Emulsion Atom Transfer Radical Polymerization Research Articles

Morphological and Physical Properties of Triblock Copolymers of Methyl Methacrylate and 2-Ethylhexyl Methacrylate

Triblock copolymers of methyl methacrylate (MMA) and 2-ethylhexyl methacrylate (EHMA) [that is, poly(MMA-EHMA-MMA)] were prepared by an emulsion atom-transfer radical polymerization. The relationships of their structural, morphological, and physical properties were investigated. The latex particles had core-shell morphologies and the block copolymers experienced phase separation. Small latex particles with a low number of cores could deform and wet silicon-wafer surfaces, but the deformation of large latex particles was restricted by the internal two-phase morphology of the particles. Latex casting produced continuous pinholefree films, in which hard poly(MMA) (PMMA) cores of different latex particles merged and provided interparticle connections. The morphology of solution-cast films depended on block composition, solvent type, and film thickness. For all the prepared polymer samples, thick films cast in toluene had poly(EHMA) (PEHMA) materials at air surface, whereas those cast in tetrahydrofuran had a sponge-like PMMA surface structure. Thin toluene-cast films from P(MMA-EHMA-MMA) with the block degrees of polymerization (DP) 200-930-200 showed spherical PMMA domains and those from 380-930-380 yielded a protruded worm-like PMMA structure. The copolymer materials were coated on a glass surface for peeling tests. The films gave good hot-melt adhesion properties when the DP of the PEHMA block was over 600. The peeling strength depended on the lengths of both PEHMA and PMMA blocks. The P(MMA-EHMA-MMA) sample with DPs of 310-930-310 yielded the highest peeling strength of 7.4 kgf·inch -1 . The developed material is demonstrated to be a good candidate for a solvent-free, hotmelt, pressure-sensitive adhesives for special-purpose applications such as medical tapes and labels.

Development of an ab Initio Emulsion Atom Transfer Radical Polymerization: From Microemulsion to Emulsion

Atom transfer radical polymerization (ATRP) has been successfully extended to an ab initio emulsion system using a "two-step" procedure, in which the final emulsion polymerization system was formed by adding monomer to an ongoing microemulsion ATRP. The newly developed AGET (activators generated by electron transfer) initiation technique was employed in the first stage of this ab initio ATRP. It allows using oxidatively stable Cu(II) species that is reduced in situ by ascorbic acid. The surfactant concentration in the final emulsion system was efficiently decreased to approximately 2 wt % (approximately 10 wt % vs monomer) by decreasing the catalyst concentration and changing the ratio of the monomer added at the microemulsion stage to the monomer added during the second stage. This two-step procedure avoids the necessity of transporting catalysts through the aqueous media during polymerization, resulting in a controlled emulsion polymerization, as evidenced by a linear first-order kinetic plot and formation of a polymer with a relatively narrow molecular weight distribution (Mw/Mn = 1.2-1.4). The polymerization typically reached 70-90% monomer conversion in 5-6 h. The resulting polymer had high chain-end functionality and was successfully chain extended to form in situ block copolymers by adding the second monomer to an ongoing emulsion polymerization. The stable latex from the ab initio emulsion ATRP had a particle size approximately 120 +/- 10 nm.

Living radical emulsion polymerization using the nanoprecipitation technique: An extension to atom transfer radical polymerization

AbstractLiving radical polymerizations of styrene were performed under emulsion atom transfer radical polymerization conditions with latexes prepared by a nanoprecipitation technique recently developed for the stable free‐radical polymerization process. Latexes were prepared by the precipitation of a solution of low‐molecular‐weight polystyrene in acetone into a solution of a surfactant in water. The resulting particles were swollen with styrene and then heated. The effects of various surfactants and hydrophobic ligands, the reaction temperature, and the ligand/copper(I) bromide ratio were studied. The best results were obtained with the nonionic surfactant Brij 98 in combination with the hydrophobic ligand N,N‐bis(2‐pyridylmethyl)octadecylamine and a ligand/copper(I) bromide ratio of 1.5 at a reaction temperature of 85–90 °C. Under these conditions, latexes with good colloidal stability with average particle diameters of 200 nm were obtained. The molecular weight distributions of the polystyrenes were narrow, although the experimental molecular weights were slightly larger than the theoretical ones because not all the macroinitiator appeared to reinitiate. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4027–4038, 2006

