Atom Transfer Radical Polymerization Of Methyl Methacrylate Research Articles

Synthesis and Characterization of ABA-Type Triblock Copolymers Using Novel Bifunctional PS, PMMA, and PCL Macroinitiators Bearing p-xylene-bis(2-mercaptoethyloxy) Core.

Syntheses of novel bifunctional poly(methyl methacrylate) (PMMA)-, poly(styrene) (PS)-, and (poly ε-caprolactone) (PCL)-based atom transfer radical polymerization (ATRP) macroinitiators derived from p-xylene-bis(1-hydroxy-3-thia-propanoloxy) core were carried out to obtain ABA-type block copolymers. Firstly, a novel bifunctional ATRP initiator, 1,4-phenylenebis(methylene-thioethane-2,1-diyl)bis(2-bromo-2-methylpropanoat) (PXTBR), synthesized the reaction of p-xylene-bis(1-hydroxy-3-thia-propane) (PXTOH) with α-bromoisobutryl bromide. The PMMA and PS macroinitiators were prepared by ATRP of methyl methacrylate (MMA) and styrene (S) as monomers using (PXTBR) as the initiator and copper(I) bromide/N,N,N',N″,N″-pentamethyldiethylenetriamine (CuBr/PMDETA) as a catalyst system. Secondly, di(α-bromoester) end-functionalized PCL-based ATRP macronitiator (PXTPCLBr) was prepared by esterification of hydroxyl end groups of PCL-diol (PXTPCLOH) synthesized by Sn(Oct)2-catalyzed ring opening polymerization (ROP) of ε-CL in bulk using (PXTOH) as initiator. Finally, ABA-type block copolymers, PXT(PS-b-PMMA-b-PS), PXT(PMMA-b-PS-b-PMMA), PXT(PS-b-PCL-b-PS), and PXT(PMMA-b-PCL-b-PMMA), were synthesized by ATRP of MMA and S as monomers using PMMA-, PS-, and PCL-based macroinitiators in the presence of CuBr/PMDETA as the catalyst system in toluene or N,N-dimethylformamide (DMF) at different temperatures. In addition, the extraction abilities of PCL and PS were investigated under liquid-liquid phase conditions using heavy metal picrates (Ag+, Cd2+, Cu2+, Hg2+, Pb2+, and Zn2+) as substrates and measuring with UV-Vis the amounts of picrate in the 1,2-dichloroethane phase before and after treatment with the polymers. The extraction affinity of PXTPCL and PXTPS for Hg2+ was found to be highest in the liquid-liquid phase extraction experiments. Characterizations of the molecular structures for synthesized novel initiators, macroinitiators, and the block copolymers were made by spectroscopic (FT-IR, ESI-MS, 1H NMR, 13C NMR), DSC, TGA, chromatographic (GPC), and morphologic SEM.

Kinetics of MMA Atom Transfer Radical Polymerization Initiated by Reducing Agent in Stirred Batch Emulsion Reactor

AbstractAb initio emulsion atom transfer radical polymerization (ATRP) differs from regular emulsion polymerization because the kinetic and thermodynamic aspects of each process are very unlikely alike. This paper presents a kinetic analysis of activator generated by electron transfer (AGET) ATRP of methyl methacrylate (MMA) in a stirred emulsion reactor. The focus of the study is to assess the variation of the monomer content in the organic phase and the rate polymerization for different reaction temperatures, as well as the impact of surfactant content and stirring speed on latex stability. Poly(methyl methacrylate) (PMMA) polymer samples are analyzed by means of gravimetry, dynamic light scattering, gel permeation chromatography, and HNMR techniques to determine monomer conversion, polymer particle diameter, molecular weight distribution, and polymer molecular structure, respectively. The results show the production of PMMA of narrow polydispersity index (Ð) and low molar mass (Mn) for MMA conversion around 60% and detect two‐regions instead of a three‐regions trend of rate of polymerization (Rp) as conventional emulsion polymerization. The reaction rate increases during the nucleation stage and then flattens over an invariant trend which confirms a living feature of the AGET ATRP polymerization. The average number of radicals per latex particle (ñ) is also debated.

Surface-Initiated Initiators for Continuous Activator Regeneration (SI ICAR) ATRP of MMA from 2,2,6,6-tetramethylpiperidine-1-oxy (TEMPO) Oxidized Cellulose Nanofibers for the Preparations of PMMA Nanocomposites.

