Synthesis of Block Copolymers of 2‐Ethylhexyl Methacrylate,n‐Hexyl Methacrylate and Methyl Methacrylate via Anionic Polymerization at Ambient Temperature

It still remains a concern to break through the bottlenecks of anionic polymerization of polar monomers, such as side reactions, low conversion and low temperature (–78°C). In this work, potassium tert‐butoxide (t‐BuOK) was chosen to initiate the anionic polymerization of 2‐ethylhexyl methacrylate (EHMA) in tetrahydrofuran. The conversions were above 99% at 0 or 30°C, and above 95% at 60°C without side reaction inhibitors. The high conversions implied t‐BuOK could suppress the side reactions. A series of block copolymers of EHMA, n‐hexyl methacrylate (HMA) and methyl methacrylate (MMA) were further synthesized at 0°C, and the conversions were all above 99%. The GPC and ¹H NMR results confirmed the successful synthesis of the block copolymers. The molecular size of monomer and the state of t‐BuOK (free ion pairs or aggregates) remarkably affected the polymerization rates and the molecular structures of the products. The DMA results indicated that the glass transition temperatures of PEHMA or PHMA block and PMMA block were 20°C and 60°C, respectively, which deviated from –2°C and 105°C of homopolymer, respectively, due to the partial compatibility of the blocks. This work explored a route of the anionic polymerization of polar monomers at room temperature.     

Anionic polymerization of methacrylate monomers initiated by lithium dialkylamides

The anionic polymerization of methacrylate monomers has been investigated with lithium dialkylamides as initiators in THF and toluene, respectively. Theoretical arguments and previous studies of mixed aggregates of lithiated organic compounds support the complexity of these systems. Lithium diisopropylamide (LDA) shows the highest initiation efficiency (e.g., f = 75% in THF at −78°C). Interestingly enough, lithium chloride has a remarkable beneficial effect on the methacrylates polymerization in THF at −78°C, due to the formation of 1 : 1 mixed dimer with LDA, which promotes a well-controlled anionic polymerization (M_w/M_n = 1.05) with a high initiation efficiency (94%). The less bulky lithium–diethylamide (LDEA) is much less efficient (f = 26%), essentially as a result of some associated “dormant” species and side reactions on the carbonyl group of MMA. Although various types of ligands have been screened, no remarkable improvement of LDEA efficiency has been observed. Lithium bis(trimethylsilyl)amide (LTMSA) has also been used to increase the steric hindrance of the initiator. This compound is, however, unable to initiate the methacrylates polymerization, more likely because of a too low basicity and a too strong Li—N bond. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3637–3644, 1997     

Controlled radical polymerization of anthracene‐containing methacrylate copolymers for stimuli‐responsive materials

Novel reversible networks utilizing photodimerization of crosslinkable anthracene groups and thermal dissociation were investigated. Reversible addition‐fragmentation chain transfer polymerization yielded well‐defined copolymers with 9‐anthrylmethyl methacrylate (AMMA) and other alkyl methacrylates such as methyl methacrylate (MMA) and 2‐ethylhexyl methacrylate (EHMA) having different AMMA compositions. Well‐controlled block copolymerization of AMMA and alkyl methacrylates was also successfully accomplished using a trithiocarbonate‐terminated poly(alkyl methacrylate) macro‐chain transfer agent. The anthracene‐containing copolymers showed reversibility via crosslinking based on photodimerization with ultraviolet irradiation and subsequent thermal dissociation. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2302–2311     

Stereocontrol in the free‐radical polymerization of methacrylates with fluoroalcohols

