Iron-based N -heterocyclic carbene (FeX 3 (NHC)) complexes were used in initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP). A series of ICAR ATRPs of methyl methacrylate (MMA) and styrene (St) were carried out using FeX 3 (IDipp) where IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene with X = Cl (I−Cl) or Br (I−Br) and FeX 3 (HIDipp) (HIDipp =1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene) with X = Cl (H− Cl) or Br (H−Br). The polymerizations showed good activity, resulting in polymers with controlled molecular weights and narrow molecular weight distribution (MWD) with low loading of catalysts (50 ppm). In particular, I−Br and H−Br generated polymers with narrower MWD. For example, ICAR ATRP of MMA with 50 ppm catalysts (H−Br) after 24 h at T = 60°C in 50% v/v anisole resulted in PMMA with M w /M n = 1.20 at 65% monomer conversion. ICAR ATRP of St after 72 h resulted in PSt with M w /M n = 1.15 at 53% monomer conversion.

Two novel phenylacetylene derivatives bearing diethylaminomethyl groups at the meta position on phenyl groups [3‐(N,N‐diethylaminomethyl)phenyl]acetylene (1) and [3,5‐bis(N,N‐diethylaminomethyl)phenyl]acetylene (2) were synthesized and polymerized with [Rh(nbd)Cl]2 (nbd: norbornadiene). Both monomers gave highly cis–transoidal stereoregular polymers that exhibited an induced circular dichroism (ICD) in the UV–visible region, probably because of a prevailing one‐handed helical conformation upon complexation with optically active carboxylic acids such as mandelic acid and lactic acid. The sign of the Cotton effects reflected the absolute configuration of the chiral acids. Therefore, these polymers can be used as a novel probe for determining the configuration of chiral acids. The polymers were stable in the presence of chiral acids in solution. The poly‐1 complexed with chiral acids exhibited a split‐type ICD, whereas the poly‐2 complexed with chiral acids showed a different, non‐split‐type ICD. The ICD pattern of the poly‐1/chiral acids complexes dramatically changed with an increase in the concentration of the chiral acids, thus showing a non‐split‐type ICD similar to those of the poly‐2/chiral acid complexes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3180–3189, 2001

Poly(N‐phenylitaconimide) (polyPhII) was prepared using initiators for continuous activator regeneration atom transfer radical polymerization of PhII using FeBr3 complexes as catalysts. Conversion reached 69% in 24 h, yielding polyPhII with a number average molecular weight Mn = 11,900 and a molecular weight distribution Mw/Mn = 1.52. Copolymerizations of PhII with styrene at various molar ratios were performed providing a range of polyPhII‐copolySt polymers. When the copolymerization was carried out with higher [St]0 > [PhII]0 ratio, a one‐pot synthesis of poly(St‐alt‐PhII)‐b‐polySt was achieved. The thermal properties of the obtained copolymers were studied by differential scanning calorimetry. PolyPhII prepared by ATRP showed high glass transition temperature (Tg) of 216 °C and the poly(St‐alt‐PhII)‐b‐polySt exhibited two Tgs, at 162 and 104 °C, corresponding to a poly(St‐alt‐PhII) and polySt segments, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 822–827