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 Polybenzoxazines:
Chemistry and Properties

Dr. K.S. Santhosh Kumar

Dr. C.P. Reghunadhan Nair

iSmithers – A Smithers Group Company

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.ismithers.net
 First Published in 2010 by

iSmithers
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK

©2010, Smithers Rapra

All rights reserved. Except as permitted under current legislation no part

of this publication may be photocopied, reproduced or distributed in any
form or by any means or stored in a database or retrieval system, without
the prior permission from the copyright holder.

A catalogue record for this book is available from the British Library.

Every effort has been made to contact copyright holders of any material
reproduced within the text and the authors and publishers apologise if
any have been overlooked.

ISBN: 978-1-84735-500-3 (hardback)

978-1-84735-501-0 (softback)
978-1-84735-502-7 (ebook)

Typeset by Argil Services

Printed and bound by Lightning Source Inc.
P
reface

The chemistry of polybenzoxazines blossomed in the mid-1990s. These thermally

stable polymeric materials have become very popular during the last decade. They
received a lot of attention in view of their potential use as high-performance polymers.
This necessitated meticulous investigation of their chemical, mechanical, thermal and
surface characteristics.

Even though >200 articles have been published and many patents applied for, a book
detailing the potential research and development of polybenzoxazines is lacking. We
hope that a book describing the up-to-date development of these high-tech polymers
will be an important resource for researchers and those working in the polymer
industry.

Polybenzoxazines obviate many shortcomings associated with their ‘parental’ phenolic

resins. They can form void-free materials (due to addition polymerisation) whereas
phenolic resins form voids during curing (because of condensation polymerisation).
For polybenzoxazines, no catalyst is needed for curing, the moisture uptake is very
low, the glass transition temperature is high, and the char yield is high.

This book is divided into four chapters. Chapter 1 describes the competency of
the properties of polybenzoxazine against other state-of-the-art polymers. Recent
developments in parent phenolic resins, epoxy resins, and cyanate esters are addressed.
The hydrogen bonding aspects in the crosslinked network of polybenzoxazines,
the regioselectivity and kinetics of polymerisation (curing) are also detailed in this
chapter.

Chapter 2 is devoted entirely to the diverse types of syntheses of benzoxzines and

their properties. The syntheses are grouped into (i) benzoxazine with additional
polymerisable groups (e.g., allyl, propargyl); and (ii) benzoxazines derived from
various precursors (based on several different amines and diphenols) without
additional polymerisable moieties. Tailored polymeric systems such as blends, alloys,
copolymers, nano-, micro- and fibre composites are described in a systematic manner in
Chapter 3. Finally, the stability and degradation of polybenzoxazines under chemical,

iii
Polybenzoxazines: Chemistry and Properties

thermal and photochemical environments are discussed in Chapter 4.

A concerted effort has been made to include all significant advancements in

polybenzoxazine science. However, in this emerging area of high-temperature
polymers, novel polymers are constantly being discovered. Suggestions from readers
are welcome and will be acknowledged gratefully.

We thank R. Sivaramakrishnan and Dr. P. Radhakrishnan Nair, VSSC, for reviewing

the manuscript and for giving fruitful suggestions. Thanks are due to the Editorial
Board and Director, VSSC, for giving permission to publish the book.

We would like to thank iSmithers Publishers for inviting us to write this book.
K.S. Santhosh Kumar

C.P. Reghunadhan Nair

India, 2010

to

Vikram Sarabhai Space Centre,

Thiruvananthapuram, India, 2010

iv
C
ontents

1 Polybenzoxazines and State-of-the-Art High-Temperature

Polymers.................................................................................................1
1.1 Introduction.................................................................................1
1.2 Epoxy Resins...............................................................................1
1.2.1 Chemistry of Epoxy Resins..............................................2
1.2.2 Reactions of Epoxy Resins and Curing Mechanisms.......3
1.2.3 Recent Developments......................................................3
1.3 Bismaleimides..............................................................................5
1.3.1 Synthesis and Features of BMI.........................................5
1.3.2 Modified BMI..................................................................6
1.3.3 Recent Developments......................................................8
1.4 Cyanate Ester Resins..................................................................12
1.4.1 Thermal Curing.............................................................12
1.4.2 Thermal Stability...........................................................13
1.4.3 Modified Systems..........................................................14
1.4.3.1 Phenolic-triazine Resins.................................15
1.5 Phenolic Resins..........................................................................17
1.5.1 Allyl-functional Phenolics..............................................19
1.5.2 Bisoxazolineñphenolics..................................................19
1.5.3 Phenolic ResinñEpoxy Systems......................................20
1.5.4 Propargyl Ether and Ethynyl Novolacs..........................21
1.5.5 Recent Developments in Phenolics.................................23

v
Polybenzoxazines: Chemistry and Properties

1.6 Polybenzoxazines.......................................................................24
1.6.1 Features of PBZ.............................................................28
1.6.2 Regioselectivity..............................................................28
1.6.2 Hydrogen-bonding Aspects...........................................31
1.6.4 Cure Monitoring and Kinetics.......................................34
1.7 Conclusion.................................................................................36

2 Structure-Property Relationships..........................................................51
2.1 Introduction...............................................................................51
2.2 Functionalised BZ (BZ Containing Addition-curable
Moieties)....................................................................................52
2.2.1 BZ-Containing Allyl Groups.........................................52
2.2.2 BZ Containing Maleimide Groups................................55
2.2.3 BZ-Containing Propargyl Groups..................................59
2.2.4 BZ-Containing Furan Groups........................................61
2.2.5 BZ-Containing Acetylene Groups..................................63
2.2.6 BZ-Containing Nitrile Groups.......................................65
2.2.7 Main-chain or High-molecular-weight PBZ...................66
2.3 BZ Derived from Various Precursors
(Non-functionalised BZ)............................................................77
2.4 Conclusion.................................................................................91

