References of "Lecomte, Philippe"
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See detailCyclic esterketone compounds, processes for the synthesis thereof and process for the preparation of poly(esterketone)polymers
Wautier, Henri; Latere, Jean-Pierre; Lecomte, Philippe ULg et al

Patent (2000)

Unsubstituted oxepane-diones useful as monomers for the production of polymers, process for the synthesis thereof by oxidation of unsubstituted cyclohexanediones, process for the preparation of ... [more ▼]

Unsubstituted oxepane-diones useful as monomers for the production of polymers, process for the synthesis thereof by oxidation of unsubstituted cyclohexanediones, process for the preparation of polyesterketone polymers by polymerisation of cyclic esterketones and polyesterketone polymers so obtained. [less ▲]

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See detailNew Functional Aliphatic Polyesters by Chemical Modification of Copolymers of ε-Caprolactone with γ-(2-Bromo-2-methylpropionate)- ε-caprolactone, γ-Bromo- ε-caprolactone, and a Mixture of β-and γ-Ene- ε-caprolactone
Detrembleur, Christophe ULg; Mazza, Michaël; Lou, Xudong et al

in Macromolecules (2000), 33(17), 7751-7760

New functional aliphatic polyesters were prepared by chemical modification of brominated copolyesters. Poly(epsilon-caprolactone)-co-poly(gamma-(2-bromo-2-methylpropionate)-epsilon-caprolactone) copolymer ... [more ▼]

New functional aliphatic polyesters were prepared by chemical modification of brominated copolyesters. Poly(epsilon-caprolactone)-co-poly(gamma-(2-bromo-2-methylpropionate)-epsilon-caprolactone) copolymer was prepared and successfully converted into copolyester bearing methacrylate double bonds by dehydrohalogenation of the pendant tertiary alkyl bromides, thus leading to cross-linkable polyester. The tertiary alkyl bromide groups of the original copolyester were also quaternized by reaction with pyridine, although some side reactions occurred which Limited the reaction yield. Nevertheless, quaternization of the bromide groups of the poly(epsilon-caprolactone)-co-poly(gamma-bromo-epsilon-caprolactone) copolymer proved to be quantitative and to occur without degradation of the polyester chains. This general strategy paves the way to either amphiphilic copolyesters or water-soluble polyesters. The poly(epsilon -caprolactone)-co-poly(gamma -bromo-epsilon-caprolactone) lactone) copolymer was also quantitatively converted into unsaturated copolyester by dehydrohalogenation with formation of double bonds including acrylic-type double bonds. As an alternative, gamma-bromo-epsilon-caprolactone was first dehydrohalogenated, and the unsaturated cyclic monomer was copolymerized with epsilon-caprolactone. Finally, the nonconjugated double bonds of the copolyesters were oxidized into epoxides, except for the acrylic-type unsaturations which remained unchanged. [less ▲]

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See detailSynthesis of new hydrophilic γ-substituted poly-ε-caprolactones
Lecomte, Philippe ULg; D'aloia, Violetta; Mazza, Michaël et al

Conference (2000, August 20)

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See detailFirst example of an unsymmetrical difunctional monomer polymerizable by two living/controlled methods
Mecerreyes, David; Humes, J.; Miller, R. D. et al

in Macromolecular Rapid Communications (2000), 21(11), 779-784

In this paper the synthesis and (co)polymerizations of 4-(acryloyloxy)-epsilon-caprolactone are reported. This new monomer can be polymerized in a living/controlled way by two different polymerization ... [more ▼]

In this paper the synthesis and (co)polymerizations of 4-(acryloyloxy)-epsilon-caprolactone are reported. This new monomer can be polymerized in a living/controlled way by two different polymerization mechanisms: atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP). ATRP, which was carried out at 90 degrees C using NiBr2(PPh3)(2), leads to new polyacrylates containing pendant caprolactone functionalities with controlled molecular weights and narrow polydispersities (M-w/M(p)similar to 1.1). Alternatively, ROP of this functional epsilon-caprolactone bearing a pendant acrylate functionality leads to new poly(4-(acryloyloxy) caprolactone) as well as random copolymers when epsilon-caprolactone and L,L-lactide are added as comonomers. The (co)polymerizations were carried out using either (Al((OPr)-Pr-i)(3) in toluene at 25 degrees C or Sn(Oct)(2) as a catalyst at 110 degrees C producing (co)polymers with controlled molecular weights and narrow polydispersities (M-w/M(n)similar to 1.2). As a potential application, the introduction of acrylate pendant groups into the polyesters facilitated the preparation of cross-linked biodegradable materials either thermally or by irradiation with ultraviolet light radical curing. [less ▲]

