Effects of comonomer sequential structure on thermal and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate)s

In this work, new investigations on the effect of comonomer sequential structure on the thermal and crystallization behaviors and biodegradability have been implemented for the biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST) as well as aliphatic poly(butylene succinate) (PBS). At first, these copolyesters were efficiently synthesized from dimethyl succinate and/or dimethyl terephthalate and 1,4‐butanediol via condensation polymerization in bulk. Subsequently, their molecular weights and macromolecular chain structures were analyzed by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. By means of differential scanning calorimeter (DSC) and wide‐angle X‐ray diffractometer (WAXD), thermal and crystallization behaviors of these synthesized aromatic–aliphatic copolyesters were further explored. It was demonstrated that the synthesized copolyesters were revealed to have random comonomer sequential structures with thermal and crystallization properties strongly depending on their comonomer molar compositions, and that crystal lattice structures of the new crystallizable copolyesters shifted from the monoclinic crystal of semicrystalline PBS to triclinic lattice of the poly(butylene terephthalate) (PBT) with increasing the terephthalate comonomer composition, and the minor comonomer components were suggested to be trapped in the crystallizable component domains as defects. In addition, the enzymatic degradability was also characterized for the copolyesters film samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1635–1644, 2006     

Thermal and mechanical properties of mandelic acid‐copolymerized poly(butylene succinate) and poly(ethylene adipate)

Phenyl side chains were introduced to poly(butylene succinate) and poly(ethylene adipate) by the polymerization of the respective monomers in the presence of mandelic acid. The increasing content of the phenyl side chains decreased the melting temperature and the crystallinity but increased the glass‐transition temperature of the aliphatic polyesters. The phenyl side branches reduced the crystallinity of poly(butylene succinate) more significantly than the ethyl or n‐octyl side branches did. The tensile strength, elongation, and tear strength of poly(ethylene adipate) decreased with an increase in the content of mandelic acid units. However, the increasing content of mandelic acid units enhanced the elongation and tear strength of poly(butylene succinate) considerably without a notable deterioration of tensile strength. The biodegradability of the copolyesters was increased as a result of the introduction of more mandelic acid units due to the decrease in the crystallinity. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1504–1511, 2000     

Block copolyesters of poly(pentamethylene p,p′‐bibenzoate) and poly(tetramethylene adipate)

Hydroxy‐terminated poly(pentamethylene p,p′‐bibenzoate) oligomers with different molecular weights were prepared. The poly(pentamethylene p,p′‐bibenzoate) oligomers showed rather high crystallinity, and some of them exhibited a monotropic smectic phase. Block copolyesters with hard segments of poly(pentamethylene p,p′‐bibenzoate) and soft segments of poly(tetramethylene adipate) were prepared by coupling the poly(pentamethylene p,p′‐bibenzoate) oligomer and a poly(tetramethylene adipate)glycol with methylene‐4,4′‐diphenylene diisocyanate in solution. The block copolyesters were characterized by IR, ¹H NMR, differential scanning calorimetry, a polarized microscope, and X‐ray diffraction. The thermal transitions of the block copolyesters were dependent on the composition and the molecular weight of the poly(pentamethylene p,p′‐bibenzoate) oligomer used. The hard segments in the block copolyesters showed no liquid crystallinity and exhibited rather low crystallinity or were even amorphous. The molecular weight of the poly(pentamethylene p,p′‐bibenzoate) oligomer used influences the glass‐transition temperature and crystalline properties of the soft segments in the block copolyesters significantly. The effect on the glass‐transition temperature of the soft segments is described as the difference in miscibility between the hard and soft segments. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2626–2636, 2002     

Nonisothermal crystallization kinetics of biodegradable poly(butylene succinate‐co‐propylene succinate)s

Poly(butylene succinate) (PBSu) and two poly(butylene succinate‐co‐propylene succinate)s were synthesized via the direct polycondensation reaction. The copolyesters were characterized as having 7.0.and 11.5 mol % propylene succinate (PS) units, respectively, by ¹H NMR. A differential scanning calorimeter (DSC) and a polarized light microscope (PLM) adopted to study the nonisothermal crystallization of these polyesters at a cooling rate of 1, 2, 3, 5, 6, and 10 °C/min. Morphology and the isothermal growth rates of spherulites under PLM experiments were monitored and obtained by curve‐fitting. These continuous rate data were analyzed with the Lauritzen?Hoffman equation. A transition of regime II → III was found at 95.6, 84.4, and 77.3 °C for PBSu, PBPSu 95/5, and PBPSu 90/10, respectively. DSC exothermic curves show that all of the nonisothermal crystallization occurred in regime III. DSC data were analyzed using modified Avrami, Ozawa, Mo, Friedman, and Vyazovkin equations. All the results of PLM and DSC measurements indicate that incorporation of minor PS units into PBSu markedly inhibits the crystallization of the resulting polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1299–1308, 2010     