3 Blends and Composites of Polybenzoxazines........................................95

3.1 Introduction...............................................................................95
3.2 PBZ-Epoxy Blends.....................................................................95
3.3 PBZ-Poly(e-Caprolactone) Blends..............................................97
3.4 PBZ-Polyimide Blends................................................................98
3.5 Other Blend Systems................................................................100
3.6 Nanocomposites of PBZ..........................................................112
3.6.1 PBZ-Clay Systems.......................................................112

vi
 Contents

3.6.2 PBZ-Polyhedral Oligomeric Silsesquioxane (POSS)

Systems........................................................................114
3.6.3 Miscellaneous Nanocomposites...................................115
3.7 Fibre Composites and Microcomposites..................................115
3.8 Conclusion...............................................................................126

4 Stability, Degradation Chemistry and Applications.............................131

4.1 Introduction.............................................................................131
4.2 Chemical Stability....................................................................132
4.3 Thermal Stability and Degradation..........................................133
4.4 UV Stability and Photochemical Degradation..........................140
4.5 Degradation Mechanism of PBZ: A Comparison
with other Thermosets.............................................................141
4.6 Applications.............................................................................145
4.7 Conclusion...............................................................................149

Abbreviations................................................................................................153

Index ..........................................................................................................161

vii
Polybenzoxazines: Chemistry and Properties

viii
1
Polybenzoxazines and State-of-the-Art
High-Temperature Polymers

1.1 Introduction

High-temperature polymers are leading the polymer market because of their variety
of applications. They find widespread use in areas such as adhesives, structural
applications in aerospace, printed circuit boards, conductive polymer elements,
and encapsulation materials for electronic applications [1]. The aerospace industry
and space programmes have created new demands for high-temperature polymers
which can withstand further higher temperatures owing to their excellent thermal
and thermo-oxidative stability, high char yield, good chemical inertness, abrasion
resistance and flame retardance. The best known members of the thermoset family
are phenolic resins, epoxy resins, unsaturated polyesters, isocyanate-derived polymers,
bismaleimides (BMI), acrylates, and cyanate esters [2]. Several challenges must be
overcome regarding processing of these materials. This includes higher melting and
processing temperatures as well as void formation during curing.

In recent years, development of the benzoxazine (BZ)-based family of phenolic resins

has attracted significant attention. Polybenzoxazines (PBZ) are a special type of
phenolic resins that do not form voids during curing due to addition polymerisation.
‘Traditional’ phenolic resins result in void-full polymers because the polymerisation
is of the condensation type. The attractive characteristics of BZ polymers include:
low melt viscosity; no release of volatiles during cure and no need of harsh catalysts
for curing; high thermal stability; good mechanical properties; excellent electrical
properties; and wide flexibility with respect to molecular design.

Before the discussion of PBZ chemistry, the state-of-the-art and other competing
thermally stable polymeric candidates are addressed in this chapter. This is followed
by discussion of the chemistry and fundamentals of PBZ.

1.2 Epoxy Resins

Epoxies are the most versatile class of polymers and have diverse applications; they
are probably the best-known thermoset polymers. The largest use of epoxies is in

1
Polybenzoxazines: Chemistry and Properties

protective coatings; other applications include printed circuit boards, laminates,

electronic materials and structural composites. Cured epoxies provide excellent
mechanical strength; toughness; outstanding resistance to chemicals, moisture and
corrosion; good thermal, adhesive and electrical properties; absence of volatiles and
low shrinkage on cure; and good dimensional stability. This unique combination of
properties is, in general, not found in any other plastic material. The patent literature
indicates that the synthesis of epoxy resins was discovered as early as the late 1890s
[3–5]. These materials are used as antenna reflectors, solar panel arrays, and optical
support structures in satellites. Epoxy-polyaromatic composite motor cases have
replaced the heavy metallic counterparts in modern launch vehicles. Satellites and other
components are also made of epoxy/carbon and epoxy/polyaromatic composites.

1.2.1 Chemistry of Epoxy Resins

The monomers of epoxy resins are characterised by more than one epoxy ring which
undergoes ring opening to produce epoxy resins. Most commercially important
epoxy resins are prepared by the coupling reaction of compounds containing at least
two active hydrogen atoms (including polyphenolic compounds, monoamines and
diamines, aminophenols, heterocyclic imides and amides, aliphatic diols and polyols
and dimeric fatty acids) with epichlorohydrin followed by dehydrohalogenation.

Epoxy resins derived from epichlorohydrin are termed as ‘glycidyl-based resins’. The
most widely used epoxy resins are the diglycidyl ethers of bisphenol A (DGEBA)
(Scheme 1.1).

O
HO OH CH 2 Cl

Bisphenol A Epichlorohydrin

OH
O O
H2 C O O CH 2 CH 2 O O CH 2

Typical bisphenol A epoxy resin

Scheme 1.1 Typical synthesis of epoxy resins

2
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

Approximately 75% of epoxy resins currently used worldwide are derived from
DGEBA. Others include brominated bisphenol A (which imparts fire resistance),
epoxy phenol novolac (EPN) resins, bisphenol F epoxy resins, epoxy cresol novolac
resins, and tetraglycidyl-4,4′-diaminodiphenylmethane.

