Journal of Polymer Research

, 26:51 | Cite as

Novel copolyhydrazides and copolyoxadiazoles based on 1,4-phenyl linkage and 1,3,4-thiadiazole moiety in the polymer Main chain to induce glass transition and to improve the thermal stability, solubility, and antimicrobial activity

  • Kamal I. AlyEmail author
  • Osama Younis
  • Nayef S. Al-Muaikel
  • Ahmed A. Atalla
  • Abu-Bakr A. A. M. El-Adasy
  • Mahmoud A. Hussein
  • Ahmed R. Abdellah


Polyhydrazides (PHs) and polyoxadiazoles (PODs) have broad potential applications, but PHs are generally not high-temperature resistant and PODs are commonly insoluble in organic solvents, degrade before melting, and do not show glass-transition temperature (Tg). These limitations make their processing quite difficult. To overcome these shortcomings, novel copolyhydrazides (CPHs) and copolyoxadiazoles (CPODs) based on 1,4-phenyl linkage and 1,3,4-thiadiazole moiety in the main chain have been synthesized. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed to assess the polymers thermal behavior. Also, the crystalline structure and surface morphology were examined using X-ray diffraction (XRD) and scanning electron microscopy (SEM). In addition, their solubility, viscosity, UV-visible absorption, antimicrobial characteristics were studied. Most of the new CPHs and CPODs showed high thermal stability and good solubility in polar aprotic solvents. Moreover, the CPODs melted and showed Tg and fortunately their Tg values are still high (>227 °C), so they are suitable for use under extreme conditions. It seems that incorporating 1,4-phenyl linkage and 1,3,4-thiadiazole moiety into the polymer main chain enhanced the solubility and suppressed the crystallinity, while kept the thermal stability. Furthermore, the CPODs gave large antibacterial and antifungal activities, confirming the possibility to be used in medicinal fields.

Graphical abstract

Effects of bulky moieties on the polymer properties.


Copolyhydrazides Copolyoxadiazoles Thiadiazoles Polymer synthesis Biological activity 



