References of "Koulic, Christian"
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See detailNanostructuring of in situ formed ABC triblock copolymers for rubber toughening of thermoplastics
Koulic, Christian; Jérôme, Robert ULg; Goossens, Johannes G. P.

in Harrats, Charef; Thomas, Sabu; Groeninckx, Gabriel (Eds.) Micro- and Nanostructured Multiphase Polymer Blend Systems: Phase Morphology and Interfaces (2005)

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See detailNanostructured polymeric materials with ultimate mechanical properties through reactive blending
Jérôme, Robert ULg; Koulic, Christian

Poster (2005, May 10)

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See detailFormation of polyamide 12-polyisoprene core-shell particles in polystyrene by reactive blending
Koulic, Christian; François, G.; Jérôme, Robert ULg

in Macromolecules (2004), 37(14), 5317-5322

Polyamide 12 (PA12)-polyisoprene (PIP) particles with a thermoplastic core and a rubbery shell have been prepared in a thermoplastic matrix (PS) by reactive blending. For this purpose, an anhydride-end ... [more ▼]

Polyamide 12 (PA12)-polyisoprene (PIP) particles with a thermoplastic core and a rubbery shell have been prepared in a thermoplastic matrix (PS) by reactive blending. For this purpose, an anhydride-end-capped PS-b-PIP diblock (PS-b-PIP-anh) has been reacted with PA12 chains end-capped (50% of them) by a primary amine and dispersed in PS. A PS-b-PIP-PA12 triblock has been formed at the interface between the PS matrix and the dispersed PA12 microdomains. Thus, the phase morphology consists of PA12 core-PIP shell particles dispersed in PS. The nonreacted PA12 with respect to PS-b-PIP-anh dictates the size of the polyamide (core) domains, and the reactive diblock (mainly the molecular weight of the PIP block) imposes the shell thickness and modulates the core size by its capacity to compatibilize PA12 and the thermoplastic matrix. [less ▲]

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See detailNanostructured polyamide by reactive blending. 1. Effect of the reactive diblock composition
Koulic, Christian; Jérôme, Robert ULg

in Macromolecules (2004), 37(9), 3459-3469

Reactive blending of phthalic anhydride end-capped polystyrene-b-polyisoprene diblock (PS-b-PIP-anh) with 80 wt % of polyamide 12 (PA12) results in the very rapid formation of a PS-b-PIP-b-PA triblock ... [more ▼]

Reactive blending of phthalic anhydride end-capped polystyrene-b-polyisoprene diblock (PS-b-PIP-anh) with 80 wt % of polyamide 12 (PA12) results in the very rapid formation of a PS-b-PIP-b-PA triblock copolymer, which self-assembles with formation of characteristic nanoobjects, within the polyamide matrix. For instance, a vesicular nanostructure is formed in the particular case of a symmetric, lamellar-forming diblock copolymer. This morphology actually complies with the lower curvature possible for ABC lamellae diluted in a continuous C phase under shear. In contrast, when the diblock composition is typically asymmetric (at constant molecular weight), vesicles disappear in favor of a core-shell morphology with a cucumber-like suborganization. This spontaneous nanostructuration of the PA12 matrix is quite general. Indeed substitution of an amorphous primary amine end-capped styrene/acrylonitrile random copolymer (SAN-NH2) for PA12 results in exactly the same phase morphology upon reactive blending with PS-b-PIP-anh. [less ▲]

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See detailNanostructured PMMA: from lamellar sheets to double-layered vesicles
Koulic, Christian; Jérôme, Robert ULg

in Macromolecules (2004), 37(3), 888-893

PMMA was nanostructured by similar to100 nm liposome-like vesicular objects by melt blending with 20 wt % of a symmetric poly(styrene)-b-poly(isoprene)-b-poly(methyl methacrylate) (PS-b-PIP-b-PMMA ... [more ▼]