An effective method of oxidation from paper pulps via 2,2,6,6–tetramethylpiperidine–1–oxy (TEMPO) compound to obtain TEMPO-oxidized cellulose nanofibers (TOCNs) was demonstrated. Following by acylation, TOCN having an atom transfer radical polymerization (ATRP) initiating site of bromoisobutyryl moiety (i.e., TOCN–Br) was successfully obtained. Through a facile and practical technique of surface-initiated initiators for continuous activator regeneration atom transfer radical polymerization (SI ICAR ATRP) of methyl methacrylate (MMA) from TOCN–Br, controllable grafting polymer chain lengths (Mn = ca. 10k–30k g/mol) with low polydispersity (PDI < 1.2) can be achieved to afford TOCN–g–Poly(methyl methacrylate) (PMMA) nanomaterials. These modifications were monitored by Fourier-transform infrared spectroscopy (FT–IR), scanning electron microscopy (SEM), electron spectroscopy for chemical analysis (ESCA), and water contact angle analysis. Eventually, TOCN–g–PMMA/PMMA composites were prepared using the solvent blending method. Compared to the pristine PMMA (Tg = 100 °C; tensile strength (σT) = 17.1 MPa), the composites possessed high transparency with enhanced thermal properties and high tensile strength (Tg = 110 °C and σT = 37.2 MPa in 1 wt% TOCN containing case) that were investigated by ultraviolet-visible spectroscopy (UV-Vis), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and tensile tests. We demonstrated that minor amounts of TOCN–g–PMMA nanofillers can provide high efficacy in improving the mechanical and thermal properties of PMMA matrix.

Photo-induced metal-free ATRP of MMA with 2,7-bi-(N-penothiazinyl)fluorenone as photocatalyst

ABSTRACTIn this study, 2,7-bi-(N-penothiazinyl)fluorenone was employed as photocatalyst (PC), ethyl α-bromophenylacetate (EBP) as atom transfer radical polymerization (ATRP) initiator, and photo-induced metal-free ATRP of methyl methacrylate (MMA) was performed at 25°C under blue light irradiation. PMMAs with well-defined architectures and precisely controlled chain lengths were synthsized. The kinetics results confirmed that molecular weights increased linearly with monomer consumption. The molecular weight distributions (Mw/Mn) of the resultant PMMA were narrow. The polymerization was activated and deactivated by periodic light control process. 1H nuclear magnetic resonance spectrometer (NMR) and gel permeation chromatography (GPC) were used to characterize the obtained PMMAs. The living characters of the polymerization system were further confirmed by chain extension of from the PMMA-Br macroinitiator.

PHEA-g-PMMA Well-Defined Graft Copolymer: ATRP Synthesis, Self-Assembly, and Synchronous Encapsulation of Both Hydrophobic and Hydrophilic Guest Molecules

A series of well-defined amphiphilic graft copolymer bearing a hydrophilic poly(2-hydroxyethyl acrylate) (PHEA) backbone and hydrophobic poly(methyl methacrylate) (PMMA) side chains was synthesized by successive reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) through the grafting-from strategy. A well-defined PHEA-based backbone with Cl-containing ATRP initiating group in every repeated unit (Mw/Mn = 1.08), poly(2-hydroxyethyl 2-((2-chloropropanoyloxy)methyl)acrylate) (PHECPMA), was first prepared by RAFT homopolymerization of 2-hydroxyethyl 2-((2-chloropropanoyloxy)methyl)acrylate (HECPMA), a Cl-containing trifunctional acrylate. ATRP of methyl methacrylate was subsequently initiated by PHECPMA homopolymer to afford the target well-defined poly(2-hydroxyethyl acrylate)-graft-poly(methyl methacrylate) (PHEA-g-PMMA) graft copolymers (Mw/Mn ≤ 1.36) with 34 PMMA side chains and 34 pendant hydroxyls in PHEA backbone using CuCl/dHbpy as catalytic system. The critical micelle concentration (cmc) of the obtained graft copolymer was determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe while micellar morphologies in aqueous media were visualized by transmission electron microscopy. Interestingly, PHEA-g-PMMA graft copolymer could self-assemble into large compound micelles rather than common spherical micelles, which can encapsulate hydrophilic rhodamine 6 G and hydrophobic pyrene separately or simultaneously.

