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Three series of polyalkanoates (adipates, suberates and sebacates) were synthesized using as monomers three sugar-based bicyclic diols derived from D-glucose (Glux-diol and isosorbide) and D-mannose (Manx-diol). Polycondensations were conducted in the melt applying similar reaction conditions for all cases. The aim was to compare the three bicyclic diols regarding their suitability to render aliphatic polyesters with enhanced thermal and mechanical properties. The ensuing polyesters had molecular weights (Mw) in the 25,000–50,000 g mol−1 range with highest values being attained for Glux-diol. All the polyesters started to decompose above 300 °C and most of them did not display perceivable crystallinity. On the contrary, they had glass transition temperatures much higher than usually found in homologous polyesters made of alkanediols, and showed a stress–strain behavior consistent with their Tg values. Glux-diol was particularly effective in increasing the Tg and to render therefore polyesters with high elastic modulus and considerable mechanical strength. [ABSTRACT FROM AUTHOR]

A series of low-molecular-weight poly(butylene succinate- co-glutarate- co−2-trimethylammonium chloride glutarate) terpolyester ionomers containing 35% mol of total glutarate units but varying in the content of charged units were synthesized by polycondensation at mild temperatures using a scandium catalyst. The terpolyester ionomers started to decompose at the temperatures of >175°C and all of them were semicrystalline and have glass transition temperature similar to poly(butylene succinate) (PBS). These terpolyesters were used to compatibilize the nanocomposites made of PBS-cloisite (CL) prepared by melt extrusion. X-ray diffraction revealed that an intercalated structure was present in these nanocomposites. The thermal properties of the three-component mixtures did not differ substantially from those of PBS-CL but the mechanical properties were significantly improved by the addition of the ionomer, in particular tenacity. The beneficial effect afforded by the terpolyester ionomer was attributed to its ability for strengthening the binding between the PBS and the nanoclay. POLYM. COMPOS., 37:2603-2610, 2016. © 2015 Society of Plastics Engineers [ABSTRACT FROM AUTHOR]

A series of poly(butylene succinate) (PBS) ionomers containing up to 14 mol% of sulfonated succinate units have been synthesized by polycondensation in the melt-phase. The copolyesters were obtained with weight average molecular weights oscillating between 33,000 and 72,000 g•mol-1. All copolyesters were semicrystalline with melting temperatures and enthalpies decreasing and glass transition temperatures increasing with the content of ionic units. The thermal stability of PBS was slightly reduced by the incorporation of these units, and it was also found that the copolyesters were stiffer but also more brittle than PBS. The hydrolytic degradability of PBS was enhanced by copolymerization, an effect that was much more pronounced in basic media. [ABSTRACT FROM AUTHOR]

ABSTRACT The backbone of poly(butylene terephthalate) (PBT) was modified with 2,4:3,5-di- O-methylene- D-glucitol (Glux) using solid-state modification (SSM). The obtained copolyesters proved to have a non-random overall chemical microstructure. The thermal properties of these semicrystalline, block-like, Glux-based materials were extraordinary, showing higher melting points, and glass transition temperatures compared with other sugar-based copolyesters prepared by SSM. These remarkable thermal properties were a direct result of the inherently rigid structure of Glux and the relatively slow randomization of the block-like chemical microstructure of the Glux-based copolyesters in the melt. SSM proved to be a versatile tool for preparing partially biobased copolyesters with superior thermal properties. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 164-177 [ABSTRACT FROM AUTHOR]

An overview on the synthesis, structure and properties of polyamides and aromatic copolyesters produced by using monomers derived from carbohydrates is provided. Two examples are selected for illustration: (a) aliphatic polyamides prepared from aldaric acids and (b) aromatic copolyesters containing alditols units. Polycondensation in solution of n-alkanediamines (n taking even values from 6 to 12) with activated pentaric (l-arabino and xylo) and hexaric (galacto and d-manno) acids bearing the secondary hydroxyl groups protected as methyl ether, afforded linear polyaldaramides PA-nSu with Mw oscillating between 25 000 and 150 000 g mol−1. They are stable above 300°C and are semicrystalline even so only PA-nMn are stereoregular. Melting temperatures of PA-nSu range between 140 and 230°C and most of them are able to crystallize from the melt at a rate that increases with the length of the polymethylene segment. Both melting and glass transition temperatures decrease with the content in sugar units. Spherulitic films, oriented fibers and lamellar single crystals could be obtained from PA-nSu. All these polyamides seem to adopt a common crystal structure made of hydrogen-bonded sheets with the sugar residue skewed to attain an efficient side-by-side packing of the polymer chains. Aromatic homopolyesters and copolyesters derived from terephthalic acid and mixtures of butylene glycol and O-methylated alditols were prepared by polycondensation in the melt with Mw in the 20 000–50 000 g mol−1 range and a random microstructure. The thermal properties of PBT containing alditols units are very depending on the sugar constitution and copolyester composition. In general they are thermally stable above 300°C and display crystallinity for contents in alditols up to 30%. Melting temperatures decrease with the content in alditols whereas an opposite trend is observed for glass transition temperatures. The crystalline structure of PBT is preserved in the crystalline copolyesters whereas a different crystal lattice is adopted by homopolyesters entirely made of alditol units. In general, polyamides and polyesters containing sugar derived units are widely soluble in organic solvents, markedly hydrophilic and more susceptible to hydrolysis than their parent polymers. [ABSTRACT FROM PUBLISHER]

