Research article Special Issues

The aliphatic counterpart of PET, PPT and PBT aromatic polyesters: effect of the molecular structure on thermo-mechanical properties

  • Received: 30 October 2015 Accepted: 01 February 2016 Published: 16 February 2016
  • The aliphatic counterparts of the most used aromatic polyesters (PET, PPT, and PBT) have been synthesized by a two-stage polycondensation process, starting from dimethyl 1,4-cyclohexane dicarboxylate and different diols. The fully aliphatic polyesters are characterized by two cis/trans isomeric ratios (50 and 90 mol%) of the 1,4-cycloaliphatic rings. According to the cis/trans content, the properties of the materials notably change. Indeed, polymers rich in trans isomer are semicrystalline, whereas polymers with low trans content are fully amorphous, due to the presence of kinks along the chain. Trans isomer is characterized by higher rigidity than the cis one and the corresponding polymers have high glass transition temperatures. Moreover, the length of the methylene sequences in the diol has a notable influence on the final thermal and mechanical properties. Therefore, tunable properties can be easily obtained. This characteristic, in association with good mechanical performances, potential sustainability of the monomers and biodegradability, makes these aliphatic polyesters an interesting class of polyesters for some specific applications.

    Citation: Morgane Albanese, Justine Boyenval, Paola Marchese, Simone Sullalti, Annamaria Celli. The aliphatic counterpart of PET, PPT and PBT aromatic polyesters: effect of the molecular structure on thermo-mechanical properties[J]. AIMS Molecular Science, 2016, 3(1): 32-51. doi: 10.3934/molsci.2016.1.32

    Related Papers:

  • The aliphatic counterparts of the most used aromatic polyesters (PET, PPT, and PBT) have been synthesized by a two-stage polycondensation process, starting from dimethyl 1,4-cyclohexane dicarboxylate and different diols. The fully aliphatic polyesters are characterized by two cis/trans isomeric ratios (50 and 90 mol%) of the 1,4-cycloaliphatic rings. According to the cis/trans content, the properties of the materials notably change. Indeed, polymers rich in trans isomer are semicrystalline, whereas polymers with low trans content are fully amorphous, due to the presence of kinks along the chain. Trans isomer is characterized by higher rigidity than the cis one and the corresponding polymers have high glass transition temperatures. Moreover, the length of the methylene sequences in the diol has a notable influence on the final thermal and mechanical properties. Therefore, tunable properties can be easily obtained. This characteristic, in association with good mechanical performances, potential sustainability of the monomers and biodegradability, makes these aliphatic polyesters an interesting class of polyesters for some specific applications.


