Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran

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

doi:10.1021/acssuschemeng.7b00745

Cited by 99 publications

(142 citation statements)

References 26 publications

(36 reference statements)

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“…Very recently, Abdelrahman et al 405 proposed an alternative thermochemical pathway to produce butadiene from biomass based on the dehydration of sugars to furfural, followed by decarbonylation and hydrogenation to THF and a final dehydration and decyclization step. Regarding the last catalytic step, dehydration and ring opening of THF, they compared a phosphorous-containing siliceous self-pillared pentasil sample (P-SPP) with a wide variety of catalysts, including ZSM-5, HY, Sn-Beta, ZrO 2 and silica-alumina.…”

Section: Hierarchical Zeolites In Catalytic Pyrolysismentioning

confidence: 99%

From 3D to 2D zeolite catalytic materials

et al. 2018

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Research activities and recent developments in the area of three-dimensional zeolites and their two-dimensional analogues are reviewed. Zeolites are the most important industrial heterogeneous catalysts with numerous applications. However, they suffer from limited pore sizes not allowing penetration of sterically demanding molecules to their channel systems and to active sites. We briefly highlight here the synthesis, properties and catalytic potential of three-dimensional zeolites followed by a discussion of hierarchical zeolites combining micro- and mesoporosity. The final part is devoted to two-dimensional analogues developed recently. Novel bottom-up and top-down synthetic approaches for two-dimensional zeolites, their properties, and catalytic performances are thoroughly discussed in this review.

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Section: Hierarchical Zeolites In Catalytic Pyrolysismentioning

confidence: 99%

From 3D to 2D zeolite catalytic materials

et al. 2018

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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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“…Tetrahydrofuran (THF) can also easily generate 1,4-BDO, which comes from five-carbon sugars such as xylose or furfural [66][67][68][69]. Therefore, Abdelrahman et al [70] developed a novel way to synthesize BD via the catalytic ring-opening dehydration of THF, which is conducted in the presence of a solid acid catalyst with a high selectivity of 85-99% to BD at a high THF conversion of 89% ( Figure 4). These encouraging data were obtained at 400 • C with a space velocity of 0.2 s −1 .…”

Section: Catalysts 2018 8 X For Peer Review 3 Of 25mentioning

confidence: 99%

“…Synthesis of BD from THF through the intermediate 3-buten-1-ol (3B1OL), and the by-products in the decyclization of THF[70].…”

mentioning

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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Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran

Cited by 99 publications

References 26 publications

From 3D to 2D zeolite catalytic materials

From 3D to 2D zeolite catalytic materials

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

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

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