New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers

The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed.     

Triphilic pentablock copolymers with perfluoroalkyl segment in central position

Adding perfluoroalkyl (PF) segments to amphiphilic copolymers yields triphilic copolymers with new application profiles. Usually, PF segments are attached as terminal blocks via Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC). The purpose of the current study is to design new triphilic architectures with a PF segment in central position. The PF segment bearing bifunctional atom transfer radical polymerization (ATRP) initiator is employed for the fabrication of triphilic poly(propylene oxide)-b-poly(glycerol monomethacrylate)-b-PF-b-poly(glycerol monomethacrylate)-b-poly(propylene oxide) PPO-b-PGMA-b-PF-b-PGMA-b-PPO pentablock copolymers by a combined ATRP and CuAAC reaction approach. Differential scanning calorimetry indicates the PF-initiator to undergo a solid–solid phase transition at 63°C before the final crystal melting at 95°C. This is further corroborated by polarized optical microscopy and X-ray diffraction studies. The PF-initiator could successfully polymerize solketal methacrylate (SMA) under typical ATRP conditions producing well-defined Br-PSMA-b-PF-b-PSMA-Br triblock copolymers that are then converted into PPO-b-PSMA-b-PF-b-PSMA-b-PPO pentablock copolymer via CuAAC reaction. Subsequently, acid hydrolysis of the PSMA blocks afforded water soluble well-defined triphilic pentablock copolymers PPO-b-PGMA-b-PF-b-PGMA-b-PPO with fluorophilic central segment, hydrophilic middle blocks, and lipophilic outer blocks. The triphilic block copolymers could self-assemble, depending upon the preparatory protocol, into spherical and filament-like phase-separated nanostructures as revealed by transmission electron microscopy.     

General strategy for a short and efficient synthesis of 3-hydroxy-4-methylprolines (HMP)

The non-proteinogenic amino acid 3-hydroxy-4-methylproline (HMP) is an active constituent of some potent antimicrobials including echinocandins, nostopeptins, pneumocandins, sporiofungin and mulundocandins. A synthesis has been achieved in 10 steps with 29% overall yield; the Evans’ aldol reaction using Crimmins’ modified method was pivotal to the success of the strategy.     

A novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate

A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, Cu^IBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities M_w/M_n ≤ 1.23. The rate of polymerization follows first‐order kinetics, k_app = 3.4 × 10^?5 s^?1, indicating the presence of low radical concentration ([P*] ≤ 10^?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (M_n,SEC) increased linearly with conversion and were found to be higher than predicted molecular (M_n,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (M_n = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (M_n = 10,300), which is achieved in 23 h. The plot of lnk_app versus 1/T gave an apparent activation energy of polymerization as (ΔE^≠_app) 58.29 KJ/mol and enthalpy of equilibrium (ΔH⁰_eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005     

Living/controlled radical copolymerization of N‐substituted maleimides with styrene in 1‐butyl‐3‐methylimidazolium hexafluorophosphate and anisole

The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < M_w/M_n < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF₆] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003     

Dicyclopentadienyl complexes of titanium,niobium, and tungsten in the controlled synthesis of poly(methyl methacrylate)

Organometallic compounds Cp₂TiCl₂, (EtC₅H₄)₂NbCl₂, and (PrⁱC₅H₄)₂WCl₂ were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed.     

New 7‐membered diazepanone alkoxyamines for nitroxide‐mediated radical polymerization

The synthesis of new 7‐membered diazepanone alkoxyamines [2,2,7,7‐tetramethyl‐1‐(1‐phenyl‐ethoxy)‐[1,4]diazepan‐5‐one ( 3 ) and 2,7‐diethyl‐2,3,7‐trimethyl‐1‐(1‐phenyl‐ethoxy)‐[1,4]diazepan‐5‐one ( 8 )] through the Beckmann rearrangement of piperidin‐4‐one alkoxyamines was developed. Both 3 and 8 were evaluated as initiators and regulators for the nitroxide‐mediated radical polymerization of styrene and n‐butyl acrylate. 8 , a sterically highly hindered alkoxyamine readily available as a crystalline solid, allowed the fast and controlled polymerization and preparation of polymers with low polydispersity indices (1.2–1.4) up to a degree of polymerization of about 100. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3332–3341, 2004     

Synthesis,dynamic light scattering,and luminescence properties of copolymers containing iridium(III) bisterpyridine in the side chain

Supramolecular block‐random copolymers containing [Ir(terpy)₂]³⁺ in the side chain were synthesized via postfunctionalization of a P(S‐b‐AC_terpy) block copolymer. Absorbance and emission spectra compared to a model compound show that the polymer backbone has a minor effect on the polymer absorbance but produces a larger shift for the phosphorescence signals to higher wavelength. Dynamic light scattering of the metal complex containing copolymer studied in various solvents showed monomodal aggregation with decreasing aggregate size as the solvent dielectric constant increased. The copolymer precursor P(S‐b‐AC_terpy) shows multimodal aggregation in different solvents with the major population consisting of single chains. This difference in behavior between the two polymers is attributed to the electrolytic nature of the complex and the amphiphilicity induced by the charged metal complex. Supramolecular copolymers like these will continue to have interesting self‐organizational properties and may find applications in multicomponent systems for photoinduced charge separation processes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1109–1121, 2007     

Diblock copolymers based on allyl methacrylate: Synthesis,characterization, and chemical modification

Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), ¹H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007     

Controlled/living polymerization of 2‐(diethylamino)ethyl methacrylate and its block copolymer with tert‐butyl methacrylate by atom transfer radical polymerization

Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003