Benzoxazine containing polyester thermosets with improved adhesion and flexibility

Article abstract of DOI:10.1002/pola.24215

High molecular weight polyesters containing thermally curable benzoxazine units in the main chain have been synthesized. For this purpose, first the diol functional monomer is synthesized through the Mannich and subsequent ring closure reactions of bisphenol-A, paraformaldehyde, and 5-amino-1-pentanol. Polycondensation of the resulting benzoxazine and pyromellitic dianhydride or 4-4'-(hexafluoroisopropylidene) diphatalic anhydride with or without dibutyltin laurate yielded the corresponding polyesters with the molecular weights between 5800 and 7000 Da. The structures of the precursor diol monomer and the resulting polyesters are confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy analysis. Curing behavior of both the monomer and polymers has also been studied bydifferential scanning calorimetry. Flexible films of the polyesters were obtained by solvent casting on tin plates and crosslinked by heating in the absence of any catalyst. The cured films exhibited high flexibility and adhesion on the tin plates as determined by ASTM and DIN tests. Thermal properties of the cured polymers were also investigated by thermogravimetric analysis (TGA).

Full text of DOI:10.1002/pola.24215

Benzoxazine Containing Polyester Thermosets with Improved
Adhesion and Flexibility
1
1
2
2
1
ALEV TUZUN, BARIS KISKAN, NESLIHAN ALEMDAR, A. TUNCER ERCIYES, YUSUF YAGCI
1
Department of Chemistry, Istanbul Technical University, Maslak, Istanbul 34469, Turkey
2
Department of Chemical Engineering, Istanbul Technical University, Maslak, Istanbul 34469, Turkey
Received 28 April 2010; accepted 29 June 2010
DOI: 10.1002/pola.24215
Published online in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: High molecular weight polyesters containing ther-
mally curable benzoxazine units in the main chain have been syn-
thesized. For this purpose, first the diol functional monomer is
synthesized through the Mannich and subsequent ring closure
reactions of bisphenol-A, paraformaldehyde, and 5-amino-1-pen-
tanol. Polycondensation of the resulting benzoxazine and pyro-
troscopy analysis. Curing behavior of both the monomer and
polymers has also been studied by differential scanning calorime-
try. Flexible films of the polyesters were obtained by solvent cast-
ing on tin plates and crosslinked by heating in the absence of any
catalyst. The cured films exhibited high flexibility and adhesion
on the tin plates as determined by ASTM and DIN tests. Thermal
properties of the cured polymers were also investigated by
thermogravimetric analysis (TGA). VC 2010 Wiley Periodicals, Inc.
0
mellitic dianhydride or 4-4 -(hexafluoroisopropylidene) diphatalic
anhydride with or without dibutyltin laurate yielded the corre-
sponding polyesters with the molecular weights between 5800
and 7000 Da. The structures of the precursor diol monomer and
the resulting polyesters are confirmed by Fourier transform infra-
red spectroscopy and proton nuclear magnetic resonance spec-
J Polym Sci Part A: Polym Chem 48: 4279–4284, 2010
KEYWORDS: adhesion; benzoxazine; crosslinking; curing; flexi-
bility; high performance; polybenzoxazine; thermoset
INTRODUCTION Polybenzoxazines are relatively new class of
materials, which are alternative to phenol formaldehyde res-
ins. They have a good combination of attractive properties,
such as (i) near zero volumetric change upon curing, (ii) low
structure. To overcome these limitations various approaches
were proposed. These include (i) synthesis of specially
1
0–18
designed novel monomers,
or fillers and fibers, or (iii) synthesis of end-chain, side
chain, or main-chain polybenzoxazines.