The free‐radical polymerization of methyl methacrylate (MMA), ethyl methacrylate (EMA), isopropyl methacrylate (IPMA), and tert‐butyl methacrylate (t‐BuMA) was carried out under various conditions to achieve stereoregulation. In the MMA polymerization, syndiotactic specificity was enhanced by the use of fluoroalcohols, including (CF₃)₃COH as a solvent or an additive. The polymerization of MMA in (CF₃)₃COH at −98 °C achieved the highest syndiotacticity (rr = 93%) for the radical polymerization of methacrylates. Similar effects of fluoroalcohols enhancing syndiotactic specificity were also observed in the polymerization of EMA, whereas the effect was negligible in the IPMA polymerization. In contrast to the polymerizations of MMA and EMA, syndiotactic specificity was decreased by the use of (CF₃)₃COH in the t‐BuMA polymerization. The stereoeffects of fluoroalcohols seemed to be due to the hydrogen‐bonding interaction of the alcohols with monomers and growing species. The interaction was confirmed by NMR measurements. In addition, in the bulk polymerization of MMA at −78 °C, syndiotactic specificity and polymer yield increased even in the presence of a small amount {[(CF₃)₃COH]/[MMA]_o < 1} of (CF₃)₃COH. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4693–4703, 2000     

Synthesis of novel tetrahydrofuran‐epichlorohydrin [poly(THF‐b‐ECH)] macromonomeric peroxy initiators by cationic copolymerization and the quantum chemically investigation of initiation system effects

Cationic polymerization of tetrahydrofuran (THF) and epichlorohydrin (ECH) was performed with peroxy initiators synthesized from bis (4,4′‐bromomethyl benzoyl peroxide (BBP) or bromomethyl benzoyl t‐butyl peroxy ester (t‐BuBP) and AgSbF₆ or ZnCl₂ system at 0 °C to obtain the poly(THF‐b‐ECH) macromonomeric peroxy initiators. Kinetic studies were accomplished for poly(THF‐b‐ECH) initiators. Poly(THF‐b‐ECH‐b‐MMA) and poly(THF‐b‐ECH‐b‐S) block copolymers were synthesized by bulk polymerization of methyl methacrylate (MMA) and styrene (S) with poly(THF‐b‐ECH) initiators. The quantum chemical calculations for the block copolymers, the initiating systems of the cationic polymerization of THF and ECH were achieved using HYPERCHEM 7.5 program. The optimized geometries of the polymers were investigated with the quantum chemical calculations. Poly(THF‐b‐ECH) initiators having peroxygen groups were used for graft copolymerization of polybutadien (PBd) to obtain poly(THF‐b‐ECH‐g‐PBd) crosslinked graft copolymers. The graft copolymers were investigated by sol‐gel analysis. Swelling ratio values of the graft copolymers in CHCl₃ were calculated. The characterizations of the polymers were achieved by FTIR, ¹H NMR, GPC, SEM, TEM, and DSC techniques. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2896–2909, 2010     

Highly heterotactic polymerization of methacrylates — Higher order stereoregulation and stereochemical significance

A combination of tert-butyllithium (t-BuLi) and bis(2,6-di-t-butylphenoxy)methylaluminium (MeAI(ODBP)₂) was found to be an efficient initiator for heterotactic living polymerization of certain alkyl methacrylates in toluene at low temperatures. The polymerization of methyl methacrylate (MMA) with t-BuLi/MeAI(ODBP)₂ (AI/Li=5 mol/mol) in toluene at −78°C gave heterotactic-rich poly(methyl methacrylate) (PMMA) with narrow molecular weight distributions (MWDs) (heterotactic triad fraction mr = 68%, ratio of weight- to number-average molecular weights M̄w/M̄n = 1.06-1.17). Other alkyl methacrylates also gave heterotactic polymers under the same conditions; in particular, ethyl and butyl methacrylates gave polymers with heterotactic triad fractions of 87%. The highest triad heterotacticity of 91.6% was obtained for the polymerization of ethyl methacrylate at −95°C. Some characteristic features of this stereospecific polymerization were discussed based on the polymerization results combined with other structural information of the polymer such as chain-end stereostructure and stereosequence distribution in the main chain.     

