Fourier transform infrared spectroscopy (FT-IR) is employed for the quantitative tracking of the structural evolution of poly(acrylonitrile-co-itaconic acid) (PAI) with different itaconic acid (IA) contents during its thermal oxidative stabilization (TOS). The TOS process includes cyclization, oxidation and tautomerization, as characterized by the evolution of the overlapping peaks of cyclic CC, CN, N–H and CO vibrations in FT-IR. The second derivatives of the spectra facilitate the identification of the position of each contributing structure. The following peak-fitting operations and the determination of the molar absorption coefficients using model compounds allow the quantitative tracking of the extent of the TOS process. PAI containing approximately 3 mol % IA exhibits the most efficient TOS process in terms of cyclization, oxygen uptake and dehydrogenation reactions. A quantitative investigation of the evolution of PAI using FT-IR is an efficient way to determine the optimal structural characteristics of the precursors for carbon materials.

A series of hybrid catalysts, comprising a tethered ligand immobilized catalyst operating in conjunction with a small amount of soluble catalyst, were evaluated for atom transfer radical polymerization (ATRP). The level of control over the ATRP of vinyl monomers was significantly improved by the addition of part per million levels of a soluble catalyst, or soluble catalyst precursor, to the immobilized catalyst. Use of a hybrid catalyst system for polymerization of vinyl monomers such as MMA, MA, and styrene provided polymers with a predetermined molecular weight and a narrow molecular weight distribution. The immobilized catalyst can be removed from the polymerization by simple filtration, or sedimentation, affording a colorless transparent polymer solution with a salient reduction in the concentration of any residual transition metal in the final polymeric products.

A new two-component catalyst system consisting of an immobilized catalyst and a soluble catalyst in ppm quantities was applied to atom transfer radical polymerization (ATRP). A high conversion of monomer (>90%) was achieved with a predetermined molecular weight and narrow molecular weight distribution (M w/Mn ) 1.1-1.3) in the ATRP of methyl methacrylate and methyl acrylate. The immobilized catalyst was removed by a filtration or sedimentation procedure. The casting of the reaction solution afforded clear and colorless polymer films. It was confirmed by the inductively coupled plasma (ICP) analysis that the residual amount of Cu in the resulting polymer was as low as 20 ppm.

Poly(n-butyl acrylate)-graft-branched polyethylene was successfully prepared by the combination of two living polymerization techniques. First, a branched polyethylene macromonomer with a methacrylate-functionalized end group was prepared by Pd-mediated living olefin polymerization. The macromonomer was then copolymerized with n-butyl acrylate by atom transfer radical polymerization. Gel permeation chromatography traces of the graft copolymers showed narrow molecular weight distributions indicative of a controlled reaction. At low macromonomer concentrations corresponding to low viscosities, the reactivity ratios of the macromonomer to n-butyl acrylate were similar to those for methyl methacrylate to n-butyl acrylate. However, the increased viscosity of the reaction solution resulting from increased macromonomer concentrations caused a lowering of the apparent reactivity ratio of the macromonomer to n-butyl acrylate, indicating an incompatibility between nonpolar polyethylene segments and a polar poly(n-butyl acrylate) backbone. The incompatibility was more pronounced in the solid state, exhibiting cylindrical nanoscale morphology as a result of microphase separation, as observed by atomic force microscopy.

Abundant, inexpensive, renewable, and nontoxic carbon dioxide (CO2) has become an attractive feedstock for chemical and polymer syntheses. The use of CO2 as a sustainable precursor for polyurethane has become prominent in polymer industry. In this study, polyols produced from CO2 were successfully incorporated into thermoplastic polyurethanes (TPUs). The thermal, mechanical, shape memory, and anticorrosion properties of the TPUs were investigated. TPUs with CO2-based polyols appeared as hard plastics with relatively high T g and tension set values. The rigid carbonate units of the CO2-based polyols reduced the softness of the polyol chains. The CO2-based polyols also afforded TPU with excellent shape memory characteristics, exhibiting shape fixity and shape recovery values of almost 100%. Interestingly, the incorporation of CO2-based polyols into TPUs improved the anticorrosion characteristics, regardless of the corrosive media. The improved anticorrosion characteristics stemmed from the robust, hydrophobic, and blocking properties of the carbonate units. This allows the TPU to be used in hard coatings for high-performance applications. CO2-based polyols are promising alternatives to conventional petroleum-based polyols and can be used for the fixation of waste CO2 and decreasing the carbon footprint of chemical processes.