(ii) blending with polymers
1
9–21
2
2–29
water absorption, (iii) high T , in some cases higher than cure
In spite of the
g
temperature, (iv) high char yield, (v) no strong acid catalysts
required for curing, and (vi) release of no by-product during
curing. The cured materials also possess thermal and flame
significant improvements on some properties, the desired
flexibility and adhesion could still not be achieved. Aiming at
expanding their industrial applicability it seemed appropriate
to prepare a family of highly flexible benzoxazine polycon-
densates tailored to meet different requirements, depending
on the specific application. Our working concept is based on
creating polymeric backbones integrating segments that
induce molecular flexibility and adhesion on metals on one
hand, and that comprise thermally curable benzoxazine moi-
eties on the other hand. This article describes synthesis,
characterization, and thermal curing of polyesters containing
benzoxazine moieties in the main chain from diacid anhy-
drides and diol containing bisbenzoxazines. As will be
shown, the obtained polymers exhibit an enhanced adhesion
and flexibility even after thermal curing.
1
retarding properties of phenolics along with better mechanical
performance. The striking feature is connected with dimen-
sional stability during the conversion from monomer to poly-
mer because of the ring opening nature of the polymerization.
In fact, the polymerization occurs through thermal activation
of the corresponding benzoxazines without any catalyst and
2
–6
without generating any by-products (see Scheme 1).
Moreover, benzoxazine monomers can be prepared simply
from inexpensive and commercially available phenols, pri-
5
,7–9
mary amines, and formaldehyde.
Therefore, the chemis-
try of benzoxazine synthesis offers a wide range of molecular
design flexibility by using appropriate starting materials and
polybenzoxazine properties can be tailored. Polybenzoxazines
prepared from the monomer precursors form some limita-
tions on their use in practical applications. The monomers
are usually powder and processing into thin films is rather
difficult. Additionally, the formed polymers are brittle as a
consequence of the short molecular weight of the network
EXPERIMENTAL
Materials
0
4,4 -Isopropylidenediphenol (Acros, 97%), paraformaldehyde
(J.T. Baker, 95%), 5-amino-1-pentanol (Aldrich, 97.0%), 1,4
dioxane (Riedel-de Ha e¨ n 99.5%), sodium hydroxide (Carlo
Correspondence to: Y. Yagci (E-mail: yusuf@itu.edu.tr)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 48, 4279–4284 (2010) V
2010 Wiley Periodicals, Inc.
C
BENZOXAZINE-CONTAINING POLYESTER THERMOSETS, TUZUN ET AL.
4279

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
SCHEME 1 Thermally activated ring open-
ing polymerization of mono- and bis-
benzoxazines.
Erba, 97%), anhydrous magnesium sulfate (Alfa Aesar,
2 2 2 2 2
1.39 (m, 4H, NACH ACH ACH ), 1.42 (m, 4H, NACH ACH ),
99.5%), chloroform (Riedel-de Ha e¨ n, 99.4%), pyromellitic
1.57 (s, 6H, isopropylidene ACH ), 1.63 (m, 4H, HOA
3
dianhydride (Merck, 97%), N,N-dimethylformamide (Merck,
CH ACH ), 2.73 (broad t, 4H NACH ), 3.60 (broad t, 4H
2
2
2
0
99.8%), dibutyltin laurate (Aldrich, 95.0%), and 4-4 -(hexa-
HOACH ), 3.69 (broad s, 2H, OH), 3.91 (s, 4H, oxazine
2
fluoroisopropylidene)diphatalic anhydride (Aldrich, 99.0%)
were used as they received.
ArACH AN), 4.80 (s, 4H, oxazine, OACH AN), 6.65–6.95
(6H, aromatics).
