Radical Copolymerization Kinetics of Bio-Renewable Butyrolactone Monomer in Aqueous Solution

Sharmaine Luk,Robin Hutchinson

doi:10.3390/pr5040055

Abstract

The radical copolymerization kinetics of acrylamide (AM) and the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB), formed by saponification of the bio-sourced monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL), are investigated to explain the previously reported slow rates of reaction during synthesis of superabsorbent hydrogels. Limiting conversions were observed to decrease with increased temperature during SHMeMB homopolymerization, suggesting that polymerization rate is limited by depropagation. Comonomer composition drift also increased with temperature, with more AM incorporated into the copolymer due to SHMeMB depropagation. Using previous estimates for the SHMeMB propagation rate coefficient, the conversion profiles were used to estimate rate coefficients for depropagation and termination (kt). The estimate for kt,SHMeMB was found to be of the same order of magnitude as that recently reported for sodium methacrylate, with the averaged copolymerization termination rate coefficient dominated by the presence of SHMeMB in the system. In addition, it was found that depropagation still controlled the SHMeMB polymerization rate at elevated temperatures in the presence of added salt.

Highlights

Water-soluble polymers are used extensively in personal products for hair care [1] and detergents [2], with crosslinked materials utilized as absorbent hydrogels in diapers or feminine products [3]
Kollár et al demonstrated that MBL could be saponified with sodium hydroxide (NaOH) to make a water-soluble monomer, sodium 4-hydroxy-2-methylene butanoate (SHMB), that was copolymerized with acrylamide (AM) and crosslinker to make superabsorbent hydrogels that exhibited superior water absorbency compared to conventional sodium acrylate:AM materials [11]
A plateau in conversion was observed for sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB):AM copolymerizations conducted at 3:7 and 4:6 molar ratios and elevated temperatures, with monomer composition drift occurring at a faster rate as temperature increased and AM incorporated faster as SHMeMB units became more prone to depropagation

Summary

Introduction

Water-soluble polymers are used extensively in personal products for hair care [1] and detergents [2], with crosslinked materials utilized as absorbent hydrogels in diapers or feminine products [3]. Γ-methyl-α-methylene-γ-butyrolactone (MeMBL) have previously been homopolymerized [7,8]. Kollár et al demonstrated that MBL could be saponified with sodium hydroxide (NaOH) to make a water-soluble monomer, sodium 4-hydroxy-2-methylene butanoate (SHMB), that was copolymerized with acrylamide (AM) and crosslinker to make superabsorbent hydrogels that exhibited superior water absorbency compared to conventional sodium acrylate:AM materials [11]. In an extension of that work, MeMBL was saponified to sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB) (see Scheme 1), which was copolymerized with AM and crosslinker to make similar superabsorbent materials [12].

Methods

Results

Conclusion