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See detailγ-bromo-ε-caprolactone, a versatile lactone for the synthesis of new functional aliphatic polyesters
D'Aloia, Violetta; Gautier, Sandrine; Halleux, Olivier et al

Poster (2000, May 02)

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See detailRing opening copolymerization of ε-caprolactone, γ-(triethylsilyloxy)-ε-caprolactone and γ-ethylene ketal-ε-caprolactonelactone: a route to hetero-graft copolyesters
Stassin, Fabrice; Halleux, Olivier; Dubois, Philippe ULg et al

in Macromolecular Symposia (2000), 153

ε-Caprolactone (ε-CL) has been copolymerized with two precursors of γ-hydroxy-ε-CL, i.e., γ-ethylene ketal-ε-caprolactone (TOSUO) and γ-(triethylsilyloxy)-ε-caprolactone (TeSCL). The triethylsilyloxy ... [more ▼]

ε-Caprolactone (ε-CL) has been copolymerized with two precursors of γ-hydroxy-ε-CL, i.e., γ-ethylene ketal-ε-caprolactone (TOSUO) and γ-(triethylsilyloxy)-ε-caprolactone (TeSCL). The triethylsilyloxy pendant groups can be selectively deprotected into hydroxyl groups followed by the deprotection of the acetal substituents. Each series of hydroxyl groups can be used to initiate the polymerization of cyclic monomers so leading to hetero-graft copolyesters with, for instance, poly-ε-CL and polylactide grafts. [less ▲]

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See detailRing-Opening Polymerization of γ-bromo-ε-caprolactone : A novel route to functionalized aliphatic polyesters
Detrembleur, Christophe ULg; Mazza, Michaël; Halleux, Olivier et al

in Macromolecules (2000), 33(1), 14-18

The synthesis, characterization, and polymerization of a new cyclic ester, gamma-bromo-epsilon-caprolactone (gamma-BrCL), are reported. The ring-opening polymerization (ROP) of this new monomer initiated ... [more ▼]

The synthesis, characterization, and polymerization of a new cyclic ester, gamma-bromo-epsilon-caprolactone (gamma-BrCL), are reported. The ring-opening polymerization (ROP) of this new monomer initiated from Al((OPr)-Pr-i)(3) as initiator in toluene at 0 degrees C was found to be living and proceeds by a coordination-insertion mechanism. Random and block copolymerizations of this gamma-BrCL with epsilon-caprolactone (epsilon-CL) were also found to be living as evidenced by the experimental molecular weight which is consistent with that expected from the monomer to initiator molar ratio, the narrow polydispersity, and the good agreement between the comonomers molar fraction in the comonomer feed and the copolymer. The thermal transitions (Tg and Tm) in the epsilon-CL/gamma-Br-CL random copolymers depend strongly on the gamma-BrCL content. Increasing the gamma BrCL content in the copolymer [F(BrCL)] increased the Tg of the copolymer from -61 degrees C for poly(epsilon-caprolactone) to -16.5 degrees C for the poly( gamma-BrCL) homopolymer but decreased the Tm of the PCL to contents of similar to 30 mol % of gamma BrCL [F(BrCL) =0.3]Beyond this value, the copolymers were found to be amorphous and exist as viscous liquids. [less ▲]

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See detailSynthesis of new hydrophilic γ-substituted poly(ε-caprolactone)s
Lecomte, Philippe ULg; D'aloia, Violetta; Mazza, Michaël et al

in Polymer Preprints (2000), 41(2), 1534-1535

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See detailNovel functionalization routes of poly(ε-caprolactone)
Lecomte, Philippe ULg; Detrembleur, Christophe ULg; Lou, Xudong et al

in Macromolecular Symposia (2000), 157

The aluminum alkoxide mediated ring opening polymerization of functional lactones, such as γ-ethylene ketal-ε-caprolactone (TOSUO), γ-(triethylsilyloxy)-ε-caprolactone (SCL) and γ-bromo-ε-caprolactone ... [more ▼]

The aluminum alkoxide mediated ring opening polymerization of functional lactones, such as γ-ethylene ketal-ε-caprolactone (TOSUO), γ-(triethylsilyloxy)-ε-caprolactone (SCL) and γ-bromo-ε-caprolactone (γBrCL), is a versatile route to polyesters containing ketal, ketone, alcohol and bromide groups. As result of living polyaddition mechanism, random and block copolymerization of εCL and γBrCL has been successfully carried out. The reactivity ratios are quite similar (1.08 for ε-CL, and 1.12 for γBrCL). These random copolymers are semicrystalline when they contain less than 30 mol% of γBrCL, otherwise they are amorphous. No transesterification reaction occurs during the sequential polymerization of ε-CL and γBrCL leading to block copolymers. Reaction of poly(εCL-co-γBrCL) with pyridine provides quantitatively a polycationic polyester. Furthermore, the reaction of this random copolymer with l,8-diazabicyclo[5.4.0] undec-7-ene (DBU) is a route to unsaturated polyesters, whose the non conjugated double bonds can be quantitatively converted into epoxides by reaction with m-chloroperbenzoic acid (mCPBA). No chain degradation is detected during these derivatization reactions of poly (εCL-co-γBrCL). [less ▲]

