Thierry Hamaide

Claude Bernard University Lyon 1 | UCBL · Faculté des sciences et technologies

Les macromolécules constituant les polymères sont souvent décrites en termes d'unités de répétition issues des monomères mis en oeuvre. Cette description basique est très rapidement mise en défaut dans le cas de nombreux copolymères. Il est donc naturel pour le chimiste de raisonner en termes d'unités monomère et non pas en unités de répétition, qu...

Various pullulan-b-Jeffamine block copolymers (Jeffamine is a PEO-b-PPO copolymer (PEO = poly(ethylene oxide), PPO = poly(propylene oxide)) are used as surfactants for vinyl acetate miniemulsion polymerization. Their influence on the kinetics, average molecular weights and colloidal stability, is compared with that of Pluronic F68, when using eithe...

Dédié aux grandes méthodes de synthèse de la chimie de polymérisation (polymérisation en chaîne, polymérisation par étape, modifications chimiques), Chimie des polymères – Exercices et problèmes corrigés est un recueil d’exercices et de problèmes systématiquement résolus, dont l’objectif est d’aider le lecteur à lever les points de blocage qui le g...

Ce livre est le fruit de la réflexion d’un certain nombre de scientifiques qui s’intéressent directement aux relations parfois conflictuelles qui se sont progressivement instaurées entre le monde industriel et la recherche académique d'une part, le grand public et les défenseurs du cadre de vie et de l’environnement d'autre part. Sous la forme d'ar...

New amphiphilic starch-polyester graft copolymer and chemically modified starch with fatty acid chains were synthesized and then cross-linked with a nontoxic agent, citric acid, in order to obtain hydrogels with a controlled hydrophilicity. They present well-defined pores, a controlled water retention degree and different time ranges for releasing...

This paper deals with the monitoring of the methyl methacrylate (MMA) droplet interface during its polymerization in one single monomer droplet by using a drop tensiometer. The droplet is stabilized by various molecular and polymer surfactants, in particular Pluronic® F68 and pullulan-block-Jeffamine®. The polymerization in one single droplet of th...

As anyone who has taught polymer chemistry to undergraduate students might already appreciate, we are faced with inherent difficulties in clearly communicating the subject matter due its interdisciplinary character. This paper is thus aimed at proposing a new educational plan to teach this fundamental course in order to overcome some inherent obsta...

Hydrogels have attracted great attention over the past decades, since they can be used for a variety of applications, including drug delivery systems and scaffolds for tissue engineering and repair. "Click chemistry", in particular copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC), has been widely used in the preparation of complex architectu...

Multifunctional hybrid silica nanoparticles with a fluorescent core and tunable organic or polymeric shell can easily be prepared by a sol-gel process followed by 1,3 dipolar cycloaddition (CuAAC) in the same reverse quaternary W/O microemulsion. Compared to a classical multistep process, this one-pot synthesis reduces greatly the number of purific...

Simple static mixers have been used as homogenization devices to perform polymerizable miniemulsion dispersions with negligible heat generation from mixtures containing vinyl acetate as the monomer and high amounts of biocompatible viscous oils (Miglyol and vitamin E acetate) as the hydrophobic components. A triblock nonionic copolymer was used as...

Novel thermoresponsive biohybrid guar-based grafted copolymers were prepared in aqueous medium by copper catalyzed 1,3-dipolar Huisgen cycloaddition between an alpha-butoxy-omega-azido-PEO-co-PPO derivative, characterized by LCST behavior, and guar gum bearing alkyne functionalities randomly distributed along the chain. The chemical pathway gives w...

Thermosensitive guar-based hydrogels are obtained in water solutions by copper-catalyzed 1,3-dipolar cycloaddition between alkyne-functionalized guars and α,ω-diazidopoly[(ethylene glycol)-co-(propylene glycol)]. Characterization by TGA, HR-MAS 1H NMR, and rheology have shown that hydrogels with tunable physico-chemical properties, such as crosslin...

Glycopolymers with mannose units were readily prepared by click chemistry of an azido mannopyranoside derivative and a poly(propargyl acrylate-co- N -vinyl pyrrolidone). These glycopolymers were used as polymer surfactants, in order to obtain glycosylated polycaprolactone nanoparticles. Optimum stabilization for long time storage was achieved by us...

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Generally, surfactants are used as stabilizers of interfaces or particles and their applications are very wide, from foams or adhesion modifiers to the orientation of chemical reactions. Siloxane surfactants are known for their ability to decrease the surface tension of liquids in such extent that is comparable only with some fluorinated compounds,...

Cellulose composites with maleic anhydride - dicyclopentadiene copolymer matrix were obtained by "in situ" free-radical polymerization. The syntheses were carried out in two different solvents: toluene and dioxane, aiming at determining their influence upon both the polymerization process and properties of the resulting materials. The composite mat...