Assessment of kinetics of photoinduced Fe‐based atom transfer radical polymerization under conditions using modeling approach

Kinetic insight into photoinduced Fe‐based atom transfer radical polymerization (ATRP) involving monomer‐mediated photoreduction was performed by modeling approach for the first time. Preliminary numerical analysis of number‐average molar mass (Mn) derivation in this specific system was given. Simulation results provided a full picture of reactant concentration and reaction rate throughout the entire polymerization. Methyl 2,3‐dibromoisobutyrate (MibBr2) generated from methyl methacrylate (MMA)‐mediated photoreduction as the leading factor for the deviation of Mn from theoretical value was confirmed by reaction contributions in α‐bromophenylacetate (EBPA) containing system. Reasonable predictions were made with respect to the polymerizations under a variety of initial conditions. Results show that increasing light intensity will shorten transition period and increase steady state polymerization rate; decreasing catalyst loading will cause the decrease in polymerization rate and Mn deviation; varying initiation activity will slightly increase the time to attain steady state of dispersity (Mw/Mn) evolution and enormously change the fraction of reaction contributions; increasing targeted chain length will extend transition period, decrease steady state polymerization rate, increase Mn deviation degree with same reaction contributions, and decrease the time to attain the steady state of Mw/Mn. The numerical analysis presented in this work clearly demonstrates the unique ability of our modeling approach in describing the kinetics of photoinduced Fe‐based ATRP of MMA. © 2017 American Institute of Chemical Engineers AIChE J, 2017

A degradable atom transfer radical polymerization inimer: Synthesis, polymerization, and cleavage of the resulting polymer products

ABSTRACTA novel degradable inimer for atom transfer radical polymerization (ATRP), 2‐(6‐(2‐((2‐bromo‐2‐methylpropanoyl)oxy)ethyl)pyridin‐2‐yl)ethyl methacrylate (PyDEBrMΑ), was synthesized by the two‐step esterification of 2,6‐pyridinediethanol, first with α‐bromoisobutyryl bromide in order to introduce the initiator moiety, and then with methacryloyl chloride in order to introduce the monomer moiety. PyDEBrMA was subsequently used to initiate the self‐condensing ATRP of methyl methacrylate (MMA) to obtain a hyperbranched MMA homopolymer which could be cleaved at the PyDEBrMA residue either by treatment under mildly alkaline hydrolysis conditions (sodium deuteroxide in d6‐DMSO at room temperature) or thermolysis at 150 °C. The lability of the PyDEBrMA residue arises from the presence in its structure of two 2‐(pyridin‐2‐yl)ethyl ester moieties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2831–2839

Non-carbene Complex [RuCl2(PPh3)2(azocane)] as Active Catalyst Precursor for ROMP and ATRP

The novel, non-carbene complex [RuCl2(PPh3)2(azocane)] (1) of trigonal bipyramid geometry was synthesized, characterized (CHN elementary analysis, FTIR, EPR, and 31P NMR), and applied as catalyst precursor for ring opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). ROMP of norbornene (NBE) resulted in 70% yield at 50 °C in 60 min, with [NBE]/[1] = 5000, and 15% yield from ROMP of norbornadiene was obtained under the same conditions. ATRP of methyl methacrylate (MMA) resulted in ca. 20% conversion at 85 °C in 9 h, with [MMA]/[1] = 1000, and increased to ca. 50% in the presence of Al(OiPr)3, with narrower PDI values. With [MMA]/[1] = 200, ca. 50% yield was obtained at 85 °C in 6 h either in the absence or presence of Al(OiPr)3. ATRP of styrene resulted in 9 and 16% conversion at 110 °C in 7 h in the absence or presence of Al(OiPr)3, respectively, with [St]/[1] = 1000. Results are discussed considering the five-coordinated molecular geometry of the starting complex and the arrangements required in ROMP and ATRP to initiate the reactions.