2
2
Synthesis of 4-(2H-1,3-benzoxazin-3(4H)-yl)Benzoic Acid
A mixture of phenol (5.0 g, 53 mmol), 4-aminobenzoic acid
Characterization
Proton nuclear magnetic resonance spectroscopy ( H NMR)
1
(
7.0 g, 51 mmol), and paraformaldehyde (3.2 g, 105 mmol)
was placed in a 500-mL round-bottom flask and 200 mL of
,4-dioxane was added to this mixture. The mixture was
spectra were recorded in deuterated chloroform with tetra-
methlysilane as an internal Standard, using a Bruker AC250
instrument at a proton frequency of 250.133 MHz. Fourier
transform infrared spectroscopy (FTIR) spectra were
recorded on a Perkin-Elmer FTIR Spectrum One spectrome-
ter via attenuated total reflectance technique with 4 cm
resolution and 20 scans and for each sample. Differential
scanning calorimetry (DSC) experiments were performed on
1
refluxed, and the reaction was monitored with thin layer
chromatography (20:1 dichloromethane/ethanol) until the
initial product disappeared (5 days). After cooling to room
temperature, the mixture was filtered and concentrated by
evaporating 4/5 of 1,4-dioxane at rotary evaporator. Ethyl
ether (150 mL) was added to the mixture with magnetic stir-
ring, and a yellow precipitate was obtained. The yellow solid
was filtered and dried under reduced pressure. (Yield: 50%)
ꢀ
1
ꢁ
Perkin-Elmer Diamond DSC with a heating rate of 10 C/min
under nitrogen flow (20 mL/min). Thermogravimetric analy-
sis (TGA) was performed on Perkin-Elmer Diamond TA/TGA
1
ꢁ
H NMR (CDCl ): d ¼ 4.81 (s, 2H, NACH AAr), 5.57 (s, 2H,
with a heating rate of 10 C/min under nitrogen flow
3
2
NACH
2
AO), 6.78–7.84 (m, 8H, aromatics), 12.45 (broad s,
(
200 mL/min). Molecular weights were determined against
polystyrene standard using size exclusion chromatography
GPC) equipped with a Waters 1515 pump and Waters styra-
1H, COOH).
(
Synthesis of 3-Phenyl-3,4-dihydro-1,3-benzoxazine
P-a Monomer)
P-a monomer was prepared via typical solventless method.
gel column (HT4) using DMF containing 5 mM NH
flow rate of 0.5 mL/min.
4 6
PF at a
(
30
1
H NMR (CDCl ): d ¼ 4.49 (s, 2H, NACH AAr), 5.37 (s, 2H,
3
2
Synthesis of Bisbenzoxazine-Diol
NACH
2
AO), 6.79–7.30 (m, 9H, aromatics).
Synthesis of diol functional bisbenzoxazine was performed
according to the following procedure. To 150 mL of 1,4-diox-
ane, paraformaldehyde (176 mmol, 5.3 g), 5-amino-1-penta-
Synthesis of Benzoxazine Containing Polyesters
Typical procedure: To 45 mL of dried DMF, BBD (3.9 mmol,
1.89 g), and 1,2,4,5-benzene-tetracarboxylic-1,2:4,5-dianhy-
dride (3.9 mmol, 0.85 g) were added and refluxed under N2
0
nol (88 mmol, 9.08 g), and 4,4 -isopropylidenediphenol (44
mmol, 10 g) were added and refluxed for 3 days. Then, 1,4-
dioxane was evaporated under vacuum. Oily raw product
was dissolved in chloroform and washed five times with 25
mL 0.2 N NaOH aqueous solution and distilled water, respec-
tively. The chloroform solution was dried with anhydrous
magnesium sulfate, filtered and evaporated under vacuum to
afford orange-yellow oil. (Yield: 62%) H NMR (CDCl ): d ¼
ꢁ
(g), at 90 C for 24 h. At the end of the reaction, polymer
was precipitated in 500 mL of water and washed with meth-
anol. Then, the polymer was dried under vacuum over two
nights. Same procedure was applied for the catalytic reac-
tions except that two drops of dibuthyltinlaurate were added
to the mixture.
1
3
4280
WILEYONLINELIBRARY.COM/JOURNAL/JPOLA

ARTICLE
SCHEME 2 Synthesis of BBD and polyesters.
ꢀ
1
Determination of Adhesion and Flexibility
Properties of Films
The samples were dissolved in DMF in 1:1 (w/w) solid to
solvent ratio. The resulting viscous solutions were applied
on tin plates by using an automatic film applicator to obtain
vibration around 3010 cm , the OAH and CAO (primary
ꢀ
1
alcohol) stretching bands at 3391 and 1054 cm , respec-
tively, were observed. Furthermore, the band at 932 cm is
the mode that arises from the benzene ring to which oxazine
ꢀ
1
3
3
ring is attached.