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See detailRing-opening metathesis polymerization of new alpha-norbornenyl poly(epsilon-caprolactone) macromonomers
Mecerreyes, David; Dahan, Dahan; Lecomte, Philippe ULg et al

in Journal of Polymer Science. Part A, Polymer Chemistry (1999), 37(14), 2447-2455

Poly(epsilon-caprolactone) (PCL) macromonomers capped by a polymerizable norbornene end-group have been synthesized and (co)polymerized by ring-opening metathesis with formation of graft copolymers and ... [more ▼]

Poly(epsilon-caprolactone) (PCL) macromonomers capped by a polymerizable norbornene end-group have been synthesized and (co)polymerized by ring-opening metathesis with formation of graft copolymers and polymacromonomers. -Norbornenyl PCL macromonomers have been synthesized by ring opening polymerization (ROP) of epsilon-caprolactone (CL) initiated by 2-diethylaluminoxymethyl-5-norbornene. Copolymerization of these PCL macromonomers with norbornene and polymerizable derivatives has been catalyzed by the [RuCl2(p-cymene)]2 PCy3/(trimethylsilyl)diazomethane complex yielding a series of poly(norbornene)-graft-poly(epsilon-caprolactone) copolymers. These new graft copolymers have been characterized by a set of analytical methods, i.e., SEC, 1H-NMR, FTIR, DSC, and TGA. Furthermore, PCL macromonomers have been polymerized into high molecular weight comb chains of narrow molecular weight distribution (Mw/Mn = 1.10) within high yields (90%). [less ▲]

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See detailSynthesis of polynorbornene grafted with poly(ε-caprolactone) by sequential controlled ring opening polymerization
Lecomte, Philippe ULg; Mecerreyes, David; Dubois, Philippe et al

Poster (1999, April 12)

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See detail4-Methoxypyridine N-Oxide: a new regulator for the controlled free radical polymerization of methyl methacrylate
Detrembleur, Christophe ULg; Lecomte, Philippe ULg; Caille, Jean-Raphaël et al

in Macromolecules (1998), 31(20), 7115-7117

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See detailProcess for radical controlled polymerization or copolymerization of (meth)acryl and vinyl monomers and thus prepared (co)polymers
Lecomte, Philippe ULg; Dubois, Philippe; Jérôme, Robert ULg et al

Patent (1998)

This process is characterized by the fact that at least one of the said monomers is polymerized or copolymerized in bulk, solution, emulsion or suspension, at a temperature that can be as low as 0 DEG C ... [more ▼]

This process is characterized by the fact that at least one of the said monomers is polymerized or copolymerized in bulk, solution, emulsion or suspension, at a temperature that can be as low as 0 DEG C., in the presence of an initiation system including: at least one compound generating radicals, other than bromofluorene, and at least one catalyst consisting of a complex of palladium in the 0 oxidation state, denoted by the following formula (I): Pd(0)L1L2L3L4 in which each of L1, L2, L3 and L4, which are identical or different, denotes a ligand which may be a chiral ligand, which is chosen from PRR'R'', P(OR)(OR')(OR''), NRR'R'', ORR', SRR', SeRR', AsRR'R'', SbRR'R'', where each of R, R' and R'' independently denotes a C1-C14 alkyl group, optionally substituted, or an optionally substituted aromatic group, it being possible for at least two of these ligands to be joined to one another by one or more divalent radicals. [less ▲]

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See detailMethod for controlled radical polymerisation
Jérôme, Robert ULg; Creutz, Serge; Dubois, Philippe et al

Patent (1998)

The invention concerns a method for making a polymer or a copolymer by radical polymerisation of at least one unsaturate monomer in the presence of a stabiliser whereby a stabiliser complying with general ... [more ▼]

The invention concerns a method for making a polymer or a copolymer by radical polymerisation of at least one unsaturate monomer in the presence of a stabiliser whereby a stabiliser complying with general formula (I) is used in which the substituents (Z)m, (R)n and Y can have different values. [less ▲]

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See detailMethod of free radical polymerization of copolymerization of (meth)acrylic and vinyl monomers under control and (co)polymer produced thereby
Lecomte, Philippe ULg; Dubois, Philippe; Jérôme, Robert ULg et al

Patent (1998)

PROBLEM TO BE SOLVED: To obtain a (co)polymer excellent in resistance to thermal decomposition by polymerizing or copolymerizing a monomer or monomers in the presence of an initiation system contg. a free ... [more ▼]