1.2.2 Reactions of Epoxy Resins and Curing Mechanisms

Crosslinking of the resin can occur through the epoxide or hydroxyl groups. It
proceeds by two types of curing mechanism, i.e., direct coupling of resin molecules
by a catalytic homopolymerisation, or coupling through a reactive intermediate. The
ability of this ring to react by several paths and with various reactants gives epoxy
resins their great versatility. The chemistry of most curing agents currently used is
based on polyadddition reactions that result in coupling as well as crosslinking. The
most widely used curing agents are compounds containing active hydrogen such as
polyamines, polyacids, polymercaptans and polyphenols [6–15].

1.2.3 Recent Developments

The fully cured fluorinated epoxy resin 1,1-bis (4-glycidylesterphenyl)-1-(3-

trifluoromethylphenyl)-2,2,2-trifluoroethane was shown to have good thermal
stability with a glass transition temperature (Tg) of 170–175 °C and temperature
at 5% weight loss of 370–382 °C in N2. It also showed mechanical properties as
good as the commercial epoxy resins. It also possessed low water absorption due to
the presence of a hydrophobic fluorine atom [16]. A novel imide ring and siloxane-
containing cycloaliphatic epoxy monomeric compound 1,3-bis[3-(4,5-epoxy-1,2,3,6-
tetrahydrophalimido) propyl] tetramethyl disiloxane (BISE) was thermally cured
with alicyclic anhydrides, hexahydro-4-methylphthalic anhydride (HMPA) and
hexahydrophthalic anhydride (HHPA), respectively. The fully cured BISE epoxy resins
have good thermal stability, high thermal decomposition temperature, and excellent
mechanical and dielectric properties. However, they gave a relatively low Tg due to
the presence of flexible propyl and siloxane segments in the epoxy backbone [17].
Blends of diethyl tolylene diamine-cured DGEBA epoxy resin have been modified by
flexible diamines, which show that the addition of flexible diamines improves the
elongation at break and impact strength [18].

New mercaptan-terminated polythiourethanes were used as curing agents for epoxy

resin, which found use as effective surface-coating materials [19]. The effect of multi-
walled carbon nanotubes (MWNT) on the cure reaction of the epoxy resin showed
that, at the early stage of the cure reaction, a low mass fraction of MWNT reduces
the activation energy of the reaction. However, excess MWNT hinder the contact

3
Polybenzoxazines: Chemistry and Properties

between functional groups, which elevates the activation energy [20]. The epoxy-
cardanol resin exhibits better properties as compared with epoxy resin (DGEBA) in
terms of increase in tensile strength, elongation, bonding with steel, and lowering of
water vapour transmission of the film [21].

Diallyl bisphenol A (DABA) was used as a curative for novolac epoxy resin (EPN).
The reaction was catalysed by triphenyl phosphine (TPP). The activation energy of
the system diminished from 91 kJ/mol to 67 kJ/mol on addition of 0.5 wt% TPP
[22]. The matrix resin provided a low Tg (80 °C). On initiating further crosslinking
by the 100% curing of the allyl groups, the mechanical properties were diminished
even though Tg was increased (Table 1.1) [23]. However, the glass composites of the
matrix system showed a marked increase in flexural strength from 369 MPa (40%
allyl curing) to 458 MPa by complete curing of allyl groups.

Table 1.1 Effect of allyl curing on the properties of a DABA-EPN system

Property 40% Allyl cured neat 100% Allyl cured neat
Tensile strength (MPa) 118 77

Flexural strength (MPa) 113 110

Tg (°C) 79 91

A polyhedral oilgomeric silsesquioxane containing eight functional hexafluorine

groups called octakis (dimethylsiloxyhexafluoropropyl ether) silsesquioxane (OF)
is a nanoporous additive. OF has been synthesised and blended with the ultraviolet
(UV)-cured epoxy resin, which resulted in remarkable thermal characteristics. OF
containing (10%) epoxy has a significantly lower dielectric constant (2.65) than the
neat epoxy (3.71) [24]. Epoxy-phenolic-based foams have also been studied [25].
Epoxy-clay nanocomposites were prepared with organically modified layered clay
with varying clay contents (1–8 wt%). The tensile modulus of the nanocomposites
increased by 47%, but improvement in tensile strength and Tg was not observed
due to the intercalated morphology of clay layers in the epoxy resin systems [26].
Epoxy-coiled carbon nanotube composites have shown high hardness and elastic
modulus [27].

4
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

1.3 Bismaleimides

Polyimides are manufactured in various forms which find use in the electronic, medical,
structural, and adhesive fields. Polyimide films are very popular, particularly in the
aerospace field, and are known as ‘Kapton films’ (DuPont). In film form, they do
not display a Tg, have good radiation resistance, and are used as bagging material for
composites, belts, wire wrapping, and thermal insulation for satellites. Condensation
and addition polyimides are used as high-performance matrices. Condensation
polyimides are typically based on high-molecular-weight poly(amic acid) precursors
that release voids during curing and decompose below their melt temperature. Addition
polyimides are low-molecular-weight resins containing unsaturated moieties such
as maleimido, ethynyl, and nadimido. They do not form voids when they undergo
curing and a void-free matrix is theoretically possible. Among addition polyimides,
BMI is the most important system used for advanced material applications due to its
high performance-to-cost ratio. However, unmodified BMI show brittleness due to
high crosslink density and lower toughness.

1.3.1 Synthesis and Features of BMI

BMI resins are synthesised by reacting diamines with maleic anhydride in two steps:
formation of bismaleimic acid and imidisation [28]. A typical synthesis is given in
Scheme 1.2.

