Introduction to Commercial Benzoxazine and Their Unique Properties

Rimdusit, Sarawut; Jubsilp, Chanchira; Tiptipakorn, Sunan

doi:10.1007/978-981-4451-76-5_1

Sarawut Rimdusit⁴,
Chanchira Jubsilp⁵ &
Sunan Tiptipakorn⁶

Part of the book series: Engineering Materials ((ENG.MAT.))

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4 Citations

Abstract

Since World War II, only few polymers, which have been developed, are able to reach the commercial stage. Polybenzoxazines are one of those few. Their ease of synthesis with tremendous molecular design flexibility allows tailor-made properties with broad range of applications. Their unique characteristics such as self-polymerizability upon heating without a need for a catalyst or curing agent, very low A-stage viscosity, near-zero volumetric shrinkage, fire-resistant behaviors, as well as their outstanding thermal and mechanical properties, make the polymer highly attractive for various applications including electronic packaging or aerospace. As a consequence, some companies start to commercialize the resins and their composites. This chapter summarizes benzoxazine resins and their related products recently commercialized by some major companies. The key properties of the polymers for engineering applications are also concisely discussed.

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References

Jubsilp C, Takeichi T, Rimdusit S (2010) Curing kinetics of benzoxazine-epoxy copolymer investigated by non-isothermal differential scanning calorimetry. Polym Degrad Stabil 95:918
Article CAS Google Scholar
Rimdusit S, Kunopast P, Dueramae I (2011) Thermomechanical properties of arylamine-based benzoxazine resins alloyed with epoxy resin. Polym Eng Sci 51:1797–1807
Article CAS Google Scholar
Rimdusit S, Ishida H (2000) Synergism and multiple mechanical relaxation observed in ternary systems based on benzoxazine epoxy and phenolic resins. J Polym Sci Pol Phys 38:1687–1698
Article CAS Google Scholar
Lui YL, Yu JM, Chou CI (2004) Preparation and properties of novel benzoxazine and polybenzoxazine with maleimide groups. J Polym Sci Pol Chem 42:5954–5963
Article Google Scholar
Ishida H, Lee YH (2000) Infrared and thermal analyses of polybenzoxazine and polycarbonate blends. J Appl Polym Sci 81:1021–1034
Article Google Scholar
Ishida H, Lee YH (2002) Study of exchange reaction in polycarbonate-modified polybenzoxazine via model compound. J Appl Polym Sci 83:1848–1855
Article CAS Google Scholar
Ishida H, Lee YH (2001) Synergism observed in polybenzoxazine and polycaprolactone blends by dynamics mechanical and thermogravimetric analysis. Polymer 42:6971–6979
Article CAS Google Scholar
Huang JM, Yang SJ (2005) Studying the miscibility and thermal behavior of polybenzoxazine/poly(ε-caprolactone) blends using DSC, DMA and solid state ¹³C NMR spectroscopy. Polymer 46:8068–8078
Article CAS Google Scholar
Rimdusit S, Bangsen W, Kasemsiri P (2011) Chemorheology and thermomechanical characteristics of benzoxazine-urethane copolymer. J Appl Polym Sci 121:3669–3678
Article CAS Google Scholar
Jamshidi S, Yeganeh H, Mehdipour-Ataei S (2011) Poly(urethane-co-benzoxazine)s via reaction of phenol terminated urethane prepolymers and benzoxazine monomer and investigation of their properties. Polym Advan Technol 22:1502–1512
Article CAS Google Scholar
Takeichi T, Guo Y, Rimdusit S (2005) Performance improvement of polybenzoxazine by alloying with polyimide: effect of preparation method on the properties. Polymer 46:4909–4916
Article CAS Google Scholar
Rimdusit S, Kampangsaeree N, Tanthapanichakoom W, Takeichi T, Suppakarn N (2007) Development of wood-substituted composites from highly filled polybenzoxazine–phenolic novolac alloys. Polym Eng Sci 47:140–149
Article CAS Google Scholar
Rimdusit S, Jiraprawatthagook V, Tiptipakorn S, Covavisaruch S, Kitano T (2006) Characterization of SiC whisker-filled polybenzoxazine cured by microwave radiation and heat. Int J Polym Anal Ch 11:441–453
Article CAS Google Scholar
