Search results for "Atom-transfer radical-polymerization"

Multi-Arm Star Polyglycerol-block-poly(tert-butyl acrylate) and the Respective Multi-Arm Poly(acrylic acid) Stars

2006

Well-defined multi-arm star block copolymers, polyglycerol-block-poly(tert-butyl acrylate) (PG-b-PtBA), with average arm-numbers of 17, 27, 36, 66 and 90 arms, respectively, have been prepared by atom transfer radical polymerization (ATRP) of tBA in acetone, using a core-first strategy. After hydrolysis with excess concentrated HCl in refluxing dioxane, full hydrolysis of the tert-butyl ester groups was achieved, resulting in multi-arm star polyelectrolytes, polyglycerol-block-poly(acrylic acid) (PG-b-PAA). The hyperbranched macroinitiators employed were prepared on the basis of hyperbranched polyglycerols via esterification with 2-bromoisobutyryl bromide. Both CuBr/PMDETA and CuBr/Me 6 TRE…

The Radical Trap in Atom Transfer Radical Polymerization Need Not Be Thermodynamically Stable. A Study of the MoX3(PMe3)3 Catalysts

2005

The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order ClBrI) for the one-electron oxidation wave. Addition of X(-) changes the voltammogram, indicating the formation of MoX(4)(PMe(3))(3) f…

New Self-Assembling Polyaspartamide-Based Brush Copolymers Obtained by Atom Transfer Radical Polymerization

2009

A simple and efficient method for the synthesis of polyaspartamide-based brush copolymers using Atom Transfer Radical Polymerization (ATRP) is here presented. The syntheses were performed by using two subsequent steps. In the first step the macroinitiator was obtained by the conjugation of a proper number of 2-bromoisobutyryl bromide (BIB) residues to the R, -poly(N-2-hydroxyethyl)-D,L-aspartamide (PHEA) side chains, obtaining the PHEA-BIB copolymer. PHEA-BIB copolymer was used as “multi-functional macroinitiator” for the polymerization via ATRP of hydrophilic methacrylic monomers, such as methacrylic acid (MA), obtaining PHEA-IB-poly(MA) copolymer, sodium methacrylate (MANa+), obtaining PH…

Synthesis and characterization of novel organic–inorganic hybrid block copolymers

2004

Novel organic–inorganic hybrid block copolymers based on poly(methylsilsesquioxanes) (PMSSQs) have been synthesized. Two routes to functionalized PMSSQs are presented and from both atom transfer radical polymerization of methylmethacrylate could be performed. Copolymers with different block ratios have been polymerized and were characterized. In particular, thermal properties were investigated by TGA and the promising thermal decomposition behaviour makes the copolymers potential candidates as pore generators in future nanoporous materials. Additionally, these copolymers were analysed as surface coatings of regular PMMA. Contact angle measurements proved the dramatic effect on the surface p…

Atom Transfer Radical Addition Catalyzed by Ruthenium–Arene Complexes Bearing a Hybrid Phosphine–Diene Ligand

2018

International audience; The synthesis and characterization of a series of arene ruthenium complexes bearing either (3,5-cycloheptadienyl)diphenylphosphine or (cycloheptyl)-diphenylphosphine are reported. Upon irradiation or heating, all these complexes lose their arene ligand but then exhibit a different behavior depending on the nature of the phosphine ligand. (Cycloheptadienyl)phosphine complexes 1 and 3 give a cationic dinuclear Ru complex 5 for which the two Ru atoms are bridged by three chlorido ligands and flanked by two tridendate (cycloheptadienyl)phosphines. (Cycloheptyl)-diphenylphosphine complexes 2 and 4 undergo arene exchange when toluene is used as solvent or degrade in dithlo…

Poly(isoglycerol methacrylate)-b-poly(d or l-lactide) Copolymers: A Novel Hydrophilic Methacrylate as Building Block for Supramolecular Aggregates

2010

On the basis of a new acetal-protected glycerol monomethacrylate monomer (cis-1,3-benzylidene glycerol methacrylate/BGMA) a series of potentially biocompatible and partially biodegradable homo- and block copolymers were synthesized. ATRP polymerization of BGMA yielded well-defined polyacrylates with pendant benzylidene acetal groups and high glass transition temperatures (115−130 °C). This hydrophobic poly(cis-1,3-benzylidene glycerol methacrylate) could be readily transformed into the hydrophilic and water-soluble poly(1,3-dihydroxypropyl methacrylate), referred to as poly(isoglycerol methacrylate) (PIGMA). It exclusively contains primary hydroxyl groups and therefore differs significantly…

A new hyaluronic acid pH sensitive derivative obtained by ATRP for potential oral administration of proteins

2013

Atom transfer radical polymerization (ATRP) has been successfully employed to obtain a new derivative of hyaluronic acid (HA) able to change its solubility as a function of external pH and then to be potentially useful for intestinal release of bioactive molecules, included enzymes and proteins. In particular, a macroinitiator has been prepared by linking 2-bromo-2-methypropionic acid (BMP) to the amino groups of ethylenediamino derivative of tetrabutyl ammonium salt of HA (HA-TBA-EDA). This macroinititor, named HA-TBA-EDA-BMP has been used for the ATRP of sodium methacrylate (MANa) using a complex of Cu(I) and 2,2'-bipyridyl (Byp) as a catalyst. The resulting copolymer, named HA-EDA-BMP-MA…

Nanoparticles with Polymeric Surfaces

2004

Controlled radical polymerization of alkyl acrylates and styrene using a half-sandwich molybdenum(III) complex containing diazadiene ligands

2003

Abstract The half-sandwich molybdenum(III) complex CpMoCl 2 ( i Pr 2 -dad) ( i Pr 2 -dad= i Pr–NCH–CHN– i Pr) proved to be an effective metal catalyst for the controlled radical polymerization of methyl acrylate, butyl acrylate, and styrene. In conjunction with an alkyl iodide [R–I: CH 3 CH(COOEt)I] as an initiator and in the presence or absence of Al(O– i -Pr) 3 as a co-catalyst, the molybdenum-based system gave polymers with narrow molecular weight distributions. The in situ addition of styrene to a macroinitiator of poly(methylacrylate) afforded an AB-type block copolymer.

How the interplay of different control mechanisms affects the initiator efficiency factor in controlled radical polymerization: An investigation usin…

2007

International audience; Compound CpMoI2(iPr2dad) (iPr2dad = iPrNdouble bondCHsingle bondCHdouble bondNiPr), obtained by halide exchange from CpMoCl2(iPr2dad) and NaI, has been isolated and characterized by EPR spectroscopy, cyclic voltammetry, and X-ray crystallography. Its action as a catalyst in atom transfer radical polymerization (ATRP) and as a spin trap in organometallic radical polymerization (OMRP) of styrene and methyl acrylate (MA) monomers has been investigated and compared with that of the dichloro analogue. Compound CpMoCl2(iPr2dad) catalyzes the ATRP of styrene and MA with low efficiency factors f (as low as 0.37 for MA and ethyl 2-chloropropionate as initiator), while it irre…