O O O O O
NH R NH C
O H2 N Ar N H2 N Ar N

C OH OH C
O O O
O O

Scheme 1.2 General synthesis of a bismaleimide monomer

BMI resins undergo curing initiated at ~150–250 °C and peak temperatures ~230–
330 °C dependent upon the structure. In general, the onset and peak exotherm
temperatures increase with the size of the bridging group between two maleimido
groups. These results arise from the reduced concentration of the maleimido groups.
Cured BMI have excellent heat and thermal resistance, and high Tg and decomposition
temperatures. Bis(4-maleimidophenyl)methane and its modified resins are the most
important advanced thermosetting materials. These resins possess a differential

5
Polybenzoxazines: Chemistry and Properties

scanning calorimetry (DSC) exotherm peak temperature of 260 °C and melting point
of 148–158 °C. The mechanical properties are good and have a Tg of 230–290 °C.
They have high property retention at elevated temperatures. Electrical properties such
as dielectric strength, volume resistivity, dielectric constant, and dissipation factor
are generally good for the fabrication of electronic components [29]. However, low
elongation to failure and poor toughness are concerns for structural applications.

Even though basic BMI resins possess good performance after thermal curing, the
toughness of the cured resin is a major concern with respect to material durability.
BMI resins modified with soft segments are useful for flexibility improvement but
drastically reduce their glass transition temperatures and property retention at elevated
temperatures. Incorporation of ether linkages in a BMI resin reduces the brittleness of
the cured thermoset. BMI resins are incorporated with aliphatic polyether to modify
the fracture strength. Introduction of engineering thermoplastic segments between
two bismaleimido groups is an attractive way to achieve high heat resistance and
improved toughness. BMI-poly(arylene ethers) show significant increase in their Tg
values after curing. Because of the improved solubility (processability) and toughness
compared with simple BMI resins, these materials are useful for the preparation of
structural composites. These composites have low tensile strength, elongation, good
heat resistance and electrical properties similar to phenolic and epoxy composites
[30]. BMI resins with low-molecular-weight compounds and oligomers require a
significant increase in molecular weight and structure modification to become useful.
A few curing reactions, such as thermal polymerisation, addition reactions, and the
Diels–Alder reaction have been developed to increase the application performance
of BMI resins.

1.3.2 Modified BMI

In general, aromatic BMI resins produce high char yield at elevated temperatures and are
self-extinguishable. The fire retardance of aromatic BMI can be enhanced by bridging
with phosphorus-containing segments [31]. They have a Tg >380 °C and anaerobic
char yield of 60–71% at 800 °C. Maleimide-terminated oligomers and maleimide
end-capping agents have been investigated for high-temperature applications [32–34].
BMI undergo Michael additions with hydrogen-active moieties such as phenol,
thiols, and amines. These reactions are used to prepare various high-performance
thermosets. One important class of high-temperature thermoset is derived from BMI
resins and allylphenyl oligomers. Upon thermal curing, the mixtures copolymerise
to produce polymers with a high Tg. For example, the mixture of 3,3′-DABA and
bis(4-maleimidophenyl)methane displays low- and high-temperature exotherms at
~130 °C and ~255 °C, respectively. The low-temperature exotherm was recognised as
an ene-reaction between allyl and maleimido groups. The high-temperature exotherm

6
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

was related to a Diels–Alder reaction of the functional groups produced in the reaction
[35]. The overall reaction, known as the ‘Alder-Ene reaction’, is illustrated in Scheme
1.3. A stiff, heat-resistant ring structure is formed by Diels–Alder polymerisation. It
is an excellent approach to increase polymer performance. Soluble BMI with good
electrical properties have been synthesised from siloxane-containing bis furans and
BMI monomers [36]. The brittleness of the cured thermoset is a major concern for
structural applications. Rubber toughening is an effective way to improve the impact
resistance, but heat and thermo-oxidative resistance goes down due to the reduction
in the Tg and the poor oxidative stability [37].

O O

HO OH N R

O O

o,o′ diallyl bisphenol-A Bismaleimide

Ene addition
O

O O
N

N R N
HO OH HO
O
O O

Ene adduct
O O

Wagner-Jauregg N R

O O
O
R
O O O
N

O N
N R N HO OH
O
OH
O O

Ene and Diadduct

Further crosslinking

Crosslinked product

Scheme 1.3 Co-reactions in the blend of DABA and BMI

7
Polybenzoxazines: Chemistry and Properties

Diamine-terminated amide resins were prepared to modify bis(4-maleimidophenyl)

methane to lower the crosslinking density and to increase the toughness of the cured
materials [38, 39]. The same resin has also been chain-extended with aliphatic amines
[40]. Polyoxyalkyleneamines are effective chain extenders that significantly improve
the flexibility and elasticity of modified resins [41]. Copolymerised BMI materials
have been prepared to improve the processability and the performance of the final
thermoset [42]. A technology using alkenyl phenols and alkenyl phenol ethers to
react with BMI to form processable prepolymers was developed by Zahir and Renner
to improve the toughness and humidity resistance of BMI resins [43]. During the
crosslinking process, allylphenyl ethers undergo thermal Claisen rearrangements to the
corresponding allylphenols, and then proceed with the crosslinking reactions through
the Ene–Alder reaction and Diels–Alder reaction. A class of thermosetting resins,
N-allyloxyphenyl maleimides, having both allyl and maleimide groups in a molecule
have been developed [44]. Polybenzimidazole is a high-temperature thermoplastic
polymer with a Tg of 435 °C that has been incorporated into BMI to increase the
fractural energy and toughness [45]. Combination of the rigid rod benzimidazole
structure, Michael addition of BMI resins, and BMI-allylphenol reactions have resulted
in the preparation of molecular composites with the simultaneous improvement of
tensile strength, modulus, and elongation [46].