  1. 1.
    Mahadevan V, Padma S, Srinivasan M (1981) Preparation and properties of novel polyhydrazides. J Polym Sci A 19(6):1409–1419Google Scholar
  2. 2.
    Imai Y (1996) Step-growth polymers for high-performance materials. American Chemical Society, Washington, DCGoogle Scholar
  3. 3.
    Agolini F, Gay FP (1970) Synthesis and properties of Azoaromatic polymers. Macromolecules 3(3):349–351CrossRefGoogle Scholar
  4. 4.
    Frazer AH, Wallenberger FT (1964) Poly(1,3,4-oxadiazolidine). J Polym Sci A 2(3):1181–1183Google Scholar
  5. 5.
    Gomes D, Barges C, Pinto JC (2004) Effects of reaction variables on the reproducibility of the syntheses of poly-1,3,4-oxadiazole. Polymer 4:4997–5004CrossRefGoogle Scholar
  6. 6.
    Schulz B, Bruma M, Brehmer L (1997) Synthesis of poly(1,3,4-oxadiazole-amide-ester)s and study of the influence of conformational parameters on their physical properties. Adv Mater 9:601–613CrossRefGoogle Scholar
  7. 7.
    Wu TY, Sheu RB, Chen Y (2004) Synthesis and optically acid-sensory and electrochemical properties of novel polyoxadiazole derivatives. Macromolecules 37:725–733CrossRefGoogle Scholar
  8. 8.
    Udayakumar D, Adhikari AV (2007) Synthesis and characterization of fluorescent poly(oxadiazole)s containing 3,4-dialkoxythiophenes. Opt Mater 29:1710–1718CrossRefGoogle Scholar
  9. 9.
    Gomes D, Roeder J, Ponce ML, Nunes SP (2008) Single-step synthesis of sulfonated polyoxadiazoles and their use as proton conducting membranes. J Power Sources 175:49–59CrossRefGoogle Scholar
  10. 10.
    Yang HH (1989) Aromatic high-strength fibers. Wiley, New YorkGoogle Scholar
  11. 11.
    Sena ME, Andrade CT (1995) Properties of heteroaromatic polymers for gas separation. Polym Bull 34:643–648CrossRefGoogle Scholar
  12. 12.
    Cai XR, Chen H, Zhang T, Xu X, Li Y, Jiang Q (2007) Synthesis and characterization of a novel main chain oxadiazole-based copolymer for n-type solar cell material. Chin Chem Lett 18:1342–1346CrossRefGoogle Scholar
  13. 13.
    Nanjan MJ (1985) Encyclopedia of polymer science and engineering. In: Kroschwitz JI (ed) Wiley, New York, p. 322–339Google Scholar
  14. 14.
    Zhang Y, Liu J, Wu Z, Bi H, Jiang G, Zhi X, Qi L, Zhang X (2019) Synthesis and characterization of thianthrene-containing preimidized soluble polyimide resins and the derived films with high refractive indices and good optical transparency. J Polym Res 26:2–12CrossRefGoogle Scholar
  15. 15.
    Yang Y, Cao X, Luo H, Cai X (2018) Thermal stability and decomposition behaviors of segmented copolymer poly(urethane-urea-amide). J Polym Res 25:242–249CrossRefGoogle Scholar
  16. 16.
    Xu Y, Feng J, Ren H, Bi Y, Zhu J, Sun Y, Wen S, Huo J, Zhang L (2017) Thermal stability, solubility, and fluorescence property of poly(arylene ether ketone)s bearing N-arylenebenzimidazole units. J Polym Res 24:90–97CrossRefGoogle Scholar
  17. 17.
    Su S-K, Gu J-H, Lee H-T, Wu C-L, Hwang J-J, Suen M-C (2017) Synthesis and properties of novel biodegradable polyurethanes containing fluorinated aliphatic side chains. J Polym Res 24:142–160CrossRefGoogle Scholar
  18. 18.
    Li C, Yi L, Xu S, Wu X, Huang W, Yan D (2017) Synthesis and characterization of polyimides from 4,4′-(3-(tert-butyl)-4-aminophenoxy)diphenyl ether. J Polym Res 24:7–15CrossRefGoogle Scholar
  19. 19.
    Ayala D, Lozano AE, Abajo JD, Campa JDL (1999) Synthesis and characterization of novel polyimides with bulky pendant groups. J Polym Sci A 37:805–814CrossRefGoogle Scholar
  20. 20.
    Wang J, Wang J, Li C, Zhao G, Wang XA (2014) Study of 2,5-dimercapto-1,3,4-thiadiazole derivatives as multifunctional additives in water-based hydraulic fluid. Industrial Lubrication and Tribology 66(3):402–410CrossRefGoogle Scholar
  21. 21.
    Hu JQ, Wei XY, Zong ZM (2006) Study on tribological and corrosion inhibiting properties of thiadiazole derivative as lubricant grease additive. Industrial Lubricants and Tribology 58:320–323CrossRefGoogle Scholar
  22. 22.
    Tamami B, Yeganeh H (2002) Synthesis and properties of novel aromatic polyamides based on 4-aryl-2,6-bis (4-chlorocarbonylphenyl)pyridines. Eur Polym J 38:933–940CrossRefGoogle Scholar
  23. 23.
    Aly KI, Moustafa AH, Ahmed EK, Abd El-lateef HM, Mohamed MG, Mohamed SM (2018) New polymer syntheses part 60: a facile synthetic route to polyamides based on thieno[2,3-b]thiophene and their corrosion inhibition behavior. Chinese J Polym Sci 36(7):835–847CrossRefGoogle Scholar
  24. 24.
    Rahman MM, Hussein MA, Aly KI, Asiri AM (2018) Thermally stable hybrid polyarylidene (azomethine-ether) s polymers (PAAP): an ultrasensitive arsenic (III) sensor approach. Designed monomers and polymers 21(1):82–98CrossRefGoogle Scholar
  25. 25.
