Chapter 1

Overview and Historical Background

of Polybenzoxazine Research
Hatsuo Ishida
Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106-7202, USA

1. INTRODUCTION abbreviated phenolic component whereas lower case char-

acters are used for the abbreviated amine component. To
1.1. Nomenclature describe the benzoxazine name, these two abbreviated
Benzoxazine is a molecule where an oxazine ring (a hetero- names are connected with a hyphen. As the flexibility of al-
cyclic six-membered ring with oxygen and nitrogen atom) dehyde is not rich and it is unusual for aldehyde other than
is attached to a benzene ring. There are several benzoxazine formaldehyde to be used, omitting the name of formalde-
structures depending on the position of the heteroatoms hyde will not usually lead to confusion. Thus, a popular
(Figure 1). For example, the traditional naming of the struc- benzoxazine monomer synthesized from bisphenol-A (ab-
ture a is a 1,3-benzoxazine (3,4-dihydro-3-methyl-2H-1,3- breviated as “BA”) and aniline (abbreviated as “a”) has
benzoxazine), whereas structure b is a 3,1-benzoxazine. an abbreviated monomeric benzoxazine name of BA-a.
The numbering is made in such a way that the oxygen When it is polymerized, one can simply describe this as
position precedes the nitrogen. Thus, structure c is a poly(BA-a). Using poly(BA-a) instead of PBA-a will
1,4-benzoxazine. This is because the benzoxazine was orig- avoid the misunderstanding of the phenolic component
inally the compound with a double bond, such as in struc- that might come from a compound that can be abbreviated
ture d. The word, dihydro, indicates the hydrogenated as PBA.
version of benzoxazine d. It is the 1,3-benzoxazines that Naming of polybenzoxazine is very complex due to the
are the subject of interest for development of polymeric ma- rich variety of structures from similar raw materials avail-
terials as this class of benzoxazines readily polymerizes via able. The cross-linked polybenzoxazine derived from
cationic ring-opening polymerization. The IUPAC name bisphenol-A and aniline-based monomeric benzoxazine
avoids the reversing of 1,3 into 3,1 from the structure a into (BA-a) is expressed as poly(BA-a) as described above.
b. Instead, the position of the oxygen is indicated by [e] for However, this abbreviation cannot be used to describe the
structure a and [d] for structure b by alphabetically counting main-chain type benzoxazine polymers (MCBP) that will
the atoms in the oxazine ring. be discussed in a later section. Instead, the uncross-linked,
While the accurate naming must still follow IUPAC no- main-chain type polybenzoxazine derived from bisphenol-
tation, it is very complex and impractical for routine use. A (BA) and methylenedianiline (mda) is abbreviated as
Thus, a convention has been developed to abbreviate the MCBP(BA-mda) to distinguish it from poly(BA-a).
name of the benzoxazine. Capital letters are used for the

O
O
O
N
N N
N
CH3 CH3 CH3 O

(a) 1, 3-Benzoxazine (b) 3, 1-Benzoxazine (c) 1, 4-Benzoxazine (d) 1, 3-Benzoxazine

FIGURE 1 Various structures of benzoxazine molecules. (a) 3-methyl-2H, 4H-benzo[e]1,3-oxazine; (b) 1-methyl-2H,4H-benzo[d]1,3-oxazine;
(c) 4-methyl-2H,3H-benzo[e]1,4-oxazine; and (d) 2H-benzo[e]1,3-oxazine.

Handbook of Benzoxazine Resins. DOI: 10.1016/B978-0-444-53790-4.00046-1

# 2011 Elsevier B.V. All rights reserved. 3
4 PART I Introduction

1.2. Historical Development of Benzoxazines high char yield, fast development of mechanical properties
and Polybenzoxazines as a function of conversion, glass transitions much higher
than curing temperatures, excellent electrical properties,
The history of small molecular weight benzoxazines dates and low water uptake despite having many hydrophilic
back to more than 60 years ago. Holly and Cope first groups. They can be synthesized from inexpensive raw ma-
reported the synthesis of benzoxazine in 1944 [1]. In the terials and polymerized by a ring-opening addition reaction,
1950s and 1960s, Burke et al. contributed significantly to yielding no reaction by-product. The superb molecular de-
the fundamental understanding of the small molecular sign flexibility of the polybenzoxazines allows the proper-
weight benzoxazine chemistry [2–9]. It was Schreiber in ties of the polymerized materials to be tailored in a wide
his patents in the early 1970s who reported the synthesis range of properties for the specific requirements of individ-
of small oligomes as a modifier for epoxy resin, though ual applications. The purpose of this chapter is to introduce
no details of the oligomer properties were reported this new class of polymers as alternatives to traditional phe-
[10,11]. In the 1980s, Higginbottom in his quest to develop nolics, polyesters, vinyl esters, epoxies, bismaleimides, cy-
a coating system was the first to develop a cross-linked anate esters, and polyimides, and further provide
polybenzoxazines based on a multifunctional benzoxa- inspirations for developing applications beyond those de-
zines, though again no polybenzoxazine properties were veloped for well-known commercial polymers. In this re-
reported in his patents [12–14]. Around the same time, view, references for the first discovery are preferentially
Riese et al. studied the reaction kinetics of benzoxaine olig- cited as much as possible to the authors’ knowledge to give
omer formation using mostly the monofunctional benzoxa- proper credit for the pioneering works.
zines, showing that large molecular weight linear A number of review articles on the development of poly-
polybenzoxazines cannot be obtained from monofunctional benzoxazines have been reported [18–37]. In this article,
benzoxazines. Several monomers studied showed the mo- the subject of benzoxazine resins (unpolymerized precur-
lecular weights roughly between a few hundreds to a few sors) as well as cross-linked polybenzoxazines will be cov-
thousands upon polymerization [15]. In 1988, Turpin and ered as wide as possible with special emphasis on the
Thrane reported in their patent the self-curable benzoxazine unique properties of benzoxazine and polybenzoxazine
functional cathodic electrocoat resin formulation [16]. They properties.
described the use of both multifunctional phenols and mul-
tifunctional amines as the raw materials for small molecular
weight benzoxazine resins. It is as recently as in 1994 that
the study on polybenzoxazine properties was reported for 2. BENZOXAZINE CHEMISTRY
the first time by Ning and Ishida [17], despite its long his- The basic chemistry of benzoxazine resins is described as
tory of discovery of small molecular weight benzoxazine in follows. These resins can be readily synthesized by a com-
1944, possibility of polymerizing it in 1973, and utilization bination of a phenolic derivative, formaldehyde, and a pri-
of a cross-linked polybenzoxazine in 1985. mary amine (Figure 2).
In the early days of polybenzoxazine development, it where X and R0 are substituents. R0 includes a group
was thought to be an attractive candidate for replacing such as CH3, C2H5, and benzene. Two examples of bifunc-
the traditional condensation chemistry phenolic resins, tional benzoxazine resins are shown in Figure 3.
as the ring-opening approach eliminated almost all the where R is a group, such as CH3 and other aliphatic
shortcomings associated with the condensation chemistry groups, or substituted benzene rings, and X is a group, such
approach. However, it is now recognized that polybenzox- as -, CH2, C(CH3)2, C(CF3)2, C¼O, SO2. Any combination
azine is not to be considered as simply a replacement ma- of a bifunctional phenol and primary amine can be used. In a
terial for the traditional phenolic resins, but as a class of similar manner, any combination of a bifunctional amine
materials that goes far beyond those materials, such as phe- and mono-functional phenol can also be used as shown in
nolics, epoxies, and bismaleimides. Benzoxazine resins Class B example, though the structure of the cross-linked
have a wide range of mechanical and physical properties polymer is somewhat different. Naturally, multifunctional
that can be tailored to various needs, reflecting the ex-
tremely rich molecular design flexibility. The material
R⬘
property balance of polybenzoxazines is excellent. Good OH O N
thermal, chemical, electrical, mechanical, and physical
properties make them attractive alternatives to existing ap- + 2 HCHO + H2N R⬘ + 2 H2O
plications. Additional new applications can be developed
by utilizing unique properties of polybenzoxazines that
have not been often observed by other well-known poly- R R
mers. Those properties include near-zero shrinkage, very FIGURE 2 Synthesis of benzoxazine resin.
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 5

R⬘
N

O X O O
N X N
N O
R⬘
Class A Class B
FIGURE 3 Monomeric type difunctional benzoxazine resins based on bisphenol and monoamine, or diamine and phenol.

01 C2
C7 C10

C1
C9 C3
N1

C6
C4
C8

C5
(a) 02 (b)

(c) (d)
FIGURE 4 (a) Crystal structure of 6-methoxy-3-methyl-2H,4H-benzo[e]1,3-benzoxazine (from Ref. [40]); (b) crystal packing along a-axis; (c) crystal
packing along b-axis; (d) crystal packing along c-axis.

amines or phenolic derivatives can also be used to synthe-

size multifunctional benzoxazines [38]. TABLE 1 Bond Lengths (nm)
Benzoxazine monomers crystallize if they are pure. Atoms Lengths (nm) Atoms Lengths (nm)
Benzoxazine monomers tend to retain a small amount of
O1-C1 0.1370 O1-C9 0.1421
solvents and impurities rather tenaciously and thus purifica-
tion can sometimes be difficult. Upon polymerization, O2-C4 0.1382 O2-C8 0.1459
polybenzoxazine exhibits amorphous structure as they are N1-C7 0.1464 N1-C8 0.1424
cross-linked. Crystal structures of some monomeric ben-
N1-C10 0.1465 C1-C2 0.1393
zoxazines and dimeric compounds have been reported
[39–44] (Figure 4; Table 1–3). C1-C6 0.1377 C2-C3 0.1387
It has been found that the six-membered heterocycle has C3-C4 0.1383 C3-C7 0.1509
an irregular chair structure with some ring strain, which pro-
C4-C5 0.1383 C5-C6 0.1399
vides the driving force for ring-opening polymerization.
However, the ring strain is not substantial, making the
6 PART I Introduction

TABLE 2 Bond Angles ( ) TABLE 3 Selected Torsional Angles ( )

Atoms Angles ( ) Atoms Angles ( ) Atoms Angles ( ) Atoms Angles ( )
C1-O1-C9 117.5 C4-O2-C8 114.1 C3-C4-O2-C8 13.4 C8-N1-C7-C3 49.8
C7-N1-C8 109.0 C7-N1-C10 112.4 C4-O2-C8-N1 43.8 C4-C3-C7-N1 22.3
C8-N1-C10 112.2 O1-C1-C2 114.9 O2-C8-N1-C7 62.7 C6-C1-O1-C9 4.6
O1-C1-C6 125.4 C2-C1-C6 119.7 O2-C8-N1-C10 62.6
C1-C2-C3 121.3 C2-C3-C4 118.6
C2-C3-C7 122.2 C4-C3-C7 119.2

O2-C4-C3 122.6 O2-C4-C5 116.6 X Y

N N
C3-C4-C5 120.7 C4-C5-C6 120.3
O O n
C1-C6-C5 119.4 N1-C7-C3 111.7
O2-C8-N1 114.1 Class C
FIGURE 5 Main-chain type polybenzoxazine that is based on bisphenol
and diamine. The polymer can further cross-link via the oxazine ring po-
lymerization in the main chain.
polymerization temperature somewhat higher in compari-
son to epoxies.
A more recent concept of benzoxazine resins involves TABLE 4 Classification of Benzoxazine Types Reported
the use of a difunctional phenolic compound and a diamine, in the Literature
yielding a linear polymer having oxazine rings in the main A. Non-functional monomer
chain as in Class C below; however, due to the reactivity on a. Monofunctional
the benzene rings, a small number of branching can take b. Difunctional
place. The oxazine rings can be used to form crosslinking i. Biphenol/bisphenol
ii. Diamine
networks. This class of materials will be described in
c. Multifunctional
Section 7 of this chapter (Figure 5). B. Functional monomer
Hundreds of papers on benzoxazine resins and their a. With polymerizable group byitself
polymers have been reported to date. Those papers can Acetylene, allyl, epoxy, glycidyl, maleimide, methacry-
be roughly classified as in Table 4. late, nitrile, norbornene, oxazoline, phthalonitrile, propar-
gyl, vinyl ester
The synthesized compound is then subjected to thermally
b. With potentially polymerizable group with an appropriate
accelerated, cationic ring-opening polymerization with or partner
without an added initiator. If the initiation takes place with Phenol, carboxyl, primary amine, methylol, ethylol, hy-
a labile proton initiator, such as phenol, it leads to a polymer droxy ethylether,
with a phenolic structure. On the other hand, if a nonlabile C. Reactive polybenzoxazines (thermoplastic/thermoset cross-
over molecules)
proton initiator, such as Lewis acid, is used to polymerize
a. Main-chain type
at a relatively low temperature, it could lead to an arylether i. Oxazine group being the only reactive group in the main
structure. However, the arylether structure is thermally chain
unstable and can undergo structural transformation to the ii. Oxazine group plus additional reactive group
phenolic-type at an elevated temperature (Figure 6). b. Side-chain type
Polystyrene, poly(vinyl chloride), poly(vinyliden fluo-
It should be cautioned that benzoxazine polymerization
ride), poly(vinyl phenol), poly(vinyl alcohol)
is not thermal polymerization as this term implies the ther- c. Telechelic
mal cleavage of a bond followed by free radical polymeri-
zation by the newly formed free radicals. The
polymerization takes place by simple heating because the
monomer typically contains a small amount of a cationic opening polymerization is readily achieved by heating the
initiator, such as phenolic raw materials and benzoxazine purified monomer, typically at temperatures in the range
oligomers, as an impurity. Heating simply increases the rate between 160 and 220  C [45], and gelation takes place in
of polymerization. Thus, it should be more appropriately a matter of minutes to tens of minutes at these temperatures
called thermally accelerated (or activated) polymerization if no initiators and/or catalysts are added. However, the po-
if the effect of temperature needs to be mentioned. The ring lymerization rate, thus the adopted temperature, depends on
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 7

R⬘ 100
O N OH

Δ N
n Cyclohexylamine
R⬘ 80

Monomer concentration (%)

n
R R
Lewis acid
60
Δ

O
40 Aniline
N
n
R⬘
Methylamine
R 20
FIGURE 6 Cationic ring-opening polymerization of benzoxazine.