Commercial addition-cure formulations based on co-reaction of diallyl phenols and

BMI such as Matrimide-5292 from Ciba-Geigy which typically contain DABA and
4,4′-bismaleimido diphenyl methane (BMM) (Scheme 1.4) are leading matrix resins
for carbon fibre composites for advanced aerospace applications.

O O

N CH 2 N

O O

4,4′ Bismaleimido diphenyl methane (BMM)

Scheme 1.4 Structure of BMM

1.3.3 Recent Developments

Interpenetrating polymer networks (IPN) of BMI-modified polyurethane-epoxy

8
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

systems were prepared by curing polyurethane-modified epoxy with aliphatic or

aromatic BMI in the presence of 4,4′-diaminodiphenylmethane. Incorporation of
aromatic BMI into the polyurethane-modified epoxy system increased the Tg, thermal
stability, and electrical properties. Decreased values of the Tg and heat distortion
temperature were obtained in the case of aliphatic BMI-modified polyurethane-
epoxy systems [47]. Epoxy systems modified with cyanate ester (CE) were made with
diaminodiphenyl methane as the curing agent. The cyanate ester-toughened epoxy
systems were further modified with the BMI N,N′-bismaleimido-4,4′-diphenylmethane
and N,N′-bismaleimido-4,4′-diphenylsulfone. Incorporation of BMI into unmodified
epoxy and CE enhanced the thermal and mechanical properties according to its
percentage content [48]. Epoxy-novolac resin modified with 4,4′-bismaleimido
diphenyl methane showed that when BMI concentration was high, the adhesive
force, degradation temperature and thermal stability were enhanced, whereas the
shear strength showed a decreasing trend [49]. Epoxy-based laminate properties were
improved with the incorporation of BMI [50]. The BMI modified-novolac resin was
synthesised by allylation of the novolac resin and its ‘ene’ reaction with BMI. The
BMI-modified allyl novolac resin with 48% degree of allylation has the best thermal
properties and the highest dynamic modulus [51].

The curing process of BMI and dicyanate ester monomers containing a naphthalene
ring involves copolymerisation between these monomers, and self-additional
polymerisation may occur in the last course of the curing process. Investigation into
the co-curing of bisphenol A-based CE and the BMI 2,2-bis[4-(4-maleimido phenoxy)
phenyl]propane (BMP) indicates no co-reaction between the two, and the system
finally formed a sequential IPN [52, 53]. The cured polymer blends were found to
undergo two-stage decomposition, with each stage corresponding to the components
of the blend.

Compositions richer in BMP were found to be relatively brittle and possessed a high
propensity to develop microvoids on curing. The system becomes brittle with BMP
content of >40%. The 2,2-bis(4-cyanatophenyl)propane (BACY)-rich systems were
good only for neat resin casting. The increase in BMP content decreased the tensile
properties, whereas these blends possessed improved flexural strength and fracture
toughness. The BACY-rich blends showed a single Tg which was observed at a slightly
lower Tg than that of polycyanaurate (~250 °C). However, the blends with BMP
content of >50% showed two glass transitions due to phase separation. Due to the
formation of IPN structure, these blends showed low moisture absorption (1.49-
1.25 wt%). The mechanical properties of BACY/BMP sequential IPN are shown in
Table 1.2.

9
Polybenzoxazines: Chemistry and Properties

Table 1.2 Mechanical properties of BACY/BMP IPN matrix systems

Content of Fracture Tensile Tensile Flexural

BMP in the IPN toughness (MN/ strength modulus strength
(wt%) m3/2) (MPa) (MPa) (MPa)
0 3.8 70 3140 95

10 3.5 68 3100 100

20 3.4 64 3531 105

30 4.1 59 3825 114

40 5.3 46 3603 117

The BMI–triazine resins (effectively a blend of CE and BMI) with different proportions
showed good thermal stability, their Tg values were >440 °C, and the residual char ratio
at 700 °C was ~60% [54]. The onset cure temperatures of the blend of bis propargyl
ether bisphenol A (PBPA) with 4,4′-bismaleimide diphenyl methane (BDM) resins
were about 20–30 °C lower than that of pure PBPA, and the cure exothermic enthalpy
of the resins also significantly reduced from 1320 J/g (PBPA) to 493 J/g (PBPA-BDM
(1.0:2.0)) [55]. Thermosetting resin systems with very high Tg values were formulated
on the basis of BMI and allylated novolac. When the allylation degree of the novolac
resin was sufficiently high, the BMI proportion was not critical to the heat resistance
of the cured resin [56, 57].

BMI and biscitraconimides with bisallyl groups and brominated BMI also showed
enhanced thermal and mechanical features [58, 59]. A series of BMI monomers
with amide groups were prepared and characterised [60]. A new type of BMI resin
containing an epoxy unit and phosphorus in the main chain was synthesised [61].
The polymers, obtained through the reactions between BMI and diamine agents, also
demonstrated excellent thermal properties and high char yield.

Novolac resin based on 2,2′-diallyl bisphenol A when co-reacted with bisphenol

A bismaleimide provided a resultant high-temperature resin with good adhesive
strength at higher temperature. The moderately crosslinked blend was conducive
for achieving optimum adhesive properties on aluminium substrates. Retention of
adhesive properties was >100% at 150 °C [62]. Phenol-(4-hydroxy)phenylmaleimide-

10
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

formaldehyde (PMF) resins were prepared from phenol, hydroxyphenylmaleimide

(HPM) and formaldehyde. These matrix resins were investigated for their adhesive
properties by blending with EPN. The lap shear strength (LSS) of PMF resin was
poor (~5 MPa) at ambient temperature. The PMF-29 resin (which contains 29% of
HPM) with EPN in a 1:1 ratio provided optimum adhesive properties with 84%
and 47% retention of the LSS at 150 °C and 175 °C, respectively, and could serve as
a potential structural adhesive for moderately load-bearing applications. The cure
reactions in the PMF-EPN system are shown in Scheme 1.5. The adhesive strength
was improved by toughening the materials through blending with high-temperature
thermoplastics [63, 64].

