A High‐Performance Recycling Solution for Polystyrene Achieved by the Synthesis of Renewable Poly(thioether) Networks Derived from <scp>d</scp>‐Limonene

Hearon, Keith; Nash, Landon D.; Rodríguez, J; Lonnecker, Alexander T.; Raymond, Jeffery E.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

doi:10.1002/adma.201304370

Cited by 45 publications

(32 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Polymer Synthesis, Micromolding and Mechanical Characterization : To synthesize PLT32o prepolymer, a one‐pot synthesis was carried out using a D‐limonene‐capped TMPTMP macromonomer similar to the M1 Macromonomer reported in Scheme 4 by Claudino et al and the co‐monomer 1,10 DDT. To create a photoreactor, a UVP CL‐1000 cross‐linking chamber with 365 nm bulbs was positioned on top of a magnetic stir plate in which UV irradiation of monomers could be carried out under vigorous stirring conditions.…”

Section: Methodsmentioning

confidence: 99%

“…Hubbell and co‐workers first described photopolymerizable degradable thiol‐acrylate systems, and Anseth and co‐workers custom synthesized and functionalized thiol‐acrylates to control degradation rate and cell‐material interactions . Hearon et al demonstrated a one‐pot synthesis of a thiol‐ene polymer wherein brief heating and/or UV irradiation of a mixture of trimethylolpropane tris(3‐mercaptopropionate) (TMPTMP) and the naturally occurring citrus‐derived extract D‐limonene afforded a homogenous solution that could be transferred to a mold without further polymer network formation occurring until subsequent exposure to UV irradiation. Synthetic, processing and environmental health and safety advantages of PLT32o make this material an attractive candidate for biomedical engineering applications where recapitulation of the niche of the target cells through fabrication of complex templates with patterned 3D pore microstructures is desired.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Poly(Limonene Thioether) Scaffold for Tissue Engineering

Fischer

Morgan

Hearon

et al. 2016

Adv Healthcare Materials

Self Cite

View full text Add to dashboard Cite

A photocurable thiol-ene network polymer, poly(limonene thioether) (PLT32o), was synthesized, characterized, fabricated into tissue engineering scaffolds, and demonstrated in vitro and in vivo. Micromolded PLT32o grids exhibited compliant, elastomeric mechanical behavior similar to grids made of poly(glycerol sebacate) (PGS), an established biomaterial. Multilayered PL32o scaffolds with regular, geometrically defined pore architectures supported heart cell seeding and culture in a manner similar to multilayered PGS scaffolds. Subcutaneous implantation of multilayered PLT32o scaffolds with cultured heart cells provided long term 3D structural support and retained the exogenous cells, whereas PGS scaffolds lost both their structural integrity and the exogenous cells over 31 days in vivo. PLT32o membrane implants retained their dry mass, whereas PGS implants lost 70 percent of their dry mass by day 31. Macrophages were initially recruited to PLT32o and PGS membrane implants but were no longer present by day 31. Facile synthesis and processing in combination with the capability to support heart cells in vitro and in vivo suggest that PLT32o can offer advantages for tissue engineering applications where prolonged in vivo maintenance of 3D structural integrity and elastomeric mechanical behavior are required.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Poly(Limonene Thioether) Scaffold for Tissue Engineering

Fischer

Morgan

Hearon

et al. 2016

Adv Healthcare Materials

Self Cite

View full text Add to dashboard Cite

show abstract

“…This aspect is common to many low transition temperature poly(thiother) networks which are elastomeric and possess poor mechanical integrity at and above 25 °C . Works are underway to involve high glass transition resins, such as polystyrene, or poly(methyl methacrylate for example, to increase modulus and improve the toughness and mechanical stress of the films …”

Section: Resultsmentioning

confidence: 99%

Renewable Photopolymer Films Derived From Low‐Grade Lampante and Pomace Olive Oils

