Rex E. Murray

A novel biobased plasticizer of epoxidized cardanol glycidyl ether: synthesis and application in soft poly(vinyl chloride) films

A novel plasticizer derived from cardanol, and epoxied cardanol glycidyl ether (ECGE), was synthesized and characterized by 1H-NMR and 13C-NMR. The effects of ECGE combined with the commercial plasticizer dioctyl phthalate (DOP), in soft poly(vinyl chloride) (PVC) films, were studied. The mechanical properties of PVC films showed both tensile strength and percent elongation increases with increasing ECGE content. Thermogravimetric analysis (TGA) was performed to characterize the thermal stabilities of the plasticized samples and showed the stability of films increased on increasing the content of ECGE. The properties of volatility, extraction, and exudation resistance of plasticizers were tested and analysis by means of solubility parameters as reported in the literature suggests the ECGE has similar or higher stability for these properties than DOP. FTIR analysis of the films also revealed that ECGE interacted with PVC. Due to its inherent chemical backbone and the modified epoxy groups, ECGE properly balanced the properties and improved the performance of PVC films compared with the neat DOP plasticizer.

CHAPTER 4:Thiol-ene and H-Phosphonate-ene Reactions for Lipid Modification

This chapter is a short introduction to the thiol-ene reaction and includes the thiol-ene reaction as a click chemistry reaction, radical chain reactions, basic mechanisms and kinetics, the use of the thiol-ene reaction for the synthesis of novel bio-based materials (polymers, lubricants and coatings), addition of H-phosphonates to double bonds, some reaction information and bio-based products, and possible applications of the products (lubricants, plasticizers and anti-microbial agents).

Plasticizers derived from cardanol: synthesis and plasticization properties for polyvinyl chloride(PVC)

Two natural plasticizers derived from cardanol (CD), cardanol acetate (CA) and epoxidized cardanol acetate (ECA), were synthesized and characterized by 1H NMR and 13C NMR. The plasticizing effects of the obtained plasticizers on semi-rigid polyvinylchloride (PVC) formulations were also investigated. Two commercial phthalate ester plasticizers, dioctyl terephthalate (DOTP) and diisononyl phthalate (DINP), were used as controls. Mechanical and thermal properties, compatibility, thermal stability, microstructure, and workability were assessed by dynamic mechanical analysis (DMA), mechanical analysis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and dynamic stability analysis, respectively. Results indicated that the natural plasticizer ECA had overallsuperior flexibility, compatibility, thermal stability, and workability comparable to both controls. The obtained CA and ECA have lower volatility resistance and similar extraction and exudation resistance than that of DOTP and DINP. The CA was further blended with DOTP in soft PVC films. Results of DMA, TGA and mechanicalanalysis indicated that CA can serve as a secondary plasticizer to improve the related properties of soft PVC formulations. These CD derived plasticizers show promise as an alternative to fully or partially replace petroleum-based plasticizers.

Decarboxylation of cinnamic acids using a ruthenium sawhorse

Abstract The ruthenium sawhorse has proven effective in the conversion of trans-cinnamic acid, and substituted trans-cinnamic acids, giving an effective source of biobased styrene and styrene analogues. The reaction is especially versatile, as it achieves product without utilising co-reagents. However, the optimum conditions and substrate scope of the reaction remain unexplored. This report covers the decarboxylation of a series of cinnamates with different structures. Apparent activation energies ranging from 66 to 142 kJ mol−1 were uncovered.

Improvement of Lubricant Materials Using Ruthenium Isomerization

Production of an effective industrial lubricant additive from vegetable oils is a high profile and difficult undertaking. One candidate is alkyl 9(10)-dibutylphosphonostearate, which has been made through a radical transformation of alkyl 9-cis-octadecanoate. It is effective, but still suffers from drawbacks. In this report, that synthesis is combined with a ruthenium based isomerization process to create not just one, but an entire series of new chemical compounds. A low level of [Ru(CO)2(EtCO2)]n is first used for the isomerization of the starting material, then radical chemistry is employed. A series of methyl dibutylphosphonooctadecanoates was made. In an analogous fashion, trans-7-tetradecene was also isomerized and then polymerized. As in the phosphonate case, the follow-up chemistry could be performed in the presence of the residual isomerization catalyst. The alkane:alkene ratio, observed by 1H NMR, was found to change from 14:1 in the isomerized starting material to a value of 41:1 in the polymerized material. This methodology, isomerization in tandem with other reactions, gives suitable routes to both biobased polyolefins, and biobased phosphonates, potential key ingredients in biobased lubrication formulations.