James Comerford

Following the environmental problems caused by non-degradable plastics there is a need to synthesise greener and more sustainable polymers. In this work we describe, for the first time, the facile enzyme-catalysed synthesis of linear polyesters using dimethyl malonate as the diester. These polymers, containing a different aliphatic diol component (...

Zeolites LiY, NaY, KY and ZnY were impregnated with small amounts of the corresponding metal halides (chloride, bromide and iodide) and tested as catalysts for the carboxylation of styrene oxide...

Furandioate-adipate copolyesters are an emerging class of bio-based biodegradable polymers with great potential to replace fossil-derived terephthalic acid-based copolyesters such as poly(butylene adipate-co-terephthalate) (PBAT). Furandioate-adipate polyesters have almost exclusively been prepared with conventional primary (1°) alcohol diols, whil...

The enzymatic synthesis of polyesters in solventless systems is an environmentally friendly and sustainable method for synthetizing bio-derived materials. Despite the greenness of the technique, in most cases only short oligoesters are obtained, with limited practical applications or requiring further chemical processing for their elongation. In th...

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. The C=C bonds present in these polyester chains allows for post-polymerization modification and such moieties are conventionally utilized in curing pr...

Following concerns over increasing global plastic pollution, interest in the production and characterization of bio-based and biodegradable alternatives is rising. In the present work, the synthesis of a series of fully bio-based alternatives based on 2,4-, 2,5-, and 2,6-pyridinedicarboxylic acid-derived polymers produced via enzymatic catalysis ar...

With increased awareness of environmental issues caused by traditional petrochemical processes, both academia and industry are making enormous efforts towards the development of sustainable practices using renewable biomass as a feedstock. In this work, the biocatalyzed synthesis of polyesters derived from renewable monomers was performed in safer,...

Seaweed powder has been found to act as an effective catalyst for the fixation of CO2 into epoxides to generate cyclic carbonates under solvent free conditions. Model background reactions were performed using metal halides and amino acids typically found in common seaweeds which showed potassium iodide (KI) to be the most active. The efficacy of th...

With the increasing society’s awareness of the problems caused by plastic pollution, the switch to renewable, biodegradable materials is nowadays a must for several producers and consumers. In the present work, the biocatalyzed synthesis of fully renewable polyesters containing lateral vinyl functionalities derived from itaconic, fumaric and maleic...

By modification of pore size and morphology, pore‐expanded variants of SBA‐15 and KIT‐6 have been utilised as mesoporous silica supports for the immobilisation of a bimetallic aluminium‐salen complex. The performance of the resulting heterogeneous catalysts in the synthesis of cyclic carbonates from carbon dioxide and terminal epoxides was assessed...

Supporting information (SI) for this article is given via a link at the end of the document. SI contains additional analytical data; assessment of triethylamine as a catalyst; additional information for kinetic study; additional data for addition to fumarate; assessment of feasibility for solvent quench.

In the present work, Candida antarctica lipase B (CaLB) was adsorbed onto polypropylene beads using different reaction conditions, in order to investigate their influence on the immobilization process and the enzyme activity of the preparations in polymerization reactions. In general, lower salt concentrations were more favorable for the binding of...

The sustainable synthesis of polymers is a field with growing interest due to the need of modern society to preserve the environment whilst making used products and food sustainable for the future generations. In this work we investigate the possibility of synthesizing aliphatic polyesters derived from various dicarboxylic acid diesters and diols i...

Development of renewable bio-based unsaturated polyesters is undergoing a renaissance, typified by the use of itaconate and fumarate monomers. The electron-deficient C=C bond found on the corresponding polyesters allows convenient post-polymerisation modification to give a wide range of polymer properties; this is notably effective for the addition...

The renaissance of the bio-based chemical industry over the last 20 years has seen an ever growing interest in the synthesis of new bio-based polymers. The building-blocks of these new polymers, so called platform molecules, contain significantly more chemical functionality than their petrochemical counterparts (such as ethane, propene and para-xyl...

Catalytic methods for the synthesis of amides are much sought after. Silica catalysts have shown promise, but yields are generally moderate and the use of toluene, a toxic and regulated solvent is re-quired. Here, the Hansen Solubility Parameters in Practice (HSPiP) software package has been used along with the Yalkowsky approximation to make predi...

A family of monomers, including 2,5-hexandiol, 2,7-octandiol, 2,5-furandicarboxylic acid (FDCA), terephthalic acid (TA), and branched-chain adipic and pimelic acid derivatives, all find a common derivation in the biomass-derived platform molecule 5-(chloromethyl)furfural (CMF). The diol monomers, previously little known to polymer chemistry, have b...

Cyclic carbonates, which are useful and nontoxic electrolytes, solvents, and chemical intermediates, can be produced by the 100% atom efficient addition of carbon dioxide to epoxides. In this chapter, we discuss the use of sustainable catalysts based on earth-abundant metals potassium, aluminum, and iron for this reaction, showcasing the most impor...

Three organozinc complexes have been synthesised and found to catalyse the carbonylation of propylene glycol with carbon dioxide to form propylene carbonate. A similar tethered organozinc complex was supported onto high loading aminopropyl functionalised hexagonal mesoporous silica and was also found to be catalytically active.

High throughput methodologies screened 81 different metal salts and metal salt combinations as catalysts for the carboxylation of propylene glycol to propylene carbonate, as compared to a 5 mol% Zn(OAc)2/p-chlorobenzene sulfonic acid benchmark catalyst. The reactions were run with added acetonitrile (MeCN) as a chemical water trap. Two new catalyst...

Diethyl carbonate is found to be a suitable, sustainable solvent for the quinine-catalyzed asymmetric Michael addition of malononitrile/α-substituted malononitriles to enones.

Diethyl carbonate is shown to be a suitable, sustainable solvent in which to carry out quinine catalysed asymmetric Michael additions of malononitriles to enones. Both malonitrile and α-substituted malononitriles can be used as substrate and the results suggest that π–π stacking interactions between the (hetero)aromatic rings of the catalyst and su...

The use of sustainable metal-based catalysts for the synthesis of five-membered ring containing cyclic carbonates from epoxides and carbon dioxide is critically reviewed. Coverage is restricted to catalysis by the abundant metals: sodium, potassium, aluminium, calcium, titanium and iron and the relative merits and limitations of each catalyst syste...

Preparation of supported nanoparticles by palladium deposition onto silica (SBA-15) from a solution of tris(dibenzylideneacetone) dipalladium(0) (Pd2(dba)3) in supercritical carbon dioxide (scCO2) was successfully achieved. Pd2(dba)3 avoided agglomeration of nanoparticles, which is typically associated with secondary processes including reduction o...

With ever-increasing demand of chemical products on a global scale, as well as poor public image in recent years, there has been increasing pressure for chemistry industry to become more efficient and sustainable.

We recently published details of an effective, reusable and benign heterogeneous amidation catalyst based on thermal treatment of amorphous K60 silica, however the loading of catalyst required was high for some reactions. We report herein our further development of a series of heterogeneous catalysts based on structured silica (SBA) that retain all...

We recently published details of an effective, reus able and benign heterogeneous amidation catalyst based on thermal treatment of amorphous K60 silica, however the loading of catalyst required was high for some reactions. We report her ein our further development of a series of heterogeneous catalysts based on structured silica (SBA) that retain a...

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We have developed a heterogeneous silica catalyst that can effectively catalyse amide synthesis from acid and amine, without production of toxic by-products and with the advantage of being readily available, low cost, environmentally benign and reusable.