Professional Documents
Culture Documents
pubs.acs.org/Macromolecules
■ INTRODUCTION
Benzoxazine resins are a new class of thermosetting polymers
more phenolic groups are formed, which promote an
autocatalytic polymerization process.6a,b
Wang and Ishida7 showed that monomers synthesized using
that are characterized by several unique properties such as near-
unsubstituted phenol exhibited variations of the ring-opening
zero shrinkage or volumetric expansion upon polymerization,
polymerization temperature. A more detailed study by Andreu
considerable molecule-design flexibility, low water absorption
et al.,8 who synthesized several substituted 3-phenyl-3,4-
and flammability, low surface energy, and high glass transition dihydro-2H-1,3-benzoxazine monomers using substituent
temperature.1 Additionally, the polymerization of benzoxazine phenol and aromatic amine, showed that increasing the
monomers takes place through thermally accelerated ring- electron-withdrawing in the para-position of phenol exhibited
opening mechanism without any added initiator or catalyst.2 a noticeable decrease in the polymerization temperature. This is
These numerous unusual properties of benzoxazine resins are attributed to the acidic phenol species that are formed due to
associated with the existence of inter- and intramolecular the electron-withdrawing groups. On the other hand, increasing
hydrogen bonds in the network structure.3a−d Therefore, in the electron-withdrawing in the para-position of the phenyl
order to understand the structure−property relationships of the substituent monomers showed an increase of the polymer-
polymer, it is of great importance to know the mechanistic ization temperature due to the destabilization of the
pathways of polymerization. propagating iminium intermediates as proposed by McDonagh
Although the polymerization chemistry of benzoxazine and Smith.9a,b However, for the electron-donating substituents
monomers still remains rather poorly understood, the high no notable effect on the polymerization was observed regardless
basicity of benzoxazine monomers, which is attributed to both of the position of the substituent.
the oxygen and the nitrogen of the oxazine ring by Lewis The effect of functionalization and copolymerization of
definition, suggests that the ring-opening polymerization of carboxylic group into benzoxazine structure has been
benzoxazine monomers proceeds through a cationic mecha- studied10a−c and a significant decrease in polymerization
nism.4a−c During the polymerization, the monomer comes to temperature was observed. Polybenzoxazine chains preferen-
equilibrium with the corresponding zwitterionic intermediate tially form intramolecular 6-membered hydrogen bond,11a−i
which eventually forms the polymer as depicted in Scheme 1. which tends to slow the propagation reaction.12a,b This
Several fundamental studies for polymerization mechanisms
were conducted to understand the polymerization pathways of Received: September 18, 2012
benzoxazine monomers.5a−c These investigations suggest that, Revised: September 21, 2012
as the polymerization of benzoxazine monomers progresses, Published: October 1, 2012
© 2012 American Chemical Society 8119 dx.doi.org/10.1021/ma301963d | Macromolecules 2012, 45, 8119−8125
Macromolecules
■
Article
occurrence of methylol condensation reaction together with closed molecular structure in comparison to open structure that
ring-opening polymerization of methylol benzoxazine mono- tends to extend.
mers has been confirmed elsewhere.18a Since both the storage and loss moduli eventually attain
Chemorheological Studies of Monomers. Viscoelastic maximum values and remain at the plateaus, the following
properties during the polymerization of each monomer were rheological fractional conversion is defined assuming reaction is
evaluated during isothermal polymerization at 140 °C. A complete:23
qualitative comparison of the rates of polymerization for the
monomers is determined by the increase of the viscoelastic G′(t )
α=
moduli as shown in Figure 4. The figure shows that methylol- G′(α) (1)
where G′(t) is the storage modulus at time t and G′(α) is the
maximum modulus at the end of polymerization. The resultant
time conversion plots are shown in Figure 5. The fractional
conversion increases rapidly immediately after the reaction is
prompted, due to the double catalytic effects of methylol and
phenol as stated above.
benzoxazine ring is less affected by methylol in the case of meta- stretching of Ar−O−C), 1033 (symmetric stretching of C−O−C),
and para-monomers as supported by the DSC thermograms. 950 (out-of-plane vibration, benzene ring to which oxazine is
■
attached).