Synthesis and kinetic modeling of biomass‐derived renewable polyesters

The biomass‐derived polyesters poly(1,3‐propylene 2,5‐furandicarboxylate) (PPF), poly(1,3‐propylene succinate) (PPS) and poly(1,3‐propylene 2,5‐furandicarboxylate‐co‐1,3‐propylene succinate) (PPFPS) have been synthesized via a two‐step process involving polycondensation and azeotropic distillation. The kinetic parameters were obtained by fitting the experimental data from a batch polymerization reactor to three different kinetic models for polyesterification reactions. The activation energies of the all monomer systems were obtained by Arrhenius plots. Given the increasing availability of biomass‐derived monomers their use in renewable polyesters as substitutes for fossil fuel derived chemicals becomes a distinct possibility. The kinetic modeling of the uncatalyzed polyesterification reactions will enable further integrative process simulation of the studied bioderived polymers and provide a reference for future practical study or industrial applications of catalyzed polyesterification reactions and other bioderived monomer systems. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2876–2887     

Poly(propylene isophthalate), poly(propylene succinate), and their random copolymers: Synthesis and thermal properties

Poly(propylene isophthalate) (PPI), poly(propylene succinate) (PPS), and poly(propylene isophthalate/succinate) (PPI‐PPS) random copolymers were synthesized and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by TGA and DSC. All the polymers showed a good thermal stability. At room temperature, they appeared as semicrystalline materials, except 20PPI‐PPS and 30PPI‐PPS: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of T_m with respect to homopolymers. A crystalline phase of PPI and PPS was evidenced at high content of PI or PS units, respectively. Amorphous samples were obtained after melt quenching and an increment of T_g, with the increment of PI units, was observed. This behavior was explained as due to the presence of stiff phenylene groups. The Wood equation described well T_g‐composition data. Lastly, the presence of a rigid‐amorphous phase was evidenced in copolymers, differently from the two homopolymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 310–321, 2007.     

Copolymerization of propylene with 1,3‐butadiene using isospecific zirconocene catalysts

Poly(propylene‐ran‐1,3‐butadiene) was synthesized using isospecific zirconocene catalysts and converted to telechelic isotactic polypropylene by metathesis degradation with ethylene. The copolymers obtained with isospecific C₂‐symmetric zirconocene catalysts activated with modified methylaluminoxane (MMAO) had 1,4‐inserted butadiene units ( 1,4‐BD ) and 1,2‐inserted units ( 1,2‐BD ) in the isotactic polypropylene chain. The selectivity of butadiene towards 1,4‐BD incorporation was high up to 95% using rac‐dimethylsilylbis(1‐indenyl)zirconium dichloride (Cat‐A)/MMAO. The molar ratio of propylene to butadiene in the feed regulated the number‐average molecular weight (M_n) and the butadiene contents of the polymer produced. Metathesis degradations of the copolymer with ethylene were conducted with a WCI₆/SnMe₄/propyl acetate catalyst system. The ¹H NMR spectra before and after the degradation indicated that the polymers degraded by ethylene had vinyl groups at both chain ends in high selectivity. The analysis of the chain scission products clarified the chain end structures of the poly(propylene‐ran‐1,3‐butadiene). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5731–5740, 2007     

Synthesis and characterization of fully aromatic thermotropic liquid‐crystalline copolyesters containing m‐hydroxybenzoic acid units

A series of fully aromatic copolyesters based on p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA), terephthalic acid (TPA), and m‐acetoxybenzoic acid (m‐ABA) were prepared by a modified melt‐polycondensation reaction. The copolyesters were characterized by DSC, thermogravimetric analysis, ¹H NMR, polarized optical microscopy, X‐ray diffraction, and intrinsic viscosity measurements. The copolyesters exhibited nematic liquid‐crystalline phases in a broad temperature range of about 150 °C, when the content of linear (p‐ABA, HQDA, and TPA) units was over 67 mol %. DSC analysis of the anisotropic copolyesters revealed broad endotherms associated with the nematic phases, and the melting or flow temperatures were found to be in the processable region. The flow temperatures and crystal‐to‐nematic and nematic‐to‐isotropic transitions depend on the type of linear monomer units, and these transitions increased as the content of the p‐ABA units increased, as compared to the HQDA/TPA units. When the content of the p‐ABA units increased, as compared to other linear units (HQDA and TPA), the intrinsic viscosity and degree of crystallinity of the copolyesters also increased, implying a higher reactivity for p‐ABA in the p‐ABA/HQDA/TPA/m‐ABA polymer system. The aromatic region in the ¹H NMR spectra of the copolyesters containing equal molar compositions of p‐ABA, HQDA, and TPA units were sensitive to the sequence distribution of aromatic rings. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3263–3277, 2001     