Ishida H, Rimdusit S (1998) Very high thermal conductivity obtained by boron nitride-filled polybenzoxazine. Thermochim Acta 320:177–186
Article CAS Google Scholar
Agag T, Takeichi T (2011) Synthesis and characterization of benzoxazine resin-SiO2 hybrids by sol-gel process: The role of benzoxazine-functional silane coupling agent. Polymer 52:2757–2763
Article CAS Google Scholar
Takeichi T, Guo Y (2011) Synthesis and characterization of poly(urethane-benzoxazine)/clay hybrid nanocomposites. J Appl Polym Sci 90:4075–4083
Article Google Scholar
Rimdusit S, Pathomsap S, Kassemsiri P, Jubsilp C, Tiptipakorn S (2011) Kevlar^TM fiber-reinforced polybenzoxazine alloys for ballistic impact application. Eng J 15:23–40
Article Google Scholar
Rimdusit S, Jongvisuttisun P, Jubsilp C, Tanthapanichakoon W (2009) Highly processable ternary systems based on benzoxazine, epoxy, and phenolic resins for carbon fiber composite processing. J Appl Polym Sci 111:1225–1234
Article CAS Google Scholar
Rimdusit S, Leingvachiranon C, Tiptipakorn S, Jubsilp C (2009) Thermomechanical characteristics of benzoxazine-urethane copolymers and their carbon fiber-reinforced composites. J Appl Polym Sci 113:3823–3830
Article CAS Google Scholar
Ishida H, Low HY (1998) Synthesis of benzoxazine functional silane and adhesion properties of glass-fiber-reinforced polybenzoxazine composites. J Appl Polym Sci 69:2559–2567
Article CAS Google Scholar
Kiskan B, Yaggi Y, Sahmetlioglu E, Toppare L (2007) Preparation of conductive polybenzoxazines by oxidative polymerization. J Polym Sci Polym Chem 45:999–1006
Article CAS Google Scholar
Wang YH, Chang CM, Liu YL (2012) Benzoxazine-functionalized multi-walled carbon nanotubes for preparation of electrically-conductive polybenzoxazines. Polymer 53:106–112
Article CAS Google Scholar
Kim SK, Kim KH, Park JO, Kim K, Ko T, Choi SW, Pak C, Chang H, Lee JC (2013) Highly durable polymer electrolyte membranes at elevated temperature: cross-linked copolymer structure consisting of poly(benzoxazine) and poly(benzimidazole). J Power Sources 226:346–353
Article CAS Google Scholar
Ye YS, Yen YC, Cheng CC, Chen WY, Wsai LT, Chang FC (2009) Sulfonated poly(ether ether ketone) membranes crosslinked with sulfonic acid containing benzoxazine monomer as proton exchange membranes. Polymer 50:3196–3203
Article CAS Google Scholar
Tasdelen CY, Erciyes AT (2013) Preparation of oil-modified polycaprolactone and its further modification with benzoxazine for coating purposes. Prog Org Coat 76:137–146
Article Google Scholar
Rimdusit S, Ishida H (2000) Development of new class electronic packaging materials based ternary systems of benzoxazine, epoxy, and phenolic resins. Polymer 41:7941–7949
Article CAS Google Scholar
Li WH, Lehmann S, Mckillen J, Wong A, Wong R, Leach D (2010) Benzoxazine matrix resins for structural composite applications. SAMPE, Europe
Google Scholar
Wu Y, Zeng M, Xu Q, Hou S, Jin H, Fan L (2012) Effects of glass to rubber transition of thermosetting resin matrix on the friction and wear properties of friction materials. Tribol Int 54:51–57
Article CAS Google Scholar
Ning X, Ishida H (1994) Phenolic materials via ring-opening polymerization of benzoxazines: effect of molecular structure on mechanical and dynamic mechanical properties. J Polym Sci Phys 32:921–927
Article CAS Google Scholar
Kim HJ, Brunovska Z, Ishida H (1999) Dynamic mechanical analysis on highly thermally stable polybenzoxazine with an acetylene functional group. J Appl Polym Sci 73:862–875
Google Scholar
Low HY, Ishida H (1999) Structural effects of phenols on the thermal and thermo-oxidative degradation of polybenzoxazines. Polymer 40:4365–4376
Article CAS Google Scholar
Yang P, Gu Y (2011) Synthesis and curing behavior of a benzoxazine based on phenolphthalein and its high performance polymer. J Polym Res 18:1725–1733
Article CAS Google Scholar
Shieh JY, Lin CY, Huang CL, Wang CS (2006) Synthesis and characterization of novel dihydrobenzoxazine resins. J Appl Polym Sci 101:342–347
Article CAS Google Scholar
Xiang H, Ling H, Wang J, Song L, Gu Y (2005) A novel high performance RTM resin based on benzoxazine. Polym Compos 26:563–571