PMMA was nanostructured by similar to100 nm liposome-like vesicular objects by melt blending with 20 wt % of a symmetric poly(styrene)-b-poly(isoprene)-b-poly(methyl methacrylate) (PS-b-PIP-b-PMMA) triblock copolymer in the dry-brush regime. Whenever the blend was prepared by casting toluene solution, thus under zero-shear conditions, a continuous network of lamellar copolymer sheets was formed in PMMA, which however underwent a transition to the aforementioned vesicles upon application of large amplitude oscillatory shear. [less ▲]

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See detailNanostructured polyamide by reactive blending. 2. Transition from nanovesicles to cucumber-like core-shell nanoobjects
Koulic, Christian; Jérôme, Robert ULg

in Progress in Colloid and Polymer Science (2004), 129

Polyamide 12 (PA 12) has been nanostructured by reactive blending with 20 wt% of a symmetric anhydride end-capped polystyrene-b-polyisoprene (PS-b-PIP-anh) The liposome-like nanovesicles which are ... [more ▼]

Polyamide 12 (PA 12) has been nanostructured by reactive blending with 20 wt% of a symmetric anhydride end-capped polystyrene-b-polyisoprene (PS-b-PIP-anh) The liposome-like nanovesicles which are originally formed in the polyamide matrix (PA 12) are converted into cucumber-like core-shell nanoobjects upon increasing the volume fraction of PS by addi-j tion of homo PS of a molecular weight lower than the PS block. The key effect of the molecular weight of homoPS with respect to the PS bloc,k has been emphasized. The same nanoobjects can be prepared by direct blending of PA12 with 20 wt% of an asymmetric reactive PS-b-PIP-anh diblock with the same molecular weight and a higher PS content compared to the symmetric diblock. The interesting point is that the thickness of the rubbery envelope of the core-shell nanoobjects changes with the method used for their preparation at constant PA12/ PS/PIP composition, as result of a change in the molecular weight of the shell forming block. [less ▲]

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See detailDependence of the interfacial reaction and morphology development on the functionality of the reactive precursors in reactive blending
Yin, Zhihui; Koulic, Christian; Pagnoulle, Christophe et al

in Macromolecular Symposia (2003), 198

PMMA containing 50 wt% of anthracene-labeled PMMA chains end-capped by a phthalic anhydride group (anth-PMMA-anh) has been melt blended at 180°C with PS containing 33 wt% of chains end-capped by an ... [more ▼]

PMMA containing 50 wt% of anthracene-labeled PMMA chains end-capped by a phthalic anhydride group (anth-PMMA-anh) has been melt blended at 180°C with PS containing 33 wt% of chains end-capped by an aliphatic primary amine (PS-NH2) and PS bearing 3.5 pendant amine groups (as an average) along the chains (PS-co-PSNBH2), respectively. The reactive chains have been synthesized by atom transfer radical polymerization. Conversion of anth-PMMA-anh into PS-b-PMMA and PS-g-PMMA copolymers has been monitored by SEC with a UV detector. The interfacial reaction mainly occurs in the initial melting and softening stage (<1.0 mm), although at a rate which strongly depends on the number of reactive groups attached to PS chains, the higher conversion being observed for the PS-co-PSNH2 containing blends. The phase morphology depends on the architecture of the in-situ formed copolymer Indeed, a coarser phase dispersion is observed in case of the graft copolymer compared to the diblock. [less ▲]

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See detailGrafting of polystyryl anions onto carbon nanotubes
Lou, Xudong; Koulic, Christian; Pagnoulle, Christian et al

Poster (2003, May 16)

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See detailNanostructuration of polyamide-based polymer blends by reactive blending
Koulic, Christian; Pagnoulle, Christian; Jérôme, Robert ULg

Poster (2003, May 16)

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See detailSynthesis of end functional (co)polymers, precursors of triblock copolymers by controlled radical polymerization
Grignard, Bruno ULg; Claes, Michaël; Sciannamea, Valérie et al

Poster (2003, May 16)

