Journal of Materials Science

, Volume 53, Issue 8, pp 6239–6250 | Cite as

Identification of side chain effect as an important factor influencing the secondary relaxation of polyesters containing cyclohexylene ring



The conformational transition of cyclohexylene ring has been recognized as the secondary transition of polyesters containing this aliphatic ring structure. Previously, the stereochemistry, i.e., trans/cis ratio, has been identified as an important factor that has a significant impact on the conformational transition of the cyclohexylene ring. In this paper, we have proposed and proved the side chain effect as another important factor that plays the same role as the stereochemistry, due to the fact that the conformational transition of the ring is usually associated with the coupled motion of it with neighboring unit. Our strategy is to design and synthesize a series of polyesters with 1,4-cyclohexanedicarboxylic acid and diols with different side chains. Polyester without any side chain has the lowest secondary relaxation temperature (T β ). Incorporation of asymmetric short side chain will result in increased T β , since it will reduce the coupled motion of the neighboring unit with the cyclohexylene ring during the conformational transition process, and thus reduces the flexibility of the chain and increases steric hindrance. However, further incorporation of long side chain will result in decreased T β because of the plasticization effect. Moreover, we also found that polyesters with low T β tend to have not only better impact strength, but also good ductility and elasticity. Our study enables people to take advantage of the cyclohexylene ring structure for the design and synthesis of thermoplastic and elastomer with better performance.



The authors are grateful for the financial support by the National Science Foundation of China (NSFC, No. 51503217), Zhejiang Province Public Welfare Project (2017C31081), Open Project Program of MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Zhejiang University (2016MSF001), and Ningbo Innovation Project (2015B11003).

Compliance with ethical standards

Conflict of interest

The authors declare no conflicts of interest.

Supplementary material

10853_2017_1984_MOESM1_ESM.docx (916 kb)
Supplementary material 1 (DOCX 916 kb)