PROBLEM TO BE SOLVED: To obtain a (co)polymer excellent in resistance to thermal decomposition by polymerizing or copolymerizing a monomer or monomers in the presence of an initiation system contg. a free-radical generator other than a bromoolefin and a catalyst comprising a Pd complex having an oxidation number of 0 and represented by a specific formula. SOLUTION: A Pd salt (e.g. Pd acetate), a ligand (e.g. triphenylphosphine), and a solvent (e.g. toluene) are charged into a reactor to form a Pd complex having an oxidation number of 0 and represented by the formula: Pd(0)L<1> L<2> L<3> L<4> [wherein L<1> to L<4> are each a ligand such as PRR'R'' (wherein R, R', and R'' are each 1-14C alkyl, etc.)]. Then, a monomer (e.g. methyl methacrylate) is added to the reactor followed by the addition of a free-radical generator (e.g. CCl4 ) in a molar ratio of Pd to the generator of 0.01-100.; The contents in the reactor are heated to 40-90 deg.C and stirred for a certain time to conduct the polymn. The reaction mixture is diluted with toluene, etc., filtered, and condensed under a reduced pressure. The resultant polymer soln. is poured into methanol, etc., and the resultant precipitate is filtered, washed, and dried to give a polymer having a number average mol.wt. of 400-10,000,000g/mol and a polydispersity lower than 2. [less ▲]

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See detailMethod for controlled radical polymerization
Jérôme, Robert ULg; Creutz, Serge; Dubois, Philippe et al

Patent (1998)

The invention concerns a method for making a polymer or a copolymer by radical polymerisation of at least one unsaturate monomer in the presence of a stabiliser whereby a stabiliser complying with general ... [more ▼]

The invention concerns a method for making a polymer or a copolymer by radical polymerisation of at least one unsaturate monomer in the presence of a stabiliser whereby a stabiliser complying with general formula (I) is used in which the substituents (Z)m, (R)n and Y can have different values. [less ▲]

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See detailProcess for radical controlled polymerization or copolymerization of (meth)acryl and vinyl monomers and thus prepared (co)polymers
Lecomte, Philippe ULg; Dubois, Philippe; Jérôme, Robert ULg et al

Patent (1998)

A process for a radical-controlled polymerisation or co-polymerisation of (meth)acrylic and/or vinylic monomers is effected en masse, solution, emulsion or suspension at a temperature which may be as low ... [more ▼]

A process for a radical-controlled polymerisation or co-polymerisation of (meth)acrylic and/or vinylic monomers is effected en masse, solution, emulsion or suspension at a temperature which may be as low as 0 degrees C, in the presence of a system comprising (i) a radical generator compound other than bromofluorene; and (ii) a catalyst consisting of a Pd complex of degree of oxidation zero, corresponding to formula Pd(0)L<1>L<2>L<3>L<4> (I), where L<1>-L<4> = ligand (possibly chiral) chosen from PRR<1>R<2>, P(OR)(OR<1>)(OR<2>), NRR<1>R<2>, ORR<1>, SRR<1>, SeRR<1>, AsRR<1>R<2> and SbRR<1>R<2>; and R, R<1>, R<2> = 1-14C alkyl (optionally substituted) or aromatic (optionally substituted), at least two of the ligands being capable of interconnecting with one or more bivalent radicals. [less ▲]

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See detailProcess for radical controlled polymerization or copolymerization of (meth)acryl and vinyl monomers and thus prepared (co)polymers
Lecomte, Philippe ULg; Dubois, Philippe; Jérôme, Robert ULg

Patent (1998)

A process for a radical-controlled polymerisation or co-polymerisation of (meth)acrylic and/or vinylic monomers is effected en masse, solution, emulsion or suspension at a temperature which may be as low ... [more ▼]

A process for a radical-controlled polymerisation or co-polymerisation of (meth)acrylic and/or vinylic monomers is effected en masse, solution, emulsion or suspension at a temperature which may be as low as 0 degrees C, in the presence of a system comprising (i) a radical generator compound other than bromofluorene; and (ii) a catalyst consisting of a Pd complex of degree of oxidation zero, corresponding to formula Pd(0)L<1>L<2>L<3>L<4> (I), where L<1>-L<4> = ligand (possibly chiral) chosen from PRR<1>R<2>, P(OR)(OR<1>)(OR<2>), NRR<1>R<2>, ORR<1>, SRR<1>, SeRR<1>, AsRR<1>R<2> and SbRR<1>R<2>; and R, R<1>, R<2> = 1-14C alkyl (optionally substituted) or aromatic (optionally substituted), at least two of the ligands being capable of interconnecting with one or more bivalent radicals. [less ▲]

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