Crystallization kinetics and morphology of biodegradable poly(butylene succinate‐co‐propylene succinate)s

The crystallization behavior of biodegradable poly(butylene succinate) and copolyesters poly(butylene succinate‐co‐propylene succinate)s (PBSPS) was investigated by using ¹H NMR, DSC and POM, respectively. Isothermal crystallization kinetics of the polyesters has been analyzed by the Avrami equation. The 2.2‐2.8 range of Avrami exponential n indicated that the crystallization mechanism was a heterogeneous nucleation with spherical growth geometry in the crystallization process of polyesters. Multiple melting peaks were observed during heating process after isothermal crystallization, and it could be explained by the melting and recrystallization model. PBSPS was identified to have the same crystal structure with that of PBS by using wide‐angle X‐ray diffraction (WAXD), suggesting that only BS unit crystallized while the PS unit was in an amorphous state. The crystal structure of polyesters was not affected by the crystallization temperatures, too. Besides the normal extinction crosses under the POM, the double‐banded extinction patterns with periodic distance along the radial direction were also observed in the spherulites of PBS and PBSPS. The morphology of spherulites strongly depended on the crystallization temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 420–428, 2007     

Synthesis of bio‐based poly(ethylene 2,5‐furandicarboxylate) copolyesters: Higher glass transition temperature,better transparency,and good barrier properties

The bio‐based polyester, poly(ethylene 2,5‐furandicarboxylate) (PEF), was modified by 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol (CBDO) via copolymerization and a series of copolyesters poly(ethylene‐co‐2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol 2,5‐furandicarboxylate)s (PETFs) were prepared. After their chemical structures and sequence distribution were confirmed by nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR), their thermal, mechanical, and gas barrier properties were investigated in detail. Results showed that when the content of CBDO unit in the copolyesters was increased up to 10 mol%, the completely amorphous copolyesters with good transparency could be obtained. In addition, with the increasing content of CBDO units in the copolyesters, the glass transition temperature was increased from 88.9 °C for PET to 94.3 °C for PETF‐23 and the tensile modulus was increased from 3000 MPa for PEF to 3500 MPa for PETF‐23. The barrier properties study demonstrated that although the introduction of CBDO units would increase the O₂ and CO₂ permeability of PEF slightly, PECF‐10 still showed better or similar barrier properties compared with those of PEN and PEI. In one word, the modified PEF copolyesters exhibited better mechanical properties, higher glass transition temperature, good barrier properties, and better clarity. They have great potential to be the bio‐based alternative to the popular petroleum‐based poly(ethylene terephthalate) (PET) when used as the beverage packaging materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3298–3307     

Partially renewable copolyesters prepared from acetalized d‐glucitol by solid‐state modification of poly(butylene terephthalate)

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     

Characterization and degradation behavior of poly(butylene adipate‐co‐terephthalate)s

Random copolyesters based on 1,4‐butanediol and different ratios between adipic and terephthalic units were synthesized from thermal polycondensation of the appropriate mixture of monomers or by melt transesterification of the mixture of homopolymers. ¹H NMR spectroscopy makes feasible the study of the average block lengths of polymers once synthesized and after degradation in different media. Calorimetric data are reported, including those referred to the study of isothermal and nonisothermal crystallizations. Degradability of samples was evaluated by different methods including NMR and thermal analysis, evaluation of molecular weight by gel permeation chromatography or from intrinsic viscosity measures, scanning electron micrographs, and changes in mechanical properties. Distilled water at 70 °C acidic conditions provided by a pH 2.3 aqueous medium and enzymatic media containing lipases from Pseudomonas cepacia or Candida cylindracea were considered in this study. The degradability of the studied copolyesters strongly depends on the terephthalate content and the degradation media. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4141–4157, 2002     

New biodegradable polymers from renewable sources: Polyester‐carbonates based on 1,3‐propylene‐co‐1,4‐cyclohexanedimethylene succinate