0
0.15 0 5 10 15 20 25 30
Time (min)
210 ºC
FIGURE 8 Conversion of benzoxazine monomer, 6-methoxy-3-methyl-
2H,4H-benzo[e]1,3-benzoxazine with methylamine, aniline, and cyclo-
hexylamine at 160  C (redrawn from Ref. [40]).
Reaction rate (min–1)

0.1
crosslinked polymer. Bifunctional or poly-functional ben-
zoxazine resins lead to crosslinked polymers [45]. If the
200 ºC para and meta positions to the phenolic OH are available,
they can also react, although the reactivity reduces in the
order from the ortho to para to meta and the meta to be
0.05
rather unreactive. Albeit with lower reactivities, these mul-
190 ºC tiple reactive sites are one of the causes for the difficulty of
developing purely linear polymers from monofunctional
180 ºC benzoxazines.
170 ºC
160 ºC The rate of ring-opening polymerization is affected in a
0 complex way from the steric hindrance and electronic prop-
0 20 40 60 80 100
erties of the surrounding groups. The steric hindrance of the
Time (min)
radicals which is attached to the nitrogen atom has a pro-
FIGURE 7 DSC study of the polymerization rate of bisphenol-A and
found effect on the monomer conversion as shown in
aniline-based benzoxazine (BA-a) as a function of time.
Figure 8 [40].
Synthesis of the monomer generally shows yields of
the purity of the benzoxazine resin produced. The higher the nearly 70-90% depending on the component, temperature,
purity, the higher the polymerization temperature needed. time, solvent, and synthetic procedure. A highly efficient
Differential scanning calorimetric (DSC) study of the solventless method for benzoxazine resin preparation is
conversion of a benzoxazine resin as a function of the poly- also developed [57,58] in addition to commonly adopted
merization time and temperature has been reported [46] synthetic method using a solvent [17,45]. This solventless
(Figure 7). approach is applicable for raw materials (phenol and amine)
The benzoxazine polymerization is autocatalyzed [47] that are both liquid, one of which is liquid, or when the com-
as the newly produced phenolic structure acts as an bination of the solid acid and solid amine leads to reduced
additional initiator and catalyst. The curing kinetics of ben- melting temperature less than approximately 150  C. The
zoxazine resins have been actively studied [46–56]. The liquidation temperature should be below 150  C so as to
mono-functional benzoxazine typically leads to a linear use low synthesis temperature to minimize oligomerization
(or perhaps branched) polymer, though the molecular and the resulting liquid needs to be reasonably low viscosity
weight is on the order of a few hundreds to a few thousands to maintain homogeneity of the reacting compounds. Mo-
[15]; however, if the benzene ring is sufficiently reactive, nomeric benzoxazines can show low viscosity, some of
even a monofunctional benzoxazine resin can lead to a which exhibit as low as 0.1-0.2 Pa.s at 100  C [59].
8 PART I Introduction

A variation of the solventless method is to add small amounts formation, the polymerization mechanism of benzoxazine
of solvents. Although this high solid synthesis has the same resin has been elusive. In fact, using exactly the same mono-
disadvantage of eliminating solvent after the synthesis, it is mer, a phenolic-based Mannich polymer and nonphenolic,
more efficient in higher quantity sample preparation than the arylether-based Mannich base polymer can be produced,
commonly used low-solid solution synthesis. depending on the initiation mode [68]. This arylether struc-
Thermal stability of this class of Mannich base polymers ture can then be converted into the phenolic structure with
is excellent despite that the usual Mannich bridge, Mannich base in usual polybenzoxazines upon heat treat-
CH2N(R) CH2 , of small molecules shows either ment around 160  C [69].
thermal degradation or a reverse Mannich reaction at mod- Various sites of benzene rings can react with varying de-
erate temperatures. Thermogravimetric analysis (TGA) re- grees of reactivity. This complicates the polymerization
sults of many polybenzoxazines do not show any evidence mechanism study. However, this rich reactivity can be uti-
of low temperature thermal degradation. In fact, bifunc- lized regioselectively to improve the mechanical and ther-
tional polybenzoxazines start degrading around 260  C mal properties. By simply using a methyl substituted aniline
with varying rates depending on the type of phenols used instead of aniline, Tg of the bisphenol-A based polybenzox-
[60]. This surprisingly good thermal stability is due to the azines increased substantially from 170 to 245  C [71,72] as
stabilization of the Mannich bridges by the very stable in- shown in Table 7. Such secondary crosslinking mechanism
tramolecular hydrogen bonding between the phenolic OH has been strongly supported by pyrolysis-MS [75,76] and
and the nitrogen atom of the Mannich bridge [61]. solid-state NMR studies [77].
While the uses of phenolic derivatives, formaldehyde, Chain propagation of benzoxazine polymerization faces
and amines are not immune to the toxicity argument, the re- difficulty due to the competing intra-molecular six-
lease of by-products, such as phenol, formaldehyde or membered ring hydrogen bonding formation [78,79]. It is
amine, during benzoxazine polymerization is substantially difficult to obtain a large molecular weight linear polyben-
less than those released during the polymerization process zoxazine from monofunctional benzoxazines. Therefore, as
of traditional phenolic resins. Furthermore, the ring opening described in a later section, a hydrogen bond forming poly-
polymerization mechanism produces no water unlike the mer as a blend partner exhibits synergism in polybenzoxa-
water-producing condensation polymerization of ordinary zine formation, showing a greater Tg than any of the pure
phenolic resins. components used.
The mechanical and physical properties of benzoxazine
resins strongly depend on the choice of components and
vary widely. Ordinary performance materials such as 4. UNIQUE PROPERTIES OF
bisphenol-A-based polybenzoxazines favorably compare BENZOXAZINES AND
with the traditional phenolic and advanced epoxy resins, POLYBENZOXAZINES
whereas high performance polybenzoxazines are compara-
ble to bismaleimides and polyimides but typically with Benzoxazine resins as precursors for cross-linked polyben-
lower raw material costs. Some properties of bisphenol-A zoxazines and the resultant cross-linked polymers exhibit a
and methylamine based polybenzoxazine (hereinafter ab- number of unique properties, as described in the following
breviated as BA-m) and bisphenol-A and aniline-based sections. These properties will allow the development of
polybenzoxazine (abbreviated as BA-a) are compared with unique applications, in addition to providing the opportu-
an epoxy and traditional phenolic resin in Table 5 [62]. nity to be the replacement materials for the existing
A higher performance polybenzoxazine based on polymers.
4,40 -dihydroxybenzophenone and aniline (abbreviated as
44O-a) benzoxazine is also compared with a thermosetting
polyimide resin (PMR-15) in Table 6 [63].
4.1. Near-Zero Volume Changes
Thermosetting resins shrink during polymerization by
about 2-10% even for low shrinkage materials, while ther-
3. POLYMERIZATION MECHANISMS
moplastics exhibit even higher polymerization shrinkage
The ring-opening polymerization of benzoxazine is thought [80–82]. Superior mechanical interlocking to a substrate
to proceed via ionic mechanism and some attempts to study can be obtained by expanding polymers, which would make
the mechanism have been reported [15,64–70]. Following them ideally suited for high performance adhesives, seal-
are some of the mechanisms proposed in references 15 ants, and coatings. Elimination or reduction of interfacial
(A), 65 (B), 68 (C), 69 (D), and [70] (E) (Figure 9). residual stress benefits composites as polymerization
While the iminium ion mechanism seems to explain shrinkage leads to residual stress which increases the ad-
many observed phenomena, it still lacks total consistency. verse effects of moisture. Zero shrinkage materials elimi-
Due to the extremely complex reaction by-products nate optical distortion as well as warping of composite
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 9

TABLE 5 Comparison of the Physical and Mechanical Properties of Cross-linked Polybenzoxazines with an Epoxy and
Phenolic Resin

Property BA-m Benzoxazine BA-a Benzoxazine Epoxy Phenolic

Tensile Properties
Modulus (GPa) 4.3 5.2 2.7 3.8
Strength (MPa) 44 64 59 48
Elongation at break (%) 1.0 1.3 4.5 1.8
Flexural Properties

Modulus (GPa) 3.8 4.5 2.9

Strength (MPa) 103 126 119
Strain at break (%) 2.6 2.9 4.5
Impact Strength (J/m, 3.2 mm thick) 31 18 32 17
Dynamic Mech. Properties
G0 at R.T. (GPa) 1.8 2.2
0
G at 50 oC above Tg (MPa) <4.5 2.2
Density
Monomer (g/cm3) 1.159 1.200 1.16
3
Polymer (g/cm ) 1.122 1.195 1.26 1.28
Coefficient of Thermal Expansion
a (x 104 cm3/cm3. C) 2.1 1.7 2.3

b (x 10 cm/cm. C)
6
69 58 65 68

Glass transition temperature ( C) 180 170 165 170
Cure shrinkage (%) 2.9/0 4.5
Water Absorption (% at R.T.)
24 h 0.17 0.11 0.12 0.23
7 day 0.40 0.28 0.62

120 day 1.15 0.98 1.8

Saturation 1.3 1.9
Diffusion coefficient (109 cm2/s) 3.6 0.5 7.2

materials. Benzoxazine resins display near-zero shrinkage

TABLE 6 The Physical and Mechanical Properties of the
with high mechanical integrity [83–85]. The majority of
Polybenzoxazines (PBZ’s) and PMR-15 Polyimide
the monomers changed their volume within 1% upon po-
lymerization. It should be noted that the volume of the resin Materials Tensile Tensile Strain at Tg ( C)
actually reduced slightly during the isothermal curing at an Strength Modulus break,
elevated temperature. However, when the room tempera- (MPa) (GPa) Tensile (%)
ture volumes before and after the polymerization are com- 44O-aa 62 >6 2.3 340
pared, very little changes in densities, and thus the volume
PMR-15 a
56 3.8 1.0 230-380
changes, are observed. The combination of slight shrinkage
at an elevated, isothermal curing temperature and eventual Polymerized at 290  C for 1 h.
a

near-zero shrinkage at room temperature seems ideal from

10 PART I Introduction

OH OH
O
–
O O
N
N H
+ OH
N
(a)

+ H
H H H
O N O N O O H
+ +
C C
H+ N H N H

(b)

R⬘
O N O

Lewis acid N
R⬘
n
(c) R R

OH
O
Δ N
N R⬘
R⬘
n
R n
(d) R

+ H
O N H +
R O N

K1 << K2

OH

N
R
n
(e)
FIGURE 9 Various polymerization mechanisms proposed in the literature.
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 11

TABLE 7 Mechanical Properties of Regioselective TABLE 8 Densities of Monomeric Benzoxazine Resins

Benzoxazine Resins Based on Bisphenol-A and and the Corresponding Polybenzoxazines at Room
Substituted Anilines, Showing the Reactivities in the Temperature (Ref. [83])
Benzene Ring of the Amine Side Group
Amine Density of Density of % shrinkage
Abbreviated BA-a BA-mt BA-35x Monomer Polymer () or
Names (g/cm3) (g/cm3) expansion (þ)
Amines used aniline m-toluidine 3,5- Aniline 1.200 1.195 0.40
dimethylbenzene
Cyclohexyl 1.123 1.118 þ0.43
Tg ( C) 170 210 245
Methyl 1.159 1.122 þ3.20
Storage 1.39 1.78 1.63
modulus at Ethyl 1.109 1.104 þ0.41
R.T. (GPa) n-Propyl 1.076 1.084 0.76
Storage 4.4 11.9 13.6 Isopropyl 1.063 1.071 0.72
modulus at
rubbery n-Butyl 1.067 1.076 0.82
plateau (MPa)
tert-Butyl 1.078 1.061 þ1.58
Molecular 610 360 325
weight
between
crosslinks (by
2
Nielsen’s Eq.a)
Cross-link 1.1  103 1.9  103 2.6  103
density (mol/
Absorption of water (%)

cm3) (by 1.5

Nielsen’s Eq.a)
a
Nielsen’s Eq. Ref. [73,74].
1

the viewpoint of demolding and minimization of residual

stress (Table 8). 0.5

4.2. Low Water Absorption

0
0 100 200 300 400 500 600
One of the common problems of polyester, vinylester, phe-
Time (days)
nolic, epoxy, bismaleimide, and polyimide resins is their rel-
atively high water up-take at saturation. Both phenolic and FIGURE 10 Percentage water absorption of polybenzoxazines derived
from bisphenol-A and methylamine-based (abbreviated as BA-m) and
epoxy resin absorb as much as 3-20% by weight upon satu- bisphenol-A and aniline-based (abbreviated as BA-a) benzoxazines at
ration [86–89]. This relatively high water absorption is due to room temperature. Experiments were conducted based on ASTM standard
the presence of polar groups in these resins. Polybenzoxa- (redrawn from Ref. [62]).
zines also contain polar groups, such as phenolic OH and
Mannich base, CH2NCH2, in each chemical repeat unit. needs to be reduced since just 1% of water absorbed will con-
However, contrary to what might be expected, polybenzox- tribute to the dielectric constant of the material roughly by 1.
azines absorb much less water than these resins. A bisphenol- Another advantage of low water up-take is that the difference
A and aniline-based (abbreviated as BA-a) polybenzoxazine between the dry Tg and wet Tg is small. In an actual applica-
is saturated at 1.9% by weight and bisphenol-A and methyl- tion of products, this is an important property.
amine-based (abbreviated as BA-m) polymer at 1.3% by
weight in water at room temperature [62] as shown in
Figure 10. No further water absorption was observed after
more than 4000 days (more than 10 years). Use of phenols
4.3. Glass Transition Temperature (Tg)
and amines with more hydrophobic radicals will further re- Cross-linked polybenzoxazines show surprisingly high
duce the water up-take. This feature of low water up-take will glass transition temperatures ranging approximately from
be advantageous when dielectric constant of the polymer 160 to 400  C. Naturally, if a sub-zero Tg is desired, it
12 PART I Introduction

can also be designed. The apparent glass transition temper- 200

ature of a thermosetting resin roughly coincides with the po-
lymerization temperature if the polymerization is carried
out below the ultimate glass transition temperature of the 150
material. However, if the polymerization mechanism is Poly(BA-a)
such that local motion of a polymer chain allows further re-