Two complementary tandem strategies based on the one-pot combination of click chemistry and atom transfer radical polymerization (ATRP) are studied. Ini-tially, functionalized random copolymers are obtained by copolymerization of methyl methacrylate and propargyl methacrylate simultaneously to the click chemistry cou-pling of a monofunctional azide...

New amphiphilic polysaccharides based on alginate-grafted-Poly (ε-caprolactone) or alg-g-PCL bearing two kinds of PCL chains with different molar masses (1250 and 530 gmol−1) with various amounts from 3% to 15% were prepared. Rheological properties in aqueous solutions of such systems have been investigated as a function of polymer concentration, a...

The unique properties of polysiloxanes recommend them for medical and personal care applications, but their liquid state at room temperature is a drawback for their use as nanoparticles in aqueous formulations. We present our first results concerning the feasibility of cross-linking reactions involving HO- terminated polydimethylsiloxane (PDMS) cha...

Drug conjugation with polymers is a very well known method for obtaining drug delivery systems. In this work, we synthesized chemically bounded conjugates, based on natural and synthetic polysaccharides (starch and 2-hydroxyethylcellulose) and two aminoacid derivatives (m-N-nitrobenzoyl asparagine and N-acetyl methionine). The variable reaction par...

RAFT polymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA, 1100 g mol À1) was first performed using cyanoisopropyl dithiobenzoate (CPDB). The control of PEGMA homopolymerization, carried out in THF ([PEGMA] ¼ 40 wt %) at 65 C (reflux) using 2,2 0 -Azobis(isobutyronitrile) (AIBN) as initiator, was shown by the linear increase of...

Siloxane-containing surfactants have been tested as stabilizers for the preparation of polymer nanoparticles by three types of chemical reactions. Two crosslinking reactions were used to obtain silicone elastomers particles: one involved HO-terminated polydimethylsiloxane and tetraethoxysilane, while the other one was a crosslinking via polyhydrosi...

New water soluble and amphiphilic PCL-grafted-alginates with two different molar masses of PCL (530 and 1250 g mol−1) and molar hydrophobe contents from 3.5 to 15% have been prepared by new aqueous micellar grafting technique. Physico-chemical behaviour in aqueous solution (pure water and NaCl 0.1 M) has been studied by means of viscosity measureme...

Water-in-oil emulsions having their aqueous internal phase gelled with starch were prepared and investigated. They were the primary emulsions required for the preparation of double w/o/w emulsions that could encapsulate hydrophilic materials inside the internal aqueous gel. The emulsification could be achieved at high temperature in spite of the hi...

Graft and crosslinked polydimethylsiloxane (PDMS)-chitosan copolymers were prepared through the reaction between mono and difunctional glycidoxypropyl-terminated PDMSs and chitosan. The transformation of amino groups of chitosan through the reaction with epoxy groups was confirmed by FT-IR and 13C cross-polarization (CP) magic-angle spinning (MAS)-...

8‐Amino‐3,6‐dioxaoctyl α ‐ D ‐mannopyranoside and 8‐amino‐3,6‐dioxaoctyl β ‐ D ‐galactopyranoside were prepared for coupling with a copolymer made from PCL macromonomers and MA. The new glycosyl compounds as well as PCL macromonomers were synthesized by appropriate techniques and fully characterized. The grafting of the latter with the functionaliz...

A novel step growth polymerization A-B strategy based on the click chemistry polyaddition of tailor-made alpha-azide-omega-alkyne low molar mass monomers was developed, leading to polytriazole (co)polymers with tunable structures and properties.

New glycopolysiloxanes were synthesized from cellobiose and commercially available reactive silicone oils or MD′M precursors. Their synthesis is based on the hydrosilylation of allyl‐functionalized cellobiose onto the reactive silicone oil, after protection of the hydroxyl functions. The subsequent deprotection step leads to a redistribution of the...

Oligomers and polymers containing triazole units were synthesized by the copper(I)-catalyzed 1,3-dipolar cycloaddition step-growth polymerization of four difunctional azides and alkynes. In a first part, monofunctional benzyl azide was used as a chain terminator for the polyaddition of 1,6-diazidohexane and α,ω-bis(O-propargyl)diethylene glycol, le...

Block copolymers poly(caprolactone)-block-poly(ethylene oxide) are promising non-ionic macromolecular surfactants for the stabilization of emulsions because they display a stronger adsorption and provide an increased long-term stability. But such amphiphilic copolymers should also allow the fabrication of the suspensions according to the emulsifica...