Double-bond-containing polyallene-based triblock copolymers via phenoxyallene and (meth)acrylate

A series of ABA triblock copolymers, consisting of double-bond-containing poly(phenoxyallene) (PPOA), poly(methyl methacrylate) (PMMA), or poly(butyl acrylate) (PBA) segments, were synthesized by sequential free radical polymerization and atom transfer radical polymerization (ATRP). A new bifunctional initiator bearing azo and halogen-containing ATRP initiating groups was first prepared followed by initiating conventional free radical homopolymerization of phenoxyallene with cumulated double bond to give a PPOA-based macroinitiator with ATRP initiating groups at both ends. Next, PMMA-b-PPOA-b-PMMA and PBA-b-PPOA-b-PBA triblock copolymers were synthesized by ATRP of methyl methacrylate and n-butyl acrylate initiated by the PPOA-based macroinitiator through the site transformation strategy. These double-bond-containing triblock copolymers are stable under UV irradiation and free radical circumstances.

Ru-dimethyl sulfoxide complexes as catalysts precursors for ROMP of norbornene and ATRP of methyl methacrylate

The catalytic activity of the five-coordinated [RuCl2(PPh3)(S-dmso)2] complex was investigated for ring-opening metathesis polymerization (ROMP) of norbornene (NBE) and for atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). Syntheses via ROMP of polyNBE were dependent on the ethyl diazoacetate (EDA) amount, used as starting carbene source, monomer concentration, temperature, and reaction time. The best polyNBE yields were obtained at 50°C for 120min with [NBE]/[Ru]=5000 in presence of 5μL of EDA. MMA polymerization via ATRP was conducted as a function of time with different ethyl 2-bromoisobutyrate initiator and monomer concentrations. The kinetic data for ATRP show linear increase between MMA conversion and molecular weight. Kinetic studies with the six-coordinated [RuCl2(S-dmso)3(O-dmso)] complex also showed an increase in the molecular weight with conversion, but with a marked deviation from theoretical molecular weights. This is consistent with the better control in the polymerization supported by electronic and steric properties of the PPh3 ligand in the title complex

Synthesis of block copolymer with photo-decomposable polyurethane and its photo-initiated domino decomposition

A block copolymer consisting of a photo-decomposable polyurethane and poly(methyl methacrylate) (PMMA) was developed. The end-functionalized polyurethane (P2) was synthesized by polycondensation with the end-functionalization reagents. P2 possesses the photosensitive o-nitrobenzyl group and the 2-bromoisobutyryl group as the initiator of the atom transfer radical polymerization (ATRP). The block copolymer (P2-b-PMMA) was synthesized by the ATRP of methyl methacrylate (MMA) with P2 as the macroinitiator. The P2 block in P2-b-PMMA was decomposed by photo-irradiation at 365nm by the initiation of the photo-fries rearrangement of the urethane linkage and the subsequent domino reaction consistent with the elimination of the aza-quinone methide and decarboxylation. The photo-initiated decomposition of the P2 segment in the thin-film state was accomplished.

Synthesis of a new donor-acceptor-donor functionalized alkoxyamine and its use in a reversibly supported catalytic hybrid system for ATRP of MMA

Abstract A new 2,6-diaminopyridine-functionalized SG1-based alkoxyamine has been synthesized and used to prepare a well-defined functional copolymer (poly(styrene-co-2-vinyl-4,4-dimethyl-5-oxazolone) – poly(S-co-VDM)) by nitroxide mediated polymerization. After post-modification of the copolymer with an atom transfer radical polymerization (ATRP) ligand (N,N-dipicolyl propylamine), the macroligand was successfully used for the homogeneous ATRP of methyl methacrylate (MMA) leading to a controlled polymerization process. The ATRP of the same monomer was also investigated with the macroligand being reversibly immobilized via hydrogen bonding onto thymine-functionalized silica nanoparticles. The ATRP of MMA involving the supported-catalyst was also effective leading to a good control over the polymerization as observed with the free macroligand and producing polymers with very low dispersity (

Photo‐Induced atom transfer radical polymerization with nanosized α‐Fe2O3 as photoinitiator

ABSTRACTPhoto‐induced atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved in poly(ethylene glycol)‐400 with nanosized α‐Fe2O3 as photoinitiator. Well‐defined poly(methyl methacrylate) (PMMA) was synthesized in conjunction with ethyl 2‐bromoisobutyrate (EBiB) as ATRP initiator and FeCl3·6H2O/Triphenylphosphine (PPh3) as complex catalyst. The photo‐induced polymerization of MMA proceeded in a controlled/living fashion. The polymerization followed first‐order kinetics. The obtained PMMA had moderately controlled number‐average molecular weights in accordance with the theoretical number‐average molecular weights, as well as narrow molecular weight distributions (Mw/Mn). In addition, the polymerization could be well controlled by periodic light‐on–off processes. The resulting PMMA was characterized by 1H nuclear magnetic resonance and gel permeation chromatography. The brominated PMMA was used further as macroinitiator in the chain‐extension with MMA to verify the living nature of photo‐induced ATRP of MMA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42389.