Tg (°C)
actions or structural rearrangement of the polymer, then the
100
Tg continues to increase beyond the polymerization temper-
ature, Tcure. Such is the case for polybenzoxazines where
there are many active sites available and the benzene rings, Epoxy
to which the active sites react, are also abundant. Thus, the 50
b-transition temperature, Tb, provides sufficient mobility
for these types of reactions. Another reason is possibly its
chain polymerization mechanism rather than the condensa- 0
0 0.2 0.4 0.6 0.8 1
tion mechanism. Yet, another possible mechanism is the Fractional conversion (–)
structural rearrangement at elevated temperatures. A 4,40 -
FIGURE 11 Relationship between the fractional conversion and glass
dihydroxybenzophenone and aniline-based benzoxazine transition temperature of cross-linked poly(BA-a) (upper curve redrawn
(abbreviated as 44O-a) shows a Tg of 350  C if it is poly- from Ref. [91]) and cross-linked epoxy resin based on diglycidylether of
merized at 290  C for 1 hour [63]. This represents Tg > Tcure bisphenol-A which is crosslinked with a stoichiometric amount of a tetra-
by 60  C. Post curing at this temperature for an additional functional aromatic diamine, trimetthylene glycol di-p-aminobenzoxate
2 h increases the Tg to 385  C, further increasing this differ- (lower curve redrawn from Ref. [92]). The upper curve is the master curve
of the polymer polymerized at Tc ¼ 155, 165, 175, and 185  C, whereas the
ence to 95  C. Furthermore, aminophenylacetylene func- lower curve is the master curve of the polymer polymerized at Tc ¼ 136,
tional benzoxazine resins show typical Tgs of 350  C 150, and 160  C.
when they are polymerized at 190  C, representing a
Tg  Tcure difference of 160  C [90]. This large discrepancy
4.5. Very High Char Yield
between the Tg and Tcure offers a processing advantage since
the majority of high performance resins, such as polyimides The flammability of materials has attracted industrial and
and phthalocyanine resins, are polymerized at much higher academic attention as federal regulations become stricter
temperatures in the range of 300-410  C. and new technologies emerge. Materials first decompose
by thermally initiated mechanisms or thermo-oxidative
degradation. Small combustible fragments move to the ma-
4.4. Fast Physical and Mechanical Property terial surface and eventually to the flame front where a rich
supply of oxygen burns the flammable gases. The heat gen-
Development erated by this process supplies the energy necessary for fur-
Condensation polymers such as epoxy resins develop phys- ther sustainable thermal degradation of the material. This
ical and mechanical properties slowly at low degrees of po- cycle is repeated as the material continues to burn. One
lymerization and require a high degree of conversion to way to reduce burning is to design intrinsically high char-
achieve good properties. Thus, the difference in degree of forming materials. Char also reduces the diffusion rate of
conversion by a few percent near the end of polymerization decomposed, flammable gases toward the flame front.
exhibits far more significant changes in mechanical proper- Thus, a high char yield polymer is desired for flame-
ties than 10-20% increase in conversion around 50% degree resistant material applications. Many polymers show low
of conversion. This is in contrast to addition polymerization char yield when the remaining weight is examined under ni-
where fast build-up of molecular weight at an early stage of trogen at 800  C. This char yield is 5-15% for epoxy resins,
polymerization is observed. Polybenzoxazines develop and 30-55% for traditional phenolic resins. Phenolic resins
their glass transition temperatures and other mechanical show one of the highest char yields among processable
properties quickly as the polymerization proceeds. For polymers. Char formation usually increases with increased
BA-a benzoxazine, 80% of the Tg development takes place content of benzene groups, although there is no straightfor-
at 50% conversion as shown in Figure 11 [91]. ward relationship between the benzene content and char
This is in strong contrast to a typical bisphenol-A type yield. This is well expressed by the fact that despite a higher
epoxy resin [92–94]. Approximately 25% of the ultimate content of aliphatic groups in polybenzoxazines, their char
Tg would be developed at the same conversion. This means yield, generally 35-75%, is higher than traditional phenolic
that even at a relatively low conversion, the green strength resins. An important property for flammability characteris-
of the polybenzoxazine product will be excellent, and may tics, according to Walters and Lyon [95], is the heat release
reduce cycle time. capacity for which molar group contribution can be used to
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 13

calculate, thus allowing theoretical comparison of flamma- 5. MOLECULAR ORIGIN OF UNUSUAL

bility. According to Walter and Lyon’s method, polyben- PROPERTIES
zoxazines can be inherently good flame-retardant
materials as molar group contribution of hydroxyl groups, Many of the unusual properties described above can be
tertially amine, and benzene groups are high. explained by complex hydrogen bond formation in poly-
A TGA curve of the high performance polybenzoxazine benzoxazines. Almost all known forms of hydrogen bonds,
based on 4,40 -dihydroxybenzophenone and aniline (abbre- including inter and intramolecular OH  OH, intramolecu-
viated as 44O-a) is shown in Figure 12 [63]. lar OH  N six-membered hydrogen bonds, and OH  p in-
The 5% decomposition temperature is above 400  C. It is teractions, are possible in polybenzoxazines. X-ray
surprising to see that more than 60% of the weight still re- crystallographic study of model dimer [129], molecular
mains in air at 600  C. A long-term thermal stability of the modeling study [130], high resolution solid-state 1H-
poly(44O-a) indicates the weight reduction is rather negligi- NMR with double quantum technique [131–133] and FTIR
ble until around 240-250  C even after 200 h exposure in air study of model oligomers [61,134–139] all strongly support
[63]. At the present time, long-term durability studies of the formation of both inter and intra-molecular hydrogen
polybenzoxazines are severely lacking in the literature. bonds. Of particular interest is the very stable six-mem-
In general, thermal degradation of the polybenzoxazines bered hydrogen bond shown in Figure 13 that explains
which is based on bisphenol and monoamine exhibits a the hydrophobicity, low dielectric constant, high char yield,
three-stage mechanism. The lowest temperature event is as- and high modulus.
sociated with the evaporation of the amine group. The de- Polybenzoxazines are not reported to be semi-crystalline
tailed mechanisms of polybenzoxazine degradation have polymers due to the cross-linked nature, branched structures
been studied by mass spectrometry and Fourier transform or, perhaps, with complex hydrogen bonding associations even
infrared spectroscopy (FTIR) [75,76,96–102]. Thus, mini- when it is basically a linear oligomer derived from a monofunc-
mizing the evaporation of the amine by adding a reactive tional benzoxazine. However, X-ray study, molecular model-
group on the dangling amine side-chain will improve the ing [39,140], and high-resolution solid-state 1H NMR with
char formation. Molecularly designed polybenzoxazines double quantum technique study [133] all point to the tendency
that are optimized for high char formation using acetylene, of local helical structure formation as shown in Figure 14.
nitrile, and phthalonitrile groups exhibit very high char Understanding this local structure is important when consider-
yield [90,103–108]. Easy processibility, relatively low cost, ing the structure-property relationships, in particular mechan-
and high char yield are the characteristics of maleimide ical strength, thermal stability, and diffusion properties.
functional [109–116] and allylamine functional [117–125] The fraction of intramolecular hydrogen bonds against
benzoxazines. Naphthoxazines usually exhibit high char intermolecular hydrogen bonds depends on the nature of
yield, though some naphthoxazines degrade at much lower the amines used. A high pKa amine, such as methylamine
temperatures than benzoxazines [121,126–128]. will have a higher intramolecular hydrogen bond fraction
than a lower pKa amine, such as aniline. However, majority
of the phenolic OH groups are intramolecularly hydrogen
bonded to the N atom in the Mannich base. This intramolec-
ular hydrogen bond is so stable that even above 300  C, it
100 can survive if it is below the glass transition temperature of
the polymer as shown in Figure 15 [61].
80
Residual weight (%)

R⬘
60 N
H
40 O R

H
20 O N
R⬘

0
0 200 400 600 800
Temperature (°C)
FIGURE 12 TGA thermograms of polybenzoxazine derived from dihy- R
droxybenzophenone and aniline-based benzoxazine under nitrogen (solid FIGURE 13 Intramolecular six-membered ring hydrogen bonding that is
circle) and air (solid square) (redrawn from Ref. [63]). the basis for unusual and useful properties of polybenzoxazines.
14 PART I Introduction

B: 7.9 ppm

CH3 CH3 H 3C CH3

O H O
A": 12.9 ppm
H
CH3 N N CH3
H
O O
A': 11.7 ppm H

H3C N H3C

CH3
A: 10.7 ppm

(a) (b)
FIGURE 14 (a) Methyl benzoxazine tetramer based on the ab initio optimized geometry. (b) The experimental frequency determined by the solid-state
1
H NMR with double quantum technique for each hydrogen-bonded proton (reproduced with permission from Ref. [133]).

1.4 studies [18,58,192,193], only in the recent several years

have detailed studies on the benefits of the main-chain type
1.2 been reported [161,163,194–205].
Integrated absorbance

0.8 7.1. Main-Chain Type

0.6 Some of the polymers studied are shown in Table 10.
Polybenzoxazines derived from monomeric benzoxa-
0.4 zines contain many chain ends that tend to degrade easier
than the main chain. Thus, the recent main-chain approach
0.2 minimizes the concentration of the dangling chain ends,
leading to improved thermal stability [71]. The main-chain
0 polymers prior to crosslinking possess good mechanical
0 50 100 150 200 250 300 350 400
Temperature (ⴗC) properties to form self-supporting films. This polymer read-
FIGURE 15 Integrated absorbance of the intramolecular six-membered
ily dissolves in solvents and can be further melt processed.
hydrogen bonds around 2700 cm1 of polybenzoxazines derived from Thus, it has the typical advantages of ordinary thermoplas-
4,40 -dihydrozybenzophenone/aniline (44O-a, closed circle) and bisphe- tic polymers. The resultant material after heating leads to a
nol-A/aniline (BA-a, closed square) as a function of temperature. Upon dis- thermosetting polymer, which possesses all the advantages
appearance of the hydrogen-bonded species, the integrated absorbance of thermosetting polymers, with synergistic advantages of
should approach zero (redrawn from Ref. [61]).
improved mechanical strength and ductility. These thermo-
plastic/thermosetting crossover molecules will be attractive
6. HISTORICAL DEVELOPMENT OF materials for many applications, such as electronic packag-
MONOMERIC BENZOXAZINES ing, printed circuit wireboard, aerospace, and membrane.
The reported monomeric-type benzoxazines are listed in The main-chain polybenzoxazine approach can be
Table 9 in the historical order [17, 45, 60, 63, 71, 83, 90, designed to form various copolymers by combining with
96, 103–105, 107–110, 113, 116, 118–123, 125–127, nonbenzoxazine comonomers. These copolymers show
141–191]. The year the new compound was first reported morphological features as shown in Figure 16 due to the
in the peer-reviewed journals rather than in patents was cited. mismatch of compatibility of the comonomers [209].

7. RECENT DEVELOPMENT OF HIGH 7.2. Side-Chain Type

MOLECULAR WEIGHT BENZOXAZINES Well-known vinyl polymers modified with benzoxazine
Although the concept of main-chain type polybenzoxazines side chains have also been reported [210–219] as shown
where oxazine rings are incorporated in the main chain of a in Table 11. These modified polymers show marked im-
polymer was reported in early days of polybenzoxazine provement in char yield over the starting polymers.
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule
Benzoxazine Monomer Structure Ref. Year
1 H3C CH3 [17] 1994
H3C CH3
N N