1
H NMR spectra, δH (300 MHz, CDCl3, TMS, ppm): 4.56 (s,
CONCLUSIONS −CH2−O), 4.64 (s, C−CH2−N), 5.37 (s, N−CH2−O−), 6.79−7.30
A series of methylol functional benzoxazine monomers with (m, Ar).
different hydroxybenzyl alcohol isomers were successfully Preparation of (3-Phenyl-3,4-dihydro-2H-benzo[e][1,3]-
synthesized. The DSC results show that exothermic peaks oxazin-6-yl)methanol [abbreviated as pHBA-a]. In a 500 mL
bottom-rounded flask, pHBA (14.95 g, 120 mmol), aniline (11.18 g,
due to condensation reaction of methylol groups and ring- 120 mmol), and paraformaldehyde (7.52 g, 250 mmol) were mixed
opening polymerization of benzoxazine are 231, 214, and 196 together and refluxed for 6 h in toluene (135 mL). The product was
°C for monomers that methylol group placed on para-, meta-, concentrated using a vacuum evaporator and redissolved in chloroform
and ortho-position, respectively. However, the exothermic peak followed by base-washed then once with water. The product was then
of unfunctionalized monomer shows a higher value of 255 °C. dried over anhydrous sodium sulfate and recrystallized from
The rheological study indicates that the onset of polymerization chloroform to yield a white product (yield: 21.15 g, 73%).
occurs at much shorter times of 6, 20, and 32 min for oHBA-a, IR spectra (KBr, cm−1): 3340 (stretching of OH of methylol), 1500
mHBA-a, and pHBA-a compared to the unfunctionalized (stretching of trisubstituted benzene ring), 1228 (asymmetric
monomer that takes 45 min. The highest reactivity of the stretching of Ar−O−C), 1032 (asymmetric stretching of C−O−C),
947 (out-of-plane vibration, benzene ring to which oxazine is
methylol monomers is attributed to the catalytic effect of the attached).
methylol group on the ring-opening due to intramolecular 1
H NMR spectra, δH (300 MHz, CDCl3, TMS, ppm): 4.55 (s,
hydrogen bonding between the methylol and the oxygen in the −CH2−OH), 4.62 (s, C−CH2−N), 5.36 (s, N−CH2−O−), 6.80−
benzoxazine ring as proposed in the polymerization mecha- 7.28 (m, Ar).
nism. Characterization and Measurements. Proton nuclear magnetic
■
resonance (1H NMR) spectra were acquired on a Varian Oxford
EXPERIMENTAL SECTION AS300 at a proton frequency of 300 MHz using an average number of
transients of 64. A relaxation time of 10 s was used for the integrated
Materials. 2-Hydroxybenzyl alcohol (oHBA) (99%), 3-hydrox- intensity determination of 1H NMR spectra. Deuterated chloroform
ybenzyl alcohol (mHBA) (99%), 4-hydroxybenzyl alcohol (pHBA) (CDCl3) was used to obtain the spectra with tetramethylsilane (TMS)
(98%), phenol (98%), and aniline (99%) were obtained from Sigma− as an internal standard. Fourier transform infrared (FT-IR) spectra
Aldrich and used as-received. Paraformaldehyde (96%) was obtained were acquired on a Bomem Michelson MB100 which was equipped
from Acros Organics, USA. Toluene, ethyl acetate, chloroform, with a deuterated triglycine sulfate (DTGS) detector at a resolution of
hexanes (a mixture of isomers), and 1,4 dioxane were obtained from 4 cm−1 with 32 coadditions. The spectra were taken by casting a thin
Fisher and used as received. film onto a KBr plate. Thermal analysis of the samples was performed