Homogeneous Fe-Mediated AGET ATRP of Methyl Methacrylate in PEG-400 in the Presence of Na2CO3

The activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully carried out in poly(ethylene glycol) (PEG-400) with CCl4/FeCl3·6H2O/N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA) as the initiating system in the presence of Na2CO3. The living nature of the polymerization was confirmed by kinetic studies, end-group analysis and chain extension. The molecular weight distribution (MWD) of the polymer obtained was quite narrow (MWD = 1.10–1.40). The effects of ligand and temperature on polymerization were investigated. Based on the slope of the plot of ln (kapp) vs. (1/T), the apparent activation energy (Eapp) of 34.1 kJ mol−1 was calculated. The recovering and recycling of PEG-400 were first investigated. After the polymerization and isolation of PMMA, the mixture containing catalysts and PEG-400 was shown to be recoverable and recyclable without further treatment.

Achieving High‐Conversion Bulk ATRP with Good Livingness and Well Controlled by Design and Optimization of Polymerization Temperature Profile

AbstractControlled radical polymerization (CRP) such as atom transfer radical polymerization (ATRP) is often conducted in solution processes and stopped at medium monomer conversions to yield well controlled polymer samples. A great challenge lies in running bulk CRP up to high conversions but still retaining system livingness and molecular weight control. In this work, we demonstrate the achievement of good living and well controlled high‐conversion bulk ATRP by means of design and optimizing polymerization thermal histories. The initiator‐for‐continues‐activator‐regeneration (ICAR) ATRP of methyl methacrylate (MMA) is used as a model system. Employing step functions in temperature, MMA conversions are pushed up to 98% and the PMMA samples possess polydispersities &lt;1.3. Chain extension experiments confirm good livingness of synthesized polymers collected at high conversions.

Photoirradiated Fe-Mediated AGET ATRP of Methyl Methacrylate in the Presence of Alcohol

In this study, photoirradiated Fe-mediated AGET (activators generated by electron transfer) atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was investigated at ambient temperature in N,N-dimethylformamide (DMF) using carbon tetrachloride as initiator, FeCl3·6H2O/bipyridine (Bpy) as catalyst complex, and alcohol as reducing agent. Linear semi-logarithmic plot of conversion vs. time was obtained from the kinetic experiments, and the number-average molecular weight increased linearly with monomer conversion and corresponded to the theoretic values with molecular weight distributions (Mw/Mn) as low as 1.25, which agreed with the character of controlled/living polymerization. The kinds of alcohol played an important role in photoirradiated Fe-mediated AGET ATRP of MMA. The living characteristics were demonstrated through chain extension experiment. The obtained polymer was characterized by proton nuclear magnetic resonance (NMR) and gel permeation chromatography.

Well‐Defined Iron Complexes as Efficient Catalysts for “Green” Atom‐Transfer Radical Polymerization of Styrene, Methyl Methacrylate, and Butyl Acrylate with Low Catalyst Loadings and Catalyst Recycling

Environmentally friendly iron(II) catalysts for atom-transfer radical polymerization (ATRP) were synthesized by careful selection of the nitrogen substituents of N,N,N-trialkylated-1,4,9-triazacyclononane (R3 TACN) ligands. Two types of structures were confirmed by crystallography: "[(R3 TACN)FeX2 ]" complexes with relatively small R groups have ionic and dinuclear structures including a [(R3 TACN)Fe(μ-X)3 Fe(R3 TACN)](+) moiety, whereas those with more bulky R groups are neutral and mononuclear. The twelve [(R3 TACN)FeX2 ]n complexes that were synthesized were subjected to bulk ATRP of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Among the iron complexes examined, [{(cyclopentyl)3 TACN}FeBr2 ] (4 b) was the best catalyst for the well-controlled ATRP of all three monomers. This species allowed easy catalyst separation and recycling, a lowering of the catalyst concentration needed for the reaction, and the absence of additional reducing reagents. The lowest catalyst loading was accomplished in the ATRP of MMA with 4 b (59 ppm of Fe based on the charged monomer). Catalyst recycling in ATRP with low catalyst loadings was also successful. The ATRP of styrene with 4 b (117 ppm Fe atom) was followed by precipitation from methanol to give polystyrene that contained residual iron below the calculated detection limit (0.28 ppm). Mechanisms that involve equilibria between the multinuclear and mononuclear species were also examined.