O O

2 H3C CH3 [45] 1994

H3C CH3 N N
N N
O O
O O

O
N N C
N N

O O O O

O
H3C C CH3
N N

O O

3 [126] 1996

N
O O
O
N N
N

O
N

N
O

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

4 [63] 1996
O
O N C

N O N N

O O

5 H3C CH3 [83] 1997

H3CH2C CH2CH3
N N

O O

H3C CH3
H3CH2CH2C CH2CH2CH3
N N

O O

H3C CH3
H3CH2CH2CH2C CH2CH2CH2CH3
N N

O O

CH3 H3C CH3 CH3 CH3 H3C CH3 CH3

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

O O O O

H3C CH3

N N

O O
6 [141] 1998
O N CH2CH2CH2Si (OCH2CH3)3 (H3C)3C N O

CH2CH CH2

(H3C)3C N O

CH2CH2CH2Si (OCH2CH3)3

7 [142] 1998

O
CH2 N
N
N N O

O O

N N
CH3
O O
CH3

8 [103] 1999

O
N C CH
HC C N
O

C CH

O O

N C C C
O

C CH

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

9 [96] 1999
H3C CH3

HC C N N C CH

O O

HC C O CH
O
N N C
HC C N N C CH
O O
O O

10 [60] 1999

O
N
N S
O N N

O O

N N
CH3
O O

O N
11 [90] 1999

CH2
N N

O O

F3C CF3
HC C N N C CH

O O

12 [104] 1999
N C C N
CH2
N N
N
C O O O
N

O N C N
N C C N
C O
N N
C
O O N

N N
C C
O
C
C N N C
N N
O O

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

13 O [105] 1999
O S O
O
N N

HC C C CH

O
HC C N N C CH

O O

14 [143] 1999

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

H3C

H3C
CH3
N N

O O
15 [71] 2000
H3C CH3
H3C CH3
N N

O O

CH3 CH3

H3C CH3

H3C N N CH3

O O

16 O [144] 2001
CH2 C CH

O N

O O
HC C H2C H3C CH3 CH2 C CH

N N

O O

17 [145] 2001
O N CH2CH2CH2Si (OCH2CH3)3
H3C

CH3

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

18 O [146] 2001

N
O N

OH

19 F F [147] 2002
F F F F F F
H3C CH3 H3C CH3

N N F N N F
F F F F
O O O O

H3C CH3
F F F F
H3C CH3
F F
N N N N
O O
F F F F O O

F F
H3C CH3

F N N F
F F
O O

20 O [127] 2002

O
21 [148] 2003
F3C CF3

N N

O O

F3C CF3
F3C CF3

N N

O O

22 [118] 2003

N O H3C CH3

O O

23 O [109] 2004
O
N
N

24 [119] 2004
O N O N

H3C
H3C CH3

25 [120] 2004
O O
N N
N N
O O
3 3
H C CH

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

26 O [110] 2005
O
N
N
O

27 H3C CH3 [149] 2005

O O O
N N N

O O O

28 CH2 [150] 2005

N N

O O

29 R R R [151] 2006
R
N N N N
O O
O P O O O P O O

R R
N N
O
R = * CH3 * *
, ,
O O P O O
C CH
30 CH3 [152] 2006
N N
O O
O C C
N N
N H3C
O

31 [153] 2006

N
O N O O
N O N

N
N O
O
O O
N N

N
N

O
N

32 [154] 2006
R O R CH3 CH3 CH3
Si
O SiO O R R = * O Si
, *O Si O
Si N
R Si O CH3 CH3
O N
O
O R Si Si
O OSi O R O
Si
R O
R

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

33 O [155] 2006
C CH2 CH2
O CH
O
O N

34 [121] 2006

O N
N
O N
O

N O

35 [156] 2006

O N

CHO

36 O O [122] 2006

N N

37 [157] 2006

N O O N
38 R [158] 2007
R O
Si R=*
O SiO O R
N O
Si
R Si O
O
O
O R Si
Si O
O R
Si O Si
R O
R CH3

39 [123] 2007

N N

O O

40 O [159] 2007
H3C
O

N CH3

41 CH3 CH3 [160] 2007

O O
N CH2CH2CH2 Si O Si CH2CH2CH2 N
CH3 CH3

42 N N [107] 2007
C O O C
H3C CH3

C N N C
N N
O O

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

43 O [113] 2007
O
N
N

O O

44 O O [161] 2008
N CF2 N
6

F F

45 N [162] 2008
O C O
N O
O N

46 H3C CH3 [163] 2008

N N
N N
N
N N O O N

47 CH2 [164] 2008

H3C CH3 H3C CH3

N N

HO O O OH
48 O [165] 2008
O O
N S N
N CH2 N
O
O O

O O
H3C CH3
N N

O O

O O

N O N

O O

49 O O [166] 2008
X X
N Y Y N

O O

50 N [167] 2008
O
O
N

51 [168] 2008
O O

N N
O
P
CH3

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

52 [169] 2008

N N

O O

53 [170] 2008

CHO
N

54 H3C O O CH3 O O [171] 2009

N CH2 N N CH2 N
n n
H3C CH3

O O
N CH2 N
n

H3C CH3 n = 2, 6, 12

55 O O [172] 2009
N CH2 CF2 CH2 N
4

F F

56 O [173] 2009
C C C C O
N O O N

H3C CH3
57 [174] 2009

N N

O O
CH3 CH3

58 O O [175] 2009
N O N

C C
N N

59 [176] 2009

O P

O
N N
O

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

60 OH [177] 2009

O N O N O N Si (OC2H5)3

R R R *
R=
*

O N Si (OC2H5)3

O N

61 [125] 2009

CH3
O O
CH3
N N

62 [178] 2009

N N
CH2
O O

63 H3C CH3 CH3 CH3

[179] 2009
H3C CH3 H3C CH3
O Si O O Si O
HC C N N C CH
CH3 CH3
O O
64 O O [116] 2010
O O
N N
N N

O X O

X = O, CH2, O O, O O, O O

65 H2N NH2 [180] 2010

H3C CH3

N N

O O

O O

N N
H2N NH2

67 Br Br Br Br [181] 2010
H3C CH3

N N
Br Br
O O

68 O [182] 2010

N N
N
O O

69 O O [183] 2010

N N H3C
R R

R=* * CH2(CH2)2CH3, CH2(CH2)6CH3

, ,

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

70 [108] 2010
N C O O C N

C C
N N
N N

O O

71 [184] 2010
O

N COOH
O

72 [185] 2010
O O
S
N N

O O

73 O O [186] 2010
O O
N N
74 O R [187] 2010
R O O
Si
O SiO O R
Si
O Si O
R O
R O O
O O Si Si
O O Si O O R N
Si Si
O R=
R O O R

N
Si

75 O [188] 2010

O N O

H 3C C N
O N
N C

CH3

76 H3C CH3 [189] 2010

O O
O N N O
x y
y x
O O

Continued
TABLE 9 Historical Development of Monomeric Benzoxazine Resins that Possess at Least two Reactive Groups in the Molecule cont’d

Benzoxazine Monomer Structure Ref. Year

77 [190] 2011
O

N
O
O
O

78 HOOC O [191] 2011

N
N

O COOH

Some are combination of a monofunctional benzoxazine and a non-benzoxazine reactive group.

TABLE 10 Historical Development of Main-Chain Type Polybenzoxazines
Main-Chain Type Polybenzoxazine Structure Ref. Year
1 H3C CH2 CH3 [58] 1995
H3C CH3

N N
CH3 CH3
O O n

2 H3C CH3 H3C CH3 [194] 2005

N N CH2 N N CH2
2 6

O O n O O n

H3C CH3

N N CH2

O O n

3 [195] 2007
O

N CH2 CH2
n

4 [161] 2008
CF 2
F3C CF3 6

N N
n
O O

F3C CF3

N N CH2 CF2 CH2

8

O O n

Continued
TABLE 10 Historical Development of Main-Chain Type Polybenzoxazines cont’d

Main-Chain Type Polybenzoxazine Structure Ref. Year

5 O O [196] 2008
H3C CH3
O O
O N N O R
n
O O

R= CH2
4

6 O O [197] 2008

H3C CH3 O N CH2 N O

N N O O
n
O O

7 CH3 CH3 [198] 2008

H3C CH3 H3C CH3
Si O Si
N N
CH3 CH3
m
O O O O x
n
OH

8 H3C CH3 [163] 2008

N N
N N N
N
N
N O O
n
9 [199] 2009
N N N N
N O O N
H3C CH3
n
N N

O O
H3C CH3
O O

N N
O O N N
N N N N n

N N N N
O O N N
N N
H3C CH3
n
N N O O

O O

10 [200] 2009

O O
H3C CH3
n
N N

O O

N
O
O n
N

Continued
TABLE 10 Historical Development of Main-Chain Type Polybenzoxazines cont’d

Main-Chain Type Polybenzoxazine Structure Ref. Year

11 CH3 CH3 [201] 2009
H3C CH3 H3C CH3
Si O Si
N N
CH3 CH3
n
O O O O
OH

12 CH3 CH3 [201] 2009

H3C CH3 H3C CH3 H3C CH3
Si O
N N
CH3 CH3
m
O O O O O O x
n
OH OH

13 H [203] 2010
H3C CH3
N
N N N
H n
O O

14 [204] 2010

H3C CH3 H3C CH3 CH3 CH3

O
N N N N m

O O n O O
x

15 [205] 2010
H3C CH3 O O

N N O O
n
O O HOOC COOH

H3C CH3 O F3C CF3 O

N N O O
n
O O HOOC COOH
16 [206] 2010
H3C CH3
O
N N Si Si
n
O O

17 [207] 2010
H3C CH3 CH3 CH3
O O
N N O
n m p
O O
x

18 [208] 2010
O N

O O O O
C R' C R C R' C N O
O N N O O N N O
x
H H H n H

CH3 CH3
R= CH2 Si O Si CH2
6 CH2 O
6 CH3 CH3
n 4 n
O CH3 O
H2C O H2C CH2 O CH2
5 n CH3
5 m

R' = CH2
5
42 PART I Introduction

FIGURE 16 AFM image of a main-chain type poly-

benzoxazine-block-polydimethylsiloxane multiblock
copolymer. The image was obtained by a tapping mode
(reproduced from Ref. [209] with permission).

(c)

0 1 μm 0 1 μm

7.3. Telechelic Type often provided as an amine derivative. Thus, upon polymer-
ization of these functional groups, it acts as anchoring group
Telechelics are macromonomers with functional terminal for the amine side group, resulting in dramatic increase in
groups. Therefore, it maintains the properties of the chain Tg and thermal stability.
while adding additional chemical reactivity to modify the
structure, such as light cross-linking or copolymerization.
Benzoxazine telechelic approach has been reported 8.1.2. Ionically Polymerizable Groups
[128,219–221] as shown in Table 12, but to date this ap-
proach has been poorly exploited. Ionically polymerizing groups such as epoxy, nitrile, oxa-
zoline, and phthalonitrile often polymerize with oxazine
8. BENZOXAZINES COMBINED WITH in a synergistic fashion as benzoxazine polymerization is
also cationic ring-opening. Sometimes, benzoxazine poly-
OTHER POLYMERIZING GROUPS
merization can accelerate the polymerization of other
Benzoxazine chemistry can be combined with other groups groups, such as phthalonitrile, reducing the polymerization
that polymerize with different mechanisms. Thus, it allows temperature significantly.
this class of benzoxazines to build fundamentally different
network structure, polymerization kinetics, and processing
control from simple benzoxazine resins. By polymerizing 8.1.3. Photopolymerizable Groups
benzoxazine and other groups independently, the resultant
Somewhat slow rate of polymerization of benzoxazine
network structure can form quasi-interpenetrating net-
resins makes photopolymerization particularly attractive
works. While the ability to accommodate other reacting
as photopolymerization takes place rapidly. Benzoxazines
groups is not unique to benzoxazine chemistry, it is none-
with photopolymerizable groups including, coumarine,
theless unusual to be able to combine with a vast number
maleimide, and vinylester are reported.
of groups. Sometimes, oxazine polymerization and other
functional polymerization act synergistically influencing
each other in a positive fashion. In such a case, the thermal
events studied by DSC are quite often indistinguishable 8.2. Combination with Potentially
from one another. On the other hand, the increased stiffness Polymerizable Group with an Appropriate
upon reaction of other functional groups may cause adverse Partner
effects on the oxazine reaction.
Groups that belong to this category are typically those with
condensation polymerization mechanism. They include al-
8.1. Combination with Polymerizable Group dehyde, azide, carboxylic acid, hydroxy ethylether, isocya-
by Itself nate, methylol, and phenol. A benzene ring provides
reactivity via nucleaphilic substitution reactions. As a re-
8.1.1. Free Radically Polymerizable Groups
sult, the monofunctional benzoxazine derived from phenol
Benzoxazines with acetylene, allyl, maleimide, norbor- and aniline provides crosslinked polybenzoxazine despite
nene, propargyl, and vinyl ester groups can be polymerized the fact that the majority of monofunctional benzoxazine
with well-known free radical initiators. These groups are produces only small molecular weight oligomers.
TABLE 11 Historical Development of Side-Chain Type Polybenzoxazines
Ref. Year
1 [210] 2001
CH CH2 CH CH2 CH CH2
n n m
C O
OC4H9

O N O N

2 [211] 2005

N
O

Br CH CH2 CH2 CH2 CH2 CH Br

n m

O
N

3 [212] 2007
CH CH2 CH CH2
n m
O

N O
N N

4 [213] 2007
n CH2 CH
n
O N O
O N O

O N O N

CN CN

Continued
TABLE 11 Historical Development of Side-Chain Type Polybenzoxazines cont’d

Ref. Year
5 OH OH [214] 2007

CH CH CH2 CF2 CH CH CH2 CF2

n m
O O

HO O HO O

N N

6 [215] 2008
CH CH2 CH CH2 CH CH2 CH CH2
n m
Cl N Cl N
N N
N N
CH2 CH2
O O

N N

O O

7 O [216] 2009
N O

N
N
N

n m
N
N
N

O N
O
8 [217] 2010

N N
N
O N
HO OH
O O
O
OH n
HO
N O
N
N N

9 [218] 2010

N O
O

CH

n
PFB

10 [190] 2011
n m
O O
O

O N
TABLE 12 Historical Development of Telechelic Type Benzoxazines
Ref. Year
1 [128] 2006

CH3 CH3
R1 R2
O N N O O N O O N O
O n O O
n m
CH3 CH3 CH3 CH3

2 [219] 2009
H3C CH3 H3C CH3 H3C CH3
H3C CH3
N N

O O C O O C O O
O O

3 [220] 2010

N O OH O N

H2C H2C CH2 CH2

N O OH O N

H2C H2C CH2 CH2

n
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 47

9. VARIOUS TECHNOLOGIES ATTRACTIVE 0.4

FOR APPLICATIONS
Polybenzoxazines can be applied to areas where polyesters, 0.35
vinylesters, epoxies, phenolics, bismaleimides, cyanate es-

