Monofunctional benzoxazine with ortho-norbornene functionality (oHPNI-a) has been synthesized via Mannich condensation. The benzoxazine monomer containing norbornene group can be polymerized by ring-opening metathesis polymerization (ROMP) to form a side-chain benzoxazine functionalized polynorbornene (poly(oHPNI-a)side) with number-average molecular weight 3840 and weight-average molecular weight 7290. The structures of synthesized monomer and side-chain functionalized linear polymer have been confirmed by 1H nuclear magnetic resonance spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The further thermal curing polymerization mechanisms of poly(oHPNI-a)side are monitored by in situ FTIR and differential scanning calorimetry (DSC). Activation energy of polymerization for poly(oHPNI-a)side is also studied by DSC. The polybenzoxazine obtained by ROMP and further thermally activated ring-opening polymerization exhibits much higher thermal stability than the polybenzoxazine directly formed by traditional thermal curing.
KimHJBrunovskaZIshidaH. Molecular characterization of the polymerization of acetylene-functional benzoxazine resins. Polymer1999; 40: 6565–6573.
2.
ZhangKLiuJOhashiS. Furans as offspring of sugars and polysaccharides and progenitors of a family of remarkable polymers: a review of recent progress. J Polym Sci A Polym Chem2015; 53: 1330–1338.
3.
ZhangKLiuJIshidaH. An ultrahigh performance cross-linked polybenzoxazole via thermal conversion from poly(benzoxazine amic acid) based on smart o-benzoxazine chemistry. Macromolecules2014; 47: 8674–8681.
4.
IshidaHLowHY. A study on the volumetric expansion of benzoxazine-based phenolic resin. Macromolecules1997; 30: 1099–1106.
5.
ShenSBIshidaH. Development and characterization of high-performance polybenzoxazine composites. Polym Comp1996; 17: 710–719.
6.
WuJXiYMcCandlessGT. Synthesis and characterization of partially fluorinated polybenzoxazine resins utilizing octafluorocyclopentene as a versatile building block. Macromolecules2015; 48: 6087–6095.
7.
IshidaHAllanD. Vitrification and devitrification of the rigid amorphous fraction in semicrystalline polymers revealed from frequency dependent heat capacity. J Polym Sci B Polym Phys1996; 34: 1019–1030.
8.
GaoYHuangFYuanQ. Synthesis of novel imide-functionalized fluorinated benzoxazines and properties of their thermosets. High Perform Polym2013; 25: 677–684.
9.
RanQCGaoNGuY. Thermal stability of polybenzoxazines with lanthanum chloride and their crosslinked structures. Polym Degrad Stab2011; 96: 1610–1615.
10.
ChernykhALiuJPIshidaH. Synthesis and properties of a new crosslinkable polymer containing benzoxazine moiety in the main chain. Polymer2006; 47: 7664–7669.
11.
AydoganBSurekaDKiskanB. Polysiloxane-containing benzoxazine moieties in the main chain. J Polym Sci A Polym Chem2010; 48: 5156–5162.
12.
TakeichiTKanoTAgagT. Preparation of high molecular weight polybenzoxazine prepolymers containing siloxane unites and properties of their thermosets. J Polym Sci A Polym Chem2010; 48: 5945–5952.
13.
WangMWLinCHJuangTY. Steric hindrance control synthesis of primary amine-containing benzoxazines and properties of the resulting poly(benzoxazine imide) thermosetting films. Macromolecules2013; 46: 8853–8863.
14.
KiskanBYagciY. Synthesis and characterization of thermally curable polyacetylenes by polymerization of propargyl benzoxazine using rhodium catalyst. Polymer2008; 49: 2455–2460.
15.
ErginMKiskanBGacalB. Thermally curable polystyrene via click chemistry. Macromolecules2007; 40: 4724–4727.
16.
KimuraHMatsumotoASugitoH. New thermosetting resin from poly(p-vinylphenol) based benzoxazine and epoxy resin. J Appl Polym Sci2001; 79: 555–565.
17.
KeLHuDLuY. Copolymerization of maleimide-based benzoxazine with styrene and the curing kinetics of the resultant copolymer. Polym Degrad Stab2012; 97: 132–138.
18.
LiuYXMaHMLiuY. Magnetic/III-V semiconductor based hybrid structures. Polymer2016; 82: 32–39.
19.
KiskanBYagciY. Synthesis and characterization of naphthoxazine functional poly(ε-caprolactone). Polymer2005; 46: 11690–11697.
20.
YildirimAKiskanBDemirelAL. Synthesis, characterization and properties of naphthoxazine-functional poly(propyleneoxide)s. Eur Polym J2006; 42: 3006–3014.
21.
NakamuraMIshidaH. Synthesis and properties of new crosslinkable telechelics with benzoxazine moiety at the chain end. Polymer2009; 50: 2688–2695.
22.
TasdelenMADurmazH. Thermally curable polyoxanorbornene by ring opening metathesis polymerization. Macromol Chem Phy2011; 212: 2121–2126.
23.
AgagTLiuJGrafR. Benzoxazole resin: a novel class of thermoset polymer via smart benzoxazine resin. Macromolecules2012; 45: 8991–8997.
24.
ZhangKIshidaH. Multi-aperture-based probabilistic noise reduction of random telegraph signal noise and photon shot noise in semi-photon-counting complementary-metal-oxide-semiconductor image sensor. Polymer2015; 66: 240–248.
25.
ZhangKFroimowiczPHanL. Hydrogen-bonding characteristics and unique ring-opening polymerization behavior of ortho-methylol functional benzoxazine. J Polym Sci A Polym Chem2016; 54: 3635–3642.
26.
ZhangKHanLFroimowiczP. A smart latent catalyst containing o-trifluoroacetamide functional benzoxazine: precursor for low temperature formation of very high performance polybenzoxazole with low dielectric constant and high thermal stability. Macromolecules2017; 50: 6552–6560.
AgagTTakeichiT. Bio-based high performance thermosets: stabilization and reinforcement of eugenol-based benzoxazine networks with BMI and CNT. Macromolecules2003; 36: 6010–6017.
29.
DunkersJIshidaH. Vibrational assignments of 3-alkyl-3,4-dihydro-6-methyl-2H-1,3-benzoxazines in the fingerprint region. Spectrochim Acta1995; 51: 1061–1074.
30.
HanLIguchiDGilPS. Oxazine ring-related vibrational modes of benzoxazine monomers using fully aromatically substituted, deuterated, 15n isotope exchanged and oxazine-ring-substituted compounds and theoretical calculation. J Phys Chem A2017; 121: 6269–6281.
31.
KissingerHE. Supplement on applicability of the Kissinger equation in thermal analysis. Anal Chem1957; 29: 1702–1706.
32.
OzawaT. Kinetic analysis of derivative curves in thermal analysis. J Thermal Anal1970; 2: 301–324.
33.
HemvichianKIshidaH. Thermal decomposition processes in aromatic amine-based polybenzoxazines investigated by TGA and GC–MS. Polymer2002; 43: 4391–4402.
