Renewable Isoprene by Sequential Hydrogenation of Itaconic Acid and Dehydra-Decyclization of 3-Methyl-Tetrahydrofuran

Abdelrahman, Omar A.; Park, Dae Sung; Vinter, Katherine P.; Spanjers, Charles S.; Ren, Limin; Cho, Hong Je; Zhang, Kechun; Fan, Wei; Tsapatsis, Michael; Dauenhauer, Paul J.

doi:10.1021/acscatal.6b03335

Cited by 86 publications

(110 citation statements)

References 24 publications

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“…Myrcene and Far are both found in nature, but can also be produced by pyrolysis of β‐pinene and microbial pathways from glucose, respectively. Although, there are new bio‐based pathways to synthesize butadiene and isoprene, myrcene and Far are made up of multiple isoprene units, which can provide different rheological properties. It was shown that bottlebrush polymers with densely packed, long side chains improve elastic properties .…”

Section: Introductionmentioning

confidence: 99%

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Luk

Marić

2019

Macro Reaction Engineering

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polymers with controlled architectures. [11,12] Styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS) triblock copolymers have long been commercialized too, such as the Kraton family of thermoplastic elastomers, which are made by anionic polymerization. [13,14] While many industrial applications use free radical polymerization, CRP precisely controls the molecular architecture of polymer chains, therefore making homopolymers, diblock and triblock copolymers with narrow molecular weight distributions (MWDs) and low dispersity. [15] Ionic polymerization is a truly "living" method, but it is intolerant to functional monomers and impurities. [16] CRP, more properly defined as reversible deactivation radical polymerization (RDRP), is a newer, more versatile technique to control the polymerization of free radicals. It utilizes activationdeactivation equilibrium or reversible chain transfer to suppress irreversible termination such that the propagating radical is primarily in its dormant state. [17] Amongst the several types of RDRP, atom transfer radical polymerization (ATRP) [18][19][20] and reversible additionfragmentation transfer (RAFT) [21][22][23] can polymerize a wide variety of functional monomers like vinyl esters and (meth) acrylates. This study will focus on nitroxide-mediated polymerization (NMP) as it is particularly adept for polymerization of styrene-diene systems. [24][25][26] NMP is able to polymerize functionalized styrene and acrylate monomers successfully, [27] however it is limited in its ability to maintain active chain ends in the polymerization of methacrylates. [28,29] It was discovered that the rate of dissociation (k d ) is very large because of steric stabilization of the propagating methacrylate radical, and the rate of combination (k c ) is very low due to steric hindrance provided by the bulky SG1-nitroxide (N-tert-butyl-N-[1-diethylphosphono-(2,2dimethylpropyl)] nitroxide). Consequently, the activationdeactivation equilibrium (K eq = k d /k c ) is high, resulting in termination by disproportionation. [30] To overcome this, small amounts of controlling comonomer like styrene or acrylonitrile can be added to effectively lower K eq . [28,31] Furthermore, the SG1-based nitroxide, BlocBuilder, can be modified with an N-succinimidyl ester group (N-succinimidyl modified commercial BlocBuilder [NHS-BB]) to better control the polymerization of methacrylates, [32] and successful polymerization of Nitroxide-Mediated Polymerization Farnesene (Far) is a bio-based terpene monomer that is similar in structure to commercially used dienes like butadiene and isoprene. Nitroxide-mediated polymerization (NMP) is adept for the polymerization of dienes, but not particularly effective at controlling the polymerization of methacrylates using commercial nitroxides. In this study, Far is statistically copolymerized with a functional methacrylate, glycidyl methacrylate (GMA), by NMP using N-succinimidyl modified commercial BlocBuilder (NHS-BB) initiator. Reactivity ratios are determined to be r Far = ...