Effective Addition of Organic Chloride Salts on Atom Transfer Radical Polymerization in Fluoroalcohols

Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in the presence of organic chloride salts, imidazolium chlorides, using alkyl bromide initiator was carried out in 2,2,2-trifluoroethanol (TFE) at 333 K. The ATRP using a sufficient large amount of chloride salts proceeded in a controlled manner to produce polymers with narrow molecular weight distributions (Mw/Mn < 1.2). The model reaction using an alkyl bromide and the imidazolium chloride indicated that a halogen exchange reaction occurred during the ATRP in TFE to form a chloride-terminated propagating species from the alkyl bromide. ATRP of MMA in TFE using an alkyl chloride initiator and CuCl catalyst, however, gave low initiation efficiency and loss of control over the polymerization. The combination of the alkyl bromide initiator, CuBr, and a sufficient amount of organic chloride salts was very effective to improve the control of ATRP in protic solvents, especially in fluoroalcohols. A methacrylate monomer bearing imidazolium chloride moiety was synthesized and polymerized by ATRP without added chloride salts to produce the polymers with well-controlled molecular weights and narrow polydispersities.

Pressure Dependence of Iron‐Mediated Methyl Methacrylate ATRP in Different Solvent Environments

Iron‐mediated atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in N‐methylpyrrolidin‐2‐one (NMP) solution is investigated via online VIS/NIR spectroscopy up to 2500 bar. The activation–deactivation equilibrium constant, KATRP, decreases towards higher NMP content due to the formation of catalytically less active FeII/NMP species. The reaction volume increases from 1 to 15 cm3 mol−1 in passing from 16 to 92 mol% NMP. The same effects are observed for monomer‐free model systems with poly(MMA)–Br as the initiator. Investigations into iron‐catalyzed ATRP of MMA in less polar solvents or even without an additional solvent (i.e., for bulk ATRP) yield KATRP values, which are by two to three orders of magnitude higher than in the presence of NMP. image

Activators regenerated by electron transfer in ATRP of methyl methacrylate with alcohol as reducing agent in the presence of a base

Poly(methyl methacrylate) (PMMA) was synthesized via activators regenerated by electron transfer (ARGET) in atom transfer radical polymerization (ATRP) (ARGET ATRP) of methyl methacrylate in N,N-dimethylformamide and using ethyl 2-bromoisobutyrate as initiator, CuCl2 as catalyst, N,N,N′,N′-tetramethylethylene-diamine as ligand and ethanol as a reducing agent. The polymerization temperature was kept at 70 °C. A well-defined PMMA with predetermined molecular weight and narrow molecular weight distribution was obtained. A linear relationship between ln([M]0/[M]) and polymerization time was found to show the living and controllable radical polymerization. The molecular weights of the obtained polymers increased linearly with monomer conversion and the data are in good agreement with the theoretical values with narrow molecular weight distribution (M w/M n). That is to say, alcohols were found to be a kind of highly efficient agents in the presence of Na2CO3 in this system. The effects of temperature, different types of alcohols and the amount of n-propanol on the polymerization were investigated. With increasing temperature (changed from 70 to 90 °C) and the amount of n-propanol (changed from 500:1:1:2:1:2 to 500:1:1:2:10:2), the conversion increased from 15.6 to 34.7 % and from 8.6 to 26.8 %, respectively. However, the value of M w/M n became broader when the molar ratio of [MMA]0/[EBiB]0/[CuCl2]0/[TMEDA]0/[n-propanol]0/[Na2CO3]0 was 500:1:1:2:1:2, indicating that the amount of n-propanol played an important role in ARGET ATRP of MMA. The activation energy was calculated to be 51.96 kJ/mol. The different types of alcohol were demonstrated to be an efficient reducing agent in this system except for tert-butyl alcohol. The “living” feature of the obtained polymer was further verified by a chain extension experiment. The obtained polymer was characterized by 1H NMR and GPC.