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Grämlich, Ludwig; Gluchowski, Peter; Horsch, Andreas; Schäfer, Klaus; Waschbusch, Gerd

doi:10.1007/978-3-8349-3668-4_13

Cited by 5 publications

(8 citation statements)

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“…The latter was discussed for example with respect to the impact of supercritical CO 2 on (meth)acrylate k p [43,44] or the variation of methacrylate k p for polymerizations in toluene. [45][46][47] Equation (1) indicates that the experimentally accessible quantities L and t allow only for the determination of the product k p •c M . Thus, data evaluation using the overall monomer concentration in the system will lead to an alteration of the rate coefficient observed in cases, where non-ideal mixing of monomer, polymer, and solvent occurs.…”

Section: Resultsmentioning

confidence: 99%

“…Another way of affecting T G is to copolymerize IP with a polar monomer, e.g., such as glycidyl methacrylate (GMA). [1,2] Moreover, complex copolymer structures such as di-, tri-, and multiblock copolymers are considered, for example, because of their phase behavior and mechanical properties. [3] While so far mostly anionic and coordination polymerizations of isoprene were performed, recently, there are reports PLP-SEC study on butadiene reported k p values of 57 L mol −1 s −1 at 30 °C.…”

Section: Introductionmentioning

confidence: 99%

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Propagation Kinetics of Isoprene Radical Homopolymerization Derived from Pulsed Laser Initiated Polymerizations

Büren

Brandl

Beuermann

2019

Macro Reaction Engineering

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The propagation kinetics of isoprene radical polymerizations in bulk and in solution are investigated via pulsed laser initiated polymerizations and subsequent polymer analyses via size‐exclusion chromatography, the PLP‐SEC method. Because of low polymerization rate and high volatility of isoprene, the polymerizations are carried out at elevated pressure ranging from 134 to 1320 bar. The temperatures are varied between 55 and 105 °C. PLP‐SEC yields activation parameters of kp (Arrhenius parameters and activation volume) over a wide temperature and pressure range that allow for the calculation of kp at technically relevant ambient pressure conditions. The kp values determined are very low, e.g., 99 L mol−1 s−1 at 50 °C, which is even lower than the corresponding value for styrene polymerizations. The presence of a polar solvent results in a slight increase of kp compared to the bulk system. The kp values reported are important for determining rate coefficients of other elemental reactions from coupled parameters as well as for modeling isoprene free‐radical polymerizations and reversible deactivation radical polymerization with respect to tailored polymer properties and optimizing the polymerization processes.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Propagation Kinetics of Isoprene Radical Homopolymerization Derived from Pulsed Laser Initiated Polymerizations

Büren

Brandl

Beuermann

2019

Macro Reaction Engineering

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“…For instance, trans-1, 4-and 3,4-configurations are semicrystalline polymers with a glass transition temperature (T g ) higher than that of the cis-1,4-isomer. Although literature reports on the free radical copolymerization of IP with polar monomers are very limited, [1] it is important to deepen the understanding of the monomer incorporation into the copolymer growing chain, as this will greatly influence the thermal and mechanical properties of the final copolymer. A recent study by Contreras-Lopéz et al examined the radical copolymerization of IP with glycidyl methacrylate (GMA), demonstrating the formation of nearly alternating copolymer and the ability to control T g over a wide range through copolymer composition, decreasing from 80 °C for GMA homopolymer to ≈30 °C for a 50/50 w/w copolymer.…”

mentioning

confidence: 99%

Propagation Kinetics of Isoprene–Glycidyl Methacrylate Copolymerizations Investigated via PLP–SEC

Brandl

Drache

Schier

et al. 2017

Macromol. Rapid Commun.

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Pulsed-laser polymerization combined with polymer analysis by NMR and size-exclusion chromatography is used to study the radical copolymerization kinetics of isoprene (IP) with glycidyl methacrylate (GMA). The copolymer is characterized by a close-to-alternating microstructure, with the addition of IP leading to a significant decrease in the composition-averaged propagation rate coefficient. A rigorous fitting strategy is developed to fit a mixed penultimate model to the data, with the selectivity of the IP, but not the GMA, macroradical dependent on the penultimate unit.

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“…To develop a procedure to yield a PI macroinitiator through one step, we investigated the copolymerization of isoprene with monomers that had a pendent primary hydroxyl group. [ 58 ] Isoprene can be polymerized through several mechanisms, but only those techniques that use radicals as a propagating center are amenable to copolymerization with hydroxylated comonomers. Commercial hydroxylated monomers HEA and HEMA have been copolymerized with isoprene under controlled radical conditions such as ATRP and RAFT.…”

Section: Copolymerized Macroinitiator Graft Copolymer Synthesismentioning

confidence: 99%

“…[ 59 ] Unfortunately, the high temperatures required to polymerize isoprene through controlled radical methods activate the Diels-Alder side reactions where synthesis targeted a post-polymerization functionalization route. [ 57 ] With post-polymerization functionalization, both natural rubber and renewably sourced PI could serve as the starting material. Furthermore, we desired to develop a modular postpolymerization functionalization system such that functional groups other than hydroxyls could be placed on the backbone for future study.…”

Section: Copolymerized Macroinitiator Graft Copolymer Synthesismentioning

confidence: 99%

Toughening Polylactide with Phase‐Separating Complex Copolymer Architectures

Gramlich

2014

Macro Chemistry & Physics

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Polylactide (PLA) is a commercially produced potentially sustainable plastic that holds promise to replace petroleum‐sourced materials. Unfortunately, the brittle nature of PLA limits its current utility to disposable packaging. Melt blends of PLA and a rubbery material can rubber toughen the plastic, but often require the addition of a compatibilizer and generate opaque materials. Current efforts explore using block and graft copolymers with a majority PLA block and minority rubbery block that phase separate on the nanometer length scale to rubber toughen PLA. With these complex architectures, the polymer matrix, the minor rubbery component, and the compatibilizer are present in one molecule. Many block and graft copolymers rely on non‐sustainable rubbery blocks, which limits the sustainability of these materials. Recent work has utilized polyisoprene (PI) as the sustainable backbone for PLA graft copolymers. Post‐polymerization functionalization and copolymerization of PI provides a method to create fully sustainable PLA/PI graft copolymers that phase separate on the nanometer‐scale to make potentially tough, sustainable plastics.

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Cited by 5 publications

References 0 publications

Propagation Kinetics of Isoprene Radical Homopolymerization Derived from Pulsed Laser Initiated Polymerizations

Propagation Kinetics of Isoprene Radical Homopolymerization Derived from Pulsed Laser Initiated Polymerizations

Propagation Kinetics of Isoprene–Glycidyl Methacrylate Copolymerizations Investigated via PLP–SEC

Toughening Polylactide with Phase‐Separating Complex Copolymer Architectures

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