Isosorbide polyesters from

Later, Braun et al. reported the synthesis of a broad range of polyesters from isosor-bide/isomannide and acid dichlorides via melt condensation [12], The acid chlorides used include linear C4-C16 alkanoyl, ortho/iso/terephthaloyl, and 1,8- and 2,6-naphthalenoyl. Relatively high aliphatic polyesters were obtained, with up to 60 000 (GPC) for poly(isosorbide sebacate). Contrary to the aliphatic polyesters, the semi aromatic polyesters are highly viscous at high temperatures, hampering polycondensation. The TgS recorded for polyesters obtained by melt polymerization of isosorbide or isomannide with terephthaloyl chloride were 147 and 156 °C, respectively. 

Storbeck and Ballauff prepared polyesters from isohexides and terephthaloyl dichloride by solution polymerization in pyridine, giving colourless, fibrous materials [13]. Isomannide and isoidide yielded semi-crystalline materials however, crystallinity could not be recovered after annealing since their glass transition temperature and melting temperature are too close to each other for them to be crystallized from the melt. Thermogravimetric analysis (TGA) of poly(isosorbide terephthalate) (PIT) showed thermal stability up to 360 °C under a nitrogen atmosphere. 

Homo-polyesters of isohexides and linear aliphatic diacids have been reported by various groups (see Table 9.5). Braun et al. reported the synthesis of polyesters from isosorbide or isomannide with a variety of linear aliphatic acid dichlorides (C4-C16) via melt condensation, giving relatively high molecular weight polymers [12]. Comparable polyesters from all three isohexides were prepared by Okada [36-38], Noordover et al. also described the synthesis... 

For use in plastics, this might require chain extension with diisocyanates, bisoxazolines, carbodiimides, bis(an-hydrides), and such. One use of the oligomers would be to form polyurethanes by reaction with isocyanates. The use of acid chlorides can be avoided if the polymers are made by ester exchange or made enzymatically, with compounds such as divinyl adipate. Poly(butylene sebacate) with a molecular weight of 46,400 has been made has been made from bis(2,2,2-trifluoroethyl)sebacate and 1,4-butane diol.150 One polyester with a molecular weight of 24,000 has been made by ester exchange from isosorbide and a... 

Figure 1.17 Repeat unit of the polyester prepared from FDA and isosorbide.

In this chapter we will discuss four types of biomass derived monomers and their application in polyesters three building blocks with a more or less unique structure from the 2004 DoF report (i.e. succinic acid, FDCA, and isosorbide), and one true drop-in replacement (i.e. bio-terephthalic acid). For each type of building block the chemical structure, raw material source, and synthesis will be described. The synthesis and properties of the polyesters will then be discussed and, depending on the type of material, current and future commercial applications will be described. 

The first patents in which isosorbide based polyesters are described are from the 1960s. Most of these were aimed at fibre applications and involved co-polyesters with terephthalic acid and other monomers [18-21]. 

Garaleh, M., Yashiro, T., Kricheldorf, H.R. et al. (2010) (Co-)Polyesters derived from isosorbide and 1,4-cyclohexane dicarboxylic acid and succinic add. Macromolecular Chemistry and Physics. 211(11), 1206-1214. 

In addition, isosorbide and other l,4 3,6-dianhydrohexitols (isomannide derived from D-mannose, isoidide derived from L-fructose) are also attractive to serve as monomers for polymer production due to their rigidity, chirality, and non-toxicity (Fig. 6). Such features may introduce special properties into the polymers formed, such as enhanced Jg and/or special optical properties. Their innocuous nature also opens the possibility of applications in packaging or medical devices. As a bifunctional monomer, isosorbide can be polymerized with other bifunctional monomers via condensation polymerization. A recent review described various isosorbide-based polymers synthesized, including polyesters, polyamides, poly(ester amide)s, poly(ester imide)s, polycarbonates, polyurethanes, and so on [308], and the present... 

Isosorbide, a double dehydration product derived from sorbitol, is an attractive monomer due to its rigidity, chirality, and non-toxicity. Various isosorbide-based polymers have been synthesized by condensation polymerization, including polyesters, polyamides, poly(ester amides), polycarbonates, and polyurethanes. Incorporation of isosorbide into polymers backbones will introduce special properties, such as enhanced glass transition temperatures and/or optical properties. 

BPA is a known endocrine disrupting chemical (EDC), but this effect is sUght and has been known since the 1930s. This fear of EDC activity led to a total ban of BPA in polycarbonate plastic bottles intended for babies. The chemical industry was not really shaken by this ban as this use was only a tiny fiaction of the market. On the other hand, finding substances that rival the favorable properties BPA is not easy, and more significantly, not cheap. Isosorbide, which can be produced by artificial sweetener sorbitol, is a possible replaeement. A promising alternative of polycarbonate plastics is named Tritan co-polyester, and is made from dimethyl terephthalate, 1,4-cyclohexanedimethanol (CHDM), and 2,2,4,4-tetramethyl-l,3-cyclobutanediol (CBDO). However, replacing BPA in all current apphcatiorrs would be difficult, very expensive, and—most importantly—unlikely to save anyone from any harm. 

Sapich B., Stumpe J., Krawinkel T., Kricheldorf H.R., New polymer syntheses. 95. Photosetting cholesteric polyesters derived from 4-hydroxycinnamic acid and isosorbide, Macromolecides, 31, 1998, 1016-1023. 

Kricheldorf H.R., Wulff D.F., Layer structures. 11. Cholesteric polyesters derived from isosorbide, 2,5-bis(dodecyloxy)tere phthalic acid and 4,4 -dihydroxybiphenyl, Polymer, 39, 1998,6145-6151. 

The double dehydration of sorbitol yields D-isosorbide (l,4 3,6-dianhydrohexitol), a white, biodegradable, nontoxic solid. It is used in medicine to treat glaucoma. Other medications are derived from isosorbide, including isosorbide dinitrate and isosorbide mononitrate used to treat angina pectoris. The high thermal stability makes isosorbide interesting as a monomeric building block for thermoplastic polymers such as polyester and polycarbonates. The electrophilic alkylation of isosorbide with dimethyl sulfate yields dimethyl isosorbide, a colorless liquid which is used as a plasticizer for vinyl polymers and as a solvent in pharmaceutical and cosmetic preparations. 

Production of polyester resins (environmentally favored resins to drug release) from isosorbide in combination with terephthalic and isophthalic acids. 

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