  1. 1.
    Wada Y, Kasahara T (1967) Relation between impact strength and dynamic mechanical properties of plastics. J Appl Polym Sci 11:1661–1665CrossRefGoogle Scholar
  2. 2.
    Liu J, Yee AF (1998) Enhancing plastic yielding in polyestercarbonate glasses by 1,4-cyclohexylene linkage addition. Macromolecules 31:7865–7870CrossRefGoogle Scholar
  3. 3.
    Chen LP, Yee AF, Goetz JM, Schaefer J (1998) Molecular structure effects on the secondary relaxation and impact strength of a series of polyester copolymer glasses. Macromolecules 31:5371–5382CrossRefGoogle Scholar
  4. 4.
    Dennis JM, Enokida JS, Long TE (2015) Synthesis and characterization of decahydronaphthalene-containing polyesters. Macromolecules 48:8733–8737CrossRefGoogle Scholar
  5. 5.
    Berti C, Celli A, Marchese P, Marianucci E, Barbiroli G, Di Credico F (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 209:1333–1344CrossRefGoogle Scholar
  6. 6.
    Matthews RG, Unwin AP, Ward IM, Capaccio G (1999) A comparison of the dynamic mechanical relaxation behavior of linear low- and high-density polyethylenes. J Macromol Sci 38:123–143CrossRefGoogle Scholar
  7. 7.
    Diaz-Calleja R, Saiz E, Riande E, Gargallo L, Radic D (1993) Relaxation properties of molecular chains with restricted conformational versatility of the backbone. Macromolecules 26:3795–3802CrossRefGoogle Scholar
  8. 8.
    Vanderschueren J, Yianakopoulos G, Niezette J, Chatry C, Gasiot J (1992) Relaxational behavior of CR-39 polycarbonate used as nuclear track detector. J Appl Polym Sci 44:1027–1042CrossRefGoogle Scholar
  9. 9.
    English AD (1984) Macromolecular dynamics in solid poly(ethylene terephthalate): proton and carbon-13 solid-state NMR. Macromolecules 17:2182–2192CrossRefGoogle Scholar
  10. 10.
    Díaz-Calleja R, Riande E, San Román J (1992) Activation parameters associated with the beta relaxation of poly(cyclohexyl acrylate). J Polym Sci Part B Polym Phys 30:1239–1246CrossRefGoogle Scholar
  11. 11.
    Laredo E, Grimau M, Bello A, Wu D (2013) Molecular dynamics and crystallization precursors in polylactide and poly(lactide)/CNT biocomposites in the insulating state. Eur Polym J 49:4008–4019CrossRefGoogle Scholar
  12. 12.
    Christoff M, Atvars TDZ (1999) Phosphorescent probes in studies of secondary relaxation of amorphous polystyrene and poly(n-alkyl methacrylate)s. Macromolecules 32:6093–6101CrossRefGoogle Scholar
  13. 13.
    Gigli M, Lotti N, Vercellino M, Visai L, Munari A (2014) Novel ether-linkages containing aliphatic copolyesters of poly(butylene 1,4-cyclohexanedicarboxylate) as promising candidates for biomedical applications. Mater Sci Eng C Mater Biol Appl 34:86–97CrossRefGoogle Scholar
  14. 14.
    Gigli M, Lotti N, Gazzano M, Siracusa V, Finelli L, Munari A, Rosa MD (2014) Biodegradable aliphatic copolyesters containing PEG-like sequences for sustainable food packaging applications. Polym Degrad Stab 105:96–106CrossRefGoogle Scholar
  15. 15.
    Gigli M, Lotti N, Gazzano M, Siracusa V, Finelli L, Munari A, Dalla M (2013) Rosa, fully aliphatic copolyesters based on poly(butylene 1,4-cyclohexanedicarboxylate) with promising mechanical and barrier properties for food packaging applications. Ind Eng Chem Res 52:12876–12886CrossRefGoogle Scholar
  16. 16.
    Celli A, Marchese P, Sisti L, Dumand D, Sullalti S, Totaro G (2013) Effect of 1,4-cyclohexylene units on thermal properties of poly(1,4-cyclohexylenedimethylene adipate) and similar aliphatic polyesters. Polym Int 62:1210–1217CrossRefGoogle Scholar
  17. 17.
    Berti C, Celli A, Marchese P, Marianucci E, Sullalti S, Barbiroli G (2010) Environmentally friendly copolyesters containing 1,4-cyclohexane dicarboxylate units, 1-relationships between chemical structure and thermal properties. Macromol Chem Phys 211:1559–1571CrossRefGoogle Scholar
  18. 18.
    Commereuc S, Askanian H, Verney V, Celli A, Marchese P (2010) About durability of biodegradable polymers: structure/degradability relationships. Macromol Symp 296:378–387CrossRefGoogle Scholar
  19. 19.
    Berti C, Celli A, Marchese P, Barbiroli G, Di Credico F, Verney V, Commereuc S (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 45:2402–2412CrossRefGoogle Scholar