CH2 OH CH2 CH2

O
CH

O O CH2 O O
N N
O

CH2 170 °C CH2

CH2 CH2 CH2
m n n
m
OH O
OH CH2 O

PMF EPN HO CH CH2

CH2 CH2 HO CH

O O

O O
N
H2 C CH2

0 °C
-25
CH2 CH2 180
m n

O
CH2 O

HO CH CH2

CH2 HO CH

O O

H2C CH2

Scheme 1.5 Cure reactions in PMF-EPN blend

11
Polybenzoxazines: Chemistry and Properties

1.4 Cyanate Ester Resins

CE resins have received considerable attention in the past few years due to their
importance as thermosetting resins for use as encapsulants in electronic devices, high-
temperature adhesives, and structural materials in aerospace applications because of
their outstanding mechanical, thermal, and adhesive properties [65–70]. This new
generation of thermoset resins encompasses the processability of epoxy resins, thermal
characteristics of BMI, and the heat resistance and fire resistance of phenolic resins.
CE resins have their own unique properties such as good strength, low dielectric
constants, radar transparency, low water absorption, and superior metal adhesion,
which make them the resin of choice in high-performance structural applications in
the electronics and aerospace industries [71, 72]. CE are formed in excellent yields
by the reaction of the corresponding phenols with cyanogen halides (Scheme 1.6).

R OH CNBr R OCN
HBr

Scheme 1.6 Synthesis of cyanate esters

1.4.1 Thermal Curing

CE can undergo thermal or catalytic polycyclotrimerisation to give polycyanurates.

The catalysts are usually Lewis acids, transition metal complexes or amines. In general,
they are cured with a transition metal catalyst or chelate catalyst in the presence of
a hydrogen donor such as nonyl phenol. It is accepted that the cyanate cure takes
place through cyclotrimerisation to give polycyanurates. However, evidence for this
mechanism is inconclusive. The thermal cure reaction of the bisphenol A cyanate
BACY using a monofunctional model compound suggested that trimerisation was
the major reaction (>80%) in the curing process [73]. There was very little outgassing
during the polymerisation reaction, which allowed for easy fabrication of void-free
composites. The thermal stability of the thermoset was much higher than that of
most epoxy-based systems.

12
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

A widely studied CE known as BACY can be processed and cured above its melting
point (80 °C). The resulting thermoset exhibits good thermal stability (95% weight
retention at 430 °C) and a Tg as high as 290 °C if fully cured [67, 74]. However, the
resulting polymer is brittle, which limits its use in many applications. Several factors
such as impurities and environment [75, 76], solvent [77], and catalysts [78] influence
the cure reaction. It has been reported that no reaction occurs if absolutely pure CE
is heated [79]. In the absence of an externally added catalyst, the reaction is believed
to be catalysed by water and residual hydrogen-donating impurities such as phenol
[80]. It was found that the Tg of the network was lowered if it cured in the presence
of solvent.

Like other thermoset resins, CE are amenable to processing by a large variety of

conventional techniques. Their processing versatility has gained them widespread
acceptability in composites for various applications. The flexibility is further enhanced
by blending with other resins such as epoxies, BMI, additives, and toughening
agents. The cure cycle is dependent upon the catalytic level. Partially polymerised
thermosetting resins retain the ability to fuse and to form further crosslinks achieving
good tackiness.

1.4.2 Thermal Stability

The cyanurate is a thermally stable crosslinking polymer responsible for the high
mass loss temperature (450 °C) of these thermosets. Polycyanurates derived from
phenol novolac cyanate esters known as phenolic-triazine (PT) resins have a high
Tg (>350 °C), which approaches their thermal decomposition temperature [81].
In addition to high thermal stability, polycyanurates form a carbonaceous char
during burning that protects the underlying material and further enhances the
fire resistance. Thermogravimetric studies of polycyanurates in air have indicated
that thermo-oxidative degradation proceeds via rapid hydrolysis of the ether
oxygen bond between the phenyl and triazine rings in the presence of moisture at
350–420 °C [82, 83]. Purely thermal degradation under anaerobic conditions is
claimed at higher temperature (545 °C) via homolytic cleavage of the hydrocarbon
backbone over a narrow temperature range (450–500 °C) independent of the chemical
structure of the linking groups between the cyanurate rings. Polycycanuarte structure
is given in Scheme 1.7.

13
Polybenzoxazines: Chemistry and Properties

R R R R

OCN NCO O N O

OCN Heat N N

Cyanate ester monomer Polycyanurate

Scheme 1.7 Structure of cyanate ester monomer and polycyanurate

1.4.3 Modified Systems

Even though most commercial CE possess good flammability and high-temperature

properties, they are too brittle to be widely used in structural applications. Many
additives have been used to strengthen the resulting CE thermoset, including epoxies
[74, 76, 84], polyesters [85] and BMI [66, 86] with varying success. Co-curing the CE
with these polymers could result in non-miscibility, which has desired and undesired
effects on the physical and thermal properties of the polymeric matrix [87, 88]. CE
could be substantially toughened by the addition of rubbery or rigid thermoplastic
components [89–97]. The most effective toughening approach has been incorporation
of thermoplastics with a high modulus and high Tg [89, 91, 94–98]. In recent years,
the addition of nanoscale fillers such as layered silicates has been used as an alternative
approach to enhance performance [99–105]. The major reason for introducing these
fillers at the nanoscale level was the pronounced improvements in properties at low
clay contents. CE resins have recently attracted the attention of composite fabricators
due to their high Tg (typically ~290 °C) [99, 106] and relatively easy, epoxy-like
processing. However, to obviate the brittleness of CE, thermoplastic resins with high
Tg values were used for blending. Resins such as polyether ketones [107], polyether
imides [108-110], polyethersulfone [111, 112] were also incorporated for improving
properties.