4
0 lm films. These films obtained from monofunctional
It is well known that 1,3-benzoxazines polymerizes with
thermal induction around 200–250 C and exhibit exotherm,
which can be monitored by DSC. The thermogram in Figure
benzoxazine P-a, 4-(2H-1,3-benzoxazin-3(4H)-yl)benzoic acid
ꢁ
(
BBA), and benzoxazine containing polyesters were cured at
ꢁ
ꢁ
160 C for 1 h and at 170 C for 2 h, respectively. The adhe-
3
1
(a) reveals a ring opening exotherm with an onset at
3
1
32
sion and flexibility properties of films thus obtained
were determined according to the related standards.
ꢁ
ꢁ
82 C and a maximum at 210 C, and 31 J/g as the exothermic
ꢁ
energy. Notably, a degradation process begins after 249 C.
RESULTS AND DISCUSSIONS
Polyesters are one of the most important and widely used
polycondensates. Depending on the nature of monomers,
polyesters exhibit an enormous variety of structures, proper-
ties, and therefore, applications. Thus, the polyester proper-
ties are governed by the design and synthesis of suitable
monomers. In our work, we selected aminoalcohol group as
the primary amine component in the benzoxazine ring form-
ing reaction to introduce hydroxyl groups in the final ben-
zoxazine. Hence, diol containing benzoxazine was synthe-
sized as the monomer for the subsequent polyesterification
process by reacting bisphenol-A, 5-amino-1-pentanol, and
paraformaldehyde as depicted in Scheme 2.
The structure was confirmed by spectral and thermal analy-
1
sis. As can be seen from Figure 1(c) the H NMR spectrum
of the monomer exhibits not only the specific signals of the
benzoxazine ring but also chemical shifts that belong to the
alkyl chain and hydroxyl groups.
Moreover, the FTIR spectrum of the diol monomer further
indicates the structure. As can be seen from Figure 2(c),
addition to the band corresponding to the CAOAC oxazine
ꢀ
1
1
ring mode at 1382 cm and broad aromatic CAH stretching
FIGURE 1 H NMR spectra of PBCT (a), PBCHP (b), and BBD (c).
BENZOXAZINE-CONTAINING POLYESTER THERMOSETS, TUZUN ET AL.
4281

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
FIGURE 3 DSC traces of BBD (a), PBCHP (b) and PBCT (c).
FIGURE 2 FTIR spectra of PBCT (a), PBCHP (b), and BBD (c).
mers with low intensity, which indicates the ring opening of
oxazine during polymerization. Same issue is also evidenced
by the peaks of phenolic OH protons at 10.2 ppm. Moreover,
COOH protons of polyesters appeared at 12.9 ppm and the
Polyesters can be synthesized by various routes. Convention-
ally, under appropriate conditions diols can react either with
diacid chlorides, diacids, or dianhydrides to form polyesters.
2
methylene protons of ArACH AN could not be detected due
0
For our convenience, pyromellitic dianhydride and 4-4 -(hex-
to the overlapping with AOACH protons of ester and broad
2
afluoroisopropylidene) diphatalic anhydride were used as
the dianhydride components to obtain desired carboxylic
acid containing polyesters (Scheme 2). The polymerization
reactions were performed without or with catalyst (dibutyl-
water peak of d -DMSO.
6
The structure of the both polyesters was also confirmed by
FTIR. Figure 2(a,b) shows the IR spectra of the polyesters.
