Functionalization of polymers prepared by ATRP using radical addition reactions

Coessens, Veerle; Pyun, Jeffrey; Miller, Peter J.; Gaynor, Scott G.; Matyjaszewski, Krzysztof

doi:10.1002/(sici)1521-3927(20000201)21:2<103::aid-marc103>3.0.co;2-h

Cited by 109 publications

(73 citation statements)

References 14 publications

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“…After initiation occurs, the initiator fragment R is present at one end of the chain while the halogen at the other end can be further transformed to various functionalities by means of standard organic procedures. Moreover, because of the radical nature of ATRP, a wide range of functional monomers can be polymerized, yielding polymers with pendant functional groups 10,11. Various functional monomers, including styrenes, (meth)acrylates and others have been (co)polymerized in a controlled fashion by ATRP, resulting in well‐defined polymers with good control over molecular weight and low polydispersity indices 10.…”

Section: Introductionmentioning

confidence: 99%

Atom Transfer Radical Polymerization of Glycidyl Methacrylate: A Functional Monomer

Cañamero

Fuente

Madruga

et al. 2004

Macro Chemistry & Physics

111

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Summary: A detailed investigation of the polymerization of glycidyl methacrylate (GMA), an epoxy‐functional monomer, by atom transfer radical polymerization (ATRP) was performed. Homopolymers were prepared at relatively low temperatures using ethyl 2‐bromoisobutyrate (EBrIB) as the initiator and copper halide (CuX) with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The high polymerization rate in the bulk did not permit polymerization control. However, homopolymerization in solution enabled us to explore the effects of different experimental parameters, such as temperature, solvent (toluene vs. diphenyl ether) and initiator concentration, on the controllability of the ATRP process. SEC analysis of the homopolymers synthesized confirmed the importance of solvent character on molecular weight control, the lowest polydispersity indices ($\overline M _{\rm w} /\overline M _{\rm n} < 1.25$) and the highest efficiencies being found when the polymerizations were performed in diphenyl ether in combination with a mixed halide technique. A novel poly(glycidyl methacrylate)‐block‐poly(butyl acrylate) (PGMA‐b‐PBA) diblock copolymer was prepared through ATRP using PGMA‐Cl as a macro‐initiator. This chain growth experiment demonstrated a good living character under the conditions employed, while simultaneously indicating a facile synthetic route for this type of functional block copolymer. In addition, the isotacticity parameter for the PGMAs obtained was estimated using 1H NMR analysis which gave a value of σGMA = 0.26 in agreement with that estimated in conventional radical polymerization.SEC chromatograms of PGMA‐Cl macroinitiator and PGMA‐b‐PBA diblock copolymer.magnified imageSEC chromatograms of PGMA‐Cl macroinitiator and PGMA‐b‐PBA diblock copolymer.

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Section: Introductionmentioning

confidence: 99%

Atom Transfer Radical Polymerization of Glycidyl Methacrylate: A Functional Monomer

Cañamero

Fuente

Madruga

et al. 2004

Macro Chemistry & Physics

111

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“…As far as it concerns the applications of polymers the halogens may be detrimental, e.g., at high temperature processing, in reactive extrusion, in reactive blending, and during the synthesis of graft‐co‐polymers, where the halogen may cause undesired side reactions. Several methods are reported in literature for the removal of the terminal halogen after the polymerization is complete, e.g., by nucleophilic substitutions, electrophilic addition reactions, addition of less reactive monomers, and radical reactions leading to end‐functional polymers 15–18. Chaumont and co‐workers19 reported that a bromo‐terminated polystyrene has been functionalized with tetraphenylethane‐based derivatives, for instance 1,1,2,2‐tetraphenyl‐1,2‐bis(trimethylsilyloxy)ethane.…”

Section: Introductionmentioning

confidence: 99%

Atom‐Transfer Radical Polymerization: A Strategy for the Synthesis of Halogen‐Free Amino‐Functionalized Poly(methyl methacrylate) in a One‐Pot Reaction

Sadhu

Pionteck

Voigt

et al. 2004

Macro Chemistry & Physics

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Summary: An initiator containing an alkyl bromide unit and a protected amine functional group is used with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA), in a 1:2 molar ratio with respect to initiator concentration, in order to obtain amino‐group terminated as well as halogen‐free poly(methyl methacrylate) (PMMA) in a one‐pot atom‐transfer radical polymerization (ATRP). The terminal bromines are replaced by hydrogen atoms of the PMDETA ligand, which acts as a transfer agent. However, terminating side reactions like disproportionation or dehydrobromination occur from the beginning of the polymerization. Kinetic studies by in‐line Raman spectroscopy and off‐line 1H NMR spectroscopy revealed that the controlled character of the ATRP is lost under these conditions. The measured molecular weights were consistently higher than the theoretical ones and the molecular weight distributions are relatively broad. Thermal analysis of the obtained poly(methyl methacrylate) shows two main degradation steps, one starting from unsaturated end groups (depolymerization), and one caused by main‐chain scission, a further proof for the occurrence of terminating side reactions.Structural analysis of PMMA by matrix‐assisted laser desorption‐ionization mass spectrometry.magnified imageStructural analysis of PMMA by matrix‐assisted laser desorption‐ionization mass spectrometry.

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“…For the same reason, there have been no efficient quenching reactions that can convert the stable but potentially active covalent carbon-halogen bonds into more stable bonds, such as COC bonds. 30 Interesting applications of the quenching with silyl enol ethers have been reported recently. 8 In addition, effective quenching reactions for living radical polymerizations will lead to the synthesis of not only end-functionalized polymers at the end but also telechelic polymers by combining the functionalized initiator method that has become more popular in living radical polymerization.…”

Section: Introductionmentioning

confidence: 99%

Quenching of metal-catalyzed living radical polymerization with silyl enol ethers

Tokuchi¹,

Ando²,

Kamigaito³

et al. 2000

J. Polym. Sci. A Polym. Chem.

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Functionalization of polymers prepared by ATRP using radical addition reactions

Cited by 109 publications

References 14 publications

Atom Transfer Radical Polymerization of Glycidyl Methacrylate: A Functional Monomer

Atom Transfer Radical Polymerization of Glycidyl Methacrylate: A Functional Monomer

Atom‐Transfer Radical Polymerization: A Strategy for the Synthesis of Halogen‐Free Amino‐Functionalized Poly(methyl methacrylate) in a One‐Pot Reaction

Quenching of metal-catalyzed living radical polymerization with silyl enol ethers

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