A comparison between the two oxidation states for the OTf salts showed that the 4+ state is a better catalyst until it is consumed or made ineffective, thereafter the 3+ state dominants, contrary to the trend observed for the CAN catalysts. 18, 2922–2934. However, in many instances long reaction times for the addition of the pendants are quoted with little or no discussion as to why this is necessary. Polym. This indicated that dimer formation is the dominant reaction in MAR. Gustin J. Bio-based platform molecules such as itaconic, fumaric, and muconic acid offer much promise in the formation of sustainable unsaturated polyester resins upon reaction with suitable diols and polyols. (2005). Instructions for using Copyright Clearance Center page for details. doi: 10.1080/15685551.2016.1231045, Pellis, A., Comerford, J. W., Maneffa, A. J., Sipponen, M. H., Clark, J. H., and Farmer, T. J. The activation energy of MAR was 98.0 kJ mol−1, which was similar in value to that of dimerization in previous studies. J. Mol. The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. Corresponding authors, a The optimum catalyst was subsequently used for the addition of diethylamine onto poly(1,8-octylene itaconate), this unsaturated polyester prepared via enzymatic polycondenzation. it in a third party non-RSC publication you must Other articles where Addition polymerization is discussed: polymerization: In addition polymerization, monomers react to form a polymer without the formation of by-products. Complete loss of all I2 from this sample should have resulted in a mass loss of just 2.5%, therefore it was hypothesized that water adsorbed onto the Al2O3 was also contributing to the observed mass loss. We can also represent the rate constant based on the Arrhenius equation, as in Eq. Information about reproducing material from RSC articles with different licences The reaction order was 2.5th, and the overall reaction rate constant was k = 3.52 × 103 × exp (−1.18 × 105/T [K]) L1.5 mol−1.5 s−1. Figure 8. Macromolecules 48, 1398–1403. Tetraphenylethene decorated with disulfide-functionalized hyperbranched poly(amido amine)s as metal/organic solvent-free turn-on AIE probes for biothiol determination. 6, 2108–2114. (2018). Chem. Kurland J, Bryant D. Shipboard polymerization of acrylic acid. The method used for determining the extent of addition and isomerization via 1H-NMR spectroscopy was modified from the model system (Figure 5) as a result of some peak overlap and loss of resolution (Figure S10 for POI, Figure S11 following addition of DEA to the polymer). In this study, based on the GPC result of a sample that was analyzed at 135 °C after 1172 min, shown in Fig. GPC chromatograms of samples after the calorimetry as shown in Fig. or in a thesis or dissertation provided that the correct acknowledgement is given Finally we discuss the applications of the polymers for gene/drug delivery and bioimaging through exploring their self-assemblies in various motifs, e.g., micelles, polyplexes particles/nanorings and hydrogels. The C=C modification sites can also act as points to add useful pendants which can alter the polymers final properties such as glass transition temperature, biodegradability, hardness, polarity, and strength. Despite extensive studies we were unable to fully ascertain the cause of this deactivation and hence sought an alternative. For the non-catalyzed reaction 0.52 g and 0.54 g (duplicate) of polymer was recovered, for the catalyzed reaction 0.33 g and 0.22 g (duplicate) of polymer was recovered. Michael Addition. Enzymatic synthesis of unsaturated polyesters: functionalization and reversibility of the aza-Michael addition of pendants. 3 Chem. Authors contributing to RSC publications (journal articles, books or book chapters) Organic Coat. doi: 10.1055/s-2007-977447, Sridharan, V., and Menendez, J. C. (2010). MAR that may induce runaway polymerization is thought to be step oligomerization. Lett. Another consideration was that the Michael adduct, 1, might be hindering the catalytic ability of CAN (both III and IV). An over-reliance of the chemical industry on non-renewable feedstocks has resulted in an ever growing interest in the utilization of bio-derived platform molecules to substitute petroleum-derived base chemicals as fundamental building-blocks for the synthesis of higher value products (Werpy and Petersen, 2004; Farmer and Mascal, 2014). Eur. Levy L, Lakin M. Emergency response shortstop inhibition during the approach to an acrylic acid runaway polymerization. Yong Liu, Yuanfeng Li, Damla Keskin, Linqi Shi. Less Common Metals 126, 101–106. Solvent-free, catalyst-free aza-Michael addition of cyclohexylamine to diethyl maleate: reaction mechanism and kinetics. Figure S5 shows a comparison of catalytic activity between the free and two different immobilized CAN(IV) catalysts and surprisingly, the same loss of activity after reuse is observed and appears to be independent of catalyst loading. Int. Understanding potentials and restrictions of solvent-free enzymatic polycondensation of itaconic acid: an experimental and computational analysis. Table 3 shows the comparison of our experimental values and previous studies on the reaction order of MAR [2, 16, 17]. As such, we additionally sought to find an appropriate means of catalyst recovery and reuse in this work. The result for 0.1 K min−1 shows that the exotherm was detected at 80 °C, and the test ended before heat flow peaked. Xiaojie Li, Xingliang Liu, Dongjian Shi, Wei Wei, Mingqing Chen. a and frequency factor A. We concluded that the apparent reaction order for the MAR of the oligomers was 2.5. Instead of amine, thiol can also be used as heteroatomic donor in Michael addition reaction [15], and the reaction of SH with acrylate has been used to prepare the polymers [16]. of the whole article in a thesis or dissertation. Controlled cross-linking strategy for formation of hydrogels, microgels and nanogels. (A) Time course of the aza-Michael addition of DEA on DMI using the CeOTF (left) and the CAN (right) catalysts alongside no catalyst control; (B) recyclability of the CeOTf (left) and the CAN (right) catalysts. Polym. Oak Ridge, TN: U.S. Department of Energy. 347, 763–766. Tough bio-based elastomer nanocomposites with high performance for engineering applications.

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