

Secondary decomposition products

O
N N
2,3-Benzofuran Isoquinoline Phenanthridine
Biphenyl
derivatives derivatives derivatives
compounds
Char formation

Scheme 3.23 General decomposition products of polybenzoxazine. (Reproduced with permission from
Elsevier, Hemvichian K, Ishida H. Polymer, 2002,43,4391.)

their unique properties. Polymers functionalized by
incorporating allyl, maleimide, furan groups, etc.,
have been explored, and co-reactions with epoxy
resin, cyanate esters, etc., have been featured as
means of improvising properties. Nanomaterials
introduced into PBz systems are attractive means
for conferring mechanical features. Behavior of
PBz toward heat and light, and the subsequent
degradations, have been elaborated upon. New
approaches such as click reactions and green chem-
istry for functional materials have shown a good
perspective for future synthetic directions of this
special polymer. This new generation polymer
remains to be fully exploited for many of the high-
tech applications in aerospace, electronics, defense,
and structural fields.
Acknowledgments
The authors thank the Director, VSSC for per-
mission to publish this book chapter. Dr. CP
Reghunadhan Nair extends his extreme happiness
to the editors for inviting him to contribute to The
Handbook of Thermoset Resins.
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