Preparation of Unsaturated Linear Aliphatic Polyesters Using Condensation Polymerization

Abstract

A versatile method for preparing linear, unsaturated polyesters through condensation polymerization of trans-β-hydromuconic acid (HMA) with a variety of diols using Sn(Oct)2 and Novozyme-435 as catalysts was explored. Poly(1,8-octanediol hydromuconoate) was the highest molecular weight homopolymer prepared with a 〈M n〉 of 10.5 × 103 g/mol and polydispersity of 2.0. These materials showed unique melting behavior that was dependent on the number of carbons in the diol. Melting points ranged from 40 to 70 °C. Copolymers where the amount of HMA was diluted by adipic acid were prepared and had a 〈M n〉 as high as 13.0 × 103 g/mol and polydispersities below 2.0. The double bonds of these materials were chemically modified through epoxidation in yields greater than 93% and with no degradation of the polymer backbone. Materials with hydroxyl end groups were prepared through stoichiometric mismatch. Unsaturated poly(ester ether)s that are amorphous liquids with T g below −40 °C were prepared using diethylene glycol as the diol.

Apoplastic Diffusion Barriers in Arabidopsis

“…Based on known polymer linkages and in vitro polymerization studies (Olson and Sheares, 2006;Olsson et al, 2007), esterases and lipases represent candidate proteins for polyester condensation . The α/β hydrolase BDG is involved in cutin formation and has been shown to be cell wall-localized (Kurdyukov et al, 2006a).…”

Azidation of polyesters having pendent functionalities by using NaN3 or DPPA–DBU and photo-crosslinking of the azidopolyesters

“…The produced maleate/fumarate units might have contributed to the dehydrobromination (Scheme 3). 18 To optimize the experimental conditions, we next examined the effect of temperature on the azidation reaction (run 2-7 in Table 1). As the reaction temperature was raised (440 1C), the azidation ratio is increased; however, the increased temperature is also known to cause crosslinks between the azide and double bond formation (data not shown) as the side reactions.…”

“…As the reaction temperature was raised (440 1C), the azidation ratio is increased; however, the increased temperature is also known to cause crosslinks between the azide and double bond formation (data not shown) as the side reactions. 19 On the other hand, as an example of the application of this procedure to non-conjugated substrates, 18 we successfully carried out azidation of poly(butylene bromoadipate) (poly(BBA)) (M n ¼5.6Â10 3 (M w /M n ¼2.29)) at room temperature for 1 h to generate poly(butylene azidoadipate) (poly(BAA)) (66% yield, M n ¼5.3Â10 3 (M w /M n ¼2.23)) without any dehydrobromination and crosslinking (Figure 2), which was soluble in chloroform as shown in Table 2.…”

Electrochemical Conversion of Biologically Produced Muconic Acid: Key Considerations for Scale-Up and Corresponding Technoeconomic Analysis

“…20, 23 In addition to its potential conversion to large-scale commodity chemicals, MA is also an intermediate to trans-3-hexenedioic acid (t3HDA), a promising monomer for the production of bioadvantaged nylons ( Figure 1) and poly(ester)ethers: the additional double bond compared to adipic acid enables the subsequent functionalization of the polyamide, thus creating nylons with tailored properties. 17,24,25 Figure 1. Potential commercial products derived from unsaturated polyamide 6,6 (UPA 6,6).…”