Viscosity (Pa s)
ters, and polyimides are used. Rich molecular design flex- 0.3
ibility allows the entire range from inexpensive to high
performance materials to be synthesized. Their high perfor-
mance mechanical and physical properties, including high 0.25
temperature properties (Tg around 350  C), make them an
obvious choice for aerospace applications. Their low vis- 0.2
cosity, high Tg, low water absorption, low coefficient of
thermal expansion, and superb electrical properties, such
as low dielectric constants (e ¼ 2.7) and loss factor (better 0.15
0 50 100 150 200 250
than 0.01), offer an unusual combination for electronic Time (min)
packaging materials. These values favorably compare with
FIGURE 17 Viscosity change of benzoxazine resins as a function of stor-
many polymers that are considered low dielectric constant age time at various temperatures: difunctional benzoxazine with 0.5% cat-
polymers [221]. Excellent processability, no volatile forma- alyst at 100  C (closed circle); difunctional benzoxazine without catalyst at
tion, and superb mechanical properties are attractive for 100  C (closed square); and monofunctional benzoxazine without catalyst
composite material manufacturing. The amphoteric nature, at 50  C (closed triangle) (redrawn from Ref. [231]).
both acidic and basic, of the polymers offers wide applica-
bility as adhesives for both basic and acidic surfaces due to density enhancer. Figure 17 shows the viscosity of benzox-
acid-base interactions [222]. For the same reasons, both azine resins that are suitable for RTM under various
acidic and basic fillers can be used effectively with benzox- temperatures.
azine resins. Melt processable, thermally accelerated poly-
merization might offer opportunities for powder coating. Of
course, high char yield, no dark smoke, self extinguishing, 9.2. Increased Rate of Polymerization
low heat release rate, and low total heat release make them The typical polymerization temperatures of benzoxazine
an attractive candidate as nonflammable materials for the resins in the range of 160-220  C may be too high for a cer-
transportation industry. tain application. Various approaches to achieve lower tem-
perature polymerization have been reported, including
addition of effective initiators or catalyst [64–66,
9.1. Processibility/Rheological Properties 237,238], initiator or catalyst-containing benzoxazines
Processibility improvement is achieved by developing ben- [239–241] and strong intermolecular association without
zoxazines with intrinsically low viscosity [26,59,223,224], addition of an initiator or catalyst [173,200,242]. In the ap-
blending with low viscosity benzoxazine resins [225] as plications where added initiator or catalyst is undesirable,
well as other resins, such as epoxy resins, as reactive dilu- such as in the electronic applications, the last approach of
ents [56,111,143,198,226–229]. Utilizing low viscosity modifying the structure of benzoxazine to achieve high re-
benzoxazine resins, resin transfer molding (RTM) of a com- activity is desirable; however, the molecular reasons for the
posite has been reported [230–233]. To be useful for RTM acceleration of the polymerization rates via intermolecular
resin, the resin must satisfy several conditions: (i) the resin interaction have been poorly understood. Ordinary benzox-
has sufficiently low viscosity so as to infiltrate the preform azines show polymerization exotherm peaks around
with the applied pressure and sometimes with additional 250  C. However, with the various approaches described
assisting evacuation; (ii) the low viscosity is maintained above, this exotherm peak temperature may be reduced to
at least during the infiltration period (up to about a few the range of 150-200  C (Figures 18 and 19).
hours); (iii) upon infiltration of the preform, efficient poly- On the other hand, the intramolecular approaches
merization takes place without void formation; (iv) the resin [243,244] are better understood for their acceleration mech-
does not shrink excessively; and (v) the resultant composite anisms. Figure 20 shows the conversion of two mono-
exhibits physical and mechanical properties to satisfy the functional benzoxazines where one has a hydroxyl group
requirement of a particular application [234–236]. There- as part of the amine structure [243]. Despite the similarity
fore, some benzoxazine resins seem to be ideal candidates in benzoxazine structure, the one that contains hydroxyl
for RTM and vacuum-assisted RTM. Blending with a small group showed significant acceleration effect. The neighbor-
amount of low viscosity epoxy resins seems particularly ing group participation of the hydroxyl group allows two
useful as the epoxy acts as the reactive diluent and cross-link extreme structures to be bridged by the zwitter ionic
48 PART I Introduction

intermediate, which is in equilibrium between the iminium viscosity [59], and the dynamic mechanical properties of
ion and carbocation as shown in Figure 21. Formation of the resultant polymers [45,90,247–250] have been studied.
such intermediate is known to accelerate the chemical reac- Polybenzoxazines show flat G0 over a wide temperature
tion. The carbocation’s highly reactive nature was proposed range and a high Tg, which are the characteristics suitable
to be one of the polymerization mechanisms in early stage for high performance composite applications.
of benzoxazine studies [65].
Another form of acceleration is through the intramolec-
ular hydrogen bonding with the oxazine ring. This, too, en-
9.3. Improved Toughness
courages the oxazine ring to open, which leads to Although polybenzoxazines can be thermoplastics, almost
accelerated polymerization rate (Figure 22). all papers published to date studied thermosetting properties.
Gelation of resins during processing is one of the impor- In general, thermosetting polymers have the advantage of
tant characteristics for product manufacturing. Rheological having high dimensional stability, excellent thermal and
properties, including gelation [59,112,228,245,246], chemical resistance, and ease of processing large objects;

O O
100
H3C CH3 241
N N OH
O N
O O

BA-appe 80
CH3
Heat flow (W/g)

Conversion (%)
60

CH3
O N
O O
H3C CH3
n
40
N N
O O
185 CH3

poly(BA-appe)
20

0 50 100 150 200 250 300 0

Temperature (°C) 0 1 2 3 4 5 6 7
FIGURE 18 DSC thermograms of monomeric benzoxazine based on Polymerization time (h)
bisphenol-A and aminophenylacetylene (BA-appe) and main-chain type FIGURE 20 Time conversion relationship for ()2-(6-methyl-2H, 4H-
polybenzoxazine derived from BA-appe by oxidative coupling of the acet-
ylene terminal group into diacetylene group.
▪
benzo[e]1,3-oxazin-3-yl)ethan-1-ol and ( ) 3,6-dimethyl-2H,4H-benzo
[e]1,3-oxazine.

FIGURE 19 Nonisothermal DSC thermograms of

H3C
N benzoxazines with liquid crystalline chromophore.
218
A CH2 CH3 Thermogram A with a short aliphatic chain did not show
O O
5 liquid crystalline feature, whereas thermogram B with a
long aliphatic chain showed nomotropic liquid crystal-
line feature (redrawn from Ref. [242]).
Heat flow (W/g)

170
B 74

H3C
Exo N

CH2 CH3
O O 11

111

50 100 150 200 250

Temperature (°C)
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 49

OH
O N OH

N O

CH3 CH3

O– O–
+ OH
+
N N
N
OH OH
n
CH3 CH3
CH3 OH

Zwitter ionic intermediate Polybenzoxazine

FIGURE 21 Proposed mechanism of the acceleration of the rate of polymerization.

interpenetrating network formation with polyurethane pre-

247 polymer [256–264] and copolymerizing with siloxanes
206 [198,201,202,209,265–267] are also reported. Evaluation
O
of various toughening concepts is also available [268].
N O H N H
N Improved toughness is typically achieved with highly
Heat flow (W/g)

N C
C
O O mobile molecules which have poor mechanical strength.
Since one of the advantages of polybenzoxazines is their ex-
cellent anti-flammability property, it is important not to di-
lute this advantage by adding a large amount of toughening
agent. One of the attractive approaches to improving the
Exo toughness without sacrificing the inherent advantages of
polybenzoxazines is to use semi-miscible toughening
agents. Optimization of toughening can be done by care-
160 180 200 220 240 260 280 300 fully designing the morphology of the toughening agent.
Temperature (°C) The requirements of achieving the targeted toughening
FIGURE 22 The influence of the amide group at the ortho and para po-
morphology are: (i) The material should be immiscible
sitions on the rate of polymerization as exhibited on the lowering of the and the toughening agent will phase separate, ideally at
exotherm temperature of the ortho-amide benzoxazine. The para-amide the nanometer level, from the matrix either before or during
benzoxazine is not capable of forming the intramolecular hydrogen the polymerization of the benzoxazine resin; (ii) The inter-
bonding. phase (the region where the toughening agent and the ma-
trix coexists with high concentrations) thickness should not
however, it has the inherent disadvantage of being brittle. be too thick to significantly dilute (degrade) the mechanical
Cross-linked polybenzoxazines derived from monomeric strength of the composite. Molecular homogeneity between
precursors are no exception to this brittleness problem. Add- the benzoxazine matrix and the toughening agent will de-
ing miscible, flexible components as a physical blend, copo- crease the mechanical strength and Tg; and (iii) The inter-
lymerizing a flexibliging agent with the benzoxazine face must be covalently bonded. Due to the complex
networks, forming interpenetrating networks, or synthesiz- nature of the toughening agent/matrix mixing, the optimum
ing benzoxazine having a flexible component will improve interphase thickness for physical blend is not well under-
the toughness, but often with the sacrifice of inherent advan- stood. The optimum thickness for the rubber interlayer that
tages of polybenzoxazines: high thermal stability, high char is used for fiber treatment has been studied and reviewed
yield, high dimensional stability, and high strength. [269,270], although systematic studies on the rubber inter-
Blending with rubber or using it as interlayer for reinforce- layers of polybenzoxazine composites have not been
ments [193,250–255], copolymerizing with urethane or reported to date. While nanoparticle toughening agents have
50 PART I Introduction

an advantage in not introducing the inclusion size of the Grif- 200 –50
fiths cracks, its systematic study on the benefits of polyben-
zoxazine toughening has also not yet been studied.
190
An attempt to predict structure-property relationships –55

Temperature (°C)

Temperature (°C)
for improved fracture toughness through molecular simula-
tion has been reported [271]. Other attempts to predict prop- 180
erties via atomistic models have also been reported –60
[140,272–274]. However, molecular simulation is still in
170
its infancy in the area of polybenzoxazine study.
A series of aliphatic diamine-based benzoxazines offer –65
choices of properties by adjusting the length of the aliphatic 160
chains and achieve the balanced properties [153,171,275].
Aromatic components usually lead to higher thermal and 150 –70
mechanical properties in comparison to the aliphatic com- 0 20 40 60 80 100
ponents. However, some of the short-chain aliphatic amines PCL concentration (wt %)
exhibit better mechanical properties by increased flexibil- FIGURE 23 The glass transition temperature of polybenzoxazine and
ity, thus reduced crack-tip sensitivity, over the aromatic poly(e-caprolactone) at various blend compositions, showing that the blend
Tg is higher than any of the components used. Continuous phase: poly(BA-a)
benzoxazines, such as bisphenol-A and aniline based. It
(); PCL ( ).
is, therefore, possible that some of the aromatic benzoxa-
zines are not exhibiting the maximum potential properties be seen in processability if a low viscosity liquid resin is added
and prematurelly fail due to the high crack-tip sensitivity. and in ductility of cross-linked polybenzoxazine if a ductile
Incorporation of aliphatic chains does not lead to as drastic polymer is added. For the latter case, improved properties in-
an increase in strain-to-failure as in typical rubbers. How- clude increased char yield, higher Tg and thermal stability, and
ever, this approach has the attractiveness for not diluting decreased hydrophilicity. Copolymers of benzoxazines with
the advantages of polybenzoxazines significantly and tai- epoxies have shown an attractive synergism in the mechanical
loring the properties by choosing the proper chain length. and physical properties. Copolymers with benzoxazine resins
have been studied [111,143,198,210,226,228,229,258,283–
9.4. Property Modification by Blending 301]. Addition of 10-30% by weight of epoxy resin to benzox-
9.4.1. Synergism Obtained with Hydrogen azine resin shows improvement in the strain to failure, flexural
Bond-forming Partners strength, and glass transition temperature [283]. Use of a low
viscosity epoxy as a reactive diluent [225], ternary mixtures of
Blending of benzoxazine resins with thermoplastic poly- benzoxazine, epoxy and phenoilic resins for improved pro-
mers, in particular hydrogen-bond forming polymers, will cessability [226,228,229,262,284,286], and reaction with
lead to synergistic effects improving the Tg of the resultant flexible isocyanate as impact modifier [256,266,287] have
polymer blend in comparison to the homopolymer of the been studied. Copolymers can be formed between benzoxa-
corresponding benzoxazine resin. Blends of benzoxazine zine resin and epoxy molecules since the ring opening poly-
resin with poly(e-caprolactone) [249,276–281] and poly merization of benzoxazine resin produces phenolic groups
(ethylene oxide) [282] have been studied. The Tg of poly- that act as reactants as well as catalyst for epoxy
benzoxazine derived from bisphenol-A and aniline-based polymerization.
benzoxazine (BA-a) was increased over the homopolymer Other reactive groups were chosen from isocyanate [256–
of the original benzoxazine as shown in Figure 23 [249]. 263] (Figure 24; Table 13), oxazoline [167,297,302–307],
maleimide [109,116,152,308,309], and cyanate ester
9.5. Property Modification by [310,311].
Copolymerizing with Nonbenzoxazine
Monomers
9.6. Flammability Control
Vast opportunities exist in modifying the properties of poly-
benzoxazines by simply copolymerizing with other nonben- It is well known that phosphorous compounds reduce flam-
zoxazine monomers, either for viscosity reduction, or mability of a polymer by enhancing char formation. De-
ductility improvement. Nonbenzoxazine monomers are creased flammability can be achieved by either blending
added not only to improve the properties of polybenzoxazines, nonbenzoxazine phosphorous compounds into benzoxa-
but also to achieve property improvement of the polymers zines or incorporating phosphorous atoms in the structure
derived from the nonbenzoxazine monomer by using benzox- as benzoxazine molecules. Phosphorous atoms have been
azine as a comonomer. For the former case, improvement can added as part of the copolymerizing epoxy or phenolic resin
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 51

200 add thermal stability and decreased flammability. Upon deg-

radation of polysiloxanes, such as polydimethylsiloxane and
polyhedral oligomeric silsesquioxanes (POSSs), thermally
150
stable silica nanoparticles will be formed at the surface of
the degrading material, which shields from further degrada-
100 tion. For this reason, these materials will also be useful for ma-
Tg (°C)

terials used under atomic oxygen environment [318].