The characteristic carbonyl stretching vibrations were
ꢁ
tin laurate) at 90 C. Because of the nature of the reaction,
ꢀ1
observed at 1718 and 1716 cm
for PBCT and PBCHP,
in every repeating unit there occurred two molecules of car-
boxylic acid adjacent to benzoxazine units. This is an impor-
tant restriction for the preservation of the benzoxazine rings
as acids readily undergo ring opening reaction with benzoxa-
zines. In fact, this issue could be monitored spectrally and
also by thermal characterization using DSC. The results of
the polymerizations are given in Table 1. In our experiments,
the amount of dibutyltin laurate, a Lewis acid catalyst, was
deliberately kept low so as to prevent ring opening reaction
of benzoxazine.
respectively. In addition, the respective COOH stretching
ꢀ1
vibrations of the polyesters at 3367 and 3373 cm
are
emerged as broad bands. Also, C ¼¼ O stretching vibration
modes of carboxylic acid are detectable at 1613 and 1612
ꢀ1
cm , respectively. DSC was used for characterizing the cur-
ing behavior of the polyesters (Fig. 3). As stated previously,
benzoxazine groups are expected to undergo ring opening
polymerization. This exothermic event was detected for both
ꢁ
polymers. PBCT exhibited an onset at 231 C and a maxi-
ꢁ
mum at 251 C with 15 J/g of exotherm energy. Similarly,
1
The H NMR spectra for polyesters were evaluated to con-
for poly(benzoxazine-co-carboxy hexafluoroisopropylidene
1
firm the structures. The H NMR spectrum of the polyesters,
phthalate), the onset of the exotherm started at about
ꢁ
ꢁ
namely poly(benzoxazine-carboxyterephthalate) (PBCT) and
poly(benzoxazine-carboxyhexafluoro isopropylidene phthal-
236 C with a maximum at 246 C, and 10 J/g as the heat of
polymerization. Expectedly, both polymers resembled almost
the same thermal properties as they are structurally similar
and every repeating unit contains one benzoxazine unit. The
slight difference observed for the amount of exotherm is
probably due to aliphatic and aromatic nature of the compo-
nents. The thermal stabilities of the both polyesters are
ate) (PBCHP), derived from pyromellitic dianhydride and
0
4
-4 -(hexafluoroisopropylidene) diphatalic anhydride, are
shown in Figure 1(a,b), respectively. The spectra reveal the
characteristic peaks assigned to methylene protons
(
OACH AN) of the oxazine ring at 4.76 ppm for both poly-
2
a
TABLE 1 Polycondensation of BBD with Anhydrides in DMF at 90 8C
ꢀ
1
ꢀ1
b
c
Polyester
Anhydride (mol L
)
Tin Laurate (mol L
–
)
Conversion (%)
M
n
w n
M /M
8.6 ꢂ 10ꢀ
8.6 ꢂ 10ꢀ
2
64
68
66
69
5,800
4,700
5,900
6,500
1.54
1.62
2.45
2.46
PBCT
2
ꢀ4
PBCT
8.4 ꢂ 10
–
ꢀ
2
2
PBCHP
PBCHP
8.6 ꢂ 10
8.6 ꢂ 10ꢀ
8.4 ꢂ 10ꢀ4
a
ꢀ2
ꢀ1
c
8
.6 ꢂ 10 mol L
.
Determined by GPC according to the polystyrene standards.
b
Determined gravimetrically based on anhydrides.
4282
WILEYONLINELIBRARY.COM/JOURNAL/JPOLA

ARTICLE
SCHEME 3 Curing of 4-(2H-1,3-benzoxazin-3(4H)-yl)benzoic acid
(
BBA).
bending over the cylinder having 20 mm diameter and the
adhesions were found to be low. The poor flexibility and ad-
hesion is due to the lacking of film forming property and
rigid structure of the network.
FIGURE 4 TGA thermograms of cured BBD (a), cured PBCT (b),
and PBCHP (c).
In contrast, the polyester samples showed good flexibility
and adhesion. The films showed no crack even upon bending
over the cylinder having 2 mm diameter and the adhesion
were found to be 5B for both polyester samples. The linear
chain segments having pentyl and ester groups provide the
flexibility in the network. Also, hydroxyl and carboxylic acid
groups promote the adhesion of molecules to metals. In Ta-
ble 3, adhesion values of the low molar mass structurally
related model benzoxazines and polyesters were tabulated.
similar. The comparative TGA curves are illustrated in Figure 4
and the results are summarized in Table 2.