Copolymers of methyl methacrylate and fluoroalkyl methacrylates: Effects of fluoroalkyl groups on the thermal and optical properties of the copolymers

Fluoroalkyl methacrylates, 2,2,2‐trifluoroethyl methacrylate ( 1 ), hexafluoroisopropyl methacrylate ( 2 ), 1,1,1,3,3,3‐hexafluoro‐2‐methyl‐2‐propyl methacrylate ( 3 ), and perfluoro t‐butyl methacrylate ( 4 ) were synthesized. Homopolymers and copolymers of these fluoroalkyl methacrylates with methyl methacrylate (MMA) were prepared and characterized. With the exception of the copolymers of MMA and 2,2,2‐trifluoroethyl methacrylate ( 1 ), the glass transition temperatures (T_gs) of the copolymers were found to deviate positively from the Gordon‐Taylor equation. The positive deviation from the Gordon‐Taylor equation could be accounted for by the dipole–dipole intrachain interaction between the methyl ester group and the fluoroalkyl ester group of the monomer units. These T_g values of the copolymers were found to fit with the Schneider equation. The fitting parameters in the Schneider equation were calculated, and R² values, the coefficients of determination, were almost 1.0. The refractive indices of the copolymers, measured at 532, 633, and 839 nm wavelengths, were lower than that of PMMA and showed a linear relationship with monomer composition in the copolymers. 2 and MMA have a tendency to polymerize in an alternating uniform monomer composition, resulting in less light scattering. This result suggests that the copolymer prepared with an equal molar ratio of 2 and MMA may have useful properties with applications in optical devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4748–4755, 2008     

A New View of the Initiation and Propagation in Anionic Polymerization

This work confirms the new view of the initiation and propagation mechanism of the anionic polymerization previously proposed, based on the investigation of anionic bulk‐polymerization of styrene and α‐methyl styrene with the help of a self designed microflow device and characterized by GPC and in situ ⁷Li NMR. It was found that n‐BuLi tended to form the hexameric‐aggregated structure and even to form the huge aggregated structure based on the former. These aggregations of initiators could directly initiate the anionic polymerization and form the supramolecule aggregations. The supramolecule aggregations inevitably blocked the diffusion of the monomers to the ion‐pairs and resulted in a stationary‐conversion platform. Then the aggregators were dissociated completely into equal binary‐aggregated species, and the polymerization continued again rapidly before the termination. Tetrahydrofuran (THF) acted as the electron donator, which could push the electron cloud to Li cation and make the aggregated ring of the active species rather loosened and facilitated the monomer to insert in. Therefore, a little THF can greatly promote the anionic polymerization. However, further addition of THF might block the channel between the ion‐pairs and decrease the propagation rate. It was also found that the aggregated structure of the active species during the anionic polymerization only depends on the initiator aggregations which were formed before the polymerization.     

Synthesis of traditional and ionic polymethacrylates by anion catalyzed group transfer polymerization

The hydrophobic ionic liquid 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide was successfully used as solvent in group transfer polymerization of traditional methacrylates (methyl methacrylate, n‐butyl methacrylate, and benzyl methacrylate) and of ionic liquid methacrylates (ILMAs). This demonstrates that this ionic liquid makes reaction conditions, which do not require the use of ultra‐dried solvents. The ILMAs were N‐[2‐(methacryloyloxy)ethyl]‐N,N‐dimethyl‐N‐alkylammonium bis(trifluoromethylsulfonyl)imides bearing methyl, ethyl, propyl, butyl, or hexyl substituents. Increasing size of the alkyl substituent at the cation results in decreasing glass transition temperature in case of both ionic liquid methacrylates and polymers derived of them. Furthermore, the glass transition temperature is significantly higher for these polymers compared with the ionic liquid methacrylates, and the effect of glass transition temperature reduction with increasing size of the alkyl substituent is stronger for the polymers. A mechanism was proposed explaining the catalytic function of the ionic liquid used as solvent for polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2849–2859     

Spontaneous Cu(I)Br–PMDETA‐mediated polymerization of isobornyl methacrylate in heterogeneous aqueous medium at ambient temperature