50

9.7. Electrical Properties

0
Polybenzoxazines offer excellent electrical properties in
part due to their low water content, thus exhibiting low di-
–50 electric constant under operating conditions. Formation of
0 20 40 60 80 100
BA-a content (wt %) intramolecular six-membered hydrogen bonding counteract
FIGURE 24 Effect of the bisphenol-A/aniline based benzoxazine (BA-a)
the polar OH and N atoms, thus showing low dielectric con-
content on the Tg increase of the copolymer (redrawn from Ref. [260]). stant despite having a high concentration of polar groups.
Extensive hydrogen-bonding networks also increase the ri-
gidity of the polymer chain, leading to lower dissipation
factor, tan d. Low tan d is particularly attractive in high fre-
quency applications above 1 GHz as the energy loss mech-
TABLE 13 Effect of Urethane Copolymerizing with
anism is more strongly influenced by the tan d rather than
Polybenzoxazine at 190  C for 1 h, Showing Marked
the dielectric constant of the material. Addition of fluorine
Increase in Elongation
atoms further decreases the dielectric constant. Fluorine
BA-a Young’s Tensile Elongation to atoms-containing benzoxazines have been reported
Content Modulus Strength Break (%) [91,147,148,161,166,172]. Some of the fluorine containing
(%) (MPa) (MPa) polybenzoxazine exhibit dielectric constant as low as 2.2
and tan d of 0.008. Nanoporous material obtained by
10 2.1 3.3 244
extracting polycaprolactone from polybenzoxazine/polyca-
15 6.7 6.7 182 prolactone blend showed dielectric constant as low as 1.95
20 195 19 39 [278] due to the increased void content as the dielectric con-
stant of the air is 1.
30 279 150 27
Polybenzoxazines are also ideal matrices for high dielec-
From Ref. [256].
tric constant composites for applications, including antennas,
since the matrix is required to have low loss tangent. The in-
creased dielectric constant is achieved typically by filling with
high dielectric constant fillers such as barium-titanate or bar-
[288,301,312–314], phosphorous containing phenol that ium-strontium-titanate. The composite exhibited very high di-
copolymerizes with polybenzoxazine [313] or in the ben- electric constant of around 30 at 1 GHz [319].
zoxazine molecules [151,168,315–317]. Various phospho-
rous structures have been incorporated into benzoxazine
resins as follows (Figures 25–27; Table 14).
The char yield in air increased significantly with phos- 9.8. Composite and Nanocomposite
phorous content, reflecting the typical mechanism of phos- Manufacturing
phorous shielding the diffusion of flammable components
9.8.1. Fiber-Reinforced Composites
from the bulk to the surface. Increased phosphorous content
also increases the limiting oxygen index (LOI) suggesting Benzoxazine resins are also ideally suited for composite
the effective flame retarding capability [168,317]. manufacturing. The reinforcement with glass fibers
A nonphosphorous approach for improved flame retardancy [141,320,321], cellulose fibers [230,293,294,296,322,323],
using brominated benzoxazine has also been reported [181]. carbon fibers [63,152,252,254,324–327], and silica fiber
Improved toughness accompanies poor anti-flammability [328] has been reported. Since the molecular structure of
characteristics as highly mobile polymers are typically quite polybenzoxazines resemble that of lignin, one of the major
flammable. An exception to this rule is polysiloxanes, which components of wood, compatibility with cellulose is good.
52 PART I Introduction

O
CH2 P CH2
3 3
CH2
O O CH CH2
H2C CH CH2 O R O CH2 CH CH2 R= H 3C CH3 , 6

O
P

H2C HC O O CH CH2
O O
FIGURE 25 Phosphorous atom containing epoxy compounds that were used to blend with benzoxazine resins. (from Ref. [301]).

9.9. Very Low Surface Energy

Unusually low surface energy of polybenzoxazine was
H3C CH3 O P observed [139,348,355–361] and it was applied as a nano-
CH3 imprinting mold release agent [360]. A superhydrophobic
surface with a contact angle of 161.1 was prepared by first
making a mixture of a benzoxazine and silica nanoparticles
HO OH
to create nanoscopic roughness on the surface, which was then
FIGURE 26 A phosphorousatomcontainingphenoliccompoundthatcan be
used as an initiator for benzoxazine resin polymerization. (from Ref. [121]).
coated with a very thin benzoxazine film [356,362], to mimic
the lotus leaf effect. The corresponding water contact angle of
the benzoxazine alone was 111.3 (Figures 29 and 30).
9.8.2. Nanocomposites
Incorporation of nanofillers, such as silicates including clay
9.10. Benzoxazines from Renewable
[50,52,69,124,174,286,287,329–336], carbon nanotube
[255,337,338], POSS [154,158,339–344], SiC whisker Resources
[292,298,345], titanium oxide [346], barium titanate nano- Benzoxazines can be synthesized from natural resources,
particles [319], silica nanoparticles [145,347,348], ex- such as terpenediphenol [143], a derivative of a reaction be-
panded graphite nanoplatelete [349] and Ni-Zn ferrite tween phenol and terpene that is obtained from pine or or-
[350], has been actively studied. ange rind. By far the most abundant renewable resource is
Table 15 shows the improved thermal properties of cellulose. This, too, can be modified with benzoxazine side
bisphenol-A/aniline–based benzoxazine (BA-a) blended chains to increase the char yield dramatically [363]. Unmo-
with the POSS-functional benzoxazine shown in Figure 28. dified cellulose has only 4% char remaining at 800  C under
Small amounts of POSS have significant effect in in- inert atmosphere while the benzoxazine-modified cellulose
creasing Tg, Td5, and char yield. However, too much shows extremely high char yield of nearly 50% (Figure 31).
POSS may lead to the deterioration of the positive effect Cardanol, cashew nut oil, is also used as a raw material
possibly due to the aggregation formation of the POSS com- for benzoxazine synthesis [177,364–367]. Incorporation of
ponent as shown in the 10 wt% POSS sample in Table 15 cardanol structure in benzoxazine improved the ductility in
[339,340]. the polymerized material as is usually the case for cardanol-
Composite application requires good adhesion at the in- modified epoxy and phenolic resins.
terface between the reinforcing material and matrix resin. Another example of the use of renewable resources is the
The ampoteric nature of the polybenzoxazines can accom- synthesis of monomeric benzoxazine based on diphenolic acid
modate a wide variety of substrates, including such tradi- [368]. Diphenolic acid is a condensation product of phenol and
tionally difficult fillers to adhere as calcium carbonate levulinic acid, both of which are inexpensive raw materials. Of
[351], boron nitride [352,353] and more recently wood flour particular interest is the availability of levulinic acid from
[296,322,323,354] and graphite powder including the ex- waste biomass. Additionally, diphenolic acid resembles the
panded graphite for fuel cell bipolar plate application structure with a commonly used raw material for benzoxazine
[349]. Despite the availability of many fillers, filled poly- synthesis, bisphenol-A, except for its lower cost than bisphe-
benzoxazine is rather poorly exploited. nol-A and additional carboxylic functionality.
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 53

FIGURE 27 Phosphous atom containing benzoxazines that R R

can be homopolymerized as polybenzoxazines. (from Ref. N N
[314]). O
O O P O O

R= CH3,
,

R R
N N
O
O O P O O

R= CH3,
,

O O

N N O P O
O
N
P
CH3 O

TABLE 14 Comparison of the Thermal Properties of 9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide

(DOPO)-Based Benzoxazine with Bisphenol-A/Aniline-Based Benzoxazine (BA-a)
Resins Phosphorus Char yielda: Char yielda: LOI (%O2 v/v)
Content (wt%) Nitrogen (wt%) Air (wt%)
DOPO-based 7.8 25 30 40.5
benzoxazines
BA-a 0 32 0 31.8
benzoxazines

Char yield at 750  C.

a

9.11. High Surface Area Materials/Selective metallic ions [371–374]. More recently, polybenzoxazines
Adsorption/membrane with high surface areas have been reported [375,376] and
are shown to be effective in metal absorbing [377]. High
Phenolic materials are well known for their preferance in surface area carbon aerogel is also effective in preparing
ion adsorption. Traditional phenolic resins [369] and calix- supercapacitors [378]. Polybenzoxazine membrane is also
renes [370] are all shown to adsorb metallic ions with some shown to be effective in ethanol-water separation [379]
selectivity depending on the structure of the host material. (Figures 32 and 33).
Polybenzoxazines are no exception for adsorption of
54 PART I Introduction

45 120
TABLE 15 Effect of POSS Concentration on the Physical
Properties of Benoxazine Nanocomposites 40

Surface free energy (mJ/m2)

100
a
POSS POSS Tg Td5 Char 35

Contact angle (°)

Concentration Concentration ( C) (oC) yieldb 80
(wt%) (mol %) (wt%) 30
60
0 0 162 310 31
25
2 0.2 174 324 48 40
20
5 0.5 176 355 52
15 20
10 1.1 180 318 35
a
5% Weight loss temperature. 10 0
b
Under nitrogen at 800  C. –20 0 20 40 60 80 100 120 140
UV exposure time (min)
FIGURE 30 Advancing contact angles of (red)water, (green)diiodo-
H3C methane, and (blue)ethylene glycol and the respective surface-free ener-
O
Si gies (g’s) (black) of polybenzoxazine films derived from bisphenol-A/
O Si N O
H3C O allylamine based benzoxazine (BA-ala) (redrawn from Ref. [357]). (For in-
Si O
O Si terpretation of the references to color in this figure legend, the reader is
CH3 O
O H3C referred to the Web version of this chapter.)
Si O
O Si CH
Si O 3
azacalixarene that contains alkyl-ether has been reported
Si O
H3C
O CH3 to take advantage of the asymmetric nature of the benzox-
FIGURE 28 Monobenzoxazine functional polyhedral oligomeric silses- azine dimer that does not propagate as a long, linear chain,
quioxane (POSS). but rather form cycles as shown in Figure 34.
This asymmetric nature of the chemical reaction is
caused by the nonequivalent hydrogen-bonded structure
50 120
as shown in Figure 35 where one phenolic OH forms a very
45 stable intramolecular six-membered hydrogen bond and the
Surface free energy (mJ/m2)

100 other phenolic OH forms intermolecular hydrogen bond if a

40 partner molecule is available. This intermolecular hydrogen
Contact angle (°)

35 bond is easy to break and participate in the reaction, allow-

80
ing the ether molecule to be attached. Hence, the probability
30 of intramolecular reaction closing the ring structure in-
25 60 creases, rather than forming the open, linear structure.

20
40 9.12. Optical Properties
15
Optical properties of polybenzoxazines are poorly studied
10 20 areas despite offering interesting potential. The polyben-
0 5 10 15 20 25
Polymerization time (h)
zoxazine derived from tert-butyl amine has been reported
to exhibit photoconductivity [400,401]. Such a property
FIGURE 29 Surface free energy change as a function of benzoxazine po-
lymerization time, indicating that there is an optimum structure and conver- can be used for storage media. Figure 36 shows the photo-
sion of polybenzoxazine formation for low surface energy surface formation. current action spectrum. This spectrum is reversible and the
photocurrent is highly dependent on the electric field
strength which suggests that the phenomenon is not an elec-
Nitrogen-containing macrocycles, such as azacalixar- trochemical origin. Another study of optical properties is
ene, have been actively studied in the area of selective ad- the synthesis of fluorene-containing benzoxazines [402].
sorption of ions [380–389]. These macrocycles contain the Fluorene groups are known to exhibit photoluminescence.
same repeating structure as the chemical repeat unit of poly- One of the important properties during the optical property
benzoxazines. Chirachanchai et al. reported extensively the study is the possibility of photodegradation as it strongly
use of benzoxazine as a precursor to synthesize these nitro- influences the durability of devices manufactured. Since
gen-containing macrocycles with some of the reactions phenolic compounds are used as a UV stabilizer by sacri-
yielding as high as 80-85% [79,390–399]. Variation of ficing itself, polybenzoxazine is no exception for the
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 55

FIGURE 31 TGA thermograms of cellulose with and

without benzoxazine side chains, showing markedly in-
100 N
creased char yield by benzoxazine modification (repro- N
N
duced from Ref. [363]). O N
HO OH
O
O
O
OH n
80 HO
N O
N

Residual Weight (%)

N
N

60
Benzoxazine-functional
cellulose

40

20
Unmodified cellulose

0
0 100 200 300 400 500 600 700 800
Temperature (°C)

photosensitivity. UV stability of polybenzoxazines has

been reported [403–406].

9.13. Electropolymerization
Electropolymerization can offer a unique thin coating that is
very tight in its structure, such as pin-hole free films. There-
fore, it is attractive for corrosion protection of metallic sub-
strates among others. Audebert et al. [407] provided an
early report of electropolymerization of benzoxazine. Using
a monofunctional benzoxazine, electropolymerization
mechanism was studied [408–410].
FIGURE 32 SEM photomirograph of the polybenzoxazine-based aerogel
showing nanometer sized voids. 10. CHARACTERIZATION OF
BENZOXAZINES
12
The characterization of benzoxazine structure and its opened
10
Mannich base can be achieved by various techniques. In the
following, characteristic features of oxazine and open Man-
Pore volume (cc/nm g)

nich base are briefly discussed. While there are many spec-
8
tral features unique to benzoxazine structures, the following
discussion will be limited to those characteristic features that
6 are particularly useful for analytical purposes.

4
10.1. Fourier Transform Infrared
2
Spectroscopy
Oxazine-related modes do not show easily recognizable
0 bands due to the heavy overlap of bands. However, There
1 2 3 4 are various bands due to the benzene ring modes that are
Pore diameter (nm) associated with the oxazine ring-attached benzene ring.
FIGURE 33 Pore size distribution of the polybenzoxazine aerogel shown The band assignments for the monomers [411] and dimers
in Figure 32 (redrawn from Ref. [377]). [412] have been reported. There is a band around
56 PART I Introduction

O O

N
H H3C CH3
CH3
O O Yes
H
N + TsO OTs
H3C
CH3 O O
CH3 No
N
CH3

CH3 CH3
n
FIGURE 34 Reaction between the benzoxazine dimer and tosylated compound, showing the preference of forming a cyclic compound.

