Isosorbide, polymers from

Fenouillot, R, Rousseau, A., Colomines, G., Saint-Loup, R., Pascault, J. R (2010). Polymers from renewable l,4 3,6-dianhydrohexitols (Isosorbide, isomannide and isoidide) A review,... 

The use of polymers from renewable 1,4,3,6-dianhydrohexitols has been reviewed (34,35). Isosorbide, isomannide, and isoidide are basically stereo isomers from dianhydrohexitol compounds. 

Okada M., Aoi K., Biodegradable polymers from l,4 3,6-dianhydro-D-glucitol (isosorbide) and its related compounds. Current Trends Poly. ScL, 7, 2002, 57-70. 

F. FenouiUot, A. Rousseau, G. Colomines, R. Saint-Loup, J.P. Pascault, Polymers from renewable 1,4 3,6-dianhydrohexitols (isosorbide, isomannide and isoidide) a review. Prog. Polym. Sci. 35 (2010) 578-622. 

PU synthesized through an isocyanate-free method has been recently reported by Besse et al. They obtained linear and branched bio-based PU from isosorbide with acceptable thermal stability suitable for coatings applications. Isosorbide, extracted from the dehydration of sorbitol, as HS provides a good rigidity to the polymer [68]. Moreover, Besse et al. studied new bio-based isocyanate-free PUs with good thermal stability for coatings [68]. These PUs do not release isocyanate during the thermal decomposition. 

Poly ethers were next synthesized from isosorbide by means of a MW-assisted PTC method (Eq. 10). In addition to increasing the rate of the reaction, the MW affected the structure of the polymer (determined by MALDI/TOF mass spectrometry Tab. 5.7). Polymers of higher molecular weights, with ethylenic groups as chain terminations, were obtained conventional heating led to shorter hydroxylated compounds [21]. 

Isosorbide polyurethanes, especially those based on aliphatic isocyanates, may be useful in the same applications as conventional polyurethanes i.e. thermoplastics, coatings, and foams. In fact, excellent rigid foams have been obtained from P(I-MDI)(5). Isosorbide has a low melting point of 61°C and it is suitable for use in reactive injection molding processes alone or in the form of a mixture with other conventional diols. In addition, its polymers may also find specific applications due to the anticipated high complexation ability of the two tetrahydrofuran rings in their isosorbide units. 

We have prepared two linear soluble polyurethanes P(LAGA-MDI) and P(LAGA-HMDI) by solution polymerization of LAGA with MDI and HMDI respectively in dimethyiacet-amide as a solvent using dibutyltin dilaurate as a catalyst at 75°C over 24 hours According to the procedure used in the preparation of the isosorbide polyurethanes as described in the experimental section. Both polymers have been isolated in quantitative yield in their lactone form by precipitation from chloroform (15). 

Isohexides exhibit excellent properties as plasticizers for polyvinyl alcohol polymers.2 Compounds obtained from isosorbide and trialkylaluminum proved to be highly active cocatalysts for polymerization of alkenes. Such derivatives, which were supposed to be oligomeric O-aluminum-isosorbides, are of glass-like appearance and exhibit pyrophoric properties.255 Isosorbide is a component of mixtures used for water-based pigment inks, having excellent dispersion stability, which is necessary for ink-jet printing.256 257... 

The ADMET polymerization of sugar-based monomers is much less explored than the ROMP approach, and only a few examples have been reported to date. Bui and Hudlicky prepared a,oo-dienes derived from a biocatalytically synthesized diene diol, from which chiral polymers (up to 20 kDa) with D-c/uro-inositol units were prepared via ADMET in the presence of 1 mol% of C4 [169]. Furthermore, several ot,co-dienes containing D-mannitol, D-ribose, D-isomannide, and D-isosorbide have been synthesized by Enholm and Mondal [170]. Also in this study, C4 was used to catalyze the ADMET polymerizations at 1 mol% catalyst loading. As pointed out by the authors, the viscosity increased as the reactions progressed and vacuum had to be applied to efficiently remove the released ethylene. Unfortunately, the polymers obtained were not further analyzed. As already mentioned above, Fokou and Meier have also reported the ADMET polymerization of a fatty acid-/D-isosorbide-based a,co-diene [126]. Furthermore, Krausz et al. have synthesized plastic films with good mechanical properties by cross-linking fatty esters of cellulose in the presence of C3 [171-173]. 

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... 

Poly(ether-ester)s have been prepared by condensation of adipoyl or terephthaloyl chloride with an isosorbide-based ether-diol (Scheme 3.10). The parent isosorbide is obtained from renewable resources, hydrogenation, and subsequent dehydration of D-glucose. The polymerizations were accelerated about five times under microwave heating using a scientific microwave unit as compared to conventional methods, and a 95% yield of the desired polymers was obtained within 5 min at 180 °C. 

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... 

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. 

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. 

Kricheldorf H.R., Sun S.J., Gerken A., Ch. Chang T., Polymers of carbonic add 22. Cholesteric polycarbonates derived from (S)-[(2-methylbutyl)thio]hydroquinone or isosorbide. Macromolecules, 29, 1996, 8077—8082. 

Kricheldorf H.R., Sun Sh.J., Chen Ch.R, Chang T.Ch., Polymers of carbonic acid. XXIV. Photoreactive, nematic or cholesteric polycarbonates derived from hydroquinone-4-hydroxybenzoate 4,4 -dihydroxychtilcone and isosorbide, J. Polym. Sci. Part A Polym. Chem., 35, 1997, 1611-1619. 

Sun S.J., Schwarz G., Kricheldorf H.R., Ch. Chang T., New polymers of cabonic acid. XXV. Photoreactive cholesteric polycarbonates derived from 2,5-bis(4 -hydroxybenzylidene)cyclopentanone and isosorbide, J. Polym. ScL Part A Polym. 

Chatti S., Bortolussi M., Loupy A., Blais F.C., Bogdal D., Majdoub M., Effldent synthesis of polyethers from isosorbide by microwave-assisted phase transfer catalyst, Eur. Polym. J., 38,2002,1851-1861. 

Fig.20. A Isosorbide (l,4 3,6-dianhydro-D-sorbitol). B Isomannide (1,4 3,6-dianhydro-D-mannitol). C Isoidide l,4 3,6-dianhydro-L-iditol (isoidide). Reprinted from (2002) Eur Polym J 38 1851 [87] with permission...

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. 

Cholesteric LC homo/copolyesters can be synthesized from isosorbide, methyl hydroquinone, and isophthaloyl chloride by solution polycondensation method in presence of mild organic base. The properties of the polymers by this method conform to any other method in terms of molecular weight, LC texture, stability etc. [58]. 

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