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See detailProbing of the reaction progress at a PMMA/PS interface by using anthracene-labeled reactive PS chains
Yin, Zhihui; Koulic, Christian; Pagnoulle, Christophe et al

in Langmuir (2003), 19(2), 453-457

The progress of the interfacial reaction of polystyrene chains end-capped by a primary amine (PS-NH2) and PMMA chains end-capped by an anhydride (PMMA-anh) has been monitored by SEC-UV, by using ... [more ▼]

The progress of the interfacial reaction of polystyrene chains end-capped by a primary amine (PS-NH2) and PMMA chains end-capped by an anhydride (PMMA-anh) has been monitored by SEC-UV, by using anthracene-labeled polystyrene chains (anth-PS-NH2) as a probe. Assemblies of an anth-PS-NH2 layer and a PMMA-anh layer were annealed at 200 degreesC for various periods of time. The interfacial reaction rate depends on the molecular weight (MW) of the reactive precursors in relation to the gammaN value of the chains. For chains of low gammaN (chiN = 6), the reaction is faster because the interface becomes more diffuse with time, as observed by TEM and AFM, consistent with compatibilization of the weakly immiscible polymers by the copolymer formed in-situ. For chains of higher molecular weight and chiN (10, instead of 6), the interface is much sharper and the residence time at the interface of the symmetric diblock copolymer of higher molecular weight is also increased, which dramatically restricts the progress of the interfacial reaction under the annealing conditions used in this work. [less ▲]

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See detailEffect of molecular weight of the reactive precursors in melt reactive blending
Yin, Zhihui; Koulic, Christian; Jeon, H. K. et al

in Macromolecules (2002), 35(24), 8917-8919

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See detailControlled synthesis of anthracene-labeled omega-amine polystyrene to be used as a probe for interfacial reaction with mutually reactive PMMA
Yin, Zhihui; Koulic, Christian; Pagnoulle, Christophe et al

in Macromolecular Chemistry and Physics (2002), 203(14), 2021-2028

Anthracene-labeled polystyrene (PS) end-capped by a primary amine has been synthesized by atom transfer radical copolymerization of styrene with 3-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate (m-TMI ... [more ▼]

Anthracene-labeled polystyrene (PS) end-capped by a primary amine has been synthesized by atom transfer radical copolymerization of styrene with 3-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate (m-TMI). The m-TMI co-monomer (5.7 mol-%) does not perturb the control of the radical polymerization of styrene. The pendant isocyanate groups of the copolymer chains of low polydispersity (M-w/M-n = 1.25) and controlled molecular weight (up to 35 000) have been derivatized into anthracene by a reaction with 9-methyl(aminomethyl)anthracene. The anthracene-labeled PS (ca. 2 mol-% label) has been conveniently analyzed by size-exclusion chromatography with a UV detector (SEC-UV). Moreover, the omega-bromide end-group of the copolymer chains has been derivatized into a primary amine, making the labeled PS chains reactive towards non-miscible poly(methyl methacrylate) (PMMA) chains end-capped by an anhydride. The interfacial coupling of the mutually reactive PS and PMMA chains has been studied under static conditions (i.e., at the interface between thin PS and PMMA films) and successfully analyzed by SEC-UV. [less ▲]

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See detailControlled nitroxide-mediated radical polymerization of styrene, styrene/acrylonitrile mixtures, and dienes using a nitrone
Detrembleur, Christophe ULg; Sciannamea, Valérie; Koulic, Christian et al

in Macromolecules (2002), 35(19), 7214-7223

Radical polymerization of styrene and copolymerization of styrene and acrylonitrile (60/40) are controlled when conducted in the presence of N-tert-butyl-alpha-isopropylnitrone, which is easily ... [more ▼]