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    [1] Gandini A, Lacerda TM (2015) From monomers to polymers from renewable resources : Recent advances. Prog Polym Sci 48: 1-39. doi: 10.1016/j.progpolymsci.2014.11.002
    [2] Reddya MM, Vivekanandhana S, Misra M, et al. (2013) Biobased plastics and bionanocomposites: Current status and future opportunities. Prog Polym Sci 38: 1653-1689. doi: 10.1016/j.progpolymsci.2013.05.006
    [3] Miller SA (2013) Sustainable polymers: opportunities for the next decade. ACS Macro Letters 2: 550-554. doi: 10.1021/mz400207g
    [4] Tschan MJL, Brule E, Haquette P, et al. (2013) Synthesis of biodegradable polymers from renewable resources. Polym Chem 3: 836-851.
    [5] PlasticsEurope, available from: http://www.plasticseurope.org.
    [6] Sheldon R (2014) Green and sustainable manufacture of chemicals from biomass: state of the art. Green Chem 16: 950-963. doi: 10.1039/C3GC41935E
    [7] Colonna M, Berti C, Fiorini M, et al. (2011) Synthesis and radiocarbon evidence of terephthalate polyesters completely prepared from renewable resources. Green Chem 12: 2543-2548.
    [8] Gandini A, Silvestre AJD, Neto CP, et al. (2009) The furan counterpart of poly(ethylene terephthalate): an alternative material based on renewable resources. J Polym Sci: Part A: Polym Chem 47: 295-298. doi: 10.1002/pola.23130
    [9] Zhu J, Cai J, Xie W, at al. (2013) Poly(butylene 2,5-furan dicarboxylate), a biobased alternative to PBT: synthesis, physical properties, and crystal structure. Macromol 46: 796-804. doi: 10.1021/ma3023298
    [10] Fache M, Boutevin B, Caillol S (2015) Vanillin, a key-intermediate of biobased polymers. Europ Polym J 68: 488-502. doi: 10.1016/j.eurpolymj.2015.03.050
    [11] Mialon L, Pemba AG, Miller SA (2010) Biorenewable polyethylene terephthalate mimics derived from lignin and acetic acid. Green Chem 12: 1704-1706. doi: 10.1039/c0gc00150c
    [12] Wilsens CHRM, Noordover BAJ, Rastogi S (2014) Aromatic thermotropic polyesters based on 2,5-furandicarboxylic acid and vanillic acid. Polymer 55: 2432-2439. doi: 10.1016/j.polymer.2014.03.033
    [13] Berti C, Binassi E, Colonna M, et al. (2010) Biobased terephthalate polyesters. US 20100168461.
    [14] Berti C, Celli A, Marchese P, et al. (2009) Novel copolyesters based on poly(alkylene dicarboxylate)s: 2. Thermal behavior and biodegradation of fully aliphatic random copolymers containing 1,4-cyclohexylene rings. Eur Polym J 45: 2402-2412.
    [15] Berti C, Celli A, Marchese P, et al. (2008) Novel copolyesters based on poly(alkylene dicarboxylate)s: 1. Thermal behavior and biodegradation of aliphatic-aromatic random copolymers. Eur Polym J 44: 3650-3661.
    [16] Tsai Y, Jheng LC, Hung CY (2010) Synthesis, properties and enzymatic hydrolysis of biodegradable alicyclic/aliphatic copolyesters based on 1,3/1,4-cyclohexanedimethanol. Polym Degrad Stab 95: 72-78. doi: 10.1016/j.polymdegradstab.2009.10.006
    [17] Berti C, Celli A, Marchese P, et al. (2008) Influence of molecular structure and stereochemistry of the 1,4-cyclohexylene ring on thermal and mechanical behavior of poly(butylene 1,4-cyclohexanedicarboxylate). Macromol Chem Phys 209: 1333-1344.
    [18] Berti C, Binassi E, Celli A, et al. (2008) Poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate): influence of stereochemistry of 1,4-cyclohexylene units on thermal properties. J Polym Sci: Part B: Polym Phys 46: 619-630. doi: 10.1002/polb.21397
    [19] Celli A, Marchese P, Sullalti S, et al. (2011) Eco-friendly poly(butylene 1,4-cyclohexanedicarboxylate): relationships between stereochemistry and crystallization behavior. Macromol Chem Phys 212: 1524-1534. doi: 10.1002/macp.201100052
    [20] Celli A, Marchese P, Sullalti S, et al. (2012) Bio-based (co)polyesters containing 1,4-cyclohexylene units: correlations between stereochemistry and phase behavior. In: Bradley EO, Lane MI, Editors, New Developments in Polymers Research. New York: Nova Science Publishers, 63-101.
    [21] Zhang B, Turner SR (2013) New poly(arylene ether sulfone)s based on 4,4′-[trans-1,4-cyclohexanediylbis(methylene)] bisphenol. Polymer 54: 4493-4500. doi: 10.1016/j.polymer.2013.06.018
    [22] Zhang B, Turner SR (2011) Synthesis and Characterization of Poly(arylene ether sulfone)s with trans-1,4-Cyclohexylene Ring Containing Ester Linkages. J Polym Sci: Part A: Polym Chem 49: 4316-4324.
    [23] Yoon WJ, Oh KS, Koo JM, et al. (2013) Advanced polymerization and properties of biobased high Tg polyester of isosorbide and 1,4-cyclohexanedicarboxylic acid through in situ acetylation. Macromol 46: 2930-2940. doi: 10.1021/ma4001435