Isobornyl methacrylate (IBMA), a bulky hydrophobic methacrylate, undergoes very fast polymerization, in bulk, with Cu(I)Br/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA)/ethyl‐2‐bromoisobutyrate system, at ambient temperature. IBMA also undergoes a spontaneous initiator‐free polymerization, at ambient temperature, with Cu(I)Br/PMDETA catalytic system in dimethyl sulfoxide–water mixtures. The rate of the polymerization is seen to increase with the water content up to 80 mol % of water. A possible intervention of air in initiation is proposed. The active Cu(0) formed by the disproportionation of Cu(I) species in aqueous medium probably plays a vital role for a possible air‐initiation of IBMA via single electron transfer‐living radical polymerization (SET‐LRP) mechanism. A high tolerance level to water under SET‐LRP conditions is demonstrated. The poly(IBMA) samples obtained exhibit low molecular weight distributions (1.1–1.3). Similar behavior was not observed with other common methacrylates such as methyl methacrylate, t‐butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Hydrogen‐transfer polymerization of vinyl monomers derived from 4‐methylbenzoyl isocyanate and acrylamide derivatives

The anionic polymerization of N‐acryloyl‐N′‐(4‐methylbenzoyl)urea (1) was carried out at 80°C for 24 h in DMF, DMSO, acetonitrile, or toluene by t‐BuOK or DBU (3 mol %) as an initiator to obtain polymer 3 in a good yield. The structure of 3 was dependent upon the initiator used, in which t‐BuOK selectively conducted the hydrogen‐transfer polymerization, while DBU partially induced the vinyl polymerization (16–20%). Likewise, N‐acryloyl‐N‐methyl‐N′‐(4‐methylbenzoyl)urea (2, i.e., an N‐methylated derivative of 1) was subjected to the hydrogen‐transfer polymerization. Although the yield of the polymer was lower in comparison with 1, the structure of the obtained polymer 4 was similarly governed by the initiator. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 465–472, 1999     

Synthesis and characterization of amphiphilic heterograft copolymers with PAA and PS side chains via “Grafting from” approach

The amphiphilic heterograft copolymers poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)ethyl methacrylate)‐graft‐(poly(acrylic acid)/polystyrene) (P(MMA‐co‐BIEM)‐g‐(PAA/PS)) were synthesized successfully by the combination of single electron transfer‐living radical polymerization (SET‐LRP), single electron transfer‐nitroxide radical coupling (SET‐NRC), atom transfer radical polymerization (ATRP), and nitroxide‐mediated polymerization (NMP) via the “grafting from” approach. First, the linear polymer backbones poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)ethyl methacrylate) (P(MMA‐co‐BIEM)) were prepared by ATRP of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA) and subsequent esterification of the hydroxyl groups of the HEMA units with 2‐bromoisobutyryl bromide. Then the graft copolymers poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)ethyl methacrylate)‐graft‐poly(t‐butyl acrylate) (P(MMA‐co‐BIEM)‐g‐PtBA) were prepared by SET‐LRP of t‐butyl acrylate (tBA) at room temperature in the presence of 2,2,6,6‐tetramethylpiperidin‐1‐yloxyl (TEMPO), where the capping efficiency of TEMPO was so high that nearly every TEMPO trapped one polymer radicals formed by SET. Finally, the formed alkoxyamines via SET‐NRC in the main chain were used to initiate NMP of styrene and following selectively cleavage of t‐butyl esters of the PtBA side chains afforded the amphiphilic heterograft copolymers poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)ethyl methacrylate)‐graft‐(poly(t‐butyl acrylate)/polystyrene) (P(MMA‐co–BIEM)‐g‐(PtBA/PS)). The self‐assembly behaviors of the amphiphilic heterograft copolymers P(MMA‐co–BIEM)‐g‐(PAA/PS) in aqueous solution were investigated by AFM and DLS, and the results demonstrated that the morphologies of the formed micelles were dependent on the grafting density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Preparation of a copolymer of methyl methacrylate with a new monomer, 2,2,6,6‐tetramethyl‐4‐benzyloxyl‐piperidinyl methacrylate,and its initiation of the graft copolymerization of styrene with a controlled radical mechanism

