High Performance Resins

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<p>ARTICLE IN PRESS</p> <p>Prog. Polym. Sci. 32 (2007) 13441391 www.elsevier.com/locate/ppolysci</p> <p>PolybenzoxazinesNew high performance thermosetting resins: Synthesis and propertiesN.N. Ghosh1, B. Kiskan, Y. YagciDepartment of Chemistry, Istanbul Technical University, Maslak, Istanbul 34469, Turkey Received 18 January 2007; received in revised form 10 July 2007; accepted 10 July 2007 Available online 2 August 2007</p> <p>Abstract Polybenzoxazine is a newly developed addition polymerized phenolic system, having a wide range of interesting features and the capability to overcome several shortcomings of conventional novolac and resole type phenolic resins. These materials exhibit (i) near-zero volumetric change upon curing, (ii) low water absorption, (iii) for some polybenzoxazines Tg much higher than cure temperature, (iv) high char yield, (v) no strong acid catalysts required for curing, and (vi) release of no toxic by-product during curing. The molecular structure of polybenzoxazines offers enormous design exibility, which allows tailoring the properties of the cured materials for a wide range of applications. In this review article, different synthetic strategies for the preparation of benzoxazine monomers and blends, their polymerization reaction mechanisms, and the structureproperty relationships of the cured materials have been discussed. r 2007 Elsevier Ltd. All rights reserved.Keywords: High performance polymers; Polybenzoxazine; Thermoset; Composites; Blends; Macromonomer</p> <p>Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1345 Chemical methodologies for synthesis of benzoxazine monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1348 2.1. Mono-functional benzoxazine monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1348 2.2. Di-functional and multifunctional benzoxazine monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1349 2.3. Step-wise controlled synthesis of dimers and oligomers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1351 2.4. Allyl-containing monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1352 2.5. Acetylene containing monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1353 2.6. Propargyl ether containing monomers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1353 2.7. Nitrile containing monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1353 2.8. Maleimide and norbornane containing monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1354 2.9. Adamantane containing monomers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1355</p> <p>Corresponding author.</p> <p>E-mail address: yusuf@itu.edu.tr (Y. Yagci). Permanent address: Chemistry Department, Birla Institute of Technology and Science-Pilani (Goa Campus), Zuarinagar, Goa 403726, India.1</p> <p>0079-6700/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.progpolymsci.2007.07.002</p> <p>ARTICLE IN PRESSN.N. Ghosh et al. / Prog. Polym. Sci. 32 (2007) 13441391 1345</p> <p>3.</p> <p>4.</p> <p>5.</p> <p>6.</p> <p>2.10. Coumarin containing monomers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1356 2.11. Epoxy containing monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1356 2.12. Naphthoxazine monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1356 Combination of polybenzoxazines with other polymeric and inorganic materials . . . . . . . . . . . . . . . . . . . . . 1357 3.1. Preparations of blends and composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1357 3.1.1. Rubber modied polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1357 3.1.2. Polycarbonate blends with polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1359 3.1.3. Poly(e-caprolactone) blends with polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1359 3.1.4. Polyurethane (PU) blends with polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1359 3.1.5. Epoxy blends with polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1360 3.1.6. Phosphorous containing blends with polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1360 3.1.7. Clay-polybenzoxazine composites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1361 3.2. Preparation of polymers with benzoxazine moieties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1362 3.2.1. Benzoxazine functionalized polystyrene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1362 3.2.2. Benzoxazine functional poly(e-caprolactone) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1363 3.2.3. Benzoxazine functional poly(methyl methacrylate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1364 3.2.4. Alternating maleimide copolymers with pendant benzoxazine groups . . . . . . . . . . . . . . . . . . 