Bouaziz

Ayadi²,

Allouche

et al. 2017

Euro J Lipid Sci & Tech

View full text Add to dashboard Cite

Thiol‐ene photoinduced copolymerization between a polythiol cross‐linker and low‐grade unsaturated olive oil provides an eco‐efficient route to dry, flexible, and rubbery films in the matter of minutes. The synthetic methodology uses low cost olive oils resulting from non‐edible grades (lampante olive oil) and waste production (pomace olive oil) without prior chemical modification. The resultant photopolymer thioether cross‐linked films contain up to 80–85% of renewable resources, and UV‐driven drying proceeds despite the limited unsaturations’ concentration. Photopolymerization is triggered with a conventional medium‐pressure mercury arc in presence of three different thiol cross‐linkers: 2,2′‐(ethylenedioxy)diethanethiol, hexanedithiol or trimethylolpropanetris(3‐mercaptopropionate) and a radical photoinitiator (2‐hydroxy 2‐methylpropiophenone). Using real‐time Fourier transform infrared spectroscopy (RT‐FTIR), we show that cross‐linking proceeds essentially via a step‐growth thiol‐ene polymerization, and to a minor extent, by a conventional photo‐oxidation mechanism. Practical Applications: Olive oil is the second largest produced vegetable oil, and in 2016 world production amounted to 3.5 million tons. An excess of low‐grade pomace and lampante olive oils is generated annually from the conventional extraction process; however, declared unfit for human consumption, they have a limited number of uses, and it is difficult to find new outlets. Despite this excess, the development of synthetic and processing methods to convert these non‐edible olive oils in useful materials has not been investigated widely. Here we report a method based on thiol‐ene photopolymerization to prepare a new range of UV‐curable films. Using time‐resolved infrared spectroscopy, this study sheds light into reaction kinetics and polymerization mechanism. We report a method based on thiol‐ene photopolymerization to prepare a new range of UV‐curable films derived from the excess of low‐grade pomace and lampante olive oils generated from the conventional extraction process of olive oil.

show abstract

“…Limonene was reacted with polythiol co‐monomers through a UV‐catalyzed thiol–ene polyaddition reaction to give nanocomposite materials in which precipitated polystyrene phases were dispersed through elastomeric poly(thioether) networks . Interestingly, limonene was simultaneously utilized as both a monomer and as a solvent for recycling polystyrene waste in this reaction, and the mechanical properties of these materials greatly surpassed those of poly(thioether) network homopolymers and polystyrene alone.…”

Section: Thiol–ene Reaction For the Synthesis Of Terpene‐based Monomementioning

confidence: 99%

Thiol–Ene (Click) Reactions as Efficient Tools for Terpene Modification

Firdaus

2017

Asian J Org Chem

View full text Add to dashboard Cite

This Focus Review highlights the application of thiol-ene (click) chemistry to the productiono fadiverse range of materials that are derived from terpenes. To present an overview concerning the potencyo ft erpenes as renewable resources, recent advances in their developmentb y using synthetic organic chemistry are initially discussed. In addition, the use of thiol-enec hemistry as an efficient approach and versatile tool for noncatalytic carbonÀheteroatom bond formation is briefly presented, including mecha-nistic and kinetic aspects, as well as some structuralc onsiderations,t hat is, the influenceo ft he thiol and olefin structures, which should be well-thought-out before applying such chemistry.T his discussiona lso coversh ow an initiator works and its effect on the reactionr ate. Moreover,t he utilization of thiol-ene reactions for the synthesis of terpenebased valuable platform chemicals, monomers, and polymers, includingr ecent examples that demonstrate its broad utility,a re highlighted.[a] Dr.M.F irdaus Scheme11. Terpene-basedp olythioethers thatwere prepared by thiol-ene photopolymerization. [100] Scheme12. Preparation of cross-linkedthin films that were derived from limonene and their possible addition type. [101] Asian

show abstract

A High‐Performance Recycling Solution for Polystyrene Achieved by the Synthesis of Renewable Poly(thioether) Networks Derived from d‐Limonene

Cited by 45 publications

References 35 publications

Poly(Limonene Thioether) Scaffold for Tissue Engineering

Poly(Limonene Thioether) Scaffold for Tissue Engineering

Renewable Photopolymer Films Derived From Low‐Grade Lampante and Pomace Olive Oils

Thiol–Ene (Click) Reactions as Efficient Tools for Terpene Modification

Contact Info

Product

Resources

About