Atom‐Transfer Radical Polymerization: A Strategy for the Synthesis of Halogen‐Free Amino‐Functionalized Poly(methyl methacrylate) in a One‐Pot Reaction

Summary: An initiator containing an alkyl bromide unit and a protected amine functional group is used with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA), in a 1:2 molar ratio with respect to initiator concentration, in order to obtain amino‐group terminated as well as halogen‐free poly(methyl methacrylate) (PMMA) in a one‐pot atom‐transfer radical polymerization (ATRP). The terminal bromines are replaced by hydrogen atoms of the PMDETA ligand, which acts as a transfer agent. However, terminating side reactions like disproportionation or dehydrobromination occur from the beginning of the polymerization. Kinetic studies by in‐line Raman spectroscopy and off‐line ¹H NMR spectroscopy revealed that the controlled character of the ATRP is lost under these conditions. The measured molecular weights were consistently higher than the theoretical ones and the molecular weight distributions are relatively broad. Thermal analysis of the obtained poly(methyl methacrylate) shows two main degradation steps, one starting from unsaturated end groups (depolymerization), and one caused by main‐chain scission, a further proof for the occurrence of terminating side reactions.

Structural analysis of PMMA by matrix‐assisted laser desorption‐ionization mass spectrometry.     

Molecular Dynamics of Poly(ethylene‐2,5‐furanoate) (PEF) as a Function of the Degree of Crystallinity by Dielectric Spectroscopy and Calorimetry

The segmental and local dynamics of the bio‐based polyester poly(ethylene‐2,5‐furanoate) (PEF) are investigated by dielectric spectroscopy (DS) at atmospheric pressure as a function of temperature and frequency for samples prepared with different degrees of crystallinity. Crystallization significantly alters the segmental process as this is manifested in the dielectric strength and the distribution of relaxation times. Enhanced crystallinity by the different annealing protocols increases the glass temperature of the mobile amorphous fraction. A two‐phase model is adequate in describing the dynamics associated with the β‐process within the glassy state. However, the same model fails in describing the segmental dynamics at and above the glass temperature. The combined differential scanning calorimetry and DS results provide evidence that for samples with a degree of crystallinity of ≈40%, approximately a third of segments are located within the restricted amorphous fraction.

     

Synthesis of Polystyrene‐block‐Poly(methyl methacrylate) with Fluorene at the Junction: Sequential Anionic and Controlled Radical Polymerization from a Single Carbon

Polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) has been synthesized by sequential anionic and reverse atom transfer radical polymerization (ATRP) or a variation of nitroxide mediated polymerization (NMP) from a single initiating site, specifically the 9‐carbon on 2,7‐dibromofluorene or fluorene. The addition of the second arm (PS) relied on thermal decomposition of 2,2′‐azoisobutyronitrile (AIBN) to generate radicals, abstracting the 9‐H on the polymer‐bound fluorene species to form the initiating radical. Styrene was not present in the reaction mixture when AIBN was decomposed, preventing competition between addition across the monomeric alkene and hydrogen abstraction from the fluorene. After 1 h, styrene was introduced and mediation of the subsequent radical polymerization was achieved by the presence of CuCl₂/ligand or TEMPO. Characterization of the diblock copolymers by gel permeation chromatography (GPC) revealed substantial shifts in number average molecular weight ( ) values compared to the anionically prepared PMMA macroinitiator, while polydispersity indices (PDI's) remained relatively low (typically < 1.5). Characterization by UV detection with GPC (at 310 nm) verified that the diblock polymer is chromophore‐bound, which was further verified by UV‐vis spectroscopy of the isolated diblock.