1364 3.2.5. Naphthoxazine functional poly(propylene oxide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1365 3.2.6. Benzoxazine functional polyhedral oligomeric silsesquioxane (POSS). . . . . . . . . . . . . . . . . . . 1365 3.3. Polymeric benzoxazine precursors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1366 3.3.1. Main-chain precursors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1366 3.3.2. Side-chain precursor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1367 Reaction mechanism of ring opening polymerization of benzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1368 4.1. Cationic polymerization of benzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1368 4.1.1. Acid catalyzed polymerization of benzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1368 4.1.2. Photoinitiated polymerization of benzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371 4.2. Thermal polymerization of benzoxazines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371 Properties of polybenzoxazines and their blends and composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1373 5.1. Properties of polybenzoxazines. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1373 5.1.1. Properties of polybenzoxazines with additional functionalities. . . . . . . . . . . . . . . . . . . . . . . . 1377 5.1.2. Properties of rubber-modied polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379 5.1.3. Polycarbonate (PC)-modied polybenzoxazine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1382 5.1.4. Properties of polycaprolactone (PCL)-modied polybenzoxazine. . . . . . . . . . . . . . . . . . . . . . 1383 5.1.5. Properties of polyurethane-polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1383 5.1.6. Properties of epoxy-polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1384 5.1.7. Polybenzoxazines with ame retarding properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385 5.1.8. Clay-polymer composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385 5.1.9. Boron nitride-polybenzoxazine composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1386 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1386 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1386</p> <p>1. Introduction Phenolic resins are widely used in various applications, from commodity and construction materials to the needs of the high technology aerospace industry. Though several desirable properties, such as good mechanical strength, dimensional stability, resistance against various solvents, ame retardance, are characteristics of phenolic resins, a number of short-comings are also associated with these materials. For example, they are brittle, have poor shelf life, acid or base catalysts are</p> <p>often used for the preparation of resin, which corrode the processing equipments, and they release by-products (such as water, ammonia compounds during curing) which sometimes affect the properties of cured resins by forming micro voids. To overcome these problems recently a new type of addition-cure phenolic system, polybenzoxazines, has recently been developed. They have gained immense interest because they have the capability to exhibit the thermal and ame retardance properties of phenolics along with mechanical performance and molecular design exibility. Although</p> <p>ARTICLE IN PRESS1346 N.N. Ghosh et al. / Prog. Polym. Sci. 32 (2007) 13441391</p> <p>Nomenclature 6,60 -bis(2,3-dihydro-3-phenyl-4H-1,3benzoxazinyl) Amine-POSS primary amine terminated polyhedral oligomeric silsesquioxane ANDAD 4-amino-N,N-dimethyl aniline dihydrochloride ATBN amine-terminated butadiene acrylonitrile rubber ATRP atom transfer radical polymerization B-35x 6,60 -(propane-2,2-diyl)bis(3-(3,5-dimethylphenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) B-a 6,60 -(propane-2,2-diyl)bis(3-phenyl-3,4dihydro-2H-benzo[e][1,3]oxazine) B-a-apa 6,60 -(propane-2,2-diyl)bis(3-(3-ethynylphenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) B-a-apa 6,60 -(propane-2,2-diyl)bis(3-(3-ethynylphenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) B-af-apa 6,60 -(peruoropropane-2,2-diyl)bis(3(3-ethynylphenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) BAF-apa 