A series of aniline-based bifunctional benzoxazines (BZs) were synthesized using solventless or solvent method via the Mannich condensation reactions. The chemical structures of these BZs were confirmed using Fourier-transform infrared and proton-nuclear magnetic resonance spectroscopies. The polymer blends were prepared by mixing silicon-containing arylacetylene (poly(dimethylsilyleneethynylenephenyleneethynylene) (PSA)) resin with BZ in weight ratios at 110°C until a homogeneous viscosity liquid was obtained. The resultant blends were characterized by solubility tests, rheological analyses, differential scanning calorimetry, dynamic mechanical analyses and thermogravimetric analyses. The good solubility and low melt viscosity of the blends indicated excellent processability. The curing reactions resulted in the formation of interpenetrating polymer networks. The cured blends exhibited high glass transition temperatures (Tgs) and thermal stabilities. The compressive strength and flexural strength of the blend casts improved when compared with pristine PSA.
ItohMMitsuzukaMIwataKInoueK. A novel synthesis and extremely high thermal stability of poly[(phenylsilylene)-ethynylene-1,3-phenyleneethynylene]. Macromolecules1994; 27: 7917–7919.
ItohMInoueKIwataKIshikawaJTakenakaY. A heat-resistant silicon-based polymer. Adv Mater1997; 9: 1187–1190.
4.
BuvatPJousseFDelnaudLLevassortCRipaultC. Synthesis and properties of new processable type polyarylacetylenes. Int SAMPE Symp Exhib2000; 46: 134–144.
5.
WangFZhangJHuangJYanHHuangFDuL. Synthesis and characterization of poly(dimethylsilyleneethynylenephenyleneethynylene) terminated with phenylacetylene. Polym Bull2006; 56: 19–26.
GhoshNKiskanBYagciY. Polybenzoxazines-new high performance thermosetting resins: synthesis and properties. Prog Polym Sci2007; 32: 1344–1391.
8.
YagciYKiskanBGhoshN. Recent advancement on polybenzoxazine: a newly developed high performance thermoset. J Polym Sci A Polym Chem2009; 47: 5565–5576.
9.
TakeichiTAgagT. High performance polybenzoxazines as novel thermosets. High Perform Polym2006; 18: 777–797.
10.
NingXIshidaH. Phenolic materials via ring-opening polymerization: synthesis and characterization of bisphenol-A based benzoxazines and their polymers. J Polym Sci A Polym Chem1994; 32: 1121–1129.
11.
AgagTTakeichiT. Synthesis and characterization of novel benzoxazine monomers containing allyl groups and their high performance thermosets. Macromolecules2003; 36: 6010–6017.
12.
KimHBrunovskaZIshidaH. Synthesis and thermal characterization of polybenzoxazines based on acetylene-functional monomers. Polymer1999; 40: 6565–6573.
13.
AgagTTakeichiT. Novel benzoxazine monomers containing p-phenyl propargyl ether: polymerization of monomers and properties of polybenzoxazines. Macromolecules2001; 34: 7257–7263.
14.
BrunovskaZIshidaH. Thermal study on the copolymers of phthalonitrile and phenylnitrile-functional benzoxazines. J Appl Polym Sci1999; 73: 2937–2949.
15.
AndreuREspinosaMGaliaMCadizVRondaJReinaJ. Synthesis of novel benzoxazine containing glycidyl groups: a study of the crosslinking behavior. J Polym Sci A Polym Chem2006; 44: 1529–1540.
16.
LiuYChouC. High performance benzoxazine monomers and polymers containing furan groups. J Polym Sci A Polym Chem2005; 43: 5267–5282.
17.
ShenSIshidaH. Synthesis and characterization of polyfunctional naphthoxazines and related polymers. J Appl Polym Sci1996; 61: 1595–1605.
18.
AgagTTakeichiT. Preparation, characterization and polymerization of maleimidobenzoxazine monomers as a novel class of thermosetting reins. J Polym Sci. A Polym Chem2006; 44: 1424–1435.
19.
RanQTianQLiCGuY. Investigation of processing, thermal, and mechanical properties of a new composite matrix-benzoxazine containing aldehyde group. Polym Adv Technol2010; 21: 170–176.
20.
WangCZhouYHuangFDuL. Synthesis and characterization of thermooxidatively stable poly(dimethylsilyleneethynylenephenyleneethynylene) with o-carborane units. React Funct Polym2011; 71: 899–904.
21.
LiQZhouYHangXDengSHuangFDuL. Synthesis and characterization of a novel arylacetylene oligomer containing POSS units in main chains. Eur Polym J2008; 44: 2538–2544.
22.
WangFZhouYHuangFDuL. Synthesis and properties of a novel poly(diethynylbenzene-siloxane) resin. High Perform Polym2012; 24: 247–253.
23.
HuangJDuWZhangJHuangFDuL. Study on the copolymers of silicon-containing arylacetylene resin and acetylene-functional benzoxazine. Polym Bull2009; 62: 127–138.
24.
HuangFHuangJGaoYZhouYDuL. The blends of a silicon-containing arylacetylene resin and an acetylene-functional benzoxazine. In: IshidaHAgagT (eds) Handbook of bexzoxazine resins. Amsterdam, Netherlands: Elsevier. Chapter22, 2011, pp. 405–414.
25.
IshidaH.Process for preparation of benzoxazine compounds in solventless systems. Patent 5543516, USA, 1996.
26.
BrunovskaZ, Liu J and Ishida H. 1,3,5-Triphenylhexahydro-1,3,5-triazine-active intermediate and precursor in the novel synthesis of benzoxazine monomers and oligomers. Macromol Chem Phys1999; 200: 1745–1752.
27.
ZhangJHuangJDuWHuangFDuL. Thermal stability of the copolymers of silicon-containing arylacetylene resin and acetylene-functional benzoxazine. Polym Degrad Stabil2011; 96: 2276–2283.
28.
KurokiSOkitaKKakiganoTIshikawaJItohM. Thermosetting mechanism study of poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene] by solid-state NMR spectroscopy and computational chemistry. Macromolecules1998; 31: 2804–2808.
29.
FangXXieXSimoneCStevensMScolaD. A solid-state 13C-NMR study of the cure of 13C-labeled phenylethynyl end-capped polyimides. Macromolecules2000; 33: 1671–1681.
30.
GaoYHuangFZhouYDuL.Synthesis and characterization of a novel acetylene and maleimide-terminated benzoxazine and its high-performance thermosets. J Appl Polym Sci. Epub ahead of print 29 June 2012. DOI: 10.1002/app.38184.
31.
KimHBrunovskaZIshidaH. Dynamic mechanical analysis on highly thermally stable polybenzoxazines with an acetylene functional group. J Appl Polym Sci1999; 73: 857–862.
32.
LowHIshidaH. Structural effects of phenols on the thermal and thermo-oxidative degradation of polybenzoxazines. Polymer1999; 40: 4365–4376.
