Thermo-reversible Diels–Alder polymerization of difurfurylidene trehalose and bismaleimides

Teramoto, Naozumi; Arai, Yohei; Shibata, Mitsuhiro

doi:10.1016/j.carbpol.2005.10.029

Cited by 67 publications

(52 citation statements)

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“…The process and kinetics of chemical recycling via thermo-reversible Diels-Alder (DA) reactions between furan and maleimide (MI) have been widely studied. [19][20][21][22][23][24][25] Yoshie and co-workers reported the synthesis of a readily recyclable DA adduct of telechelic furfurylamide-terminated PBS and 1,2-bis (maleimide)ethane. 24 Chujo and co-workers reported the synthesis of organic-inorganic polymer hybrids by the sol-gel reaction of tetraethoxysilane in the presence of poly(furfuryloxymethylstyrene-co-styrene) and maleimidemethyl 3-(triethoxysilyl)propylcarbamate (MTES).…”

Section: Introductionmentioning

confidence: 99%

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

Shibata

Teramoto

Akiba

et al. 2011

Polym J

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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

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Section: Introductionmentioning

confidence: 99%

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

Shibata

Teramoto

Akiba

et al. 2011

Polym J

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“…The DA cycloaddition of furan and maleimide can be accomplished at or slightly above room temperature, while the rDA reaction is performed at elevated temperatures. Thermally rDA reactions have been used in numerous studies including polymer synthesis [10][11][12][13][14][15][16][17], dendrimers [18][19][20][21], epoxy resins [22][23][24][25], crosslinked polymer networks [26][27][28][29][30], organic-inorganic polymer hybrids [31][32][33], surfactants [34], surface modification [35,36] and remendable selfhealing polymers [37]. Due to the fact that these reactions can proceed under mild conditions without a catalyst, they are attractive for designing covalently reversible bonds with furan and maleimide functional groups which are responsible for association and disassociation [35,37,38].…”

Section: Introductionmentioning

confidence: 99%

Thermally reversible cross-linked poly(ether-urethane)s

Găină¹,

Ursache²,

Gaina³

et al. 2013

Express Polym. Lett.

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Abstract. Cross-linked poly(ether-urethane)s were prepared by Diels-Alder (DA) reaction of the furan-containing poly(ether-urethane) to bismaleimides and showed thermal reversibility evidenced by differential scanning calorimetry and attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy (ATR-FTIR). The furan-containing poly(ether-urethane)s were synthesized by the polyaddition reaction of 1,6-hexamethylene diisocyanate (HMDI) or 4,4!-dibenzyl diisocyanate (DBDI) to poly(tetramethylene ether) glycol (PTMEG having M n = 250, 650, 1000, 1500 and 2000) and 2-[N,N-bis(2-methyl-2-hydroxyethyl)amino]furfuryl as chain extender by the solution prepolymer method. The molar ratio of isocyanate: PTMEG:chain extender varied from 2:1:1 to 4:1:3, which produces a molar concentration of furyl group ranging between 3.65·10 -4 and 1.25·10 -3 mol/g.

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“…[3][4][5][6] We had already established a facile synthetic strategy to prepare trehalose-based linear polymers using the regioselective reaction of 4,6,4 0 ,6 0 hydroxyl groups of ,-Dtrehalose with terephthalaldehyde bis(dimethylacetal) or terephthalaldehyde. 4 However, the weight average molecular weight (M w ) of the obtained polymers was not more than 8500, probably because of the formation of sterically crowded benzylideneglucopyranoside moieties during the polymerization reaction.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of Thermoplastic Alternating Copolymers Containing Trehalose and Siloxane Units by Hydrosilylation Reaction

Teramoto

Unosawa

Matsushima

et al. 2007

Polym J

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ABSTRACT:A trehalose-based diallyl compound (I) was synthesized by the acetalization reaction of ,-Dtrehalose with 4-allyloxybenzaldehyde. Alternating copolymers containing trehalose units and siloxane units were synthesized by the hydrosilylation reaction of the diallyl monomer I and telechelic SiH-containing siloxanes in the presence of Karstedt's catalyst. As the SiH-containing siloxanes, 1,1,3,3,5,5-hexamethyltrisiloxane with the molecular weight of 208 (II) and dimethylsiloxane oligomers with the molecular weights of ca. 600 (III) and ca. 1000 (IV) was used. The structure of the obtained copolymers were fully characterized with 1 H-NMR and FT-IR spectroscopy. The weight average molecular weight (M w ) of the copolymers ranged from 5900 to 50000 (GPC). The copolymer with the highest M w was obtained by the reaction of I and III in toluene at 80 C for 72 h. All the polymers showed two glass transition temperatures (T g ), suggesting microphase separation. The lower T g was around À110C, which did not depend on the length of the siloxane oligomer segment; and the higher T g was ranging from 152 C to 96 C, which decreased with an increase in the length of the siloxane oligomer segment. Trehalose has a non-reducing character and relatively stable toward acid and heat compared to other sugars. Recently, Hayashibara Co. Ltd developed a low-cost manufacturing process of ,-D-trehalose from starch via enzymatic reactions.2 In this view, trehalose is one of promising monomers based on renewable resources for the production of linear polymers. [3][4][5][6] We had already established a facile synthetic strategy to prepare trehalose-based linear polymers using the regioselective reaction of 4,6,4 0 ,6 0 hydroxyl groups of ,-Dtrehalose with terephthalaldehyde bis(dimethylacetal) or terephthalaldehyde. 4 However, the weight average molecular weight (M w ) of the obtained polymers was not more than 8500, probably because of the formation of sterically crowded benzylideneglucopyranoside moieties during the polymerization reaction. In addition, the polymer showed no glass transition temperature up to the decomposition temperature.Our new strategy in order to improve these drawbacks is composed of the synthesis of a trehalosederived diallyl compound (I) using the regioselective acetalization reaction of ,-D-trehalose with 4-allyloxybenzaldehyde, and subsequent polymerization with flexible SiH-terminated dimethylsiloxane oligomers by use of hydrosilylation reaction (Scheme 1). We expect that thermoplasticity of rigid trehalosebased polymers will be improved by incorporation of the flexible units. While trehalose-based polymers are rigid polymers as reported previously, polydimethylsiloxane, whose T g is quite low, is not a self-standing polymer and often used as rubber after crosslinking process because of the flexibility of backbones. It is important to obtain a self-standing thermoplastic polymer from the prospective of environmental friendliness and material recycling. There have been many literatures on the synthesis of pol...

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Thermo-reversible Diels–Alder polymerization of difurfurylidene trehalose and bismaleimides

Cited by 67 publications

References 21 publications

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

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

Thermally reversible cross-linked poly(ether-urethane)s

Synthesis and Properties of Thermoplastic Alternating Copolymers Containing Trehalose and Siloxane Units by Hydrosilylation Reaction

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