α,ω‐Dihydroxy‐terminated copolymeric oligomers of a 1,3‐propylene/1,4‐cyclohexanedimethylene succinate structure were obtained by the thermal polycondensation of 1,3‐propanediol/1,4‐cyclohexanedimethanol/succinic acid mixtures. They were subsequently chain‐extended via phosgene synthesis to high molecular weight aliphatic/alicyclic copolyester‐carbonates. These new polymers, besides having a biodegradable backbone, originate from two monomers, namely, 1,3‐propanediol and succinic acid, which can be obtained by renewable sources. Therefore, they have a potential as environmentally friendly materials. All synthesized materials were characterized in reference to their molecular structure by ¹H NMR and ¹³C NMR. Their molecular weights and molecular weight distributions were determined by size exclusion chromatography, and their main thermal properties were measured by DSC. Spectroscopic characterizations were in full agreement with the proposed structures. 1,4‐Cyclohexanedimethanol was used as a diol comonomer to improve the overall thermal properties of poly(1,3‐propylene succinate). The results of the characterization performed show that the initial expectations were only partially satisfied. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2508–2519, 2001     

Synthesis and characterization of poly(butylene succinate) and its copolyesters containing minor amounts of propylene succinate

High molecular weight poly(butylene succinate) (PBSu), poly(propylene succinate), and PBSu-rich copolyesters were synthesized using an effective catalyst, titanium tetraisopropoxide. The compositions of the copolyesters were determined in three ways from ¹H and ¹³C NMR spectra, and good agreement between the results was obtained. The analysis of the carbonyl carbon spectra indicates a random distribution of the comonomers. Thermal properties were studied using a differential scanning calorimeter and a thermogravimetric analyzer. No significant difference exists among the thermal stabilities of these polyesters. However, the window between the glass transition and the melting temperatures becomes narrower with the increase in the concentration of propylene succinate in the copolymers. Additionally, the cold crystallization ability reduces considerably. Wide-angle X-ray diffractograms of isothermally crystallized copolyesters also follow the same trend.     

The microstructure determination of ethylene‐styrene‐propylene terpolymers at triad level by high‐temperature two‐dimensional NMR spectra

To further extend temperature range of application and low temperature performance of the ethylene‐styrene copolymers, a series of poly(ethylene‐styrene‐propylene) samples with varying monomer compositions and relatively low glass‐transition temperatures (T_g = −28 – 22 °C) were synthesized by Me₂Si(Me₄Cp)(N‐t‐Bu)TiCl2/MMAO system. Since the ¹³C NMR spectra of the terpolymers were complex and some new resonances were present, 2D‐¹H/¹³C heteronuclear single quantum coherence and heteronuclear multiple bond correlation experiments were conducted. A complete ¹³C NMR characterization of these terpolymers was performed qualitatively and quantitatively, including chemical shifts, triad sequence distributions, and monomer average sequence lengths. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 340–350     

Anionic bulk oligomerization of ethylene and propylene carbonate initiated by bisphenol‐A/base systems

When the bulk oligomerization of 1,3‐dioxolan‐2‐one (ethylene carbonate, EC) and 4‐methyl‐1,3‐dioxolan‐2‐one (propylene carbonate, PC) with the 2,2‐bis(4‐hydroxyphenyl)propane (bisphenol‐A, BPA)/base system (bases such as KHCO₃, K₂CO₃, KOH, Li₂CO₃, and t‐BuOK) was investigated at elevated temperature, significant differences were observed. Oligomerization of EC initiated by BPA/base readily takes place, but the oligomerization of PC is inhibited. The very first propylene carbonate/propylene oxide unit readily forms a phenolic ether bond with the functional groups of BPA phenolate, but the addition of the second monomer unit is rather slow. The oligomerization of EC yields symmetrical oligo(ethylene oxide) side chains. According to IR studies the oligomeric chains formed from PC with BPA contain not only ether but also carbonate bonds. The in situ step oligomerization of the BPA dipropoxylate was also identified by SEC, and a possible reaction mechanism is proposed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 545–550, 1999     

Blocky poly(ɛ‐caprolactone‐co‐butylene 2,5‐furandicarboxylate) copolyesters via enzymatic ring opening polymerization

Cyclic oligo(butylene 2,5‐furandicarboxylate) and ɛ‐caprolactone were copolymerized in bulk at 130–150 °C by enzymatic ring opening polymerization using CALB as catalyst. Copolyesters within a wide range of compositions were thus synthesized with weight‐average molecular weights between 20,000 and 50,000, the highest values being obtained for equimolar or nearly equimolar contents in the two components. The copolyesters consisted of a blocky distribution of the ɛ‐oxycaproate (CL) and butylene furanoate (BF) units that could be further randomized by heating treatment. The thermal stability of these copolyesters was comparable to those of the parent homopolyesters (PBF and PCL), and they all showed crystallinity in more or less degree depending on composition. Their melting and glass‐transition temperatures were ranging between those of PBF and PCL with values increasing almost linearly with the content in BF units. The ability of these copolyesters for crystallizing from the melt was evaluated by comparative isothermal crystallization and found to be favored by the presence of flexible ɛ‐oxycaproate blocks. These copolyesters are essentially insensitive to hydrolysis in neutral aqueous medium but they became noticeably degraded by lipases in an extend that increased with the content in CL units. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 290–299     