Synthesis and characterization of poly(n‐butyl methacrylate)‐b‐polystyrene diblock copolymers by atom transfer radical emulsion polymerization

AbstractPoly(n‐butyl methacrylate) (PBMA)‐b‐polystyrene (PSt) diblock copolymers were synthesized by emulsion atom transfer radical polymerization (ATRP). PBMA macroinitiators that contained alkyl bromide end groups were obtained by the emulsion ATRP of n‐butyl methacrylate with BrCH3CHCOOC2H5 as the initiator; these were used to initiate the ATRP of styrene (St). The latter procedure was carried out at 85°C with CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as the catalyst and polyoxyethylene(23) lauryl ether as the surfactant. With this technique, PBMA‐b‐PSt diblock copolymers were synthesized. The polymerization was nearly controlled; the ATRP of St from the macroinitiators showed linear increases in number‐average molecular weight with conversion. The block copolymers were characterized with IR spectroscopy, 1H‐NMR, and differential scanning calorimetry. The effects of the molecular weight of the macroinitiators, macroinitiator concentration, catalyst concentration, surfactant concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2123–2129, 2005

Emulsion atom transfer radical polymerization of 2-ethylhexyl methacrylate

The emulsion atom transfer radical polymerization (ATRP) of 2-ethylhexyl methacrylate (EHMA) was carried out with ethyl 2-bromoisobutyrate (EBiB) as an initiator and copper bromide (CuBr)/4,4′-dinonyl-2,2′-bipyridyl (dNbpy) as a catalyst system. The effects of surfactant type and concentration, temperature, monomer/initiator ratio, and CuBr 2 addition on the system livingness, polymer molecular weight control, and latex stability were examined in detail. It was found that the polymerization systems with Tween 80 and Brij 98 as surfactants at 30 °C gave the best latex stability. The polymer samples prepared under these conditions had narrow molecular weight distributions ( M w/ M n=1.1–1.2) and linear relationships of number-average molecular weight versus monomer conversion.

Studies on atom transfer radical emulsion polymerization of n-butyl methacrylate

Atom transfer radical polymerization (ATRP) of n-butyl methacrylate (BMA) in water-borne media, catalyzed and initiated by CuCl/4,4-di (5-nonyl)-2,2-bipyridine (dNbpy) and Ethyl 2-bromopropinate (BrCH3CHCOOC2H5) was conducted. The influence of several factors, such as the amount of surfactant, catalyst, initiator and the reaction time, temperature on the stability of the latexes and the control of the polymerization was investigated. The nucleation mechanism of the latexes, thermodynamic data and activation parameters for the ATRP emulsion polymerization of BMA were also reported.

Synthesis and characterization of PBMA-b-PSt-b-PBMA triblock copolymers by atom transfer radical emulsion polymerization

Poly(n-butyl methacrylate)-b-polystyrene-b-poly(n-butyl methacrylate) (PBMA-b-PSt-b-PBMA) triblock copolymers were successfully synthesized by emulsion atom transfer radical polymerization (ATRP). Difunctional polystyrene (PSt) macroinitiators that contained alkyl chloride end-groups were prepared by ATRP of styrene (St) with CCl4 as initiator and were used to initiate the ATRP of butyl methacrylate (BMA). The latter procedure was carried out at 85°C with CuCl/4,4-di (5-nonyl)-2,2- bipyridine (dNbpy) as catalyst and polyoxyethylene (23) lauryl ether (Brij35) as surfactant. Using this technique, triblock copolymers consisting of a PSt center block and PBMA terminal blocks were synthesized. The polymerization was nearly controlled, ATRP of St from those macroinitiators showed linear increases in the number average molecular weight (Mn) with conversion. The block copolymers were characterized with infrared (IR) spectroscopy, hydrogen-1 nuclear magnetic resonance (1HNMR), and differential scanning calorimetry (DSC). The effects of the molecular weight of macroinitiators, concentration of macroinitiator, catalyst, emulsion, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP were also reported