Well‐defined glyco‐polyorganosiloxanes were synthesized by the Cu( I )‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction (often simply referred to as “click” chemistry). N ‐propargylglycosylamines 2 and 4 were first synthesized from cellobiose ( 1 ) and xylogluco‐oligosaccharide XGOs 3 without protecting groups. The azide function was introduced...

Cellulose-containing composites based on copolymers of acrylic acid with styrene, 4-chloro-methyl-styrene and maleic anhydride were prepared for proton conducting membranes. The influence of the substrate on the copolymer composition as well as the copolymer/cellulose ratio on the basic properties of composite materials is discussed using the FT-IR...

N-Vinyl-2-pyrrolidone (NVP) and maleic anhydride (MA) copolymers were synthesized via radical polymerization. The synthesized copolymers were grafted with methoxypolyethylene glycol (MPEG) chains of different average molecular weights (350, 550, 750 Da). The grafted copolymers were used as surfactants in the synthesis of poly(ε-caprolactone) (PCL)...

In this study we show that mechanical properties of bioceramic scaffolds can be significantly improved by repeated infiltration with a low-viscosity polycaprolactone solution. Biphasic calcium phosphate (BCP: 70% hydroxyapatite, 30% β-tricalcium phosphate) scaffolds characterized by a bimodal pore size distribution and a global porosity of 70% have...

In this work, polycaprolactone-coated alumina scaffolds were produced and characterized to validate the concept of polymer–ceramic composites with increased fracture resistance. Alumina scaffolds were sintered using a foam replication technique. An open-porous structure was achieved with ∼70% porosity and 150 μm mean pore size. The polymer coating...

N-Vinyl-2-pyrrolidone (NVP) and itaconic anhydride (IA) copolymers were synthesized via radical polymerization. The synthesized copolymers were grafted with MPEG chains of different average molecular weights (350, 550, 750Da). The grafted copolymers were used as surfactants in the synthesis of poly(ε-caprolactone) (PCL) nanoparticles in water by so...

Various PEG-b-PCL block copolymers have been synthesized from anionic polymerization of e -caprolactone by using MPEG based aluminium alcoolate as initiator and MPEG as transfer agent. These copolymers have been characterised by NMR and mass spectroscopy. The chain lengths were in the range 8 - 113 for PEG and in the range 5-40 for PCL. They have b...

Polymeric nanoparticles are widely used as drug carriers in order to achieve the targeting of drug to the ill tissue. N-vinyl-2-pyrrolidone and itaconic anhydride were copolymerized and the alternating copolymer was then grafted with PEG of different molecular weight, to form amphiphilic copolymers. The grafted copolymers have been used to prepare...

Carbohydrate-modified cyclosiloxanes were synthesized by hydrosilylation reactions of protected allyl-monosaccharides and subsequent deprotection with a gel-type ion exchanger. They were characterized by 1H and 13C-NMR, FT-IR, GPC and surface tension measurements. These compounds, as well as other water soluble, carboxylate-based siloxanes were tes...

RESUME Des nanoparticules de poly(acétate de vinyle) renfermant une teneur élevée en agent hydrophobe d'intérêt pharmaceutique (Miglyol, acétate de vitamine E) ont été obtenues par polymérisation en miniémulsion. Afin d'obtenir un système totalement non ionique, ces particules ont été stabilisées par un polymère tensioactif non ionique et un amorce...

Oligocaprolactone macromonomers functionalized with vinyl ether have been synthesized by polymerization of ε-caprolactone in the presence of hydroxy ethyl or butyl vinyl ether and characterised by NMR and Maldi time-of-flight mass spectroscopy. These macromonomers have been copolymerized with maleic anhydride and N-vinyl pyrrolidone to give terpoly...

Encapsulation of hydrophobic compounds in non ionic nanoparticles can easily be performed directly by miniemulsion polymerization of vinyl acetate or styrene with Pluronic F68 as nonionic surfactant and AIBN as initiator. Triglycerides from fatty acid (Miglyol(R) or mixture of benzyl benzoate and oligocaprolactones have been used as the hydrophobe...

Monosaccharide functionalized polysiloxanes bearing either terminal or pendant mannose moieties have been obtained starting from the allyloxyethyl glycoside and appropriate H-containing siloxane compounds, via hydrosilylation reactions. The starting modified monosaccharide was reacted as trimethylsilyl protected derivative and a convenient method f...

The composition of the copolymers of 1,3-dioxolane with 1,3-dioxepane was investigated using FT-IR and DSC. The first method produce accurate values for the overall composition, the later allows discriminating between the copolymer and the mixture of homopolymers.

Grafting active centres on a solid porous support and using alcohol molecules as a transfer agent permitted coordinated anionic ring opening polymerization of oxygenated heterocycles by a continuous process. Dehydrated porous silica or alumina have been employed as solid supports. After grafting aluminium alkoxides on these supports, ε-caprolactone...