A copolymer [P(MMA‐co‐TBPM)] was prepared by the radical polymerization of methyl methacrylate (MMA) and 2,2,6,6‐tetramethyl‐4‐benzyloxyl‐piperidinyl methacrylate (TBPM) with azobisisobutyronitrile as an initiator. TBPM was a new monomer containing an activated ester. Both the copolymer and TBPM were characterized with NMR, IR, and gel permeation chromatography in detail. It was confirmed that P(MMA‐co‐TBPM) could initiate the graft polymerization of styrene by the cleavage of the activated ester of the TBPM segment. This process was controllable, and the molecular weight of the graft chain of polystyrene increased with the increment of conversion. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4398–4403, 2002     

Polymerization of acrylates and bulky methacrylates with the use of zirconocene precursors: Block copolymers with methyl methacrylate

The polymerization behavior of cyclohexyl methacrylate and trimethylsilyloxyethyl methacrylate with the catalytic system Cp₂ZrMe₂/B(C₆F₅)₃/ZnEt₂ was examined. Block copolymers of these bulky methacrylates with methyl methacrylate (MMA), having high molecular weights and relatively narrow molecular weight distributions, were prepared. n‐Butyl acrylate and tert‐butyl acrylate were polymerized with various catalytic systems based on zirconocene complexes. These polymerizations seemed to proceed to a nonquantitative yield, producing polymers with high molecular weights and relatively low polydispersities. This behavior indicated the presence of termination reactions in the initiation step, which appeared to be faster than the propagation step. Block copolymers of these acrylates with MMA were synthesized with the catalytic system rac‐Et(Ind)₂ZrMe₂/[B(C₆F₅)₄]⁻[Me₂NHPh]⁺/ZnEt₂, starting from the polymerization of MMA. The block copolymers produced were well defined in most cases, as indicated by size exclusion chromatography, NMR, and differential scanning calorimetry measurements. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3337–3348, 2005     

Synthesis of Hydroxy-Functional PMMA Macromonomers by Anionic Polymerization

Living anionic polymerization has been utilized to synthesize hydroxy end-functionalized PMMA macromonomers with styryl or allyl functionalities as the polymerizable end-groups. Protected hydroxy-functionalized alkyl lithium initiators have been used to initiate anionic polymerization of MMA. Subsequently the living chains with protected hydroxyl function have been terminated using 4-vinylbenzyl chloride (4-VBC) or allyl methacrylate (ALMA) to form α-hydroxy-ω-styryl and α-hydroxy-ω-allyl PMMA, respectively. These protected hydroxy-functionalized PMMA macromonomers have been characterized by GPC and ¹H-NMR. Termination using 4-VBC led to 50% functionalization, whereas that using allyl methacrylate led to 100% functionalization of the hydroxy-PMMA.     

Living anionic polymerization of lauryl methacrylate and synthesis of block copolymers with methyl methacrylate

Anionic polymerization of lauryl methacrylate (LMA) with 1,1‐diphenylhexyl lithium in tetrahydrofuran (THF) at ?40 °C resulted in a multimodal and broad molecular weight distribution (MWD) with poor initiator efficiency. In the presence of additives such as dilithium salt of triethylene glycol (G₃Li₂), LiCl, and LiClO₄, the polymerization resulted in polymers with a narrow MWD (≤ 1.10). Diblock copolymers of methyl methacrylate (MMA) and LMA were synthesized by anionic polymerization using DPHLi as initiator in THF at ?40 °C with the sequential addition of monomers. The molecular weight distribution of the polymers was narrow and without homopolymer contamination when LMA was added to living PMMA chain ends. Diblock copolymers with broad/bimodal MWD were obtained with a reverse‐sequence monomer addition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 875–882, 2004     

Computational study of alkyllithium/pyridine derivative systems as initiators for the living anionic polymerization of methyl methacrylates

