Self-curing allyl-functional phthalonitriles-containing benzoxazine (DABA-ph) has been designed and synthesized. These formed a resin through a curing process involving the sequential polymerization of allyl moieties, ring-opening polymerization of oxazine rings, and ring-forming polymerization of nitrile groups. The introduction of allyl moieties was found to improve the processability as the process started at a lower temperature of 160–200°C than is needed for related resins. After self-curing, the resins exhibited high cross-linking degrees and excellent thermal stabilities. The glass transition temperature (Tg) was increased compared to similar resins to 380°C with good thermal stability (5% weight loss temperature > 490°C). These outstanding properties suggest the DABA-ph polymers are suitable candidates as matrices for high-performance composites.
GouriCNairCPRRamaswamyR. Adhesive characteristics of alder-ene adduct of diallyl bisphenol A novolac and bisphenol A bismaleimide. High Perform Polym2000; 12: 497–514.
3.
AndreSGuida-PietrasantaFRousseauA. Synthesis, characterization, and thermal properties of anhydride terminated and allyl terminated oligoimides. J Polym Sci A: Polym Chem2000; 38: 2993–3003.
4.
LinKFLinJSChengCH. Synthesis, curing, and decomposition of allylamine-adducted 3, 3′-bismaleimidodiphenylsulphone resins. J Polym Sci A: Polym Chem1997; 35: 2469–2478.
5.
IshidaHLowHY. Synthesis of benzoxazine functional silane and adhesion properties of glass-fiber-reinforced polybenzoxazine composites. J Appl Polym Sci1998; 69: 2559–2567.
6.
NarayananJJungmanMJPattonDL. Hybrid dual-cure polymer networks via sequential thiol–ene photopolymerization and thermal ring-opening polymerization of benzoxazines. React Funct Polym2012; 72: 799–806.
7.
AgagTTakeichiT. Synthesis and characterization of novel benzoxazine monomers containing allyl groups and their high performance thermosets. Macromolecules2003; 36: 6010–6017.
8.
RaoBSPalanisamyA. Monofunctional benzoxazine from cardanol for bio-composite applications. React Funct Polym2011; 71: 148–154.
9.
DominguezDDJonesHNKellerTM. The effect of curing additive on the mechanical properties of phthalonitrile-carbon fiber composites. Polym Compos2004; 25: 554–561.
10.
LaskoskiMDominguezDDKellerTM. Synthesis and properties of a bisphenol A based phthalonitrile resin. J Polym Sci A: Polym Chem2005; 43: 4136–4143.
11.
LaskoskiMNealAKellerTM. Improved synthesis of oligomeric phthalonitriles and studies designed for low temperature cure. J Polym Sci A: Polym Chem2014; 52: 1662–1668.
12.
KellerTMDominguezDD. High temperature resorcinol-based phthalonitrile polymer. Polymer2005; 46: 4614–4618.
13.
DominguezDDKellerTM. Properties of phthalonitrile monomer blends and thermosetting phthalonitrile copolymers. Polymer2007; 48: 91–97.
14.
KellerTMGriffithJR. Polyphthalocyanine resins. Am Chem Soc Sym Ser1980; 132: 25–26.
DuRHLiWTLiuXB. Synthesis and thermal properties of bisphthalonitriles containing aromatic ether nitrile linkages. Polym Degrad Stab2009; 94: 2178–2183.
18.
YangXLLeiYJZhongJC. Preparation and thermal properties of novel phthalonitrile oligomer containing biphenyl ethernitrile/bisphthalonitrile blends. J Appl Polym Sci2011; 119: 882–887.
19.
GuoHLeiYJZhaoX. Curing behaviors and properties of novolac/bisphthalonitrile blends. J Appl Polym Sci2012; 125: 649–656.
20.
ChenZRGuoHTangHL. Preparation and properties of bisphenol A-based bis-phthalonitrile composite laminates. J Appl Polym Sci2013; 129: 2621–2628.