  20. 20.
    Liu F, Zhang J, Wang J, Liu X, Zhang R, Hu G, Na H, Zhu J (2015) Soft segment free thermoplastic polyester elastomers with high performance. J Mater Chem A 3:13637–13641CrossRefGoogle Scholar
  21. 21.
    Genovese L, Lotti N, Gazzano M, Finelli L, Munari A (2015) New eco-friendly random copolyesters based on poly(propylene cyclohexanedicarboxylate): structure-properties relationships. Express Polym Lett 9:972–983CrossRefGoogle Scholar
  22. 22.
    Wang L, Xie Z, Bi X, Wang X, Zhang A, Chen Z, Zhou J, Feng Z (2006) Preparation and characterization of aliphatic/aromatic copolyesters based on 1,4-cyclohexanedicarboxylic acid. Polym Degrad Stab 91:2220–2228CrossRefGoogle Scholar
  23. 23.
    Qiu J, Liu F, Zhang J, Chen J, Na H, Zhu J (2017) Controlling the stereostructure of non-planar ring to induce the transition from plastic to elastomer in poly(butylene adipate-co-1,4-cyclohexane dicarboxylate) and implement of polylactic acid toughness. Polym Eng Sci 47:21–25Google Scholar
  24. 24.
    Qiu J, Liu F, Zhang J, Na H, Zhu J (2016) Non-planar ring contained polyester modifying polylactide to pursue high toughness. Compos Sci Technol 128:41–48CrossRefGoogle Scholar
  25. 25.
    Chen LP, Yee AF, Moskala EJ (1999) The molecular basis for the relationship between the secondary relaxation and mechanical properties of a series of polyester copolymer glasses. Macromolecules 32:5944–5955CrossRefGoogle Scholar
  26. 26.
    Liu J, Goetz JM, Schaefer J, Yee AF, Li L (2001) Effect of the local motions of chemical linkages on segmental mobility in poly(ester carbonate) block copolymers. Macromolecules 34:2559–2568CrossRefGoogle Scholar
  27. 27.
    Stempfle F, Ortmann P, Mecking S (2016) Long-chain aliphatic polymers to bridge the gap between semicrystalline polyolefins and traditional polycondensates. Chem Rev 116:4597–4641CrossRefGoogle Scholar
  28. 28.
    Heijboer J (1977) Secondary loss peaks in glassy amorphous polymers. Int J Polym Mater 6:11–37CrossRefGoogle Scholar
  29. 29.
    Soccio M, Lotti N, Finelli L, Gazzano M, Munari A (2008) Neopenthyl glycol containing poly(propylene terephthalate)s: structure–properties relationships. J Polym Sci Part B Polym Phys 46:170–181CrossRefGoogle Scholar
  30. 30.
    Berti C, Binassi E, Celli A, Colonna M, Fiorini M, Marchese P, Marianucci E, Gazzano M, Credico FDI, Brunelle DJ (2008) Poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate): influence of stereochemistry of 1,4-cyclohexylene units on the thermal properties. J Polym Sci Part B Polym Phys 46:619–630CrossRefGoogle Scholar
  31. 31.
    Li X, Yee AF (2003) Design of mechanically robust high-T g polymers: synthesis and dynamic mechanical relaxation behavior of glassy poly (ester carbonate) s with cyclohexylene rings in the backbone. Macromolecules 36:9411–9420CrossRefGoogle Scholar
  32. 32.
    Li X, Yee AF (2004) Design of mechanically robust high-T g polymers: mechanical properties of glassy poly(ester carbonate)s with cyclohexylene rings in the backbone. Macromolecules 37:7231–7239CrossRefGoogle Scholar
  33. 33.
    Mason JA, Hertzberg RW (1973) Fatigue failure in polymers. CRC Crit Rev Macromol Sci 1:433–500Google Scholar
  34. 34.
    Genovese L, Lotti N, Siracusa V, Munari A (2017) Poly(neopentyl glycol furanoate): a member of the furan-based polyester family with smart barrier performances for sustainable food packaging applications. Materials.
  35. 35.
    Liu F, Qiu J, Wang J, Zhang J, Na H, Zhu J (2016) Role of cis-1,4-cyclohexanedicarboxylic acid in the regulation of the structure and properties of a poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate) copolymer. RSC Adv 6:65889–65897CrossRefGoogle Scholar
  36. 36.
    Stona AJ (1996) The theory of intermolecular forces. Clarendon Press, LondonGoogle Scholar

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Authors and Affiliations

  1. 1.College of Materials Science and EngineeringQingdao University of Science and TechnologyQingdaoChina
  2. 2.Key Laboratory of Bio-based Polymeric Materials of Zhejiang Province, Ningbo Institute of Materials Technology and EngineeringChinese Academy of SciencesNingboChina

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