Kinetic Study of the Homogeneous Atom Transfer Radical Polymerization of Methyl Methacrylate

Abstract

The homogeneous controlled/“living” radical polymerization of methyl methacrylate (MMA) using the atom transfer radical polymerization (ATRP) with CuCl/4,4‘-di(5-nonyl)-2,2‘-bipyridine catalytic system and diphenyl ether as the solvent generated well-defined polymers with polydispersities M w/M n ≤ 1.2. The evolution of the molecular weights of the polymers follows the ratio of the mass of the consumed monomer to the initial initiator concentration. The rate of polymerization follows first-order kinetics with respect to the decrease of monomer concentration. The polymerization rate reaches a maximum when the ratio of ligand-to-CuICl is one-to-one. ATRP of MMA shows first-order kinetics with respect to both CuICl and the initiator, alkyl or sulfonyl chloride. The rate of polymerization did not obey simple negative first-order kinetics with respect to the concentration of CuIICl, partially due to a persistent radical effect, which resulted in the increase of [CuIICl] in the initial stage of polymerization. Thermodynamic data and activation parameters for the solution ATRP of MMA are reported.

The electrochemical detection of Ru(II) in a methyl methacrylate solution

“…The bode plots obtained in a MMA solution with different concentrations of TBABF 4 are shown in Fig. 2a and b, which show the behaviour of, respectively, log|Z| and the phase angle versus log f. As expected the resistance drops by adding TBABF 4 .…”

“…A home prepared Ag|AgNO 3 |CH 3 CN reference electrode (RE) was used for the experiments in methyl methacrylate and a double junction containing TBABF 4 in MMA was used in order to avoid CH 3 CN entering the electrochemical cell. A platinum net (Goodfellow, UK) acted as counter electrode.…”

“…In this potential range where RuCl 2 (PPh 3 ) 3 is electroactive, additional reactions of the solvent or electrolyte were not observed. Table 1 Resistance R , conductivity κ and molar conductivity Λ measured, respectively, calculated for different TBABF 4 concentrations In Fig and −0.04 V versus RE. The reduction processes are located at −0.92, −0.66, −0.41 and −0.2 V versus RE.…”

“…One of the most successful methods to make well-defined polymers is through atom transfer radical polymerization (ATRP) [1][2][3][4][5][6][7][8]. This method employs a redox process with transition metal complexes in which a halogen ion is transferred reversibly between the transition metal and the polymer chain end.…”

Modelling polycarbonate synthesis rates on the example of bulk heteropolyaddition of diphenyl carbonate and bisphenol A diglycidyl ether

“…This value is related to the reaction and not to the reagent. In looking to associate the rate of reaction not with the reaction but reagent [2], this paper used the concept of partial reaction rate constant, replacing the reaction rate constant by a product of partial reaction rate constants as shown below:…”