Self-cured phthalonitrile resin via multistage polymerization mediated by allyl and benzoxazine functional groups

Abstract

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 (T _g) 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.

Keywords

Ring-opening polymerization cross-linking processability thermal mechanical property thermal stability

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References

Liang

. Toughening bismaleimide resins by nallyl aromatic amine. Polym J 1997; 29: 553–556.

Gouri

Nair

CPR

Ramaswamy

. Adhesive characteristics of alder-ene adduct of diallyl bisphenol A novolac and bisphenol A bismaleimide. High Perform Polym 2000; 12: 497–514.

Andre

Guida-Pietrasanta

Rousseau

. Synthesis, characterization, and thermal properties of anhydride terminated and allyl terminated oligoimides. J Polym Sci A: Polym Chem 2000; 38: 2993–3003.

Lin

Cheng

. Synthesis, curing, and decomposition of allylamine-adducted 3, 3′-bismaleimidodiphenylsulphone resins. J Polym Sci A: Polym Chem 1997; 35: 2469–2478.

Ishida

Low

. Synthesis of benzoxazine functional silane and adhesion properties of glass-fiber-reinforced polybenzoxazine composites. J Appl Polym Sci 1998; 69: 2559–2567.

Narayanan

Jungman

Patton

. Hybrid dual-cure polymer networks via sequential thiol–ene photopolymerization and thermal ring-opening polymerization of benzoxazines. React Funct Polym 2012; 72: 799–806.

Agag

Takeichi

. Synthesis and characterization of novel benzoxazine monomers containing allyl groups and their high performance thermosets. Macromolecules 2003; 36: 6010–6017.

Rao

Palanisamy

. Monofunctional benzoxazine from cardanol for bio-composite applications. React Funct Polym 2011; 71: 148–154.

Dominguez

Jones

Keller

. The effect of curing additive on the mechanical properties of phthalonitrile-carbon fiber composites. Polym Compos 2004; 25: 554–561.

10.

Laskoski

Dominguez

Keller

. Synthesis and properties of a bisphenol A based phthalonitrile resin. J Polym Sci A: Polym Chem 2005; 43: 4136–4143.

11.

Laskoski

Neal

Keller

. Improved synthesis of oligomeric phthalonitriles and studies designed for low temperature cure. J Polym Sci A: Polym Chem 2014; 52: 1662–1668.

12.

Keller

Dominguez

. High temperature resorcinol-based phthalonitrile polymer. Polymer 2005; 46: 4614–4618.

13.

Dominguez

Keller

. Properties of phthalonitrile monomer blends and thermosetting phthalonitrile copolymers. Polymer 2007; 48: 91–97.

14.

Keller

Griffith

. Polyphthalocyanine resins. Am Chem Soc Sym Ser 1980; 132: 25–26.

15.

Sastri

Keller

. Phthalonitrile polymers: cure behavior and properties. J Polym Sci A: Polym Chem 1999; 37: 2105–2111

16.

Sumner

Sankarapandian

McGrath

. Flame retardant novolac–bisphthalonitrile structural thermosets. Polymer 2002; 43: 5069–5076.

17.

Liu

. Synthesis and thermal properties of bisphthalonitriles containing aromatic ether nitrile linkages. Polym Degrad Stab 2009; 94: 2178–2183.

18.

Yang

Lei

Zhong

. Preparation and thermal properties of novel phthalonitrile oligomer containing biphenyl ethernitrile/bisphthalonitrile blends. J Appl Polym Sci 2011; 119: 882–887.

19.

Guo

Lei

Zhao

. Curing behaviors and properties of novolac/bisphthalonitrile blends. J Appl Polym Sci 2012; 125: 649–656.

20.

Chen

Guo

Tang

. Preparation and properties of bisphenol A-based bis-phthalonitrile composite laminates. J Appl Polym Sci 2013; 129: 2621–2628.

21.

Cao

Chen

Wei

. Synthesis and characterization of a novel bisphthalonitrile containing benzoxazine. Express Polym Lett 2007; 1: 512–518.

