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A comparative study of new linear and hyperbranched polyurethanes built up from a synthesized isocyanate-terminated polyester/urethane

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Abstract

In the present study, the effects of architecture and structural building blocks of the polyurethane chains on their properties were studied. New linear and hyperbranched polyurethanes (LPU and HPU) were prepared via A2 + B2 and A2 + B3 methodologies, respectively. Polyethylene glycol (PEG-1000) and castor oil (CO) were used as bi- and trifunctional monomers (B2 and B3), respectively. However, A2 monomers were synthesized by the reaction between ethylene glycol (EG) with terephthaloyl chloride (TPC) and reacting the product with excess toluene diisocyanate (TDI) to produce isocyanate-terminated PU (NCO-PU). NCO-PU was reacted with PEG to synthesize LPU; however, its reaction with CO synthesized HPU. NCO-PU, LPU and HPU were characterized by FTIR, H-NMR, GPC, TEM, TGA, DSC and XRD. The prepared PUs were applied as coatings and their physical, chemical and mechanical properties were investigated. The results showed that the degree of branching of HPU was 79%. No phase separation was observed in NCO-PU as indicated by its DSC curve. However, two phases are detected in HPU and LPU that represent to the hard and soft segments. NCO-PU displayed the highest crystallinity index (CrI = 89.26%). However, the high degree of branching in HPU led to lower CrI than LPU. The lack of entanglements in HPU led to its slightly lower solution viscosity than LPU. TEM images showed spherical PU nano-particles. The surface of HPU coating showed the highest gloss which is due to its low degree of crystallinity. HPU and LPU exhibited excellent chemical resistivity.

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References

  1. Zia F, Zia KM, Zuber M, Ahmad HB, Muneer M (2016) Glucomannan based polyurethanes: a critical short review of recent advances and future perspectives. Int J Biol Macromol 87:229–236

    Article  CAS  Google Scholar 

  2. Firdaus M, Meier MAR (2013) Renewable polyamides and polyurethanes derived from limonene. Green Chem 15:370–380

    Article  CAS  Google Scholar 

  3. Pacios VG, Costa V, Colera M, Martinez JMM (2011) Waterborne polyurethane dispersions obtained with polycarbonate of hexanediol intended for use as coatings. Prog Org Coat 71:136–146

    Article  Google Scholar 

  4. Efstathiou K (2011) Synthesis and characterization of a polyurethane prepolymer for the development of a novel acrylate-based polymer foam. Budapest University of Technology and Economics (BME), pp 11–14

  5. Mohamed HA, Morsi SMM, Badran BM, Rabie AM (2017) Eco-friendly protective coatings based on poly(urethane sulfone amide) dispersions for carbon steel. J Coat Technol Res 14:437–446

    Article  CAS  Google Scholar 

  6. Lopez DA, Crespo MAD, Huerta AMT, Vela AF, Adame JA, Rosales HD (2013) Analysis of degradation process during the incorporation of ZrO2:SiO2 ceramic nanostructures into polyurethane coatings for the corrosion protection of carbon steel. J Mater Sci 48:1067–1084

    Article  Google Scholar 

  7. M. V. Pergal, J. V. D!unuzovic, R. Poreba, D. Micic, P. Stefanov, L. Pezo, M. $pírková (2013) Surface and thermomechanical characterization of polyurethane networks based on poly(dimethylsiloxane) and hyperbranched polyester, Express Polymer Letters, 7:806–820

  8. Mahmood N, Yuan Z, Schmidt J, Xu C (2016) Depolymerization of lignins and their applications for the preparation of polyols and rigid polyurethane foams: a review. Renew Sustain Energy Rev 60:317–329

    Article  CAS  Google Scholar 

  9. Vanjinathan M, Shanavas A, Raghavan A, Nasar AS (2007) Synthesis and Properties of Hyperbranched Polyurethanes, hyperbranched polyurethane copolymers with and without ether and ester groups using blocked isocyanate monomers. J Polym Sci 45:3877–3893

    Article  CAS  Google Scholar 

  10. Mishra AK, Narayan R, Aminabhavi TM, Pradhan SK, Raju KVSN (2012) Hyperbranched polyurethane-urea-imide/o-clay-silica hybrids: synthesis and characterization. J Appl Polym Sci 125:E67–E75

    Article  CAS  Google Scholar 

  11. Głowinska E, Datta J (2014) A mathematical model of rheological behavior of novel bio-based isocyanate-terminated polyurethane prepolymers. Ind Crops Prod 60:123–129

    Article  Google Scholar 

  12. Król P (2008) Basic raw materials for the production of linear polyurethanes. In: Linear polyurethanes: synthesis methods, chemical structures, properties and application, chap 2. CRC Press, Boca Raton, Florida, USA, pp 6–15

  13. Liu J, Lin L, Jia X, Liu R, Zhang S, Liu X (2014) Synthesis and properties of UV-curable hyperbranched polyurethane and its application in the negative-type photoresist, Journal of Wuhan University of Technology-Mater. Sci Ed 29:208–212

    Google Scholar 

  14. Zeng SM, Chen AF, Yao C, Liu D, Yi CF, Xu ZS (2009) Synthesis and properties of hyperbranched polyurethane with a long chain between the branching points. Des Monomers Polym 12:221–231

    Article  CAS  Google Scholar 

  15. Karak N, Rana S, Cho JW (2009) Synthesis and characterization of castor-oil-modified hyperbranched polyurethanes. J Appl Polym Sci 112:736–743

    Article  CAS  Google Scholar 

  16. Liu Y, Zhang X, Gao N (2014) Synthesis and characterization of isocyanate-functionalized hyperbranched polyurethane and its cocuring with benzoxazine. Polym Eng Sci 55:604–613