Preparation of 3-Phenyl-3,4-dihydro-2H-benzo[e][1,3]- via differential scanning calorimetry (DSC) using TA Instruments
oxazine [abbreviated as P-a]. P-a was prepared from phenol, DSC model 2920 with temperature ramped at 10 °C/min and a
aniline and paraformaldehyde following the reported method.8 IR nitrogen flow rate of 65 mL/min. All samples were crimped in
spectra (KBr, cm−1): 1230 (asymmetric stretching of Ar−O−C), 1035 hermetic aluminum pans with lids. The evolution and comparison of
(symmetric stretching of C−O−C), 946 (out-of-plane vibration, rheological properties during polymerization for each of the different
benzene ring to which oxazine is attached). benzoxazine monomers were performed utilizing an Anton Paar
1
H NMR spectra, δH (300 MHz, CDCl3, TMS, ppm): 4.74 (s, C− Rheometer (Model Physica MCR 501) with disposable parallel upper
CH2−N), 5.48 (s, N−CH2−O−). 6.99−7.44 (m, Ar). and lower plates, measuring 25 mm and 50 mm in diameter,
Preparation of (3-Phenyl-3,4-dihydro-2H-benzo[e][1,3]- respectively. Small amplitude oscillatory shear time sweep experiments
oxazin-8-yl)methanol [abbreviated as oHBA-a]. Into a 100 mL
over temperatures at 140 °C were performed using a constant
bottom-rounded flask were mixed oHBA (3.73 g, 30 mmol), aniline
frequency of 10 rad/s for all experiments, but continuously increasing
(2.8 g, 30 mmol), and paraformaldehyde (1.9 g, 60 mmol) and the
stress between a minimum of 1 Pa and a maximum of 400 Pa.
mixture refluxed in 1,4-dioxane (35 mL) for 4 days. The product was
Although the actual stress ramp varied per experiment, it was always
filtered and then concentrated using a rotary evaporator. The product
set to a range of values that kept the fluids’ response in the linear
was then redissolved in ethyl acetate and base-washed followed by
viscoelastic regime, while providing a high enough strain to provide
once with water. The organic layer was then dried over sodium sulfate
reproducible results.
■
anhydrous, followed by vacuum evaporation to afford viscous oily
product (yield: 3.71 g, 51%).
IR spectra (KBr, cm−1): 3320 (stretching of OH of methylol), 1505 AUTHOR INFORMATION
(stretching of trisubstituted benzene ring), 1226 (asymmetric Corresponding Author
stretching of Ar−O−C), 1032 (symmetric stretching of C−O−C), *E-mail: sxq@case.edu.
945 (out-of-plane vibration, benzene ring to which oxazine is
attached). Notes
1
H NMR spectra, δH (300 MHz, CDCl3, TMS, ppm): 4.64 (s, The authors declare no competing financial interest.
−CH2−OH), 4.66 (s, C−CH2−N), 5.41 (s, N−CH2−O−), 6.90− §
On leave from Azzaytuna University, Libya.
7.29 (m, Ar). ⊥
On leave from Tanta University, Tanta, Egypt.
■
Preparation of (3-Phenyl-3,4-dihydro-2H-benzo[e][1,3]-
oxazin-7-yl)methanol [abbreviated as mHBA-a]. In a 100 mL
bottom-rounded flask, mHBA (7.52 g, 60 mmol), aniline (5.64 g, 60 ACKNOWLEDGMENTS
mmol), and paraformaldehyde (3.61 g, 120 mmol) were mixed M. Baqar acknowledges the Ministry of Higher Education and
together and refluxed for 48 h in 1,4 dioxane (65 mL). The product Scientific Research of Libya and Azzaytuna University-Libya for
was concentrated using a vacuum evaporator and redissolved in ethyl a scholarship.
