Sugar based polymers ester

Poly (Vinylalcohol sugar ester) Figure 10. Strategy for PVA type sugar based polymer... 

It should be pointed out that the raw materials for VAM and its related polymers (i.e. ethylene and acetic acid) are produced from fossil resources, mainly crude oil. It is possible to completely substitute the feedstock for these raw materials and switch to ethanol, which can be produced from renewable resources like sugar cane, com, or preferably straw and other non-food parts of plants. Having that in mind, the whole production of PVAc, that nowadays is based on traditional fossil resources, could be switched to a renewable, sustainable and C02-neutral production process based on bioethanol, as shown in Fig. 3. If the vinyl acetate circle can be closed by the important steps of biodegradation or hydrolysis and biodegradation of vinyl ester-based polymers back to carbon dioxide, then a tmly sustainable material circle can be established. 

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]. 

DCC is also used in nucleotide chemistry to esterify a sugar hydroxyl group with a phosphate group in another nucleotide or oligonucleotide unit. Also p-styrene based polymers with a pyridyl-2-ethanol end group are reacted in pyridine with 3 -0-acetyl-desoxythimidine-5 -phosphate in the presence of DCC." The reaction of mono esters of phosphoric acid with alcohols or phenols, in the presence of DCC, affords phosphoric acid diesters in high yield." This reaction is widely used in nucleic acid chemistry. 

Extrusion is a cost effective manufacturing process. Extrusion is popularly used in large scale production of food, plastics and composite materials. Most widely used thermoplastics are processed by extrusion method. Many biopolymers and their composite materials with petroleum-based polymers can also be extruded. These include pectin/starch/poly(vinyl alcohol) (Fishman et al. 2004), poly(lactic acid)/sugar beet pulp (Liu et al. 2005c), and starch/poly(hydroxyl ester ether) (Otey et al. 1980), etc. In this study, composite films of pectin, soybean flour protein and an edible synthetic hydrocolloid, poly(ethylene oxide), were extruded using a twin-screw extruder, palletized and then processed into films by compression molding process or blown film extrusion. The films were analyzed for mechanical and structural properties, as well as antimicrobial activity. 

Both polymer glycosides and polymer esters of the first sugar unit have been made. No problems due to incompatibility of polymer and reactants have been reported. Since highly protected sugars are employed in the synthesis, the normal hydrophilic nature of the sugars seems to be decreased, making them compatible with styrene-based polymers. This also seems to permit the use of weakly polar solvents such as benzene and methylene chloride in oligosaccharide synthesis. 

Warwel et al. applied catalytic methods of olefin chemistry to achieve polymer building blocks as well as polymers like functionalized polyolefins, polyesters, polyethers, polyamides as well as sugar-based surfactants [4]. The fundamental approach was the polymer synthesis based on unsaturated fatty acid methyl esters, which are available by industrially applied transesterification of fats and oils with methanol. In Figure 18 is reported a schematic representation of the potential of plant oil components in the preparation of different polymeric materials. 

Kricheldorf [17] studied liquid-crystalline cholesteric copoly(ester-imide)s based on 1 or 2. The comonomers to obtain these chiral thermotropic polymers were N-(4-carboxyphenyl)trimellitimide, 4-aminobenzoic trimellitimide, 4-aminocinnamic acid trimellitimide, adipic acid, 1,6-hexanediol, and 1,6-bis(4-carboxyphenoxyl) hexane. Apparently the poly (ester imide) chains are so stiff that the twisting power of the sugar diol has little effect. 

The backbone of a nucleic acid is a polymer of ribofuranoside rings (five-membered rings of the sugar ribose) linked by phosphate ester groups. Each ribose unit carries a heterocyclic base that provides part of the information needed to specify a particular amino acid in protein synthesis. Figure 23-21 shows the ribose-phosphate backbone of RNA. 

Nucleic acids are unquestionably top level molecules because they store our genetic information. They are polymers whose building blocks (monomers) are the nucleotides, themselves made of three parts—a heterocyclic base, a sugar, and a phosphate ester. A nucleoside lacks the phosphate. In the example alongside, adenine is the base (black), adenosine is the nucleoside (base and sugar), and the nucleotide is the whole molecule (base + sugar + phosphate). 

The repair and replication of cells involves metabolism - interconversions of hundreds of low molecular weight metabolites that ultimately yield the precursors for much larger, more complex macromolecules such as phospholipids (based on phosphatidic. acids or long chain fatty acid esters of glycerol phosphate), polynucleotides such as RNA and DNA (polymers of nucleotide monomers), proteins (polypeptides or amino acid monomers linked by peptide bonds) and polysaccharides (polymers of simple sugars or monosaccharides). 

The base and the sugar combine as shown in Fig. 22.36(a) to form a unit that in turn reacts with phosphoric acid to create the nucleotide, which is an ester [see Fig. 22.36(b)]. The nucleotides become connected through condensation reactions that eliminate water to give a polymer of the type represented in Fig. 22.37 on page 1058 such a polymer can contain a billion units. 

The )8-(1 2)- and a-(1 5)-linked arabinose residues are incorporated into the polymer from the activated polyprenyl sugar phosphate 10, which is in turn synthesized from glucose via 5-phosphoribose pyrophosphate (pRpp) [46-48]. Elongation of the polymer chain is believed to involve a family of arabinosyltransferases (AraT s) that recognize both 10 and arabinofuranoside-based acceptors of differing structures (Fig. 5) [18,19,49,50]. In AG biosynthesis, the entire polysaccharide appears to be assembled as a polyprenol diphosphate intermediate, which is transferred to peptidoglycan prior to the addition of the mycolate esters [18]. In LAM biogenesis, the arabinan portion is believed to be synthesized as a polyprenol phosphate that is transferred to lipomannan [51]. 

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