14
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

1.4.3.1 Phenolic-triazine Resins

PT precursor resin is a reaction product between novolac resin and cyanogen

halides. A PT network is formed by the thermal cyclotrimerisation of the cyanate
ester of novolac [113] (Scheme 1.8). The networks have low melt viscosity, resinous
consistency, long gel time, good thermal expansion and a Tg up to 399 °C dependent
upon post-cure conditions. However, the ultimate cure temperature must be high
(>300 °C) to achieve optimum cure and a higher Tg (>300 °C). PT resins possess
better thermo-oxidative stability and char yield than conventional phenolics because
they are mostly crosslinked by triazine groups. The decomposition starts at ~420 °C
and the char yield is ~65–70%. PT resin is commercially available under the trade
name Primaset PT-15, PT-30, PT-60 and PT-90. They essentially differ in their molar
masses [114].

O
OH OCN
N N
CH 2 CNBr CH 2
Heat
Triethyl amine O N O

CH 2 CH 2

Novolac Novolac cyanate ester Phenolic-triazine network

Scheme 1.8 Synthesis of PT resins

Many structural alterations have been attempted to confer specific properties to

polycyanurate matrices. Thus, a flame-retardant and atomic oxygen-resistant cyclo-
matrix phosphazene-triazine network was derived by employing Alder-ene chemistry.
Co-reaction of a blend of allyl phenoxy triazine and allyl phenoxy phosphazene with
BMI gave rise to a phosphazene-triazine network [115] (Scheme 1.9).

15
Polybenzoxazines: Chemistry and Properties

NC O
CH3
C
CH3

O N OPh
P P
PhO O
N N CH3
P C
O OPh CH3

O CN
CH3
C
CH3
PNC-3

NCO Heat

Ph
O N O
P P O O N O
PhO
N N
P N N
O OPh
O

O O
O Ph
N P
N N N
Ph
O O O P P O
N N O
Ph O

CH3

Where, = C
CH3

Scheme 1.9 Formation of phosphazene-triazine network polymers

16
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

1.5 Phenolic Resins

Despite the emergence of several new classes of high-performance thermosets that are
superior in some aspects, phenolic resins retain industrial and commercial interest one
century after their introduction. These resins have several desirable characteristics such
as superior mechanical strength, heat resistance, and dimensional stability, as well as
high resistance against various solvents, acids and water. Although phenolics cannot
be substituted for epoxies and polyimides in many engineering areas, their composites
find a major market in thermo-structural applications in the aerospace industry due
to good heat resistance and flame resistance, excellent ablative properties, and low
cost. These key properties mean that phenolic resins can cope with the ever-changing
requirements and challenges of advanced aerospace technologies [116–120].

The simple and inexpensive synthesis of phenolic prepolymers is well established. The
commonest types of phenolic-based prepolymers are resoles and novolacs. Syntheses
of resole and novolac prepolymers are carried out using phenol or its derivatives
and formaldehyde under acidic or basic conditions. Novolacs are formed under
highly acidic conditions with an excess of phenol. Resoles are synthesised under
basic conditions with an excess of formaldehyde. The conversion of novolacs into
insoluble and infusible networks requires catalysts, whereas resoles require only
heating over a certain time period [121–123]. The phenolic networks are highly
aromatic and resistant to thermal oxidation. However, some of the inherent qualities
derived from their special chemical structures hamper their acceptance as universal
polymeric materials in many engineering areas. These resins cure at moderately high
temperature by a condensation mechanism with the evolution of volatiles. The need
for a catalyst for curing and the limited shelf-life of resins at ambient conditions are
major shortcomings of these systems. When compared with many known thermally
stable polymers, their thermo-oxidative stability is low. The rigid aromatic units
tightly held by short ethylene linkages make the matrix brittle. The degradation of
phenolic resins is depicted in Scheme 1.10.

In view of this, a new chemistry is needed to modify the cure of phenolic resins.
Addition cure phenolic resins can obviate the shortcomings associated with
condensation-type phenolics. The major strategies in designing addition-cure phenolics
are: (i) incorporation of thermally stable addition-curable groups onto a novolac
backbone; (ii) structural modification (transformation) involving phenolic hydroxyl
groups; (iii) curing of novolac by suitable curatives through addition reactions of
OH groups; and (iv) reactive blending of structurally modified phenolic resin with
a functional reactant [124–127]. A brief account of addition-cure phenolic resin
chemistry is discussed in the following section.

