It’s all about diffusion: Measurements and modeling of particle morphologies in dispersed-phase polymerization

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Contrasting acrylate versus methacrylate crosslinking reactions and the impact of temperature

Divinyl monomers containing multiple vinyl groups are commonly used in polymerization reactions to introduce crosslinked networks. The reactivity of the second vinyl group in a crosslinker monomer decreases once it becomes incorporated in a polymer chain. This Reduced Reactivity Parameter (Ψ) depends on the monomer-crosslinker pair. To date, our group has developed this concept exclusively from methacrylate-based copolymerization systems1,2. Acrylate co-monomers introduce another level of complexity from a competing mechanism toward gel content and macromolecular network development; long chain branching from chain transfer to polymer. The later form networks via α-hydrogen abstraction, which is a prominent reaction with acrylates. Moreover, the differences in reactivity ratio between acrylates and methacrylates add another layer of heterogeneity through the polymerization which also impacts the kinetics and ultimate network structure. In this work, we compare the network formation reaction and the Ψ-parameters for 1,4 butanediol dimethacrylate (BDDMA, containing methacrylate groups) with its acrylate-based counterpart (BDDA, containing acrylate groups) in copolymerization reactions with either n-butyl methacrylate (nBMA) or n-butyl acrylate (nBA). The Ψ-parameter for all systems is estimated by comparing the experimental results with Monte Carlo simulations of the polymerization reactions. The goal of the work is to decouple the contributions of pendent-vinyl based crosslinking and long-chain branching (α-hydrogen abstraction) from the resulting kinetic profile that the Ψ parameter is determined from. Moreover, we contrast the balance of contributions from propagation, chain transfer, reactivity ratios, and utility of the pendent vinyl groups for crosslinking between reactions at either 60 or 70 °C. Even this seemingly small shift in temperature has a marked impact on the kinetics and resulting network for the different pairs of (meth)acrylate comonomers. Tripathi, A.K.; Neenan, M.L.; Sundberg, D.C.; Tsavalas, J.G., Influence of n-Alkyl Ester Groups on Efficiency of Crosslinking for Methacrylate Monomers Copolymerized with EGDMA: Experiments and Monte Carlo Simulations of Reaction Kinetics and Sol-Gel Structure , Polymer (2016), 96, 130–145, DOI:10.1016/j.polymer.2016.04.017 Tripathi, A.K.; Tsavalas, J.G.; Sundberg, D.C., “Monte Carlo Simulations of Free Radical Polymerizations with Divinyl Crosslinker: Pre- and Post-Gel Simulations of Reaction Kinetics and Molecular Structure , Macromolecules (2015) 48, 184−197, DOI: 10.1021/ma502085

Mechanistic insights into topological network formation in free radical co-polymerization

The first part of the talk will discuss reaction kinetics and molecular architecture development during free-radical, bulk copolymerizations of a homologous series of methacrylate monomers with a series of dimethacrylate crosslinkers of varying alkyl spacer lengths. The overall objective of this work was to determine the extent to which the ester side chains of the methacrylate monomers hinder chain-end radical propagation reactions through the pendent vinyl groups of the crosslinking monomer. We have determined that this steric hindrance is quite significant and increases to the point where the sweeping radius of the pendent vinyl can be obstructed by the neighboring monomer ester side groups. The effective sweeping radius of the pendent vinyl can be equivalently expressed by various combinations of dimethacrylate and methacrylate. Please download the file below for full content

Waterborne hyperbranched alkyd-acrylic resin obtained by miniemulsion polymerization

Abstract Four waterborne hyperbranched alkyd-acrylic resins (HBRAA) were synthesized by miniemulsion polymerization from a hyperbranched alkyd resin (HBR), methyl methacrylate (MMA), butyl acrylate (BA) and acrylic acid (AA), by using benzoyl peroxide (BPO) and ammonium persulfate (AP) as initiators. The reaction between HBR and acrylic monomers was evidenced by differential scanning calorimetric (DSC), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The conversion percentage, glass transition temperature (Tg), content of acrylic polymer (determined by soxhlet extraction) and molecular weight increased with the content of acrylic monomers used in the synthesis. The main structure formed during the synthesis was the HBRAA. The analysis by dynamic light scattering (DLS) showed that the particle size distribution of HBRAA2, HBRAA3 and HBRAA4 resins were mainly monomodal. The film properties (gloss, flexibility, adhesion and drying time) of the HBRAA were good

A fluorescence approach to investigate repartitioning of coalescing agents in acrylic polymer emulsions

Repartitioning of co-solvents between particles of latex emulsions was investigated by means of a fluorescence method based on the detection of the amount of co-solvent via the solvatochromic shift of the emission maximum of a fluorescent probe, copolymerized at a low concentration. Complete repartitioning of co-solvents between particles of latex materials with a low Tg (ca. 25 °C) occurred within minutes. For a hydrophilic latex with a Tg of 68 °C, equilibration was achieved within an hour. Repartitioning was faster for more hydrophobic co-solvents. For a hydrophobic latex of similar Tg, co-solvent repartitioning took place on the same time scale, but complete equilibration was not reached. Possibly, there is an additional slow component in the repartitioning, or the prolonged presence of co-solvent causes a structural change in the latex particles that affects the outcome of the experiment