Molecular weight step-growth polymerizations

The preceding discussions of the kinetics and molecular weight distributions in the step-growth polymerization of AB monomers are clearly exemplified by the esterification reactions of such monomers as glycolic acid or co-hydroxydecanoic acid. Therefore one method for polyester synthesis is the following ... 

Thiol-ene polymerization was first reported in 1938.220 In this process, a polymer chain is built up by a sequence of thiyl radical addition and chain transfer steps (Scheme 7.17). The thiol-ene process is unique amongst radical polymerizations in that, while it is a radical chain process, the rate of molecular weight increase is more typical of a step-growth polymerization. Polymers ideally consist of alternating residues derived from the diene and the dithiol. However, when dienes with high kp and relatively low A-, monomers (e.g. acrylates) are used, short sequences of units derived from the diene are sometimes formed. 

Linear step-growth polymerizations require exceptionally pure monomers in order to ensure 1 1 stoichiometry for mutually reactive functional groups. For example, the synthesis of high-molecular-weight polyamides requires a 1 1 molar ratio of a dicarboxylic acid and a diamine. In many commercial processes, the polymerization process is designed to ensure perfect functional group stoichiometry. For example, commercial polyesterification processes often utilize dimethyl terephthalate (DMT) in the presence of excess ethylene glycol (EG) to form the stoichiometric precursor bis(hydroxyethyl)terephthalate (BHET) in situ. 

Linear novolac resins prepared by reacting para-alkylphenols with paraformaldehyde are of interest for adhesive tackifiers. As expected for step-growth polymerization, the molecular weights and viscosities of such oligomers prepared in one exemplary study increased as the ratio of formaldehyde to para-nonylphenol was increased from 0.32 to 1.00.21 As is usually the case, however, these reactions were not carried out to full conversion, and the measured Mn of an oligomer prepared with an equimolar phenol-to-formaldehyde ratio was 1400 g/mol. Plots of apparent shear viscosity versus shear rate of these p-nonylphenol novolac resins showed non-Newtonian rheological behavior. 

Like other step-growth polymerization methods, factors such as the monomer purity, ratio of the monomers, conversion, temperature, and concentration will greatly influence the transition metal coupling polymerization. These factors have to be taken into account when higher molecular weight polymers need to be prepared.33... 

Conditions that are important to all chemical reactions such as stoichiometry and reactant purity become critical in polymer synthesis. In step growth polymerization, a 2% measuring and/or impurity error cuts the degree of polymerization or the molecular weight in half. In chain growth polymerization, the presence of a small amount of impurity that can react with the growing chain can kill the polymerization. 

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