The reactivity of n‐butyllithium (n‐BuLi) toward pyridine derivatives (pyridine, pyridazine, pyrimidine, and 1,3,5‐triazine) was subjected to a computational study to determine the most suitable n‐BuLi/heterocyclic ring system as an initiator for the anionic polymerization of methyl methacrylate (MMA). These systems were suggested to prevent side reactions occurring through n‐BuLi attack on the carbonyl carbon of MMA by sterically blocking the initiator. The initiation reaction was modeled with the B3LYP methodology 6‐31+G*. Activation barriers were used to analyze the reactivity of each n‐BuLi/heterocyclic ring system. Computational results showed that n‐BuLi/triazine had a significantly lower activation barrier. Therefore, n‐BuLi/triazine was the suggested initiator system for the anionic polymerization of poly(methyl methacrylate). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 455–467, 2005     

Preparation and functionalization of linear and reductively degradable highly branched cyanoacrylate‐based polymers

Ethyl cyanoacrylate (ECA) was polymerized radically in the presence of small amounts of trifluoroacetic acid as effective inhibitor of incidental anionic polymerization. Methyl methacrylate and other functional vinyl monomers (e.g., 2‐chloroethyl and 2‐bromoethyl methacrylate) were copolymerized with ECA, yielding linear ECA‐rich copolymers, which could readily undergo further modifications, for instance nucleophilic substitution with azide. In the presence of a disulfide‐containing dimethacrylate crosslinker and a chain transfer agent (CBr₄) during the free radical copolymerizations of ECA with methacrylates, highly branched ECA‐based polymers containing disulfide groups at the branching points were obtained prior to gelation. The polymers degraded upon addition of reducing agents. The prepared polymers, which contained peripheral (chain end) alkyl bromide groups as well as pendant alkyl chloride or bromide groups were then reacted with sodium azide, affording azide‐containing polymers that were reacted with functional alkynes under copper‐catalyzed “click” chemistry conditions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3683–3693     

Polymerization of o‐quinodimethanes. V. Ionic polymerization of o‐quinodimethanes generated by thermal isomerization of corresponding benzocyclobutenes

The ionic polymerization of substituted o‐quinodimethanes via thermal isomerization of benzocyclobutenes is described. In the cationic polymerizations of 1‐methoxy‐o‐quinodimethane in the presence of various cationic initiators at 110 °C for 12 h, chain transfer reactions also considerably underwent besides the polymerization. Meanwhile, cationic polymerizations of 1‐trimethylsilyloxy‐o‐quinodimethane under the same conditions gave good yields of the corresponding polymer. Anionic polymerizations of 1‐cyano‐o‐quinodimethane in the presence of anionic initiators such as n‐BuLi or t‐BuOK were performed at various temperatures for 12 h. Good yields of hexane‐insoluble polymer, which was produced by anionic polymerization of corresponding o‐quinodimethane as an intermediate, were obtained above 120 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 844–850, 2008     

Ligand‐free Cu(0)‐mediated controlled radical polymerization of methyl methacrylate at ambient temperature

For the first time, ligand‐free Cu(0)‐mediated polymerization of methyl methacrylate (MMA) was realized by the selection of ethyl‐2‐bromo‐2‐phenylacetate as initiator at ambient temperature. The polymerization can reach up to 90% conversion within 5 h with dimethyl sulfoxide (DMSO) as solvent, while keeping manners of the controlled radical polymerization. Extensive investigation of this system revealed that for a well‐controlled Cu(0)‐mediated polymerization of MMA, the initiator should be selected with the structure as alkyl 2‐bromo‐2‐phenylacetate, and the solvent should be DMSO or N,N‐dimethylformamide. The selectivity for solvents indicated a typical single‐electron transfer‐living radical polymerization process. Scanning for other monomers indicated that under equal conditions, the polymerizations of other alkyl (meth)acrylates were uncontrollable. Based on these results, plausible reasons were discussed. The ligand‐free Cu(0)‐mediated polymerization showed its superiority with economical components and needless removal of Cu species from the resultant products. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012