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A facile soap-free miniemulsion polymerization of methyl methacrylate (MMA) was successfully carried out via a reverse ATRP technique, using a water-soluble potassium persulfate (KPS) or 2,2′-azobis(2-methylpropionamidine) dihydrochloride (V-50) both as the initiator and the stabilizer, and using an oil-soluble N,N-n-butyldithiocarbamate copper (Cu(S2CN(C4H9)2)2) as the catalyst without adding any additional ligand. Polymerization results demonstrated the 'living'/controlled characteristics of ATRP and the resultant latexes showed good colloidal stability with average particle size around 300-700 nm in diameter. The monomer droplet nucleation mechanism was proposed. NMR spectroscopy and chain-extension experiments under UV light irradiation confirmed the attachment and livingness of UV light sensitive SC(S)N(C4H9)2 group in the chain end. [ABSTRACT FROM AUTHOR]

In this work, copolymerization of two functional monomers, glycidyl methacrylate (GMA) and N, N-dimethylaminoethyl methacrylate (DMAEMA), was firstly carried out via reversible addition-fragmentation chain transfer (RAFT) polymerization successfully. The copolymerization kinetics was investigated under the molar ratio of n[GMA+DMAEMA]0/ n[AIBN]0/ n[CPDN]0=300/1/3 at 60°C. The copolymerization showed typical "living" features such as first-order polymerization kinetics, linear increase of molecular weight with monomer conversion and narrow molecular weight distribution. The reactivity ratios of GMA and DMAEMA were calculated by the extended Kelen-Tüdös linearization methods. The epoxy group of the copolymer PGMA- co-PDMAEMA remained intact under the conditions of RAFT copolymerization and could easily be post-modified by ethylenediamine. Moreover, the modified copolymer could be used as a gene carrier. [ABSTRACT FROM AUTHOR]

Hyperbranched polycaprolactone with controlled structure was synthesized by reversible addition-fragmentation chain transfer radical ring-opening polymerization along with self-condensed vinyl polymerization (SCVP) of 2-methylene-1,3-dioxepane (MDO). Vinyl 2-[(ethoxycarbonothioyl) sulfanyl] propanoate (ECTVP) was used as polymerizable chain transfer agent. Living polymerization behavior was proved via pseudo linear kinetics, the molecular weight of polymers increasing with conversion and successful chain extension. The structure of polymers was characterized by 1H NMR spectroscopy, tripe detection gel permeation chromatography, and differential scanning calorimetry. The polymer composition was shown to be able to tune to vary the amount of ester repeat units in the polymer backbone, and hence determine the degree of branching. As expected, the degree of crystallinity was lower and the rate of degradation was faster in cases of increasing the number of branches. [ABSTRACT FROM AUTHOR]

Butyl acrylate is polymerized in the living way under the irradiation of purple light-emitting diode (LED) or sunlight without photocatalyst at ambient temperature. 2-((Phenoxycarbonothioyl)thio) ethyl propanoate) is exclusively added and acted as an initiator and a chain transfer agent simultaneously in the current system. Poly(butyl acrylate) with well-regulated molecular weight and relatively narrow molecular weight distribution ( Ð < 1.30) is synthesized. High conversion (>95%) can be achieved within several minutes. Polymerization shows oxygen tolerance. Near quantitative end-group fidelity of polymer is demonstrated by 1H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectra. [ABSTRACT FROM AUTHOR]

Vinyl acetate is polymerized in the living way under the irradiation of blue light-emitting diodes (LEDs) or sunlight without photocatalyst at ambient temperature. 2-(Ethoxycarbonothioyl)sulfanyl propanoate is exclusively added and acts as initiator and chain transfer agent simultaneously in the current system. Poly(vinyl acetate) with well-regulated molecular weight and narrow molecular weight distribution (Ð < 1.30) is synthesized. Near quantitative end group fidelity of polymer is demonstrated by nuclear magnetic resonance (NMR) and matrix-assisteed laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). [ABSTRACT FROM AUTHOR]

A novel Janus compound containing azo-based thermal initiator and bromo-based atom transfer radical polymerization (ATRP) initiator group is synthesized. Such compound can be applied in the living radical polymerization of alkyl methacrylate monomers, such as methyl methacrylate, tert-butyl methacrylate, and 2-( N, N-dimethylamino) ethyl methacrylate. Polymers with controlled molecular weights and narrow molecular weight distributions are obtained. The structure of polymers is identified by 1H NMR spectroscopy and matrix-assisted laser desorption ionization time-of-flight mass spectrum. A modified initiator for continuous activator regeneration ATRP mechanism is proposed according to the polymerization behavior, hydrolysis of chain backbone, and end group identification. [ABSTRACT FROM AUTHOR]

ABSTRACT The living free radical polymerizations of vinyl acetate (VAc) were successfully achieved in the presence of a novel organic selenium compound (diselenocarbonates), with 2,2′-azobisisobutyronitrile (AIBN) as the initiator. The living characteristics of the VAc polymerization were confirmed by the linear first-order kinetic plots and linear increase of molecular weights ( Mn) of the polymers with monomer conversions, while keeping the relatively low molecular weight distributions. In addition, the end of the polymers contains selenium element which may be useful in biotechnological and biomedical applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3159-3165 [ABSTRACT FROM AUTHOR]