    [24] Chen T, Zhang J (2015) Non-isothermal cold crystallization kinetics of poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate) (PETG) copolyesters with different compositions. Polym Testing 48: 23-30. doi: 10.1016/j.polymertesting.2015.09.008
    [25] Finelli L, Lorenzetti C, Messori M, et al. (2004) Comparison between titanium tetrabutoxide and a new commercial titanium dioxide based catalyst used for the synthesis of poly(ethylene terephthalate). J Appl Polym Sci 92: 1887-1892. doi: 10.1002/app.20171
    [26] Berti C, Bonora V, Colonna M, et al. (2003) Effect of carboxyl end groups content on the thermal and electrical properties of poly(propylene terephthalate). Eur Polym J 39: 1595-1601. doi: 10.1016/S0014-3057(03)00064-8
    [27] Pilati F (1989) Polyesters, In: Allen, G., Bevington, J.C. Editors, Comprehensive Polymer Science, 1 Eds., Oxford: Pergamon Press, 308.
    [28] Fakirov S, Seganov I, Kurdowa E (1981) Effect of chain composition of poly(ethylene terephthalate) structure and properties. Makromol Chem 182: 185-197. doi: 10.1002/macp.1981.021820120
    [29] Yu T, Bu H, Chen J, et al. (1986) The effect of units derived from diethylene glycol on crystallization kinetics of poly(ethylene terephthalate). Makromol Chem 187: 2697-709. doi: 10.1002/macp.1986.021871120
    [30] Colonna M, Berti C, Binassi E, et al. (2011) Poly(cyclohexylenedimethylene-1,4cyclohexanedicarboxylate): analysis of parameters affecting polymerization and cis-trans isomerization. Polym Int 60: 1607-1613. doi: 10.1002/pi.3128
    [31] Commereuc S, Lacoste J (1997) Photo- and thermo-oxidation of polyoctenamer. Photostability of hydroperoxides. Polym Degrad Stab 57: 31-41. doi: 10.1016/S0141-3910(96)00225-X
    [32] Wang L, Xie Z, Bi X, et al. (2006) Preparation and characterization of aliphatic/aromatic copolyesters based on 1,4-cyclohexanedicarboxylic acid. Polym Degrad Stab 91: 2220-2228. doi: 10.1016/j.polymdegradstab.2006.01.003
    [33] Celli A, Marchese P, Sisti L, et al. (2013) Effect of 1,4-cyclohexylene units on thermal properties of poly(1,4-cyclohexylenedimethylene adipate) and similar aliphatic polyesters. Polym Int 62: 1210-1217.
    [34] Ki HC, Ok Park O (2001) Synthesis, characterization and biodegradability of the biodegradable aliphatic-aromatic random copolyesters. Polymer 42: 1849-1861. doi: 10.1016/S0032-3861(00)00466-3
    [35] Kelsey DR, Kiibler KS, Tutunjian PN (2005) Thermal stability of poly(trimethylene terephthalate). Polymer 46: 8937-8946.
    [36] Tonelli AE (1973) Effect of the terephthaloyl residue on chain flexibility of poly(ethylene terephthalate). J Polym Sci Polym Lett Ed 11: 441-447. doi: 10.1002/pol.1973.130110703
    [37] Tonelli AE (2002) Conformational characteristics of Poly(ethylene phthalate)s. J Polym Sci Polym Phys 40: 1254-1260. doi: 10.1002/polb.10189
    [38] Gonzalez CC, Riande E, Bello A, et al. (1988) Conformational characteristics of polyesters ased on terephthalic acid with an ether group in the glicol residue. Macromolecules 21: 3230-3234. doi: 10.1021/ma00189a017
    [39] Sandhya TE, Ramesh C, Sivaram S (2007) Copolyesters based on poly(butylene terephthalate)s containing cyclohexyl and cyclopentyl ring: effect of molecular structure on thermal and crystallization behaviour. Macromolecules 40: 6906-6915. doi: 10.1021/ma071272q
    [40] Wunderlich B (1980) Crystal Melting, In: Wunderlich, B. Author, Macromolecular Physics, New York: Academic Press.
    [41] Hoffman JD, Weeks JJ (1962) Melting process and equilibrium melting temperature of poly(chlorotrifluoroethylene). J Res Natl Bur Stand 66A: 13-28.
    [42] Chisolm BJ, Zimmer JG (2000) Isothermal crystallization kinetics of commercially important polyalkylene terephthalates. J Appl Polym Sci 76: 1296-1307. doi: 10.1002/(SICI)1097-4628(20000523)76:8%3C1296::AID-APP10%3E3.0.CO;2-N
    [43] Avrami M (1939) Kinetics of phase change. I. General theory. J Chem Phys 7: 1103-1112.
    [44] Avrami M (1940) Kinetics of phase change. II. Transformation-time relations for random distribution of nuclei. J Chem Phys 8: 212-224.
    [45] Avrami M (1941) Granulation, phase change and microstructure. Kinetics of phase change. III. J Chem Phys 9: 177-184.
    [46] Wunderlich B (1976) Crystal Nucleation, Growth, Annealing, In: Wunderlich, B. Author, Macromolecular Physics, New York: Academic Press.
    [47] Dangseeyun N, Srimoaon P, Supaphol P, et al. (2004) Isothermal melt-crystallization and melting behavior for three linear aromatic polyesters. Thermochimica Acta 409: 63-77. doi: 10.1016/S0040-6031(03)00331-9
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