Cured PBCT exhibited slightly higher char yield due to the
rigid aromatic group in the structure imparted by terephtha-
late group. Interestingly, the thermal degradation of this
ꢁ
polymer occurs faster in 315–515 C temperature range
than cured PBCHP. Although they possess COOH groups in
the structure, which may undergo decarboxylation, the char
yields of cured polyesters are higher than that of cured diol
monomer. In fact, this value is even comparable with that of
In conclusion, novel polyesters containing benzoxazine moi-
eties in the main chain were synthesized and characterized.
Two kinds of polyesters with the molecular weights between
ꢁ
PP-a, which has a 34% char at 800 C. The observed
5
800–7000 Da were readily obtained by polycondensation of
enhancement in the thermal stability can again be attributed
to the aromatic groups and increased crosslink density
through additional hydrogen bonding.
0
bisbenzoxazine-diol with pyromellitic dianhydride and 4-4 -
(
hexafluroisopropylidene)diphatalic anhydride. Flexible thin
films were formed by solvent casting on tin plates and fur-
ther crosslinked by thermally activated ring opening reaction
of the benzoxazine groups present in the main chain. The
cured polyesters exhibited comparable thermal stability with
respect to low molar mass analogous. They also showed high
flexibility induced by the soft pentyl and esters groups.
Moreover, these cured films showed striking adhesion on tin
plates because of the phenolic hydroxyls and carboxylic acid
groups. The synthetic strategy presented may open new
pathway to prepare other thermoplastic elastomers that can
thermally be cured in the absence of any catalyst leading to
materials with improved properties. Further studies in this
line are in progress.
The film forming property of the polyesters were also inves-
tigated. The adhesion and flexibility of the cured films were
3
1,32
measured by ASTM and DIN tests
that of the cured conventional monofunctional benzoxazine
Pa) and carboxylic acid containing benzoxazines, BBA (see
and compared with
(
Schemes 1 and 3, respectively for the structures). In each
case, the films from the corresponding compounds were pre-
pared on tin plates and thermally cured at 170 C for 2 h. In
the case of cured P-a and BBA, the films were very brittle
and adhesion were very poor. Cracks were formed even by
ꢁ
TABLE 2 Thermal Properties of the Cured Bisbenzoxazine-Diol
and the Polyesters
a
TABLE 3 Adhesion of Various Thermally Cured Benzoxazines
a
ꢁ
ꢁ
ꢁ
Cured Polymer
T
5% ( C)
T
10% ( C)
T
max ( C)
c
Y (%)
Benzoxazine
Adhesion
BBD
PBCT
PBCHP
a
285
301
285
ꢁ
305
334
361
394
419
426
10
32
27
P-a
2B
2B
5B
5B
P-BBA
b
PBCT
Cured in TGA at 220 C for 15 min under N
2
stream (20 mL/min).
b
T
T
5%: The temperature for which the weight loss is 5%.
PBCHB
10%: The temperature for which the weight loss is 10%.
ꢁ
a
ꢁ
c
Y : Char yields at 800 C under nitrogen atmosphere.
Cured at 170 C for 2 h.
b
T
max: The temperature for maximum weight loss.
Polymers obtained with or without catalyst.
BENZOXAZINE-CONTAINING POLYESTER THERMOSETS, TUZUN ET AL.
4283

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
The authors thank Istanbul Technical University, Research
Fund and Henkel AG and Co. KGaA for partial financial support.
16 Lin, C. H.; Chang, S. L.; Hsieh, C. W.; Lee, H. H. Polymer
2
008, 49, 1220–1229.
1
7 Andreu, R; Reina, J. A.; Ronda, J. C. J Polym Sci Part A:
Polym Chem 2008, 46, 3353–3366.
REFERENCES AND NOTES
18 Andreu, R; Reina, J. A.; Ronda, J. C. J Polym Sci Part A:
Polym Chem 2008, 46, 6091–6101.