Intramolecular 1500 cm1 [Wilson number 19b] [413] which is a charac-

6-memberedH-bond teristic mode of trisubstituted benzene. This mode shifts
to around 1490 cm1 upon benzoxazine polymerization
H forming the tetrasubstituted benzene structure. Thus, the
O O frequency shift of this mode can be used as the direct evi-
H
dence of benzoxazine polymerization. On the other hand,
H3C
N
the mode in the range of 960-910 cm1 [Wilson number
CH3 10a] that is sufficiently isolated with strong enough inten-
CH3
sity is useful to recognize the oxazine ring structure. This
FIGURE 35 The benzoxazine dimer showing the heterogeneous nature band is due to the benzine ring mode of the benzene to
of the phenolic hydroxyl groups with intramolecular six-membered ring
which oxazine is attached, but it is not the oxazine ring
hydrogen bond and another phenolic hydroxyl group that does not have
the partner to form intramolecular hydrogen bond. The reaction first takes mode. When oxazine ring opens, this mode disappears. It
place at this latter hydroxyl group followed by the consumption of the in- is important to note that disappearance of this mode is
tramolecularly hydrogen boded hydroxyl group after a long reaction time. not the evidence of oxazine polymerization, but it is a sim-
ple indication that the oxazine ring opened. Therefore, this
mode can disappear even upon hydrolysis of the oxazine
ring. Nonetheless, when hydrolysis is not a concern, the dis-
2 appearance of this mode is often associated with the poly-
OH
merization of the oxazine group (Figure 37).
Hyphenated techniques, such as FTIR-TGA, are particu-
N
H
larly useful for the study of polybenzoxazine degradation
n
1.5 [76,96,99]. Shown in Figure 38 is the evolved gas FTIR spec-
H3C CH3
trum of bisphenol-A/methylamine-based benzoxazine (ab-
Photocurrent (μA/m2)

CH3
breviated as BA-m). Below 400  C, the spectral feature is
dominated by the decomposing methylamine and other
1 amines as a result of the structural changes of the decom-
posed fragments. Above 400  C, phenolic compounds
started evolving as is evident by the sharp band around
3650 cm1 of the free OH group of the phenolic compounds.
0.5
10.2. Raman Spectroscopy
The ring breathing mode of benzoxazines appears
around 770-750 cm1 with medium-to-strong intensity
0
2 2.5 3 3.5 4 [411]. This mode is often isolated from the other modes
Energy (eV) and can be useful for recognizing benzoxazine structure.
FIGURE 36 Photocurrent action spectrum of tert-butyl functional poly- Despite potential usefulness of Raman spectroscopy,
benzoxazine at 40 V/mm (redrawn from Ref. [401]). due in part to the fluorescence problems of some of
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 57

FIGURE 37 FTIR spectra of model benzoxazines CH2CH2CH2CH2CH3

940
with (a) amyl; (b) butyl; (c) propyl; (d) ethyl; (e) N
methyl/CH2; and (f) methyl/CD2 substituents.
H3C O
(a)
CH2CH2CH2CH3
N

H3C O
(b)
CH2CH2CH3
N

Absorbance
H3C O
(c) CH2CH3
N

H3C O
(d)
CH3
N

(e)
H3C O
CH3
D2C N
CD2
(f)
H3C O

1300 1200 1100 1000 900

Wavenumbers (cm –1)

FIGURE 38 FTIR spectra were recorded in-situ as the poly-

benzoxazine derived from bisphenol-A/methylamine based
monomer was heated in TGA, reflecting evolution of various
*
460 °C
gaseous species. (reproduced from Ref. [76] with permission).
410 °C

300 °C
Absorbance

285 °C

260 °C

4000 3200 2400 1600 800

Wavenumber (cm–1)

benzoxazine compounds, it has not been actively utilized. (CH3)  groups, respectively. The integrated intensity ratio
The fluorescence is especially problematic for polybenzox- of these resonances is 1:1. While small molecular weight
azines as polymerization by-products often fluoresce: how- benzoxazines do not show serious problems due to the high
ever, monomers that are purified are quite manageable molecular mobilities, it is nonetheless important that the re-
(Figure 39). laxation time of about 10 s is used for quantitative intensity
measurement if accurate measurement is desired. The gen-
10.3. Nuclear Magnetic Resonance eral frequency ranges for these resonances are 3.8-4.8 ppm
for the former and 4.7-5.7 ppm for the latter resonance.
Spectroscopy (NMR) The separation of these resonances is about 0.8-0.9 ppm.
The resonances due to the CH2 groups of oxazine ring are par- Therefore, these two resonances are easy to recognize and
ticularly useful for identifying the formation, existence, or are very useful for analytical purposes. In particular, this
disappearance of the oxazine ring [414]. The characteristic near-constant frequency separation of the two oxazine reso-
1
H resonances of oxazine CH2 are seen at 3.91 and nances is very useful to verify the correctness of the
4.76 ppm for PhCH2N(CH3) and O CH2N assignment.
58 PART I Introduction

747 CH2CH2CH2CH2CH3
FIGURE 39 Raman spectra of model benzoxazines with (a)
N amyl; (b) butyl; (c) propyl; (d) ethyl; (e) methyl/CH2; and (f)
methyl/CD2 substituents (redrawn from Ref. [412]).
(a) H3C O

CH2CH2CH2CH3
N

(b) H 3C O
Counts (arb. unit)

CH2CH2CH3
N

(c) H 3C O

CH2CH3
N

(d) H 3C O

CH3
N

(e) H3C O

CH3
D2 C N
(f) CD2
H3C O

900 800 700 600 500

Wavenumbers (cm–1)

CH3
83.7
N
52.1
4.76 H3C O

CH3
N
3.91
H3C O

8 7 6 5 4 3 2 1 0 150 110 70 30 –10

ppm ppm
FIGURE 40 1H NMR spectrum of 3,6-dimethyl-2H,4H-benzo[e]1,3- FIGURE 41 13C NMR spectrum of 3,6-dimethyl-2H,4H-benzo[e]1,3-
oxazine (redrawn from Ref. [411]). oxazine (redrawn from Ref. [411]).

The characteristic 13C resonances of oxazine CH2 are

seen at 83.7 and 52.1 ppm for PhCH2N(CH3) and
OCH2 N(CH3) groups, respectively. The general
frequency ranges for these resonances are 79-84 ppm for
the former and 49-54 ppm for the latter resonance. The lat-
ter resonance can sometimes split into a doublet. In such a
case, the lower frequency may extend to 45 ppm
(Figures 40–43; Table 16–18).
Solid-state NMR spectroscopy is very useful for the
study of cross-linked polybenzoxazines as the polymer is 8 6 4 2 0
insoluble and infusible [77,279,415]. Phenolic structure for- ppm
mation as a result of the oxazine ring opening can be studied FIGURE 42 1H NMR spectrum of benzoxazine model trimer (repro-
by following the 13C resonance of the aromatic carbon that duced from Ref. [414] with permission).
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 59

FIGURE 43 13C NMR spectrum of model benzox-

azine trimer (reproduced from Ref. [414] with
permission).

160 140 120 100 80 60 40 20 ppm 0 ppm

phenolic OH appears near 7 ppm. Of particular interest is

TABLE 16 1H and 13C NMR Frequency Assignments for the proton that is part of the intramolecular six-membered
3,6-Dimethyl-2H,4H-Benzo[e]1,3-Oxazine ring hydrogen-bonded system that arises in the range of
7 10-13 ppm [131]. This proton is shared by both oxygen
8 O 1
6 CH2 and nitrogen atoms and stays with the nitrogen atom for a
9 10 time duration that can be detected by NMR as an NH group,
N
H3C 5 3 CH2 CH3 despite the fact that no NH groups are produced as a result
4 2 of hydrogen bond formation. Two-dimensional solid-state
1
H single quantum-double quantum spectroscopy is very
useful to study the local conformation of the polybenzoxa-
1 13
Atoms H NMR Frequency C NMR Frequency zine chains. As shown in Figure 44, the off-diagonal signals
(ppm) (ppm) indicate the groups that are present at less than 0.4 nm in
C1 4.76 83.7 distance. As a result of this mapping, the local conformation
C2 3.91 52.1
as shown in Figure 45 has been proposed [133] (Table 19).
The fundamental understanding of the hydrogen bond-
C3 – 119 ing is important in understanding the structure and proper-
C4 6.79 128 ties of polybenzoxazines. Rotor-encoded solid-state 15N
C5 – 130
NMR was used to determine the position of the proton in
the six-membered ring for the first time using a 15N-
C6 6.66, 6.70 128 enriched benzoxazine dimer [132].
C7 6.91, 6.94 116
C8 – 151

C9 2.25 20.1 10.4. Thermal and Thermomechanical

C10 2.59 39.3
Characterization
10.4.1. Differential Scanning Calorimetry (DSC)
Benzoxazines typically show a symmetric exotherm in the
is bonded to the oxygen in the benzoxazine monomer (2,20 - range of 200-250  C with the heat of polymerization in the
(3-methyl-4-dihydro-1,3,2 benzoxazine) propane (abbrevi- range of 150-600 J/g if the sample is pure (Figure 46). Impu-
ated as BA-m)). In its monomeric form, this resonance ap- rities, such as phenolic compound and amines used as the raw
pears at 152 ppm, whereas opened phenolic structure shows materials for the monomer synthesis, act as initiators and cat-
a resonance at 157 ppm [77]. 15N NMR provides direct in- alysts. These compounds shift this exotherm peak to lower
formation on the monomeric (78 ppm) and open Mannich temperatures with an asymmetric shape. In an extreme case,
base structure (71 ppm) [415]. there will be multiple peaks. If the lowering of the polymeri-
Unique capability of high-resolution solid-state proton zation phenomenon takes place due to the intrinsic nature of
NMR is particularly noteworthy for the study of hydrogen the benzoxazine structure, rather than the impurities or added
bonding in the polybenzoxazine systems [131–133]. The initiators or catalysts, the lowering of the exotherm peak ac-
ordinary intermolecularly hydrogen bonded 1H in the companies with relatively symmetric shape. Therefore, it is
60 PART I Introduction

TABLE 17 1H NMR Frequency Assignments for Model Benzoxazine Trimer

1 OH OH OH OH
3
H3C CH3
N N N
CH3 CH3 CH3
4 5 6 7 7 6 5 4
2
CH3 CH3 CH3 CH3

Atoms Trimer, 1H NMR Frequency (ppm) Tetramer, 1H NMR Frequency (ppm)

H1 2.19 2.19

H2 2.22 2.22
H3 3.66 3.65
H4 6.67 6.68
H5 6.88 6.74
H6 6.88 6.85
H7 – 6.92

TABLE 18 13C NMR Frequency Assignments for Model

Benzoxazine Trimer

OH OH OH
1
4 13
H3C 7 6 5 14 CH3
N N
CH3 9 9 CH3
11 8 11
12 10
3
CH3 CH3 CH3
2

Atoms Trimer, 13C NMR Atoms Trimer, 13C NMR

Frequency (ppm) Frequency (ppm)
C1 C8

C2 C9
C3 C10
C4 C11
C5 C12
C6 C13 FIGURE 44 (a) 1H MAS spectrum and (b) 2D rotor-synchronized 1H-1H
C7 C14 DQ MAS spectrum of the 15N-labelled methyl benzoxazine dimer acquired
with 1/2tR excitation time (nR ¼ 30 kHz and 700 MHz Lamor frequency)
(reproduced with permission from Ref. [132]).
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 61

extremely important to purify the benzoxazine as much as pos- components than traditional condensation-type phenolic
sible or determine the accurate purity for kinetic studies. resins. There are a few polymers that exceed this char yield
characteristics of polybenzoxazines. However, those poly-
mers typically accompany great processing difficulties.
10.4.2. Thermogravimetric Analysis Polybenzoxazines generally decompose in three stages in
TGA can be used to study the rate of degradation, degrada- the temperature range around 300, 400, and 500  C, which
tion process, and char yield. These data are useful for ther- might arise from the decomposition of the chain ends of the
mal stability and degradation mechanism studies. The char
yield is most commonly defined as the residual weight un-
der nitrogen at 800  C, although there is no universal agree- TABLE 19 Solid-State 1H NMR Frequency Assignment of
ment of the definition. The char yield of polybenzoxazines Benzoxazine Model Dimer
ranges from 35% to 80%, which is one of the highest of all Atoms Single Double Double
processable polymers despite having more aliphatic quantum quantum quantum
chemical coherence chemical
shift (ppm) shift (ppm)
NH (A) 11.2 AB 18.3
AD 13.2
OH (B) 7.2 – –
Aromatic 6.0 CC 12.0
H (C)
CE 7.3
CH2 2.0 –
(D)
CH3 (E) 1.3 EE 2.6
FIGURE 45 Structure of model dimer crystal based on the solid-state 1H
NMR study shown in Figure 42.