■
acetate followed by base-washed then once with water. The product
was then dried over sodium sulfate anhydrous, followed by vacuum
evaporation to afford a viscous product (yield: 9.12 g, 63%). REFERENCES
IR spectra (KBr, cm−1): 3325 (stretching of OH of methylol), 1500 (1) Ishida, H.; Agag, T., Eds. Handbook of Benzoxazine Resins;
(stretching of trisubstituted benzene ring), 1242 (asymmetric Elsevier: Amsterdam, 2011.
(2) Ghosh, N. N.; Kiskan, B.; Yagci, Y. Prog. Polym. Sci. 2007, 32, (22) (a) Nair, C. P. R.; Bindu, R. L.; Ninan, K. N. J. Appl. Polym. Sci.
1344−1391. 2001, 81, 3371−3377. (b) Zhou, D. P.; Du, S.; Yu, L.; Liu, Z. J. Appl.
(3) (a) Sawaryn, C.; Landfester, K.; Taden, A. Macromolecules 2011, Polym. Sci. 2011, 121, 1938−1945.
44, 7668−7674. (b) Su, Y. C.; Kuo, S. W.; Yei, D. R.; Xu, H.; Chang, F. (23) Kumar, K. S. S.; Nair, C. P. R.; Ninan, K. N. Thermochim. Acta
C. Polymer 2003, 44, 2187−2191. (c) Kim, H. D.; Ishida, H. 2006, 441, 150−155.
Macromolecules 2003, 36, 8320−8329. (d) Kuo, S. W.; Wu, Y. C.;
Wang, C. F.; Jeong, K. U. J. Phys. Chem. C 2009, 113, 20666−20673.
(4) (a) Wang, Y. X.; Ishida, H. Polymer 1999, 40, 4563−4570.
(b) Chutayothin, P.; Ishida, H. Macromolecules 2010, 43, 4562−4572.
(c) Liu, C.; Shen, D.; Sebastian, R. M.; Marquet, J.; Schönfeld, R.
Macromolecules 2011, 44, 4616−4622.
(5) (a) Riess, G., Schwob, M., Guth, G., Roche, M., Lande, B. In:
Culbertson, B. M., McGrath, editors. Advances in Polymer Synthesis;
Plenum: New York, 1985. (b) Dunkers, J.; Ishida, H. J. Polym. Sci., Part
A: Polym. Chem. 1999, 37, 1913−1921. (c) Sudo, A.; Kudoh, R.;
Nakayama, H.; Arima, K.; Endo, T. Macromolecules 2008, 41, 9030−
9034.
(6) (a) Ishida, H.; Rodriguez, Y. Polymer 1995, 36, 3151−3158.
(b) Santhosh, K. S.; Reghunadhan, C. P.; Ninan, K. N. Thermochim.
Acta 2006, 441, 150−155.
(7) Wang, Y. X.; Ishida, H. J. Appl. Polym. Sci. 2002, 84, 1107−1113.
(8) Andreu, R.; Reina, J. A.; Ronda, J. C. J. Polym. Sci., Part A: Polym.
Chem. 2008, 46, 3353−3366.
(9) (a) McDonagh, A. F.; Smith, H. E. J. Org. Chem. 1968, 33, 8−12.
(b) McDonagh, A. F.; Smith, H. E. J. Org. Chem. 1968, 33, 1−8.
(10) (a) Dunkers, J.; Ishida, H. J. Polym. Sci., Part A: Polym. Chem.
1999, 37, 1913−1921. (b) Andreu, R.; Reina, J. A.; Ronda, J. C. J.
Polym. Sci., Part A: Polym. Chem. 2008, 46, 6091−6101. (c) Wang, Y.
X.; Ishida, H. Macromolecules 2000, 33, 2839−2847.
(11) (a) Wirasate, S.; Dhumrongvaraporn, S.; Allen, D. J.; Ishida, H.