Article CAS Google Scholar
Brunovska Z, Ishida H (1999) Thermal study on the copolymers of phthalonitrile and phenylnitrile-functional benxozazines. J Appl Polym Sci 73:2937–2949
Article CAS Google Scholar
Ishida H (1996) Process of preparation of benzoxazine compounds in solventless systems. US patent 5,543,516, 6 Aug 1996
Google Scholar
Rimdusit S, Mongkhonsi T, Kamonchivanich P, Sujirote K, Thiptipakorn S (2008) Effects of polyol molecular weight on properties of benzoxazine-urethane polymer alloys. Polym Eng Sci 48:2238–2246
Article CAS Google Scholar
Harper CA (2004) Handbook of building materials for fire protection 2004. McGraw Hill, New York
Google Scholar
Jubsilp C, Ramsiri B, Rimdusit S (2012) Effects of aromatic carboxylic dianhydrides on thermomechanical properties of polybenzoxazine-dianhydride copolymers. Polym Eng Sci 52:1640–1648
Article CAS Google Scholar
Rimdusit S, Thamprasom N, Suppakarn N, Jubsilp C, Takeichi T (2013) Effect of triphenylphosphate flame retardant on properties of arylamine-based benzoxazine. Eng J (in press)
Google Scholar
Yasmin A, Daniel IM (2004) Mechanical and thermal properties of graphite platelet/epoxy composites. Polymer 38:4165–4176
Google Scholar
Takeichi T, Guo Y, Aga T (2000) Synthesis and characterization of poly(urethane-benzoxazine) films as novel type of polyurethane/phenolic resin composites. J Polym Sci A 38:4165–4176
Article CAS Google Scholar
Rao BS, Reddy KR, Pathak SK, Pasala AR (2005) Benzoxazine-epoxy copolymers: effect of molecular weight and crosslinking on thermal and viscoelastic properties. Polym Int 54:1371–1376
Article CAS Google Scholar
Kasemsiri P, Hiziroglu S, Rimdusit S (2011) Effect of cashew nut shell liquid on gelation, cure kinetics, and thermomechanical properties of benzoxazine resin. Themochim Acta 520:84–92
Article CAS Google Scholar
Jupsilp C, Takeich T, Rimdusit S (2011) Property enhancement of polybenzoxazine modified with dianhydride. Polym Degrad Stabil 96:1047–1053
Article Google Scholar
Lin CH, Cai SX, Leu TS, Hwang TY, Lee HH (2006) Synthesis and properties of flame-retardant benzoxazines by three approaches. J Polym Sci 44:3454–3468
CAS Google Scholar
William E, Brenzovich J, Misty Do, Joana PS, Christopher JA (2003) Structure and properties of some cresolphthalein derivatives. Dyes Pigm 59:251–261
Article Google Scholar
Mi Y, Zheng S, Chan CM, Guo Q (1998) Blends of phenolphthalein poly(ether ether ketone) and a thermotropic liquid crystalline copolyester. J Appl Polym Sci 69:1923–1931
Article CAS Google Scholar
Cao HW, Xu RW, Liu H, Yu DS (2006) Mannich reaction of phenolpthalein and synthesis of a novel polybenzoxazine. Des Monomers Polym 9:369–382
Article CAS Google Scholar
Hougham G, Tesoro G, Shaw J (1994) Synthesis and properties of highly fluorinated polyimides. Macromolecules 27:3642–3649
Article CAS Google Scholar
Tietze R (2007) The 5th triennial international aircraft fire and cabin safety research
Google Scholar
AdMat specialty components selector guide 03.12_EN_EU (2012) Huntsman corporation
Google Scholar
Chow WS, Grishchuk S, Burkhart T, Kocsis JK (2012) Gelling and curing behaviors of benzoxazine/epoxy formulations containing 4,4′-thiodiphenol accelerator. Thermochim Acta 543:172–177
Article CAS Google Scholar
Aerospace product selector guide (2012) Henkel corporation
Google Scholar
Ardanuy M, Perez MA, Saja J, Velasco JI (2011) Foaming behavior, cellular structure and physical properties of polybenzoxazine foams. Polym Adv Tech 23:841–849
Article Google Scholar
Gurit http://www.gurit.com. Accessed 10 Jan 2013
Araldite benzoxazine thermoset resins selector guide (2009) Huntsman corporation
Google Scholar
Li W, Wong A, Leach D (2010) Advances in benzoxazine resins for aerospace applications. SAMPE Europe
Google Scholar
Agag T, Takeichi T (2000) Polybenzoxazine-montmorillonite hybrid nanocomposites synthesis and characterization. Polymer 41:7083–7090
Article CAS Google Scholar
Takeichi T, Zeidam R, Agag T (2002) Polybenzoxazine/clay hybrid nanocomposites: Influence of preparation method on the curing behavior and properties of polybenzoxazine. Polymer 43:45–53