H3C CH3
H3C CH3

N N

O O
H3C CH3

N N

O O

H3C CH3
N N
CH3 CH3
Heat flow (W/g)

O O

H3C CH3

H3C N N CH3

O O

CH3 CH3

H3C CH3

H3C N N CH3

O O

150 180 210 240 270 300

Temperature (°C)
FIGURE 46 DSC thermograms of benzoxazines obtained with bisphenol A as the phenol and 3,5-xylidine, m-toluidine, o-toluidine, aniline, and
p-toluidine as the amine components (redrawn from Ref. [71]).
62 PART I Introduction

branches and main chain, decomposition of the main-chain polymers, the glassy modulus is typically much greater than
amine, and decomposition of the phenolic component, in those polymers (Figure 48).
the case of polybenzoxzines derived from bisphenol and Table 20 and 21 list various spectroscopic and thermal
monoamine-based monomeric benzoxazines. By examin- data for selected benzoxazine monomers to aid analytical
ing the main-chain type polybenzoxazine degradation, the studies.
lowest temperature degradation mechanism is found to be
greatly suppressed as the numbers of chain end groups
are minimized (Figure 47). 10.5. Mass Spectrometry
While matrix-assisted laser desorption/ionization-time of
10.4.3. Dynamic Mechanical Analysis (DMA) flight (MALDI-TOF) technique is potentially useful for
the studies of monomers, oligomers, and linear polybenzox-
Typical dynamic mechanical spectra of polybenzoxazine
azines with oxazine groups in the main chain or side chain
derived from bisphenol-A and aniline-based monomer is
[188], it has not been actively used to date for the analysis of
shown in Figure 48. The glass transition temperature of
benzoxazines. Along with TGA-FTIR, another hyphenated
polybenzoxazine ranges from sub-zero temperatures to near
technique actively used is TGA-GC-MS or pyrolysis MS
400  C. Therefore, there is no analytical value even if the Tg
techniques. Due to the cross-linked nature of the polyben-
of a polymer is known. Usually, the Tgs of polybenzoxa-
zoxazines, fragmentation by TGA or other pyrolizer is
zines are rather high ranging from 150 to 400  C unless a
necessary to study the structure of the polymer. The
flexible component is purposely incorporated. This unex-
TGA-GC-MS technique can be used by collecting the
pectedly high Tg originates from the existence of extensive
evolved gases into a solvent, such as chloroform, and run
hydrogen bonding, reducing the chain mobility. In the case
the GC-MS analysis [97,98,417]. While this approach is
of the extensively studied poly(BA-a) shown in Figure 48,
simple, the reformation of the fragmented species in the sol-
Tg is around 170  C. The b- and g-transitions arise near 100
vent prior to the GC-MS analysis complicates the study. To
[45,416] and 90  C, respectively [45]. The storage shear
avoid this difficulty, TGA/GC-MS interface is needed. An-
modulus in the glassy region is usually in the range of
other technique that does not require such an interface is py-
1-3 GPa.
rolysis MS technique where a pyrolyzer is equipped in a
The intermolecular hydrogen bonds break-up near the
high vacuum device of the mass spectrometer
Tg of the polymer, leading to the fast reduction of the G0 .
[101,102,418]. This technique allows the observation of to-
The degree of this reduction is steeper than the polymers
tal ion current (TIC) from which the number of mechanisms
whose moduli do not depend heavily on the hydrogen bond-
can be studied as each peak usually corresponds to an indi-
ing. Thus, the rubbery plateau moduli of polybenzoxazines
vidual degradation mechanism. The TIC curve agrees well
are smaller than epoxy and traditional phenolic resins,
with the derivative TGA thermogram as shown in Figure 49
reflecting the lower cross-link density than those polymers.
since individual weight loss events in the TGA thermogram
Despite the lower cross-link density than those common
also correspond to different degradation mechanisms.
Pyrolysis MS can also measure the evolution of individual
0.5
390 °C
Derivative residual weight (%/min)

1010 101
0.4 H C CH
Polymer from N
3 3
N

O O
a
0.3 470 °C 109 100

310 °C
G* (Pa)

tan d

0.2
108
b
g
0.1
107 10–2

0
106
100 200 300 400 500 600 700 800 –140 – 64 12 88 164 240
Temperature (°C) Temperature (°C)
FIGURE 47 Derivative TGA thermogram of polybenzoxazine derived FIGURE 48 Dynamic mechanical spectra (G0 and tan d) of the polyben-
from bisphenol-A and aniline-based benzoxazine monomer (BA-a) zoxazine derived fron bisphenol-A and aniline-based monomer (BA-a)
(redrawn fron Ref. [72]). (redrawn fron Ref. [45]).
TABLE 20 Various Spectroscopic Data Unique to Benzoxazine Monomers to Recognize the Presence of Oxazine Group and Physical Properties of the Cross-
Linked Polybenzoxazines Derived Therefrom
Abbr. Phenol Amine 1
H-NMR 1
H-NMR 13
C-NMR 13
C-NMR IR Tg Char T5% TDH DH
(ppm) (ppm) (ppm) (ppm) (cm1) ( C) Yield ( C) ( C) (J/g)
(%)
24DMP- 2,4-Dimethyl phenol o-Toluidine 5.17 4.37 80.84 50.94 933
ot
24DMP- ” m-Toluidine 5.33 4.56 79.30 50.27 940 282.9 170.7
mt
24DMP- ” p-Toluidine 5.31 4.53 79.85 50.56 944 285.6 159.8
pt
24DPMP- ” 3,5-Xylidine 5.32 4.55 79.30 50.25 940 269.8 170.9
35x

4TBUPH- 4-t-Butyl phenol Aniline 5.34 4.64 79.10 50.71 951 271.9 255.1
a

4TBUPH- ” o-Toluidine 5.16 4.41 80.82 51.09 944 272.3 224.1

ot
4TBUPH- ” m-Toluidine 5.33 4.63 79.04 50.77 950 265.6 264.9
mt
4TBUPH- ” p-Toluidine 5.31 4.60 79.59 50.97 948 268.6 228.2
pt
4TBUPH- ” 3,5-Xylidine 5.31 4.61 79.93 50.81 947 247.0 236.4
35x
BA-a Bisphenol A Aniline 5.34 4.59 947 170 30 315 251 340
BA-ot ” o-Toluidine 5.17 4.36 947 114 32 228 247 289
BA-mt ” m-Toluidine 5.32 4.58 947 210 31 350 231 325

BA-pt ” p-Toluidine 5.30 4.54 947 158 32 305 259 310

BA-35x ” 3,5-Xylidine 5.31 4.57 947 245 28 350 217 298
II 2,4-Dimethyl phenol 4-Aminophthalo- 5.4 4.6 73 414
nitrile
I 2-Phenol ” 5.4 4.6 76 450
III 4,40 -Dihydroxy-benzophenone ” 80 544
IV Bisphenol A ” 68 423
Phenol Aniline 5.3 4.5
Phenol o-Benzonitrile 5.32 4.6 954 180

” m-Benzonitrile 956

Continued
TABLE 20 Various Spectroscopic Data Unique to Benzoxazine Monomers to Recognize the Presence of Oxazine Group and Physical Properties of the Cross-
Linked Polybenzoxazines Derived Therefrom cont’d

Abbr. Phenol Amine 1

H-NMR 1
H-NMR 13
C-NMR 13
C-NMR IR Tg Char T5% TDH DH
(ppm) (ppm) (ppm) (ppm) (cm1) ( C) Yield ( C) ( C) (J/g)
(%)
Bisphenol AF Aniline 5.4 4.6 916 218 57
PH-apa Phenol 3-Aminophenyl- 950 329 79 520 221
acetylene
BF-apa Bisphenol F ” 950 368 78 470
HQ-apa Hydroquinone ” 948 81 530 182
0
BA-apa 4,4 -Isopropylenediphenol ” 954 356 74 458 186
(bisphenol A)
BP-apa 4,40 -Dihydroxybiphenyl ” 944 73 462 194
0
TP-apa 4,4 -Thiodiphenol ” 943 79 489
BAF-apa Bisphenol AF ” 938 362 71 494
0
BS-apa 4,4 -Dihydroxybenzosulfone ” 928 78 440 180
(bisphenol-S)
BO-apa 4,40 -Oxydiphenol (bisphenol-O) ” 946 75 415
0
BZ-apa 4,4 -Dihydroxybenzophenone ” 934 80 580 179
NP-apa 2,7-Dihydroxynaphthalene 76 380
PC-a p-Cresol Aniline 20
BA-a Bisphenol A ” 32
HQ-a Hydroquinone ” 44
0
22P-a 2,2 -Biphenol ” 52
0
44O-a 4,4 -Dihydroxybenzophenone ” 61
15N-a 1,5-Dihydroxynaphthalene ” 71
0
TP-a 4,4 -Thiobiphenol ” 57
TrisP-a 1,1,1-tris(p-hydroxyphenyl)- ” 47
ethane
pC-m p-Cresol Methylamine 4.7 3.9 83.7 52.2
0
22P-a 2,2 -Dihydroxybiphenyl Aniline 940 200 45
0 0
4,4 O-a 4,4 -Dihydroxybenzophenone ” 933 340 65 297
P-ad2 Phenol Ethlenediamine 4.91 4.05 82.64 50.31 930 184 41 291 185 575
P-ad4 Phenol 1-4- 4.86 3.99 82.42 50.12 930 160 32 270 225 418
Diaminobutane
P-ad6 Phenol 1-6- 4.85 3.98 82.37 50.17 930 169 19 280 225 367
Diaminohexane

P-ad8 Phenol 1-8- 4.86 3.98 82.38 50.20 930 151 13 287 236 288
Diaminooctane

P-ad12 Phenol 1-12- 4.86 3.99 82.39 50.22 930 118 6 286 241 255
Diaminododecane
MIB-a 1-(4-Hydroxy-phenyl)-pyrrole- Aniline 5.49 4.73 80.50 49.19 935 252 56 375 244 295
2,5-dione
NOB-a p-Hydroxyphenylnadimide Aniline 5.47 4.69 80.48 53.18 935 58 365 261
pC-a Cresol Aniline 5.35 4.57 83.1 51.3 946 257

pC-m Cresol Methylamine 4.79 3.92 83.1 51.3

24DMP-a 2,4-Dimethylphenol Aniline 5.35 4.57 79.3 50.3
24DMP- 2,4-Dimethylphenol Methylamine 4.77 3.90 83.4 51.7
m
24DMP- 2,4-Dimethylphenol p-Toluidine 5.56 4.77 79.1 50.1
pt
24DMP- 2,4-Dimethylphenol p-Methoxyaniline 5.29 4.51 79.1 53.4
pma

24DMP- 2,4-Dimethylphenol Perfluorinated 5.10 4.49 79.1 50.5

pfa aniline

Methyl 3,5-dihydroxybenzoate Methylamine 4.76 4.23 83.59 51.51

doublet 3.87 83.42 47.83
Methyl 3,5-dihydroxybenzoate 2,4,6- 5.05 4.63 81.05 49.10
Trimethylaniline
doublet 4.27 80.79 45.65
Phenyl 3,5-dihydroxybenzoate 2,4,6- 5.07 4.69 81.12 49.23
Trimethylaniline
doublet 4.32 80.79 45.73

BHPPO-a Bis-(4-hydroxyphenyl) Aniline 5.42 4.64 935 46 302

phenylphosphine oxide
BHPPO- Bis-(4-hydroxyphenyl) Methylamine 4.85 3.94 920 48 250
m phenylphosphine oxide

Continued
TABLE 20 Various Spectroscopic Data Unique to Benzoxazine Monomers to Recognize the Presence of Oxazine Group and Physical Properties of the Cross-
Linked Polybenzoxazines Derived Therefrom cont’d

Abbr. Phenol Amine 1

H-NMR 1
H-NMR 13
C-NMR 13
C-NMR IR Tg Char T5% TDH DH
(ppm) (ppm) (ppm) (ppm) (cm1) ( C) Yield ( C) ( C) (J/g)
(%)
BHPPO- Bis-(4-hydroxyphenyl) 3-Ethynylaniline 5.40 4.63 936 64 405
ea phenylphosphine oxide
BPPPO-a Bis-(4-benzyloxyphenoxy-40 - Aniline 5.27 4.48 930 51 259
phenyl)phenylphosphine oxide

BPPPO- Bis(4-benzyloxyphenoxy-40 - Methylamine 4.71 3.85 940 30 212

m phenyl)phenylphosphine oxide

BPPPO- Bis(4-benzyloxyphenoxy-40 - 3-Ethynylaniline 5.28 4.52 944 76 403

ea phenyl)phenylphosphine oxide
BPHPPO- Aniline 5.30 4.54 940 52 315
a
BPHPPO- Methylamine 4.76 3.90 925 34 279
m
BPHPPO- 3-Ethynylaniline 5.30 4.58 944 63 351
ea

Suggested abbreviations for the monomers are also indicated.

Chapter 1 Overview and Historical Background of Polybenzoxazine Research 67

TABLE 21 1H-NMR and 13C-NMR Resonances of the CH2 Groups in the Mannich Base of Model Dimers that Correspond
to the Polymerized Benzoxazine Resins
1 13
Chemical Structure H-NMR (ppm) C-NMR (ppm)

OH OH 3.66 59.25

H3C CH3
N

CH3

CH3 CH3

OH OH 4.26 55.68

H3C CH3
N

CH3 CH3

OH 3.69, 3.58 61.50, 61.03

H3C
N

CH3

CH3

OH 4.31, 4.27 57.68, 55.19

H3C
N

CH3

N 3.51 61.85

CH3

N 4.65 54.15

OH OH OH 3.68 59.59, 58.78

H 3C CH3
N N
CH3 CH3

CH3 CH3 CH3

Continued
68 PART I Introduction

TABLE 21 1H-NMR and 13C-NMR Resonances of the CH2 Groups in the Mannich Base of Model Dimers that Correspond
to the Polymerized Benzoxazine Resins cont’d
1 13
Chemical Structure H-NMR (ppm) C-NMR (ppm)

OH OH OH OH 3.66, 3.63 59.59. 58.38, 57.57

H3C CH3
N N N
CH3 CH3 CH3

CH3 CH3 CH3 CH3

OH OH 3.66 59.3

H3C CH3
N

CH3

CH3 CH3

OH OH 4.36 55.7

H3C CH3
N

CH3 CH3

OH OH 4.33 58.8

H3C CH3
N

CH3 CH3

CH3

OH OH 3.74 58.8

H3C CH3
N

CH3 CH3

OCH3
Chapter 1 Overview and Historical Background of Polybenzoxazine Research 69

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