A set of polyurethanes containing isosorbide units were synthesized by polymerization in solution from HDI and MDI diisocyanates and 1,4-butanediol (BD), isosorbide (Is) or diisosorbide diurethanes (Is2HDI and Is2MDI) as diols. The thermal properties and stability, and crystal structure of the polyurethane homopolymers and copolymers containing isosorbide were evaluated and compared with those of the polyurethane analogues entirely made of BD. Incorporation of isosorbide produced significant changes in Tg, Tm and Td but no noteworthy differences were found between copolymers made from Is or Is2 monomers. Degradation assays revealed that incorporation of Is units increased slightly the hydrolysis rate. [ABSTRACT FROM AUTHOR]

This work explores for the first time the enzymatic synthesis of poly(butylene-co-ε-caprolactone) (PBSCL) copolyesters in bulk using commercially available monomers (dimethyl succinate (DMS), 1,4-butanediol (BD), and ε-caprolactone (CL)). A preliminary kinetic study was carried out which demonstrated the higher reactivity of DMS over CL in the condensation/ring opening polymerization reaction, catalyzed by Candida antarctica lipase B. PBSCL copolyesters were obtained with high molecular weights and a random microstructure, as determined by 13C NMR. They were thermally stable up to 300 °C, with thermal stability increasing with the content of CL in the copolyester. All of them were semicrystalline, with melting temperatures and enthalpies decreasing up to the eutectic point observed at intermediate compositions, and glass transition temperatures decreasing with the content of CL in the copolyester. The use of CALB provided copolyesters free from toxic metallic catalyst, which is very useful if the polymer is intended to be used for biomedical applications. [ABSTRACT FROM AUTHOR]

Cyclic butylene furandicarboxylate (c(BF)n) and butylene isophthalate (c(BI)n) oligomers obtained by high dilution condensation reaction were polymerized in bulk at 200 °C with Sn(Oct)2 catalyst via ring opening polymerization to give homopolyesters and copolyesters (coPBFxIy) with weight average molar masses in the 60,000–70,000 g·mol−1 range and dispersities between 1.3 and 1.9. The composition of the copolyesters as determined by NMR was practically the same as that of the feed, and they all showed an almost random microstructure. The copolyesters were thermally stable up to 300 °C and crystalline for all compositions, and have Tg in the 40–20 °C range with values decreasing almost linearly with their content in isophthalate units in the copolyester. Both melting temperature and enthalpy of the copolyesters decreased as the content in butylene isophthalate units increased up to a composition 30/70 (BF/BI), at which the triclinic crystal phase made exclusively of butylene furanoate units changed to the crystal structure of PBI. The partial replacement of furanoate by isophthalate units decreased substantially the crystallizability of PBF. [ABSTRACT FROM AUTHOR]

• Polyester-polypeptide diblock copolymers are synthesized avoiding organo-metals. • Both copolymer molecular weight and composition are well-controlled in the synthesis. • In the solid state the copolymers have the two blocks separated and orderly arranged. • The copolymers become self-assembled in water as spheres of 200–400 nm diameter. • They are precursors for charged copolymers suited for stimuli-responsive biomaterials. Diblock copolymers (PPDLx- b -pPAAy) were prepared from ω-pentadecalactone and l -glutamic acid or l -lysine amino acids by ring opening polymerization initiated by amino groups. Telechelic amino-ended poly(ω-pentadecalactone) with a length of 15–20 repeating units was firstly synthesized by enzymatic polymerization by means of CALB and then used as macroinitiator for the polymerization of the N -carboxyanhydrides of the two α-amino acids conveniently protected as benzyl and ε N -carbobenzoxy derivatives, respectively. The molecular weight of the polypeptide block was accurately controlled by adjusting the amino acid/macroinitiator ratio used in the feed. Copolymers with M n ranging between ∼5000 and ∼40,000 g·mol−1 and varying ester/peptide ratio were obtained and characterized in detail by GPC and NMR spectroscopy. The thermal properties of these copolymers were evaluated by TGA and DSC, and their structure in the solid-state including their response to heating, were examined by FTIR and XRD at variable temperature. It was shown that the polypentadecalactone segment was crystallized for all compositions and that the polypeptide counterpart adopted a two-dimensional hexagonal packing of α-helices at temperatures above melting of the polyester block. SAXS revealed the presence of a biphasic nanostructure with a repeating distance of 27 nm for the case of glutamic-based copolymers. It was demonstrated that both glutamic and lysine-based PPDL x - b -pPAA y copolymers could self-assemble in well-shaped nanospheres with a diameter in the ∼200–400 nm range and a negative zeta-potential. [ABSTRACT FROM AUTHOR]