Article CAS Google Scholar
Agag T, Tsuchiya H, Takeichi T (2004) Novel organic-inorganic hybrids prepared from polybenzoxazine and titania using sol-gel process. Polymer 45:7903–7910
Article CAS Google Scholar
Lee YJ, Huang JM, Kuo SW, Chen JK, Chang FC (2005) Synthesis and characterizations of a vinyl-terminated benzoxazine monomer and its blending with polyhedral oligomeric silsesquioxane (POSS). Polymer 46:2320–2330
Article CAS Google Scholar
Yei DR, Fu HK, Chen WY, Chang FC (2005) Synthesis of a novel benzoxazine monomer-intercalated montmorillonite and the curing kinetics of polybenzoxazine/clay hybrid nanocomposites. J Polym Sci B poly mer physi 44:347–358
Article Google Scholar
Gietl T, Lengsfeld h, Altstadt V (2006) The efficiency of various toughening agents in novel phenolic type thermoset resin systems. J Mater Sci 41:8226–8243
Article CAS Google Scholar
Agag T, Taepaisitphongse V, Takeichi T (2007) Reinforcement of polybenzoxazine matrix with organically modified mica. Polym Composite 28:680–687
Article CAS Google Scholar
Lin CH, Chang SL, Hsieh CW, Lee HH (2008) Aromatic diamine-based benzoxazines and their high performance thermosets. Polymer 49:1220–1229
Article CAS Google Scholar
Lu CH, Su YC, Wang CH, Haung CF, Sheen YC (2008) Thermal properties and surface energy characteristics of interpenetrating polyacrylate and polybenzoxazine networks. Polymer 49:4852–4860
Article CAS Google Scholar
Takeichi T, Saito Y, Agag T, Muto H, Kawauchi T (2008) High-performance polymer alloys of polybenzoxazine and bismaleimide. Polymer 49:1173–1179
Article CAS Google Scholar
Sponton M, Ronda C, Glia M, Cadiz V (2009) Development of flame retardant phosphorus- and silicon-containing polybenzoxazines. Polym Degrad Stabil 94:145–150
Article CAS Google Scholar
Yang L, Zhang C, Pilla S, Gong S (2008) Polybenzoxazine-core shell rubber–carbon nanotube nanocomposites. Compos Part A: Appl S 39:1653–1659
Article Google Scholar
Chang HC, Lin CH, Lin HT, Dai SA (2011) Deprotection-free preparation of propargyl ether-containing phosphinated benzoxazine and the structure-property relationship of the resulting thermosets. J Polym Sci 50:1008–1017
Google Scholar
Narayanan J, Jungman MJ, Patton DL (2012) Hybrid dual-cure polymer networks via sequential thiol–ene photopolymerization and thermal ring-opening polymerization of benzoxazines. React Funct Polym 72:799–806
Article CAS Google Scholar
Celina MC, Giron NH, Rojo MR (2012) An overview of high temperature micro-ATR IR spectroscopy to monitor polymer reactions. Polymer 53:4461–4471
Article CAS Google Scholar
Kaleemullah M, Khan SU, Kim JK (2012) Effect of surfactant treatment on thermal stability and mechanical properties of CNT/polybenzoxazine nanocomposites. Compos Sci Technol 72:1968–1976
Article CAS Google Scholar

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Authors and Affiliations

Department of Chemical Engineering, Chulalongkorn University, Bangkok, 10330, Thailand
Sarawut Rimdusit
Department of Chemical Engineering, Srinakharinwirot University, Nakhon Nayok, 26120, Thailand
Chanchira Jubsilp
Department of Chemistry, Kasetsart University, Nakhon Pathom, 73140, Thailand
Sunan Tiptipakorn

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Sarawut Rimdusit
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Chanchira Jubsilp
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Sunan Tiptipakorn
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Rimdusit, S., Jubsilp, C., Tiptipakorn, S. (2013). Introduction to Commercial Benzoxazine and Their Unique Properties. In: Alloys and Composites of Polybenzoxazines. Engineering Materials. Springer, Singapore. https://doi.org/10.1007/978-981-4451-76-5_1

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DOI: https://doi.org/10.1007/978-981-4451-76-5_1
Published: 17 July 2013
Publisher Name: Springer, Singapore
Print ISBN: 978-981-4451-75-8
Online ISBN: 978-981-4451-76-5
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