Synthesis and characterization of epoxy-based nanocomposites obtained by frontal polymerization Alberto Mariani 1, Valeria Alzari 2, Orietta Monticelli

Synthesis and characterization of epoxy-based nanocomposites obtained by frontal polymerization

Alberto Mariani1, Valeria Alzari2, Orietta Monticelli3, Giuseppe Caria1, José M. Kenny2, Saverio Russo3

1. INSTM e Dipartimento di Chimica – Università di Sassari1. INSTM e Dipartimento di Chimica – Università di Sassari

2. INSTM e Centro di Scienza e Tecnologia dei Materiali – Università di Perugia, Terni2. INSTM e Centro di Scienza e Tecnologia dei Materiali – Università di Perugia, Terni

3. INSTM e Dipartimento di Chimica e Chimica Industriale – Università di Genova3. INSTM e Dipartimento di Chimica e Chimica Industriale – Università di Genova

VI Convegno Nazionale sulla Scienza e la Tecnologia dei MaterialiVI Convegno Nazionale sulla Scienza e la Tecnologia dei MaterialiUniversità di Perugia, 12-15 giugno 2007Università di Perugia, 12-15 giugno 2007

The domino effect


Frontal PolymerizationFrontal Polymerization

thermalthermal

isothermalisothermal


Frontal PolymerizationFrontal Polymerization

thermalthermal

isothermalisothermal It’s a mode of converting monomer into polymer via a localized reaction zone that propagates through the coupling of thermal diffusion and temperature-dependent reaction rates

It’s a mode of converting monomer into polymer via a localized reaction zone that propagates through the coupling of thermal diffusion and temperature-dependent reaction rates


Frontal PolymerizatonFrontal Polymerizaton

thermalthermal

isothermalisothermal


polyurethane – fumed silica nanocomposites polyurethane – fumed silica nanocomposites

consolidation of porous materials (stone, wood, paper)consolidation of porous materials (stone, wood, paper)

polyacrylates – POSS nanocompositespolyacrylates – POSS nanocomposites

Polymeric composite materials previously obtained by us via FP

polyacrylate – organic liquid crystal compositespolyacrylate – organic liquid crystal composites


Polymeric nanocomposites obtained in this work via FP

Mariani et al. J. Polym. Sci. Polym. Chem. 2007, 45, 2204 Mariani et al. J. Polym. Sci. Polym. Chem. 2007, 45, 2204

Epoxy resin – montmorillonite nanocompositesEpoxy resin – montmorillonite nanocomposites

Mariani et al. J. Polym. Sci. Polym. Chem. 2007, 00, 0000Mariani et al. J. Polym. Sci. Polym. Chem. 2007, 00, 0000

Epoxy resin – POSS nanocompositesEpoxy resin – POSS nanocomposites


Bisphenol A diglycidyl ether (DGEBA)

diethylene triamine (DETA)

H2N

HN

NH2

Polymeric nanocomposites obtained in this work via FP

OO

OO

Mariani et al. J. Polym. Sci. Polym. Chem. 2007, 45, 2204 Mariani et al. J. Polym. Sci. Polym. Chem. 2007, 45, 2204



Epoxy resin – montmorillonitenanocomposites





Samples obtained by CP

Method A: 4h at 100 °C; 16 h at 150 °C; 12 h at 200 °C Method B: 24 h at room temperature, 4h at 100 °C

Samples obtained by CP

Method A: 4h at 100 °C; 16 h at 150 °C; 12 h at 200 °C Method B: 24 h at room temperature, 4h at 100 °C



Temperature profileTemperature profile


Front positionFront position



nanocomposite syntheses starting from non thermally pre- treated (□) and pre-treated (●)

mixtures

nanocomposite syntheses starting from non thermally pre- treated (□) and pre-treated (●)

mixtures

150

175

200

225

250

0 2 4 6 8 10amount of C30B (wt.-%)

Tm

ax (

°C)

Tmax vs. C30B amountTmax vs. C30B amount


0.5

0.6

0.7

0.8

0.9

1

0 2 4 6 8 10amount of C30B (wt.-%)

Vf (

cm

/min

)

Vf vs. C30B amountVf vs. C30B amount







individual dispersion of delaminated sheetsindividual dispersion of delaminated sheets


POSS (POSS (Polyhedral Oligomeric SilSesquioxanesPolyhedral Oligomeric SilSesquioxanes))

Epoxy resin – POSSnanocomposites




Bisphenol A diglycidyl ether (DGEBA)

OO

OO

diethylene triamine (DETA)

H2N

HN

NH2











Polymerresidua

l H(J/g)

total H

(J/g)

degree ofconversion

(%)

B0 0 -553.8 100

F0 0 -553.8 100

B1 0 -507.6 100

F1 0 -507.6 100

B3 0 -503.0 100

F3 0 -503.0 100

B5 -2.44 -522.9 99.5

F5 0 -522.9 100

B7 -2.87 -476.9 99.4

F7 -2.59 -476.9 99.5

B10 0 -475.8 100

F10 0 -475.8 100




SE: secondary electron emission

BS: back scattering emission

SE: secondary electron emission

BS: back scattering emission

no Si aggregates are visible in the micron scaleno Si aggregates are visible in the micron scale


Conclusions

Frontal Polymerization is an easy and low-cost technique for the obtainment of Frontal Polymerization is an easy and low-cost technique for the obtainment of polymer materials, including nanocomposites, polymer materials, including nanocomposites, often in almost quantitative often in almost quantitative yieldsyields..

Their properties are comparable, sometimes even better, than those of samples Their properties are comparable, sometimes even better, than those of samples prepared by the classical methods.prepared by the classical methods.

Why not considering frontal polymerization as the first option?Why not considering frontal polymerization as the first option?

They are obtained in very short times!They are obtained in very short times!They are obtained in very short times!They are obtained in very short times!


Documents

Synthesis and characterization of epoxy-based nanocomposites obtained by frontal polymerization Alberto Mariani 1, Valeria Alzari 2, Orietta Monticelli