High-performance hybrid materials prepared by the thermo-reversible Diels–Alder polymerization of furfuryl ester-terminated butylene succinate oligomers and maleimide compounds

Abstract

A furfuryl ester-terminated butylene succinate oligomer (FBSO) with M n 1800 and M w 2800 was synthesized by the condensation of furfuryl alcohol with a carboxyl-terminated butylene succinate oligomer. The reaction of FBSO and 1,1¢-(methylenedi-4,1-phenylene)bismaleimide (BMI) in chloroform at 60 1C for 48 h yielded an exo-rich Diels-Alder (DA) adduct ((P(FBSO-BMI)) with M n 9000 and M w 15 500. The gel permeation chromatography analysis of the products of heating a reaction mixture of P(FBSO-BMI) in dimethylformamide (DMF) at 120 1C for 1 h revealed that FBSO and BMI are quantitatively recovered by the retro DA reaction. Maleimide/phenyl-substituted oligomeric silsesquioxane (MPOSS) was synthesized by the reaction of maleimidemethyl 3-(triethoxysilyl)propylcarbamate and triethoxyphenylsilane in the presence of hydrochloric acid. The DA reaction of FBSO and MPOSS in DMF at 60 1C for 48 h gave a partially crosslinked hybrid composite insoluble in general organic solvents. When the hybrid composite was heated in DMF at 140 1C, the retro DA reaction proceeded smoothly. The hybrid film prepared by casting a DMF solution of FBSO and MPOSS and subsequently heating at 60 1C for 48 h had a much higher flexural strength than FBSO did. Polymer Journal (2011) 43, 455-463; doi:10.1038/pj.2011.14; published online 2 March 2011 Keywords: bio-based polymer; Diels-Alder reaction; furan; maleimide; organic-inorganic hybrid; poly(butylene succinate); silsesquioxane INTRODUCTION Recently, biodegradable polymers derived from renewable agricultural and biomass feedstocks have been receiving considerable attention as sustainable and eco-efficient replacements for polymer products based exclusively on petroleum feedstocks. [1][2][3][4][5] For example, polylactide is a biodegradable polyester produced from starch by the fermentation of glucose via L-lactic acid. 6,7 Poly(butylene succinate) (PBS) is an industrially available biodegradable and potentially bio-based aliphatic polyester. [8][9][10] However, these aliphatic polyesters are inferior in mechanical and thermal properties to the conventional petroleumbased polymers. As environmentally benign reinforcing materials for bio-based and biodegradable polyesters, layered silicate nanocomposites have been the subject of many recent publications. 11-15 These nanocomposites often exhibit properties superior to those of conventional composites, including greater stiffness, thermal stability, improved barrier properties and enhanced flame retardant behavior. However, the influence of layered silicates on the biodegradability of the polyesters is still controversial, 11-13 and the environmental and toxicological implications of such nano-sized fillers are not fully understood. 15 We had already reported the crosslinking reaction of

Synthetic Biodegradable Polymers with Chain End Modification: Polylactide, Poly(butylene succinate), and Poly(hydroxyalkanoate)

“…For example, a furfuryl ester-terminated butylene succinate oligomer with a M n of 1,800 was synthesized by the condensation of furfuryl alcohol with a carboxyl-terminated butylene succinate oligomer. 73 This polymer was used for condensation by the Diels-Alder reaction. Also, the two carboxylic acid groups of PBS were modified for azide to use a click reaction with hydrophilic polyacrylic acid derivatives.…”

Cross-Linking of Polypropylene with Thiophene and Imidazole

“…The same peak (υCH=CH) appeared in the spectrum of cross-linked grafted imidazole products (IMG1) at 1510 cm −1 ( Figure 2 b), overlapping with the peak of imidazole ring stretching (υ imidazole ring) [ 40 , 44 ]. As can be seen in Figure 2 b, an additional peak at 702 cm −1 which is assigned to =CH out of plane bending vibration of the maleimide ring (γ = CH), appears in the spectra of IMG1 [ 46 , 47 ].…”

Synthesis and Properties of Thermosets from Tung Oil and Furfuryl Methacrylate

“…This indicated that a specific proportion of the raw materials took part in cross-linking reactions. Cross-link density was calculated using the formula E' = 3nRT (where E' is the storage modulus at the rubbery region, n is the cross-linking density, R is the universal gas constant and T is absolute temperature in K (T = Tg + 25 °C)) [10,27]. Figure 7 displays the DMA analysis of the film samples which demonstrates the variation of the storage and loss modulus with temperature.…”