Dataset Information

Mid-Chain Radical Migration in the Radical Polymerization of n-Butyl Acrylate.

ABSTRACT: The occurrence of intramolecular transfer to polymer in the radical polymerization of acrylic monomers has been extensively documented in the literature. Whilst it has been largely assumed that intramolecular transfer to polymer leads to short chain branches, there has been some speculation over whether the mid-chain radical can migrate. Herein, by the matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry (MS) of poly(n-butyl acrylate) synthesized by solution polymerization under a range of conditions, it is shown that this mid-chain radical migration does occur in the radical polymerization of acrylates conducted at high temperatures, as is evident from the shape of the molecular weight distribution. Using a mathematical model, an initial approximation of the rate at which migration occurs is made and the distribution of branching lengths formed in this scenario is explored. It is shown that the polymerizations carried out under a low monomer concentration and at high temperatures are particularly prone to radical migration reactions, which may affect the rheological properties of the polymer.

SUBMITTER: Ballard N

PROVIDER: S-EPMC6403819 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Mid-Chain Radical Migration in the Radical Polymerization of <i>n</i>-Butyl Acrylate.

Ballard Nicholas N Veloso Antonio A Asua José M JM

Polymers 20180712 7

The occurrence of intramolecular transfer to polymer in the radical polymerization of acrylic monomers has been extensively documented in the literature. Whilst it has been largely assumed that intramolecular transfer to polymer leads to short chain branches, there has been some speculation over whether the mid-chain radical can migrate. Herein, by the matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry (MS) of poly(<i>n</i>-butyl acrylate) synthesized by sol ...[more]

PMID: 30960690

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Project description:The purpose of this work was to investigate the effect of multifunctionality on material properties of synthetic polymer aerogels. For this purpose, we present the synthesis and characterization of monolithic dendritic-type urethane-acrylate monomers based on an aliphatic/flexible (Desmodur N3300), or an aromatic/rigid (Desmodur RE) triisocyanate core. The terminal acrylate groups (three at the tip of each of the three branches, nine in total) were polymerized with 2,2'-azobis(isobutyronitrile) (AIBN) via free radical chemistry. The resulting wet-gels were dried with supercritical fluid (SCF) CO₂. Aerogels were characterized with ATR-FTIR and solid-state 13C NMR. The porous network was probed with N₂-sorption and scanning electron microscopy (SEM). The thermal stability of aerogels was studied with thermogravimetric analysis (TGA). Most aerogels were macroporous materials (porosity > 80%), with high thermal stability (up to 300 °C). Aerogels were softer at low monomer concentrations and more rigid at higher concentrations. The material properties were compared with those of analogous aerogels bearing only one acrylate moiety at the tip of each branch and the same cores, and with those of analogous aerogels bearing norbornene instead of acrylate moieties. The nine-terminal acrylate-based monomers of this study caused rapid decrease of the solubility of the growing polymer and made possible aerogels with much smaller particles and much higher surface areas. For the first time, aliphatic/flexible triisocyanate-based materials could be made with similar properties in terms of particle size and surface areas to their aromatic/rigid analogues. Finally, it was found that with monomers with a high number of crosslinkable groups, material properties are determined by multifunctionality and thus aerogels based on 9-acrylate- and 9-norbornene-terminated monomers were similar. Materials with aromatic cores are carbonizable with satisfactory yields (20⁻30% w/w) to mostly microporous materials (BET surface areas: 640⁻740 m² g-1; micropore surface areas: 360⁻430 m² g-1).

Project description:Electrophotographic printing and copying processes primarily use toner, which is a mixture of colorant, polymer, and additives. Toner can be made using traditional mechanical milling techniques or more contemporary chemical polymerization techniques. Suspension polymerization provides spherical particles with less stabilizer adsorption, homogeneous monomers, higher purity, and easier control of the reaction temperature. In contrast to these advantages, however, the particle size resulting from suspension polymerization is too large for toner. To overcome this disadvantage, devices such as high-speed stirrers and homogenizers can be used to reduce the size of the droplets. This research investigated the use of carbon nanotubes (CNTs) instead of carbon black as the pigment in toner development. We succeeded in achieving a good dispersion of four different types of CNT, specifically modified with NH2 and Boron or unmodified with long or short chains in water rather than chloroform, using sodium n-dodecyl sulfate as a stabilizer. We then performed polymerization of the monomers styrene and butyl acrylate in the presence of the different CNT types and found that the best monomer conversion and largest particles (in the micron range) occurred with CNTs modified with boron. The insertion of a charge control agent into the polymerized particles was achieved. Monomer conversion of over 90% was realized with all concentrations of MEP-51, whereas conversion was under 70% with all concentrations of MEC-88. Furthermore, analysis with dynamic light scattering and scanning electron microscopy (SEM) indicated that all polymerized particles were in the micron size range, suggesting that our newly developed toner particles were less harmful and environmentally friendly products than those typically and commercially available. The SEM micrographs clearly showed good dispersion and attachment of the CNTs on the polymerized particles (no CNT aggregation was found), which has never been published before.

Dataset Information

Mid-Chain Radical Migration in the Radical Polymerization of n-Butyl Acrylate.

Publications

Mid-Chain Radical Migration in the Radical Polymerization of <i>n</i>-Butyl Acrylate.

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