1
Ghosh, N. N.; Kiskan, B.; Yagci, Y. Prog Polym Sci 2007, 32,
1344–1391.
19 Ishida, H.; Lee, Y. H. Polymer 2001, 42, 6971–6979.
2
3
4
Schreiber, H. German Pat. 2,255,504; 1973.
20 Ishida, H.; Lee, Y. H. J Appl Polym Sci 2002, 83, 1848–1855.
Schreiber, H. German Pat. 2,323,936; 1973.
21 Zheng, S. X.; Lu, H.; Guo, Q. P. Macromol Chem Phys 2004,
2
05, 1547–1558.
Riess, G.; Schwob, M.; Guth, G.; Roche, M.; Lande, B. In
Advances in Polymer Synthesis; Culbertson, B. M.; McGrath,
J. E., Eds.; Plenum: New York, 1985; pp 27–49.
22 Yagci, Y.; Kiskan, B.; Ghosh, N. N. J Polym Sci Part A:
Polym Chem 2009, 47, 5565–5576.
5
Ning, X.; Ishida, H. J Polym Sci Part A: Polym Chem 1994,
23 Kiskan, B.; Aydogan, B.; Yagci, Y. J Polym Sci Part A: Polym
32, 1121–1129.
Chem 2009, 47, 804–811.
6
Ning, X.; Ishida, H. S. J Polym Sci Part B: Polym Phys 1994,
24 Kiskan, B.; Demiray, G.; Yagci, Y. J Polym Sci Part A: Polym
32, 921–927.
Chem 2008, 46, 3512–3518.
7
Burke, W. J.; Weatherbee, C. J Am Chem Soc 1950, 72,
25 Kiskan, B.; Yagci, Y. Polymer 2008, 49, 2455–2460.
4691–4694.
2
6 Kiskan, B.; Yagci, Y.; Ishida, H. J Polym Sci Part A: Polym
8
Burke, W. J.; Bishop, J. L.; Glennie, E. L. M.; Bauer, W. N.
Chem 2008, 46, 414–420.
J Org Chem 1965, 30, 3423–3427.
2
7 Kiskan, B.; Yagci, Y.; Sahmetlioglu, E.; Toppare, L. J Polym
9
Katritzky, A. R.; Xu, Y. J.; Jain, R. J Org Chem 2002, 67,
Sci Part A: Polym Chem 2007, 45, 999–1006.
8234–8236.
2
8 Kukut, M.; Kiskan, B.; Yagci, Y. Des Mon Polym 2009, 12,
10 Kiskan, B.; Yagci, Y. J Polym Sci Part A: Polym Chem 2007,
167–176.
45, 1670–1676.
2
9 Yildirim, A.; Kiskan, B.; Demirel, A. L.; Yagci, Y. Eur Polym J
11 Agag, T.; Takeichi, T. Macromolecules 2001, 34, 7257–7263.
2006, 42, 3006–3014.
12 Agag, T.; Takeichi, T. J Polym Sci Part A: Polym Chem 2006,
30 Ishida, H. US Pat. 5,543,516; May 18, 1996.
44, 1424–1435.
3
1 ASTM D 3359–90, Standard Test Methods for Measuring
1
3 Ishida, H.; Ohba, S. Polymer 2005, 46, 5588–5595.
Adhesion by Tape Test, Test Method B, 1991; Vol. 06. 01,
pp 511–514.
14 Lin, C. H.; Cai, S. X.; Leu, T. S.; Hwang, T. Y.; Lee, H. H.
J Polym Sci Part A: Polym Chem 2006, 44, 3454–3468.
5 Kiskan, B.; Koz, B.; Yagci, Y. J Polym Sci Part A: Polym
Chem 2009, 47, 6955–6961.
32 DIN 53152, Deutsche Normen, Deutscher Normenausschuss,
1
959.
1
33 Dunkers, J.; Ishida, H. Spectrochim Acta A 1995, 51, 855–867.
4284
WILEYONLINELIBRARY.COM/JOURNAL/JPOLA