21.
CaoGPChenWJWeiJJ. Synthesis and characterization of a novel bisphthalonitrile containing benzoxazine. Express Polym Lett2007; 1: 512–518.
22.
ZuoFLiuXB. Synthesis and curing behavior of a novel benzoxazine-based bisphthalonitrile monomer. J Appl Polym Sci2010; 117: 1469–1475.
23.
XuMZYangXLZhaoR. Copolymerizing behavior and processability of benzoxazine/epoxy systems and their applications for glass fiber composite laminates. J Appl Polym Sci2013; 128: 1176–1184.
24.
XuMZHuJQZouXQ. Significant increments in the mechanical and thermal properties of composite laminates by in situ reaction with carboxyl functionalized CNTs. J Appl Polym Sci2013; 129: 2629–2637.
25.
XuMZLiuMDDongSH. Active diluents effects of 4-nonylphenoxy-1, 2-dinitrilbenzene on phthalonitrile containing benzoxazine and their copolymerization behaviors. Express Polym Lett2013; 7: 984–995.
26.
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.
27.
AgagTTakeichiT. Novel benzoxazine monomers containing p-phenyl propargyl ether: polymerization of monomers and properties of polybenzoxazines. Macromolecules2001; 34: 7257–7263.
28.
WangZZhaoJCRanQC. Research on curing mechanism and thermal property of bis-allyl benzoxazine and N,N-(2,2,4-trimethylhexane-1,6-diyl) dimaleimide blend. React Funct Polym2013; 73: 668–673.
29.
ZouXQXuMZJiaK. Synthesis, polymerization, and properties of the allyl-functional phthalonitrile. J Appl Polym Sci. Epub ahead of print 14 July 2104. DOI: 10.1002/app.41203.
30.
BurchillPJ. On the formation and properties of a high-temperature resin from a bisphthalonitrile. J Polym Sci A: Polym Chem1994; 32: 1–8.
31.
DunkersJIshidaH. Vibrational assignments of N,N-bis (3,5-dimethyl-2-hydroxybenzyl)methylamine in the fingerprint region. Spectrochim Acta A1995; 51: 855–867.
32.
BurkeWJBishopJLGlennieEL. A new aminoalkylation reaction. condensation of phenols with dihydro-1, 3-aroxazines. J Org Chem1965; 30: 3423–3427.
33.
RussellVMKoenigJLLowHY. Study of the characterization and curing of benzoxazines using13C solid-state nuclear magnetic resonance. J Appl Polym Sci1998; 70: 1413–1425.
34.
RanQCTianQLiC. Investigation of processing, thermal, and mechanical properties of a new composite matrix-benzoxazine containing aldehyde group. Polym Adv Technol2010; 21: 170–176.
35.
AïssaANour-EddineEB. How carbon nanotubes affect the cure kinetics and glass transition temperature of their epoxy composites? A review. Express Polym Lett2009; 3: 588–594.
36.
ChowTS. Molecular interpretation of the glass transition temperature of polymer-diluent systems. Macromolecules1980; 13: 362–364.
37.
HancockBCZografiG. The relationship between the glass transition temperature and the water content of amorphous pharmaceutical solid. Pharm Res1994; 11: 471–477.
38.
ForrestJADalnoki-VeressKStevensJR. Effect of free surfaces on the glass transition temperature of thin polymer films. Phys Rev Lett1996; 7: 2002–2005.
39.
ForrestJADalnoki-VeressKDutcherJR. Interface and chain confinement effects on the glass transition temperature of thin polymer films. Phys Rev E1997; 56: 5705–5716.
40.
LowHYIshidaH. Mechanistic study on the thermal decomposition of polybenzoxazines: effects of aliphatic amines. J Polym Sci B: Polym Phys1998; 36: 1935–1946.
41.
KuznetsovAASemenovaGK. Perspective thermally stable thermoset binders for polymer composite materials. Russ J Gen Chem2010; 80: 2170–2180.