    Article  Google Scholar 

  17. Deka H, Karak N (2009) Bio-based hyperbranched polyurethanes for surface coating applications. Prog Org Coat 66:192–198

    Article  CAS  Google Scholar 

  18. Datta J, Głowinska E (2014) Effect of hydroxylated soybean oil and bio-based propanediol on the structure and thermal properties of synthesized bio-polyurethanes. Ind Crops Prod 61:84–91

    Article  CAS  Google Scholar 

  19. Mohamed HA, Morsi SMM, Badran BM, Rabie AM (2017) Polyurethane/aromatic polyamide sulfone copolymer dispersions from transesterified castor oil. Polym Bull 74:531–554

    Article  CAS  Google Scholar 

  20. Thakur S, Karak N (2013) Castor oil-based hyperbranched polyurethanes as advanced surface coating materials. Prog Org Coat 76:157–164

    Article  CAS  Google Scholar 

  21. Mohamed HA, Badran BM, Rabie AM, Morsi SMM (2014) Synthesis and characterization of aqueous (polyurethane/aromatic polyamide sulfone) copolymer dispersions from castor oil. Prog Org Coat 77:965–974

    Article  CAS  Google Scholar 

  22. Głowinska E, Datta J (2016) Bio polyetherurethane composites with high content of natural ingredients: hydroxylated soybean oil based polyol, bio glycol and microcrystalline cellulose. Cellulose 23:581–592

    Article  Google Scholar 

  23. Dias RCM, Góes AM, Serakides R, Ayres E, Oréfice RL (2010) Porous biodegradable polyurethane nanocomposites: preparation, characterization, and biocompatibility tests. Mater Res 13(2):211–218

    Article  CAS  Google Scholar 

  24. Hölter D, Burgath A, Frey H (1997) Degree of branching in hyperbranched polymers 48:30–35

    Google Scholar 

  25. Wyatt VT, Strahan GD (2012) Degree of Branching in Hyperbranched Poly(glycerol-co-diacid)s Synthesized in Toluene. Polymers 4:396–407

    Article  Google Scholar 

  26. Krol P, Krol B, Pielichowska K, Špírková M (2015) Composites prepared from the waterborne polyurethane cationomers—modified graphene. Part I. Synthesis, structure, and physicochemical properties, Colloid Polymer. Science 293:421–431

    CAS  Google Scholar 

  27. Wang Z, Yu L, Ding M, Tan H, Li J, Fu Q (2011) Preparation and rapid degradation of nontoxic biodegradable polyurethanes based on poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid) and l-lysine diisocyanate. Polymer Chemistry 2:601–607

    Article  CAS  Google Scholar 

  28. Cowie JMG, Henshall SAE (1976) The influence of chain length and branching on the glass transition temperature of some polyglucosans. Eur Polymer J 12:215–218

    Article  CAS  Google Scholar 

  29. Li Y, Luo X, Hu S (2015) Polyols and polyurethanes from vegetable oils and their derivatives. In: Bio-based polyols and polyurethanes, compact volumes of 50 to 125 pages, chap 2, SpringerBriefs in green chemistry for sustainability. Springer, pp 15–43

  30. Guimarães DH, Brioude MM, Fiúza RP, Prado LASA, Boaventura JS, José NM (2007) Synthesis and characterization of polyesters derived from glycerol and phthalic acid. Materials Research 10:257–260

    Article  Google Scholar 

  31. Monteavaro LL, Riegel IC, Petzhold CL, Samios D (2005) Thermal stability of soy-based polyurethanes. Polimeros Ciencia e Tecnologia 15:151–155

    Article  Google Scholar 

  32. Chowdhury MNK, Ismail AF, Khan MR, Beg MDH, Othman MHD, Gohari RJ, Moslehyani A (2015) Physicochemical and micromechanical investigation of a nanocopper impregnated fibre reinforced nanocomposite. R Soc Chem 5:100943–100955

    Google Scholar 

  33. Patel MR, Shukla JM, Patel NK, Patel KH (2009) Biomaterial based novel polyurethane adhesives for wood to wood and metal to metal bonding. Mater Res 12:385–393

    Article  CAS  Google Scholar 

  34. Monteavaro LL, Riegel IC, Petzhold CL, Samios D (2005) Thermal stability of soy-based polyurethanes. Polímeros 15:151–155

    Article  Google Scholar 

  35. Guimarães DH, Brioude MM, Fiúza RP, Prado LASA, Boaventura JS, José NM (2007) Synthesis and characterization of polyesters derived from glycerol and phthalic acid. Mater Res 10:257–260

    Article  Google Scholar 

  36. Tena A, Shishatskiy S, Filiz V (2015) Poly(ether–amide) vs. poly(ether–imide) copolymers for post-combustion membrane separation processes. R Soc Chem 5:22310–22318

    CAS  Google Scholar 

  37. Datta J (2010) Synthesis and investigation of glycolysates and obtained polyurethane elastomers. J Elastomers Plast 42:117–127

    Article  CAS  Google Scholar 

  38. Mai Y, Zhou Y, Yan D, Hou J (2005) Quantitative dependence of crystallinity on degree of branching for hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane]. New J Phys 7:42

    Article  Google Scholar 

Download references

Acknowledgements

The authors like to express their appreciations to the research project assistance given by the National Research Center (NRC), Egypt, the research project sector that funded this research work under the Project Number P100101.

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Correspondence to Heba A. Mohamed.

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Morsi, S.M.M., Mohamed, H.A. A comparative study of new linear and hyperbranched polyurethanes built up from a synthesized isocyanate-terminated polyester/urethane. Polym. Bull. 74, 5011–5027 (2017). https://doi.org/10.1007/s00289-017-1996-0

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  • DOI: https://doi.org/10.1007/s00289-017-1996-0

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