6,60 -(peruoropropane-2,2-diyl)bis(3(3-ethynylphenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) B-ala bis(3-allyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane B-a-ot 6,60 -(propane-2,2-diyl)bis(3-o-tolyl-3,4dihydro-2H-benzo[e][1,3]oxazine) B-appe 6,60 -(propane-2,2-diyl)bis(3-(4-(prop-2ynyloxy)phenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) (2-Benzoxazine) adamantine and methyl amine based benzoxazine (3-Benzoxazine) adamantine and aniline based benzoxazine BF-apa bis(3-(3-ethynylphenyl)-3,4-dihydro-2Hbenzo[e][1,3]oxazin-6-yl)methane B-m 6,60 -(propane-2,2-diyl)bis(3-methyl-3,4dihydro-2H-benzo[e][1,3]oxazine) B-mt 6,60 -(propane-2,2-diyl)bis(3-m-tolyl-3,4dihydro-2H-benzo[e][1,3]oxazine) BO-apa 6,60 -oxybis(3-(3-ethynylphenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) BP benzophenone BP-apa 3,30 -bis(3-ethynylphenyl)-3,30 ,4,40 -tetrahydro-2H,20 H-6,60 -bibenzo[e][1,3]oxazine 440-a</p> <p>B-pt</p> <p>6,60 -(propane-2,2-diyl)bis(3-p-tolyl-3,4dihydro-2H-benzo[e][1,3]oxazine) BS-apa 6,60 -sulfonylbis(3-(3-ethynylphenyl)-3,4dihydro-2H-benzo[e][1,3]oxazine) BZ-apa bis(3-(3-ethynylphenyl)-3,4-dihydro-2Hbenzo[e][1,3]oxazin-6-yl)methanone BZPOSS Mono-functional benzoxazine monomer containing polyhedral oligomeric silsesquioxane CAPRO 6-aminocaproic acid CQ camphorquinone CTBN carboxyl-terminated butadiene acrylonitrile rubber. CTX chlorothioxanthone. DGEBA diglycidyl ether of bisphenol A DMAc dimethylacetamide DMPA 2,20 -dimethoxy-2-phenylacetophenone 24DMP-m 3,6,8-trimethyl-3,4-dihydro-2H-benzo[e][1,3]oxazine DODEC dodecylamine Dopo dibenzo[c,e][1,2]oxaphosphinine 6-oxide DOPO-Gly glycidyl phosphinate Dopotriol dibenzo[c,e][1,2]oxaphosphinine 6-oxide based benzoxazine DSC differential scanning calorimetry EPO732commercial name of a exible epoxy resin F-a 6,6-bis(3-phenyl-3,4-dihydro-2H-1,3benzoxazineyl) methane FT-IR Fourier transform infra red HPM N-(4-hydroxyphenyl) malemide HPM-Ba 1-(3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)-1H-pyrrole-2,5dione H-POSS hydro-silane functionalized polyhedral oligomeric silsesquioxane HQ-apa bisbenzoxazine derived from hydroquinone and 3-ethynylaniline HTBD hydroxyl terminated polybutadiene IHPOGly isobutyl bis(glycidylpropylether) phophine oxide IPDI isophorone diisocyanate IPN Inter penetrating network ITX isopropyl thixanthone 15Na naphthalene-1,5-diol based bisbenzoxazine 26Na naphthalene-2,6-diol based bisbenzoxazine 27Na naphthalene-2,7-diol based bisbenzoxazine</p> <p>ARTICLE IN PRESSN.N. Ghosh et al. / Prog. Polym. Sci. 32 (2007) 13441391 1347</p> <p>2,20 -p-phenylene-bis-(2,3-dihydro-1Hnapth[1,2-e]-m-oxazine) MIB benzoxazine with maleimide group MMA methyl methacrylate MMT montmorillonite NMR nuclear magnetic resonance NO-apa bisbenzoxazine derived from naphthalene-1,5-diol and 3-ethynylaniline NOB p-hydroxyphenylnadimide derived benzoxazine OCNE o-Cresol novolac-type epoxy resin OMMT organically modied montmorillonite 22P-a 8,80 -bis(3,4-dihydro-3-phenyl-2H-1,3benzoxazine) 22P-a PBZ poly(8,80 -bis(3,4-dihydro-3-phenyl2H-1,3-benzoxazine)) P-a N-phenyl-3,4-dihydro-2H-1,3-benzoxazine P-ala 3-allyl-3,4-dihydro-2H-1,3-benzoxazine P-alp 3-phenyl-3,4-dihydro-8-allyl-2H-1,3-benzoxazine P-appe 3-(4-(prop-2-ynyloxy)phenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine PB-a poly(6,60 -(propane-2,2-diyl)bis(3-phenyl3,4-dihydro-2H-benzo[e][1,3]oxazine)) PB-ala poly(bis(3-allyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane) PBO (2,20 -(1,3-phenylene)-bis(4,5-dihydro-oxazoles)) 440-a PBZ poly(6,60 -bis(2,3-dihydro-3-phenyl4H-1,3-benzoxazinyl)) PC polycarbonate p-Ca 3-benzyl-3,4-dihydro-6-methyl-2H-1,3benzoxazine PCL poly(e-caprolactone) pC-m 3,6-dimethyl-3,4-dihydro-2H-benzo[e][1,3]oxazine PGE phenyl glycidyl ether Ph-apa 3-(3-ethynylphenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine 2Naa</p> <p>Ph-apc (4-(3-(4-ethynylphenyl)-3,4-dihydro-2Hbenzo[e][1,3]oxazin-6-yloxy)phenyl)(4(phenylethynyl)phenyl)methanone PHEN p-phenetidine Poly VPpoly(p-vinylphenol) POSS polyhedral oligomeric silsesquioxane PP-a poly(N-phenyl-3,4-dihydro-2H-1,3-benzoxazine) PP-alp poly(3-phenyl-3,4-dihydro-8-allyl-2H1,3-benzoxazine) PU polyurethane SEC size exclusion chromatography St styrene 1,3-Ta 6,60 -(4-isopropyl-1-methylcyclohexane1,3-diyl)bis(3-phenyl-3,4-dihydro-2Hbenzo[e][1,3]oxazine) 2,8-Ta 6-(1-methyl-4-(2-(3-phenyl-3,4-dihydro2...</p>

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