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Section: Introductionmentioning

confidence: 99%

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Luk

Marić

2019

Macro Reaction Engineering

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“…Even in cases where helium gas cylinders are used, it is possible to set up helium cylinder multi-packs in conjunction with manifolds for such equipment, enabling continuous operation for weeks without requiring replacement. Setting up liquid feed dosing using syringe pump/HPLC pumps remains manual but is usually quick; as pointed out before, for applications only requiring an initial estimation of product distributions, a significantly simpler version of this setup as a transient pulsed micro-reactor from our earlier works 26 , 27 can be utilized, which would barely require any manual intervention in setting up feeds, as the dosing is through the GC autosampler itself. Similarly, for chemistries utilizing light gases as feeds (e.g., methane activation, carbon dioxide valorization), it is possible to set up individual lines with separate mass flow controllers (MFCs), and such systems can run practically indefinitely for a given catalyst bed.…”

Section: Resultsmentioning

confidence: 99%

“…One straightforward implementation of low-cost automated micro-reactors with broad applicability among previously reported approaches is the pulsed-flow technique, which involves dosing a pulse of reactant over a catalytic material to study product distribution trends. This approach is readily integrated within a commercial GC, 26 , 27 , 28 , 29 , 30 , 31 , 32 but the transient nature of the technique limits kinetic parameter estimation. In addition, the product distributions under such transient conditions may vary from corresponding steady-state values.…”

Section: Introductionmentioning

confidence: 99%

Catalysis-in-a-Box: Robotic Screening of Catalytic Materials in the Time of COVID-19 and Beyond

Kumar

Bossert

McDonald

et al. 2020

Matter

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This work describes the design and implementation of an automated device for catalytic materials testing by direct modifications to a gas chromatograph (GC). The setup can be operated as a plug-flow isothermal reactor and enables the control of relevant parameters such as reaction temperature and reactant partial pressures directly from the GC. High-quality kinetic data (including reaction rates, product distributions, and activation barriers) can be obtained at almost one-tenth of the fabrication cost of analogous commercial setups. With these key benefits including automation, low cost, and limited experimental equipment instrumentation, this implementation is intended as a high-throughput catalyst screening reactor that can be readily utilized by materials synthesis researchers to assess the catalytic properties of their synthesized structures in vapor-phase chemistries.

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“…Therefore, it is a promising and competitive route to convert biomass-derived feedstocks into isoprene via chemical processes. Itaconic acid from glucose [89] was employed as raw material by Abdelrahman [74]. Firstly, itaconic acid was converted into 3-methyl-tetrahydrofuran (3-MTHF) with a yield of about 80% in a liquid phase using Pd-Re/C as a catalyst.…”

Section: Synthesis Of Isoprenementioning

confidence: 99%

Synthesis of 1,3-Butadiene and Its 2-Substituted Monomers for Synthetic Rubbers

Liu

et al. 2019

Catalysts

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Synthetic rubbers fabricated from 1,3-butadiene (BD) and its substituted monomers have been extensively used in tires, toughened plastics, and many other products owing to the easy polymerization/copolymerization of these monomers and the high stability of the resulting material in manufacturing operations and large-scale productions. The need for synthetic rubbers with increased environmental friendliness or endurance in harsh environments has motivated remarkable progress in the synthesis of BD and its substituted monomers in recent years. We review these developments with an emphasis on the reactive routes, the products, and the synthetic strategies with a scaling potential. We present reagents that are primarily from bio-derivatives, including ethanol, C4 alcohols, unsaturated alcohols, and tetrahydrofuran; the major products of BD and isoprene; and the by-products, activities, and selectivity of the reaction. Different catalyst systems are also compared. Further, substituted monomers with rigid, polar, or sterically repulsive groups, the purpose of which is to enhance thermal, mechanical, and interface properties, are also exhaustively reviewed. The synthetic strategies using BD and its substituted monomers have great potential to satisfy the increasing demand for better-performing synthetic rubbers at the laboratory scale; the laboratory-scale results are promising, but a big gap still exists between current progress and large scalability.

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Renewable Isoprene by Sequential Hydrogenation of Itaconic Acid and Dehydra-Decyclization of 3-Methyl-Tetrahydrofuran

Cited by 86 publications

References 24 publications

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Catalysis-in-a-Box: Robotic Screening of Catalytic Materials in the Time of COVID-19 and Beyond

Synthesis of 1,3-Butadiene and Its 2-Substituted Monomers for Synthetic Rubbers

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