J. Appl. Polym. Sci. 1998, 70, 1299−1306. (b) Schnell, I.; Brown, S. P.;
Low, H. Y.; Ishida, H.; Spiess, H. W. J. Am. Chem. Soc. 1998, 120,
11784−11795. (c) Kim, W. K.; Mattice, W. L. Comp. Theor. Polym. Sci.
1998, 8, 339−351. (d) Goward, G. R.; Shnell, I.; Brown, S. P.; Spiess,
H. W.; Kim, H. D.; Ishida, H. Magn. Reson. Chem. 2001, 39, S5−S17.
(e) Kim, H. D.; Ishida, H. J. Phys. Chem. A 2002, 106, 3271−3280.
(f) Goward, G. R.; Sebastiani, D.; Schnell, I.; Spiess, H. W.; Kim, H.
D.; Ishida, H. J. Am. Chem. Soc. 2003, 125, 5792−5800. (g) Kim, H.
D.; Ishida, H. Macromol. Symp. 2003, 195, 123−140. (h) Wang, C. F.;
Wang, Y. T.; Tung, P. H.; Kuo, S. W.; Lin, C. H.; Sheen, Y. C.; Chang,
F. C. Langmuir 2006, 22, 8289−8292. (i) Kuo, S. W.; Wu, Y. C.;
Wang, C. F.; Jeong, K. U. J. Phys. Chem. C 2009, 113, 20666−20673.
(12) (a) Laobuthee, A.; Chirachanchai, S.; Ishida, H.; Tashiro, K. J.
Am. Chem. Soc. 2001, 123, 9947−9955. (b) Chirachanchai, S.;
Laobuthee, A.; Phongtamrug, S. J. Heterocycl. Chem. 2009, 46, 714−
721.
(13) Kim, H. D.; Ishida, H. J. Appl. Polym. Sci. 2001, 79, 1207−1219.
(14) (a) Kiskan, B.; Yagci, Y.; Ishida, H. J. Polym. Sci., Part A: Polym.
Chem. 2008, 46, 414−420. (b) Kiskan, B.; Koz, B.; Yagci, Y. J. Polym.
Sci., Part A: Polym. Chem. 2009, 47, 6955−6961.
(15) Kudoh, R.; Sudo, A.; Endo, T. Macromolecules 2009, 42, 2327−
2329.
(16) Sudo, A.; Du, L. C.; Hirayama, S.; Endo, T. J. Polym. Sci., Part A:
Polym. Chem. 2010, 48, 2777−2782.
(17) Oie, H.; Sudo, A.; Endo, T. J. Polym. Sci., Part A: Polym. Chem.
2010, 48, 5357−5363.
(18) (a) Baqar, M.; Agag, T.; Ishida, H.; Qutubuddin, T. J. Polym. Sci.,
Part A: Polym. Chem. 2012, 50, 2275−2285. (b) Baqar, M.; Agag, T.;
Ishida, H.; Qutubuddin, S. Polymer 2011, 52, 307−317. (c) Baqar, M.;
Agag, T.; Ishida, H.; Qutubuddin, S. React. Funct. Polym. 2012, http://
dx.doi.org/10.1016/j.reactfunctpolym.2012.04.017.
(19) Dunkers, J.; Ishida, H. Spectrochim. Acta 1995, 51A, 1061−1074.
(20) (a) Agag, T.; Takeichi, T. Macromolecules 2003, 36, 6010−6017.
(b) Dunkers, J.; Ishida, H. Spectrochim. Acta 1995, 51A, 855−867.
(21) (a) Holopainen, T.; Alvila, L.; Rainio, J.; Pakkanen, T. T. J. Appl.
Polym. Sci. 1998, 69, 2175−2185. (b) Holopainen, H.; Alvila, L.;
Pakkanen, T. T.; Rainio, J. J. Appl. Polym. Sci. 2003, 89, 3582−3586.