In this study, rigid thermoset polymers were prepared from radical copolymerization of the soybean oil monoglyceride maleates with styrene In the first part of the study, soybean oil monoglycerides (SOMGs) were obtained from the reaction of soybean oil with glycerol at 220–240°C with an optimization of the reaction to maximize the monoglyceride yield In the following step, SOMG were reacted with maleic anhydride at temperatures around 100°C to produce the SOMG maleate half esters Different catalysts and different reaction conditions were examined to increase the maleate half esters' yields The reactions were followed by IR and 1H NMR, and the products were characterized by mass spectrometry In the final step, the radical initiated copolymerization of the SOMG maleates with styrene produced rigid, thermoset polymers The emulsion copolymerization of the SOMG maleates with styrene was also carried out successfully without the addition of an emulsifier The obtained polymers were characterized by IR and the crosslinked network structure of the copolymers was examined with the swelling behavior in different solvents Mechanical properties of the cured resin such as Tg, dynamic flexural modulus, and surface hardness were also determined © 2001 John Wiley & Sons, Inc J Appl Polym Sci 81: 69–77, 2001

Rigid, thermosetting liquid molding resins from renewable resources. I. Synthesis and polymerization of soy oil monoglyceride maleates

In this study, castor oil was alcoholyzed with both aliphatic alcohols, such as glycerol and pentaerythritol, and an aromatic alcohol, bisphenol A propoxylate. The resulting alcoholysis products were then malinated and cured in the presence of styrene. Soybean oil pentaerythritol glyceride maleates were also prepared for a direct comparison of the properties of the castor oil and soybean oil based resins. Castor oil was directly malinated as well to see the effect of the alcoholysis step on the properties of the castor oil based resins. The monomers synthesized were characterized by 1 H-NMR spectroscopy, and the styrenated resin liquid properties, such as viscosity and surface energy values, were determined. The conversion of polymerization was determined using time resolved FTIR analysis for the styrenated soybean oil pentaerythritol glyceride maleates, castor oil maleates, and castor oil pentaerythritol glyceride maleates. The effect of monomer identity and styrene content on the conversion of polymerization was explored.

Soybean and castor oil based monomers: Synthesis and copolymerization with styrene

Results of investigations on novel formulations, structure-property relationships, curing, and compositions with fillers and reinforcing fibers (1997--2004) are reviewed with about 200 references to articles and several references to patents. The following topics are considered in particular: novel dibasic acids, glycols, crosslinking monomers, and curing systems, “vinyl ester” resins, fire retardant materials, IPNs and other systems comprising built-in thermoplastic polymers and oligomers with terminal functional groups. Information on unsaturated polyesters manufactured using PET scrap is given. Analytical (mainly spectrometric) methods for studying the chemical structure of crosslinked unsaturated polyester resins are presented. Approaches to the decrease in styrene emission on processing of unsaturated polyester resins are also discussed.

Unsaturated Polyester Resins: Chemistry and Technology

Biobased, unsaturated polyesters derived from isosorbide, maleic anhydride and succinic acid were synthesized and characterized. The presence of maleic anhydride units in the structure of the polyesters allowed converting them into cured coatings by radical copolymerization with cross-linking agents such as 2-hydroxyethyl methacrylate, N-vinyl-2-pyrrolidinone, acrylic acid or methacrylamide. The investigated polyesters were obtained via bulk polycondensation, catalyzed by titanium(IV) n-butoxide. 2D NMR and MALDI-Tof-MS spectroscopy proved that this polymerization resulted in isomerization of maleic acid units into fumaric ones and in the formation of slightly branched structures by the reaction of isosorbide (end) groups with main chain unsaturated bonds. Moreover, some double bonds proved to have reacted with the condensation by-product water. The resulting polyesters displayed the expected correlation between variables such as molecular weight and content of unsaturated bonds and their Tg values. Since the thermal properties of the obtained polyesters were appropriate for coating applications, the polymers were cross-linked with unsaturated monomers by radical copolymerization. The cross-linking process was studied using FT-IR spectroscopy and by measurements of the soluble part of the cured coatings.

Unsaturated, biobased polyesters and their cross-linking via radical copolymerization

Biobased multiblock copolymers: Synthesis, properties and shape memory behavior of poly(hexamethylene 2,5-furandicarboxylate)-b-poly(ethylene glycol)

The polyesterification reaction of maleic anhydride and 1,4-butylene glycol was carried out, using p-toluensulphonic acid as catalyst The resulting material was characterized by IR and H1-NMR spectroscopy, end group analysis, and gel permeation chromatography It is shown that there is a relationship between maleate to fumarate isomerization and steric interaction among condensed groups on the one hand and the tendency of the reacting system to crosslink or gel

Unsaturated polyesters, III. Polyester from maleic anhydride and 1,4‐butylene glycol

The polycondensation reaction between maleic anhydride and 1,6-hexanediol, with p-toluenesulfonic acid as catalyst has been carried out. The product has been analyzed spectroscopically and the molecular weight determined by endgroup analysis and gel permeation chromatography. The influence of spatial interactions between condensed groups on the isomerization of maleate into fumarate is discussed, as well as the effects of even- and odd- numbered carbon atom glycols. © 1993 John Wiley & Sons, Inc.

Gilberto A. Perdomo Mendoza

Papers

Unsaturated polyesters, III. Polyester from maleic anhydride and 1,4‐butylene glycol

Unsaturated polyesters. V. Polyester from maleic anhydride and 1,6‐hexanediol