Radical polymerization of styrene and copolymerization of styrene and acrylonitrile (60/40) are controlled when conducted in the presence of N-tert-butyl-alpha-isopropylnitrone, which is easily synthesized from cheap reagents. However, for the control to be effective, the nitrone has to be prereacted with the radical initiator. Nitroxides are then formed "in situ", such that this nitrone system is an attractive alternative for the classical nitroxide-mediated polymerization (NMP), which may require a multistep synthesis of nitroxides or alkoxyamines. The choice of the radical initiator is important because it dictates the structure of the nitroxide and thus its capacity to control the radical polymerization. Well-defined poly(styrene)-b-poly(styrene-co-acrylonitrile), poly(styrene)-b-poly(n-butyl acrylate), and poly(styrene)-b-poly(isoprene) copolymers have been successfully synthesized by this process. [less ▲]

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See detailVesicular nanostructures prepared by reactive melt blending
Koulic, Christian; Yin, Zhihui; Pagnoulle, Christophe et al

in Angewandte Chemie (International ed. in English) (2002), 41(12), 2154-2156

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See detailReactive blending of functional PS and PMMA: interfacial behavior of in situ formed graft copolymers
Yin, Zhihui; Koulic, Christian; Pagnoulle, Christophe et al

in Macromolecules (2001), 34(15), 5132-5139

ω-Isocyanate PMMA, α-anhydride PMMA, and PS-co-PSNH2 have been prepared by atom transfer radical polymerization (ATRP) with controlled molecular weights (104 and 3.5 × 104) and low polydispersity (1.2 ... [more ▼]

ω-Isocyanate PMMA, α-anhydride PMMA, and PS-co-PSNH2 have been prepared by atom transfer radical polymerization (ATRP) with controlled molecular weights (104 and 3.5 × 104) and low polydispersity (1.2). They have been used as precursors of PS-g-PMMA copolymers and let to react in the melt (170 °C, for 10 min) under moderate shear rate. The well-controlled molecular characteristics of these precursors are a substantial advantage to study the effect of the kinetics of the interfacial reaction on the phase morphology. When the grafting reaction is fast (NH2/anhydride pair) and low molecular weight chains are used, the interfacial reaction is quasi-complete and a nanophase morphology is observed, whereas limited reaction and formation of microphases are observed in all the other cases. A high reaction yield requires not only that the functional groups are highly mutually reactive but also that the interface is anytime made available to the functional polymers for the reaction to progress. Then, a nanophase morphology may be observed, which is that of the copolymer formed by the interfacial reaction. A low reaction yield is dictated by either a slow interfacial reaction or a slow diffusion of the copolymer away from the interface. In the latter case, the phases formed by the unreacted precursors are stabilized by the copolymer which resides at the interface. [less ▲]

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See detailPremade versus in situ formed compatibilizer at the PS/PMMA interface: contribution of the Raman confocal microscopy to the fracture analysis
Koulic, Christian; Yin, Zhihui; Pagnoulle, Christophe et al

in Polymer (2001), 42(7), 2947-2957

The interface of a two-layer assembly of polystyrene (PS) and poly(methyl methacrylate) (PMMA) was modified by an intermediate layer of either a premade poly(styrene-g-methyl methacrylate) copolymer (P(S ... [more ▼]

The interface of a two-layer assembly of polystyrene (PS) and poly(methyl methacrylate) (PMMA) was modified by an intermediate layer of either a premade poly(styrene-g-methyl methacrylate) copolymer (P(S-g-MMA)) or a preblend of mutually reactive PS and PMMA synthesized by atom transfer radical polymerization (ATRP). No significant difference was found in the interfacial fracture toughness measured by the double cantilever beam test, although the morphology of the interfacial region was not the same when observed by transmission electron microscopy. The premade copolymer formed a distinct interphase, in contrast to the sharp interface that was observed in the case of the reactive system. The analysis of the fracture surfaces by Raman confocal microscopy showed that the fracture occurred alternatively in the PS phase and either at the PS/copolymer interface for the non reactive system or at the PS/PMMA interface for the reactive one. [less ▲]

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