22.

Zuo

Liu

. Synthesis and curing behavior of a novel benzoxazine-based bisphthalonitrile monomer. J Appl Polym Sci 2010; 117: 1469–1475.

23.

Yang

Zhao

. Copolymerizing behavior and processability of benzoxazine/epoxy systems and their applications for glass fiber composite laminates. J Appl Polym Sci 2013; 128: 1176–1184.

24.

Zou

. Significant increments in the mechanical and thermal properties of composite laminates by in situ reaction with carboxyl functionalized CNTs. J Appl Polym Sci 2013; 129: 2629–2637.

25.

Liu

Dong

. Active diluents effects of 4-nonylphenoxy-1, 2-dinitrilbenzene on phthalonitrile containing benzoxazine and their copolymerization behaviors. Express Polym Lett 2013; 7: 984–995.

26.

Ning

Ishida

. Phenolic materials via ring-opening polymerization: synthesis and characterization of bisphenol-A based benzoxazines and their polymers. J Polym Sci A: Polym Chem 1994; 32: 1121–1129.

27.

Agag

Takeichi

. Novel benzoxazine monomers containing p-phenyl propargyl ether: polymerization of monomers and properties of polybenzoxazines. Macromolecules 2001; 34: 7257–7263.

28.

Wang

Zhao

Ran

. 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 Polym 2013; 73: 668–673.

29.

Zou

Jia

. 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.

Burchill

. On the formation and properties of a high-temperature resin from a bisphthalonitrile. J Polym Sci A: Polym Chem 1994; 32: 1–8.

31.

Dunkers

Ishida

. Vibrational assignments of N,N-bis (3,5-dimethyl-2-hydroxybenzyl)methylamine in the fingerprint region. Spectrochim Acta A 1995; 51: 855–867.

32.

Burke

Bishop

Glennie

. A new aminoalkylation reaction. condensation of phenols with dihydro-1, 3-aroxazines. J Org Chem 1965; 30: 3423–3427.

33.

Russell

Koenig

Low

. Study of the characterization and curing of benzoxazines using¹³C solid-state nuclear magnetic resonance. J Appl Polym Sci 1998; 70: 1413–1425.

34.

Ran

Tian

. Investigation of processing, thermal, and mechanical properties of a new composite matrix-benzoxazine containing aldehyde group. Polym Adv Technol 2010; 21: 170–176.

35.

Aïssa

Nour-Eddine

. How carbon nanotubes affect the cure kinetics and glass transition temperature of their epoxy composites? A review. Express Polym Lett 2009; 3: 588–594.

36.

Chow

. Molecular interpretation of the glass transition temperature of polymer-diluent systems. Macromolecules 1980; 13: 362–364.

37.

Hancock

Zografi

. The relationship between the glass transition temperature and the water content of amorphous pharmaceutical solid. Pharm Res 1994; 11: 471–477.

38.

Forrest

Dalnoki-Veress

Stevens

. Effect of free surfaces on the glass transition temperature of thin polymer films. Phys Rev Lett 1996; 7: 2002–2005.

39.

Forrest

Dalnoki-Veress

Dutcher

. Interface and chain confinement effects on the glass transition temperature of thin polymer films. Phys Rev E 1997; 56: 5705–5716.

40.

Low

Ishida

. Mechanistic study on the thermal decomposition of polybenzoxazines: effects of aliphatic amines. J Polym Sci B: Polym Phys 1998; 36: 1935–1946.

41.

Kuznetsov

Semenova

. Perspective thermally stable thermoset binders for polymer composite materials. Russ J Gen Chem 2010; 80: 2170–2180.

42.

Demir

Kiskan

Aydogan

. Thermally curable main-chain benzoxazine prepolymers via polycondensation route. React Funct Polym 2013; 73: 346–359.

43.

Wang

Ishida

. Cationic ring-opening polymerization of benzoxazines. Polymer 1999; 40: 4563–4570.