A general kinetic method to predict sequence length distributions for non-linear irreversible multicomponent polymerizations

Abstract

A method to predict the sequence length distribution (SLD) for homogeneous non-linear irreversible multicomponent polymerizations is described. With more than two monomers, it also predicts chain length distributions of the sub-domains containing a prescribed sub-set of the repeating units, but in all possible orderings. Its goal is the analysis of polymerization systems involving complex kinetic schemes in an automated way. The radical terpolymerization of two vinyl monomers with a divinyl monomer and a radical copolymerization including branching by transfer to polymer and by propagation on terminal double bonds are considered as case studies showing the interest of our approach. Finally, the concept of gelation of sequences is presented and discussed in comparison with the related and better known gelation of the population of polymer molecules.

Time Programmed Feed of Semi‐Batch Reactors with Non‐Linear Radical Copolymerizations: An Experimental Study of the System Styrene + Divinylbenzene Using SEC/MALLS

“…[8][9][10] Twenty nine different chemical species are considered as shown in Table 1. The copolymerization of styrene with commercial divinylbenzene (mixture of isomers), eventually in the presence of an inhibitor and/or a retarder (besides initiator, solvent and a chain transfer agent) is considered.…”

Kinetic Modeling of Hyperbranched Polymer Synthesis through Atom‐Transfer and Nitroxide‐Mediated Radical Polymerization of Vinyl/Divinyl Monomers

“…A general kinetic approach allowing the prediction of molecular size distributions, sequence size distributions and z-average radius of gyration for irreversible non-linear polymerizations has been recently developed [16][17][18][19] based upon a study from the early 1990's [20]. This method can be applied before and after gelation and is capable of dealing with important complexities of non-linear polymerizations, e.g., the existence of multiple kinds of radicals and double bonds.…”

“…As presented in detail elsewhere [16][17][18][19][20], for irreversible polymerizations it is possible to write generating functions of the rate equations of formation of polymer species by chemical reactions, which will be generically represented here by G R P , G R S and G R Hn in Eqs. (4)- (6).…”

Prediction of mean square radius of gyration of tree-like polymers by a general kinetic approach

“…Successful calculation of MSD before and after gelation by this method has already been presented using a non-linear radical polymerization as an example [23]. Recently, this approach was also extended to the calculation of sequence length distributions for non-linear irreversible multicomponent polymerizations [25].…”