17
Polybenzoxazines: Chemistry and Properties

HO
CH 2

OH

O2

HO OOH HO O
CH CH
OH OH

HO OH
CH O
HO
OH C

OH

OH OH OH O
CO OH C. .
+ O C O + OH

OH
.
+ C O

Scheme 1.10 Thermal degradation of phenolic resins

18
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

1.5.1 Allyl-functional Phenolics

Allyl phenol–formaldehyde novolac, synthesised by the allylation of novolac, can cure

thermally at 180 °C without the evolution of volatiles. The allyl derivatives of phenols
have been used for the manufacture of glass fibre-reinforced plastics and mouldings,
as well as casting or impregnating compositions with high heat resistance, mechanical
strength and chemical stability [126]. However, the cured matrix is not thermally
stable due to the thermal fragility of the crosslinks arising from the polymerisation of
allyl groups [127]. The thermal stability of the allyl phenolic novolac resins could be
further improved by reactive blending with BMI compounds. Studies by Enoki and
co-workers [128] showed that the reaction between the two components proceeds
via the Ene reaction. The unsaturated Ene adduct intermediate undergoes a further
Diels–Alder type reaction with BMI to give the -bis and -tris adducts. The intermediate
step (Diels–Alder) is sometimes referred to as the Wagner–Jauregg reaction [129].
Ideally, a ratio 1:3 (allyl:maleimide) provides maximum crosslinking and enhanced
thermal stability, but this could lead to brittle matrices. In most cases, a compromise
of various properties was achieved at an allyl:BMI ratio of 1:2.

Commercial addition-cure formulations based on the co-reaction of diallyl phenols and

BMI are available such as Matrimide-5292. Matrimide-5292 is used as a matrix resin
in carbon fibre composites for advanced aerospace applications. Suitably formulated,
the resin system made up of 4,4′-bismaleimido diphenyl methane, DABA and desirable
catalysts can give a high Tg (315 °C) matrix that is stable up to 450 °C [130]. The
Alder–ene polymers can be conferred good ablative properties by introducing boron
into the molecular backbone of allyl compounds [131]. Allyl naphthols can replace
allyl phenols in Alder–ene adducts [132].

1.5.2 Bisoxazoline–phenolics

The unusual addition co-reaction of novolac phenolic resins with phenylene

bisoxazoline has been explored to derive a new class of non-conventional phenolic
thermosetting resins by Culbertson and co-workers [133]. The polymerisation involves
a tertiary phosphine-catalysed reaction of bisoxazoline with a phenol-free novolac
resin, leading to an ether–amide copolymer. The reactions and cure chemistry are
shown in Scheme 1.11. The systems are suitable for high-performance composite
applications [134]. These materials have low cure shrinkage, high neat resin modulus,
no volatiles during cure, low coefficient of thermal expansion, and excellent toughness.
The fibre-reinforced copolymers possess the low smoke and heat-release requirements
of materials for aircraft interior applications [135]. Based on this chemistry, several
compositions with many interesting properties have been patented. Electrical, physical
and mechanical properties of the neat resin suggest that these new thermosets could be

19
Polybenzoxazines: Chemistry and Properties

useful in various electrical applications. Incorporation of siloxane and montmorillonite

clay is very effective in enhancing the flame resistance of the bisoxazoline–phenolic
system [136]. A Tg of 220 °C was observed for the 8% polysiloxane-modified material,
compared with the Tg of 248 °C for the unmodified system.

OH OH
N N
C C
O O

1,3-Phenylene bisoxazoline
(PBOX) PHEN

175-225°C

O O
C NH CH 2 CH 2 O O CH 2 CH 2 NH C

PBOX-PHEN

Scheme 1.11 Addition polymerisation of the bisoxazoline-phenolic system

1.5.3 Phenolic Resin–Epoxy Systems

Curing of epoxy with novolac by making use of the OH–epoxy reaction appears to be
the simplest way to design an addition-cure phenol system. Although less preferred,
polyphenols are used as curative for epoxies because the addition-curing results in
void-free products that are comparatively tougher due to the formation of flexible
ether networks [137–140]. Interest in these systems has been revived further by the
need for void-free, low moisture-absorbing matrices with low dielectric properties
for various electronic applications. Their cure kinetics have been studied extensively
[141–155].

20
 Polybenzoxazines and State-of-the-Art High-Temperature Polymers

Novel phenolic novolac resins bearing maleimide groups (PMF resin) can undergo
cure mainly through addition polymerisation of these groups. They were synthesised
by polymerising a mixture of phenol and HPM with formaldehyde in the presence of
an acid catalyst [156] (Scheme 1.12). The thermal curing of the PMF system through
polymerisation of the maleimide group resulted in comparatively brittle matrices
[157].

O O
HCHO
N
O O + CH2OH
N H2 C
H+ CH 2 CH2 CH2
OH
OH OH OH
OH

HPM Soluble PMF resin

Scheme 1.12 Synthesis of PMF resin from N-(4-hydroxy phenyl) maleimide

and phenol

1.5.4 Propargyl Ether and Ethynyl Novolacs

Although less commercially exploited, propargyl ether-functional phenolic resins (PN

resins) were developed as a potential hydrophobic substitute for epoxies in advanced
composites, electronics, adhesives and coatings. Most thermosets such as epoxy and
BMI absorb moisture up to 5%, resulting in low hot/wet physico-chemical properties.
This problem could be avoided by using propargyl phenolics.

The structural similarity of propargyl ether to epoxy resins is useful for the preparation,
processing and development of thermally stable polymers [158]. The curing of
propargyl ether resins proceeds by a Claisen rearrangement followed by addition
polymerisation of the resultant chromene [159]. A Tg of ~300 °C and moisture
absorption of ~0.3–0.4% have been observed. Addition-curable phenolic resins
bearing terminal ethynyl groups anchored to a benzene ring through a phenyl azo
linkage such as ethynyl phenyl azo novolac were realised by a simple synthetic strategy
involving the coupling reaction between novolac and 3-ethynyl phenyl diazonium
sulfate [160] (Scheme 1.13). These resins showed a broad cure exotherm in DSC in
the 140–240 °C range due to the curing of acetylene groups. The cured resin retained
a char yield of 70%.

21
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