Skip to main content
Log in

Structure—property relationships in the development of bituminous foams from MDI based prepolymers

  • Original Contribution
  • Published:
Rheologica Acta Aims and scope Submit manuscript

Abstract

Stable bituminous foams based on diphenyl methane-4,4′ diisocyanate (MDI–isocyanate prepolymers) that combine bituminous membranes and polyurethane foams into one material are promising new materials. They are produced in a two-step process: firstly, a reactive modified bitumen is obtained by mixing a bitumen and a prepolymer, and, secondly, a bituminous foam is formed by a reaction of an excess of water with the remaining isocyanate groups. The prepolymer was formed from a polypropylene glycol (PPG) polymer of a molecular weight of about 2,000 g/mol and MDI. The main goal of this study was to investigate the effect that both free MDI (not bonded to the PPG) and polyol (soft segment) exert on the thermorheological behaviour of bituminous polyurethane materials. The results obtained show that free MDI molecules are mostly responsible of the improvement of the viscoelastic and viscous response at high in-service temperatures due to the chemical reaction that give rise to rigid polyurethane and polyurea rigid blocks. PPG molecules partially inhibit the abovementioned effect but improve the low-temperature properties (lower glass transition temperatures). In general, for the used polyol, a good balance of rigidity and flexibility can be obtained if enough amount of a prepolymer containing a molar ratio of MDI/PPG of 5 is used.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  • Becker Y, Müller AJ, Rodríguez Y (2003) Use of rheological compatibility criteria to study SBS modified asphalts. J Appl Polym Sci 90:1772–1782

    Article  Google Scholar 

  • Chattopadhyay DK, Webster DC (2009) Thermal stability and flame retardancy of polyurethanes. Prog Polym Sci 34:1068–1133

    Article  Google Scholar 

  • Cheung CY, Cebon D (1997) Deformation mechanisms of pure bitumen. J Mater Civil Eng 9:117–129

    Article  Google Scholar 

  • Choi SW, Seo DW, Lim YD, Jeong YG, Mollah MSI, Park H, Hong TW, Kim WG (2011) Synthesis and properties of multihydroxy soybean oil from soybean oil and polymeric methylene-diphenyl-4,4′-diisocyanate/multihydroxy soybean oil polyurethane adhesive to wood. J Appl Polym Sci 121:764–769

    Article  Google Scholar 

  • Claudy P, Letoffe JF, King GN, Brule B, Planche JP (1991) Characterization of paving asphalts by differential scanning calorimetry. Fuel Sci Techonol Int 9(1):71–92

    Article  Google Scholar 

  • Collong W, Göbel A, Kleuser B, Lenhard W, Sonntag M (2002) 2K waterborne clearcoat—a competition between crosslinking and side reactions. Prog Org Coat 45:205–209

    Article  Google Scholar 

  • Cuadri AA, Partal P, Navarro FJ, García-Morales M, Gallegos C (2011) Bitumen chemical modification by thiourea dioxide. Fuel 90:2294–2300

    Article  Google Scholar 

  • Fields SM, Grether HJ, Grolimund K (1989) Analysis of organic isocyanates using capillary supercritical-fluid chromatography. J Chromatogr 472:175–195

    Article  Google Scholar 

  • Frazier CE, Ni J (1998) On the occurrence of network interpenetration in the wood-isocyanate adhesive interphase. Int J Adhes Adhes 18:81–87

    Article  Google Scholar 

  • Gurke T (2002) New advances in polymeric MDI variants. Eurocoat, Barcelona

    Google Scholar 

  • Hapburn C (1991) Polyurethane elastomers. Elsevier, Oxford

    Google Scholar 

  • Iqbal MH, Hussein IA, Al-Abdul Wahhab HI, Amin MB (2006) Rheological investigation of the influence of acrylate polymers on the modification of asphalt. J Appl Polym Sci 102:3446–56

    Article  Google Scholar 

  • Izquierdo MA, Navarro FJ, Martínez-Boza FJ, Gallegos C (2011) Novel stable MDI isocyanate-based bituminous foams. Fuel 90:681–688

    Article  Google Scholar 

  • Izquierdo MA, Navarro FJ, Martínez-Boza FJ, Gallegos C (2012) Bituminous polyurethane foams for building applications: influence of bitumen hardness. Constr Build Mater 30:706–713

    Article  Google Scholar 

  • Javni I, Zhang W, Petrovic ZS (2004) Soybean-oil-based polyisocyanurate rigid foams. J Polym Environ 12:123–129

    Article  Google Scholar 

  • Jeong HM, Kim BK, Choi YJ (2000) Synthesis and properties of thermotropic liquid crystalline polyurethane elastomers. Polymer 41:1849–1855

    Article  Google Scholar 

  • Kornbau ND, Ziegler DC (1970) Quantitative analysis of a moisture-cure polyurethane coating by gel-permeation chromatography. Anal Chem 42(11):1290–1293