Synthesis and liquid crystalline properties of new amide‐modified poly(1,4‐cyclohexanedimethylene terephthalate)

New series of cycloaliphatic poly(ester‐amide)s, poly(1,4‐cyclohexanedimethyleneterephthalate‐co‐1,3‐cyclohexanedimethylene terephthalamide), were synthesized through solution polymerization route. The compositions of ester/amide units in the copolymers were varied from 0 to 100% by varying the amount of 1,4‐cyclohexanedimethanol and 1,3‐cyclohexanebis(methylamine) in the feed. The structures of the polymers were confirmed by NMR and FTIR, and the molecular weights were determined by inherent viscosity. The composition analysis by NMR reveals that the reactivity of the diamine toward the acid chlorides is lowered than that of diol, which results in the formation of more ester content in the poly (ester‐amides). The thermal analysis indicate that the new poly(ester‐amide)s having less than 10 mol % of amide linkages are thermotropic liquid crystalline from 200 to 250 °C and a thread like nematic phases are observed under the polarizing microscope. WXRD studies suggest that the liquid crystalline domains promote the nucleation process in the polyester chains and increases the percent crystallinity of the poly(ester‐amide)s. The glass transition temperature of the copolymers initially increases with increase in amide units because of the presence of nematic phases and subsequently follows the Flory–Fox behavior. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 42–52, 2006     

Thermal transitions and structure of epoxy networks based on α, ω‐diamino terminated poly(propylene oxide)‐block‐poly(ethylene oxide)‐block‐poly(propylene oxide) swollen in water

Thermal transitions in epoxy networks prepared by reaction of α, ω‐diamino terminated poly(propylene oxide)‐block‐poly(ethylene oxide)‐block‐poly(propylene oxide) and diglycidyl ether of brominated Bisphenol A, swollen in water, were studied by differential scanning calorimetry (DSC) in a broad temperature range (from ?100 °C to 20 °C). Networks of two different values of initial molar ratio of amino and epoxy groups were prepared, r (r = 1.00, 2.00), and swollen with different amounts of water up to equilibrium concentration values. The qualitatively different kinds of experimental thermograms have been obtained for two networks and classified according to the amount of water in the sample on the basis of the phase diagram of the system. Also, the concentration dependence of the curves in this diagram (glass transition, melting, and crystallization) as well as the fraction of noncrystallizable water supply some information about the morphology of the system. In this sense, the existence of a microphase separated structure of swollen networks is suggested. The structure consists of hydrophilic and hydrophobic domains and depends on the initial molar ratio of the reactive groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 699–708, 2005     

Metal‐free synthesis of novel biobased dihydroxyl‐terminated aliphatic polyesters as building blocks for thermoplastic polyurethanes

Using the organic compound 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) as a catalyst for step‐growth polymerization, a series of well‐defined hydroxyl‐telechelic renewable aliphatic polyesters (including poly(1,3‐propylene adipate); poly(1,4‐butylene adipate); poly(1,12‐dodecylene sebacate); and poly(1,2‐dimethylethylene adipate), PDMEA) were synthesized and studied. PDMEA is a novel polyester, which has not been reported before. The results of ¹H NMR and Matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry indicate that the polymers are fully hydroxyl terminated. From differential scanning calorimetry (DSC) thermograms, we found that the glass transition temperatures (T_g) of these polyesters are below ?20 °C. Only a T_g but no melting peak is observed in the DSC curve of the novel PDMEA. This indicates that PDMEA, contrary to the other renewable polyesters, is totally amorphous. Furthermore, using hexamethylene diisocyanate and hexamethylene diamine, poly(ester urethane urea)s (PEUUs) based on PDMEA were successfully synthesized. The T_g of the prepared PEUUs is below 0 °C, and no melting behavior of the soft‐segment is observed. The PEUU, with a flow temperature of over 200 °C, thus behaves as an elastomer at room temperature. Its mechanical properties, such as a relatively low tensile E‐modulus (≈20 MPa) at room temperature and a sufficiently high strain at break (≈560%), make it suitable for use in, for example, biomedical applications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011