    Sun J, Aly KI, Kuckling D (2017) Synthesis of hyperbranched polymers from vegetable oil based monomers via ozonolysis pathway. J Polym Sci A Polym Chem 55(12):2104–2114CrossRefGoogle Scholar
  26. 26.
    Sun J, Aly KI, Kuckling D (2017) A novel one-pot process for the preparation of linear and hyperbranched polycarbonates of various diols and triols using dimethyl carbonate. RSC Adv 7(21):12550–12560CrossRefGoogle Scholar
  27. 27.
    Aly KI, Kuckling D (2015) New polymer syntheses part 59. Synthesis and characterization of new polyamides and copolyamides containing thianthrene moiety and based on methyl-and/or tertiarybutyl. J Res Updates Polym Sci 4(3):157–167CrossRefGoogle Scholar
  28. 28.
    Aly KI, Younis O, Mahross MH, Tsutsumi O, Mohamed MG, Sayed MM (2018) Novel conducting polymeric nanocomposites embedded with nanoclay: synthesis, photoluminescence, and corrosion protection performance. Polym J 51:77–90. CrossRefGoogle Scholar
  29. 29.
    Raghu AV, Jeong HM (2008) Synthesis, characterization of novel Dihydrazide containing polyurethanes based on N1,N2-Bis[(4- hydroxyphenyl)methylene]ethanedihydrazide and various Diisocyanates. J Appl Polym Sci 107:3401–3407CrossRefGoogle Scholar
  30. 30.
    Aly KI (2004) New polymer syntheses XXVIII. Synthesis and thermal behavior of new organometallic polyketones and copolyketones based on diferrocenylidenecyclohexanone. J Appl Polym Sci 94:1440–1448CrossRefGoogle Scholar
  31. 31.
    Aly KI, Kandeel MM (1996) New polymer syntheses IV. Synthesis and characterization of new polyamides containing bis-benzthiazolyl sulphone units in the main chain. High perform Polym 8:307–314CrossRefGoogle Scholar
  32. 32.
    Li M-L, Zhang Y-M, Wei T-B (2007) Synthesis and bioactivity study of 2,5-bismercapto-1,3,4-thiadiazole heterocyclic derivatives. Indian Journal of Chemistry Section B (IJC-B) 46B(3):544–549Google Scholar
  33. 33.
    Al-Muaikel NS, El-Emary TI (2003) Synthesis and characterization of new polyhydrazides based on 2,5-bis(mercapto-acetichydrazide)-1,3,4-thiadiazole moiety. Eur Polym J 39:211–218CrossRefGoogle Scholar
  34. 34.
    Bair TI, Morgan PW, Killian FL (1977) Poly(1,4-phenyleneterephthalamides): polymerization and novel liquid-crystalline solutions. Macromolecules 10(6):1396–1400CrossRefGoogle Scholar
  35. 35.
    Joseph KA, Srinivasan M (1993) Synthesis and characterization of polyamides containing arylene sulfide-sulfone groups. Polym Int 30(3):327–335CrossRefGoogle Scholar
  36. 36.
    Reddy RK, Raghu AV, Jeong HM (2008) Synthesis and characterization of novel polyurethanes based on 4,4′-{1,4-phenylenebis[methylylidenenitrilo]} diphenol. Polym Bull 60:609–616CrossRefGoogle Scholar
  37. 37.
    Raghu AV, Jeong HM, Kim JH, Lee YR, Cho YB (2008) Synthesis and characterization of novel polyurethanes based on 4-{(4-Hydroxyphenyl)iminomethyl}phenol. Macromol Res 16(3):194–199CrossRefGoogle Scholar
  38. 38.
    Reddy KR, Raghu AV, Jeong HM, Siddaramaiah (2009) Synthesis and characterization of pyridine-based polyurethanes. Designed Monomers and Polymers 12:(2) 109–118Google Scholar
  39. 39.
    Aly KI (1998) New polymer syntheses VIII. Synthesis, characterization and morphology of new unsaturated copolyesters based on dibenzylidenecycloalkanones. Polym Int 47(4):483–490CrossRefGoogle Scholar
  40. 40.
    Hammam AS, Abdel-Rahman MA, Hassan AA, Younis OM (2013) Synthesis and characterization of pyrrolo[2,3-f] indole-3,7-dicarbonitriles. International journal of advance in. Medical Science 1(1):11–17Google Scholar
  41. 41.
    Donawade DS, Raghu AV, Gadaginamath GS (2007) Synthesis and antimicrobial activity of novel linearly fused 5-Substituted-7-acetyl-2,6-dimethyloxazolo[4,5-f]indoles. Indian Journal of Chemistry Section B (IJC-B) 46B:690–693Google Scholar
  42. 42.
    Donawade DS, Raghu AV, Muddapur UM, Gadaginamath GS (2005) Chemoselective reaction of benz[g]indole dicarboxylate towards hydrazine hydrate: Bisheterocycles: synthesis and antimicrobial activity of some new 1-[2-hydroxyethyl]-3-ethoxycarbonyl-5-oxadiazolyl/triazolyl/pyrrolylaminocarbonyl methoxy-2-methylbenz[g]indoles. Indian Journal of Chemistry Section B (IJC-B) 44B:1470–1475Google Scholar

Copyright information

© The Polymer Society, Taipei 2019

Authors and Affiliations

  1. 1.Polymer Research Laboratory, Chemistry Department, Faculty of ScienceAssiut UniversityAssiutEgypt
  2. 2.Chemistry Department, Faculty of ScienceThe New Valley UniversityEl-KharjaEgypt
  3. 3.Laboratory of Polymer Materials Chemistry, Department of Applied ChemistryRitsumeikan UniversityKusatsuJapan
  4. 4.Chemistry Department, College of ScienceJouf UniversitySkakaSaudi Arabia
  5. 5.Department of Chemistry, Faculty of ScienceAl-Azhar University at AssiutAssiutEgypt

Personalised recommendations