    Article  Google Scholar 

  • Lesueur D, Gerard JF, Claudy P, Letoffe JM, Planche JM, Martin D (1996) A structure-related model to describe asphalt linear viscoelasticity. J Rheol 40(5):813–836

    Article  Google Scholar 

  • Martín-Alfonso MJ, Partal P, Navarro FJ, Garcìa-Morales M, Gallegos C (2008a) Use of a MDI-functionalized reactive polymer for the manufacture of modified bitumen with enhanced properties for roofing applications. Eur Polymer J 44:1451–61

    Article  Google Scholar 

  • Martín-Alfonso MJ, Partal P, Navarro FJ, Garcìa-Morales M, Gallegos C (2008b) Role of the water in the development of new isocyanate-based bituminous products. Ind Eng Chem Res 47:6933–6940

    Article  Google Scholar 

  • Martín-Alfonso MJ, Partal P, Navarro FJ, Garcìa-Morales M, Bordado JCM, Diogo AC (2009) Effect of processing temperature on the bitumen/MDI-PEG reactivity. Fuel Process Technol 90:525–530

    Article  Google Scholar 

  • Masson JF, Pelletier L, Collins P (2001) Rapid FTIR method for quantification of styrene-butadiene type copolymers in bitumen. J Appl Polym Sci 79:1034–1041

    Article  Google Scholar 

  • Mondal P, Khakhar DV (2004) Regulation of cell structure in water blown rigid polyurethane foam. Macromol Symp 216:241–254

    Article  Google Scholar 

  • Navarro FJ, Partal P, Martínez-Boza F, Gallegos C, Bordado JCM, Diogo AC (2006) Rheology and microstructure of MDI-PEG reactive prepolymer-modified bitumen. Mech Time-Depend Mater 10:347–59

    Article  Google Scholar 

  • Oertel G (1985) Polyurethane handbook. Hanser Publisher, Munich

    Google Scholar 

  • Pearson RG (1987) Specialty polymers. Chapman and Hall, New York

    Google Scholar 

  • Peramanu S, Pruden BB, Rahimi P (1999) Molecular weight and specific gravity distributions for Athabasca and Cold Lake bitumens and their saturate, aromatic, resin, and asphaltene fractions. Ind Eng Chem Res 38:3121–3130

    Article  Google Scholar 

  • Polacco G, Stastna J, Biondi D, Antonelli F, Vlachovicova Z, Zanzotto LJ (2004a) Rheology of asphalts modified with glycidylmethacrylate functionalized polymers. Colloid Interf Sci 280:366–73

    Article  Google Scholar 

  • Polacco G, Stastna J, Vlachovicova Z, Biondi D, Zanzotto L (2004b) Temporary networks in polymer-modified asphalts. J Polym Eng Sci 44:2185–93

    Article  Google Scholar 

  • Singh B, Gupta M, Tarannum H (2004) Evaluation of TDI production waste as a modifier for bituminous waterproofing. Constr Build Mater 18:591–601

    Article  Google Scholar 

  • Sriram V, Sundar S, Dattathereyan A, Radhakrishnan G (2005) Synthesis and characterization of cationomeric AB crosslinked polyurethane polymers based on different chain extenders. React Funct Polym 64(1):25–34

    Article  Google Scholar 

  • Stuart B (2004) Infrared spectroscopy: fundamentals and applications. Wiley, New Jersey

    Book  Google Scholar 

  • Szycher M (1999) Szycher’s handbook of polyurethanes. CRC Press, New York

    Google Scholar 

  • Thompson CM, Taylor SG, McGee WW (1990) Gel Permeation chromatographic analysis of polyurethane prepolymer synthesis kinetics I. The effect of catalyst. J Polym Sci Part A Polym Chem 28:333–334

    Article  Google Scholar 

  • Thompson CM, Taylor SG, McGee WW (1994) Gel permeation chromatographic analysis of polyurethane prepolymer synthesis kinetics II. The effects of stoichiometry and type of diisocyanate. J Polym Sci Part A Polym Chem 32:113–120

    Article  Google Scholar 

  • Ulrich H (2001) Chemistry and technology of isocyanates. Wiley, Chichester

    Google Scholar 

  • Wang TL, Lyman DJ (1992) The effect of reaction conditions on the urethane prepolymer formation. Polym Bull 27:549–555

    Article  Google Scholar 

Download references

Acknowledgments

This work is part of a research project sponsored by a MEC-FEDER programme (research project MAT2007-61460) and by a Junta de Andalucía Programme (TEP6689). The authors gratefully acknowledge its financial support.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to F. J. Navarro.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Izquierdo, M., Navarro, F., Martínez-Boza, F.J. et al. Structure—property relationships in the development of bituminous foams from MDI based prepolymers. Rheol Acta 53, 123–131 (2014). https://doi.org/10.1007/s00397-013-0747-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00397-013-0747-x

Keywords

Navigation