Intercalative polymerization of cyclic esters in layered silicates : thermal vs. catalytic activation

in Composite Interfaces (2003), 10(4-5), 423-433

Poly(ε-caprolactone) layered silicate nanocomposites were synthesized by in situ inter-calative ring-opening polymerization (ROP) of ε-caprolactone. The polymerization was promoted by thermal or catalytic ... [more ▼]

Poly(ε-caprolactone) layered silicate nanocomposites were synthesized by in situ inter-calative ring-opening polymerization (ROP) of ε-caprolactone. The polymerization was promoted by thermal or catalytic initiation starting from either non-modified natural sodium-montmorillonite (MMT-Na) or montmorillonite modified by different ammonium cations bearing either non-functional alkyl chains or chains terminated by carboxylic acid or hydroxyl functions. The resulting compositions were analyzed by small-angle X-ray diffraction and transmission electron microscopy. The clay dispersion depended on the structure of the alkyl ammonium. Exfoliated nanocomposites were formed when hydroxyl-containing alkyl-ammonium was used; otherwise, partially intercalated/partially exfoliated structures were observed. Moreover, caving to the inherent catalytic properties of the montmo-rillomte surface, it was also possible to prepare intercalated nanocomposites by in situ polymerization of ε-caprolactone in presence of non-modified montmorillonite-Na (MMT-Na) without any added catalyst. [less ▲]

Biodegradable polyester layered silicate nanocomposites based on poly(epsilon-caprolactone)

in Polymer Engineering & Science (2002), 42(9), 1928-1937

Nanocomposites based on biodegradable poly(epsilon-caprolactone) (PCL) and layered silicates (montmorillonite, MMT) were prepared either by melt intercalation with PCL or by in situ ring-opening ... [more ▼]

Nanocomposites based on biodegradable poly(epsilon-caprolactone) (PCL) and layered silicates (montmorillonite, MMT) were prepared either by melt intercalation with PCL or by in situ ring-opening polymerization of epsilon-caprolactone as promoted by the so-called coordination-insertion mechanism. Both non-modified clays (Na+-MMT) and silicates modified by various alkylammonium cations were studied. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. Even at a filler content as low as 3 wt% of inorganic layered silicate, the PCL-layered silicate nanocomposites exhibited improved mechanical properties (higher Young's modulus) and increased thermal stability as well as enhanced flame retardant characteristics as a result of a charring effect. It was shown that the formation of PCL-based nanocomposites depended not only on the nature of the ammonium cation and related functionality but also on the selected synthetic route, melt intercalation vs. in situ intercalative polymerization. Interestingly enough, when the intercalative polymerization of epsilon-caprolactone was carried out in the presence of MMT organo-modified with ammonium cations bearing hydroxyl functions, nanocomposites with much improved mechanical properties were recovered. Those hybrid polyester layered silicate nanocomposites. were characterized by a covalent bonding between the polyester chains and the clay organo-surface as a result of the polymerization mechanism, which was actually initiated from the surface hydroxyl functions adequately activated by selected tin (II) or tin (IV) catalysts. [less ▲]

Poly(epsilon-caprolactone)/clay nanocomposites prepared by melt intercalation: mechanical, thermal and rheological properties

in Polymer (2002), 43(14), 4017-4023

(Nano)composites of poly(epsilon-caprolactone) (PCL) were prepared by melt blending the polymer with natural Na+ montmorillonite and montmorillonite modified by hydrogenated tallowalkyl (HTA)-based ... [more ▼]

(Nano)composites of poly(epsilon-caprolactone) (PCL) were prepared by melt blending the polymer with natural Na+ montmorillonite and montmorillonite modified by hydrogenated tallowalkyl (HTA)-based quaternary ammonium cations, such as dimethyl 2-ethylhexyl HTA ammonium and methyl bis(2-hydroxyethyl) HTA ammonium. Microcomposites or nanocomposites were prepared depending on whether neat or modified montmorillonites was used, as assessed by X-ray diffraction and transmission electron microscopy. Mechanical and thermal properties were studied as a function of the filter content by tensile testing, Izod impact testing, thermogravimetric analysis and differential scanning calorimetry. The rheological behaviour at 80 degreesC was also analysed in relation to the structure and content of the layered silicate. Effect of exfoliated silicates on the mechanical properties, thermal stability and flame resistance of PCL was considered. Stiffness and thermal stability improved with the filler loading until a content of 5 wt%. Further loading resulted in the levelling off and possibly in a decrease of these properties. A marked charring effect was observed upon exposure to a flame. [less ▲]

Polyester layered silicate nanohybrids by controlled grafting polymerization

in Journal of Materials Chemistry (2002), 12(12), 3528-3535

Poly( epsilon-caprolactone) (PCL) layered silicate nanohybrids were synthesized by ring opening polymerization of epsilon-caprolactone according to a well-controlled coordination-insertion mechanism ... [more ▼]

Poly( epsilon-caprolactone) (PCL) layered silicate nanohybrids were synthesized by ring opening polymerization of epsilon-caprolactone according to a well-controlled coordination-insertion mechanism. Montmorillonites were surface-modified by non functional (trimethylhexadecylammonium) and hydroxy functional alkylammonium cations, i.e., (2-hydroxyethyl) dimethylhexadecylammonium. The hydroxy functions available at the clay surface were activated into tin( II or IV) or Al(III) alkoxide initiators for lactone polymerization, thus yielding surface-grafted PCL chains. The surface-grafted PCL chains were recovered by an ionic exchange reaction with lithium chloride and they were analyzed by size exclusion chromatography. The PCL molar mass was measured as a function of the hydroxy content of the clay that was modulated by exchanging the Na cations with mixtures of non-functional and hydroxy functional ammonium cations of different compositions. Nanohybrids were also characterized by small-angle X-ray diffraction, transmission electron microscopy and thermogravimetry. The PCL molar mass and the nanocomposite morphology (i.e., exfoliation and/or intercalation) were readily tuned by the content of the hydroxy groups available at the clay surface. Surface-grafted aluminium trialkoxide species proved highly efficient in initiating polymerization that leads to PCL chains of controlled molar mass and narrow molecular weight distribution with polydispersity indices as low as 1.2. [less ▲]

Anionic synthesis of cyclic anhydride end-capped poly(methyl methacrylate)

in Polymer (2000), 41(14), 5535-5539

This paper reports on the anionic synthesis of poly(methyl methacrylate) chains end-capped by cyclic anhydride. The method is based on the chemical derivatization of a precursor tert-butyl diester end ... [more ▼]

This paper reports on the anionic synthesis of poly(methyl methacrylate) chains end-capped by cyclic anhydride. The method is based on the chemical derivatization of a precursor tert-butyl diester end-group. Compared to the thermal modification, which was previously used, this method allows intermolecular coupling and polymer degradation to be avoided. But up to now, the final anhydride content remains moderate and has still to be improved. [less ▲]