Skip to main content
Log in

Pretreatment of hydroxy-terminated polybutadiene (HTPB)/toluene diisocyanate (TDI) binder system for biodegradation

  • Original Research
  • Published:
Advanced Composites and Hybrid Materials Aims and scope Submit manuscript


Hydroxy-terminated polybutadiene/toluene diisocyanate (HTPB/TDI) binder system is widely used in composite solid propellants. Expiration of weapons and ammunitions results in a significant amount of abandoned propellants. After recovery of energetic components, biodegradation is a potential treatment technology for the remaining material to convert into a harmless substance with low molecular weight. Due to high molecular weight and the presence of carbon-carbon long chain segments lacking electronegative elements, this binder system is difficult to be biodegraded. Nevertheless, some pretreatments will improve biodegradation. A two-step pretreatment of the binder system was performed using CH3-ONa/CH3-OH as a depolymerization reagent and HCOOH/H2O2 as an epoxidizing reagent so as to obtain an initial substrate for biodegradation. FT-IR and GPC analyses show that depolymerization breaks the urethane bonds in the binder system, and the hydroxyl-terminated depolymerization product has a structure similar to that of HTPB and significantly reduced molecular weight close to that of HTPB. Subsequent epoxidation makes some carbon-carbon double bonds in the hydroxyl-terminated depolymerization product convert into epoxy groups. The biodegradability tests show that there are richer potential degrading microorganisms for the epoxidation product as the sole carbon source vs. the original binder system, and the epoxidation product has a higher weight loss in biodegradation. As a pretreatment, depolymerization and epoxidation can reduce the molecular weight of substrate, improve the hydrophilicity, and make the biodegradability of pretreatment product superior to the HTPB/TDI binder system.

Graphical abstract

Pretreatment of HTPB/TDI binder can reduce the molecular weight of substrate, improve the hydrophilicity, and make the biodegradability superior to HTPB/TDI binder system.

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

Similar content being viewed by others


  1. Hangen C, Xiangmei W, Xiaoli Z, Rui LJCP, Materials P (2013) Research progress in mechanical properties of HTPB-isocyanate curing system

  2. Ramos VD, da Costa HM, Soares VLP, Nascimento RSV (2005) Modification of epoxy resin: a comparison of different types of elastomer. Polym Test 24:387–394

    Article  CAS  Google Scholar 

  3. Celina M, Minier L, Assink R (2002) Development and application of tools to characterize the oxidative degradation of AP/HTPB/Al propellants in a propellant reliability study. Thermochim Acta 384:343–349

    Article  CAS  Google Scholar 

  4. Stepien AE, Zebrowski J, Piszczyk Ł, Boyko VV, Riabov SV, Dmitrieva T, Bortnitskiy VI, Gonchar M, Wojnarowska-Nowak R, Ryszkowska J (2017) Assessment of the impact of bacteria Pseudomonas denitrificans, Pseudomonas fluorescens, Bacillus subtilis and yeast Yarrowia lipolytica on commercial poly(ether urethanes). Polym Test 63:484–493

    Article  CAS  Google Scholar 

  5. Hung CS, Zingarelli S, Nadeau LJ, Biffinger JC, Drake CA, Crouch AL, Barlow DE, Russell JN Jr, Crookes-Goodson WJ (2016) Carbon catabolite repression and impranil polyurethane degradation in Pseudomonas protegens strain Pf-5. Appl Environ Microbiol 82:6080–6090

    Article  CAS  Google Scholar 

  6. Schmidt J, Wei R, Oeser T, Dedavid ESLA, Breite D, Schulze A, Zimmermann W (2017) Degradation of polyester polyurethane by bacterial polyester hydrolases. Polymers (Basel) 9

  7. Mahajan N, Gupta P (2015) New insights into the microbial degradation of polyurethanes. RSC Adv 5:41839–41854

    Article  CAS  Google Scholar 

  8. Alvarez-Barragan J, Dominguez-Malfavon L, Vargas-Suarez M, Gonzalez-Hernandez R, Aguilar-Osorio G, Loza-Tavera H (2016) Biodegradative activities of selected environmental fungi on a polyester polyurethane varnish and polyether polyurethane foams. Appl Environ Microbiol 82:5225–5235

    Article  CAS  Google Scholar 

  9. Krasowska K, Janik H, Gradys A, Rutkowska M (2012) Degradation of polyurethanes in compost under natural conditions. J Appl Polym Sci 125:4252–4260

    Article  CAS  Google Scholar 

  10. Peng YH, Shih YH, Lai YC, Liu YZ, Liu YT, Lin NC (2014) Degradation of polyurethane by bacterium isolated from soil and assessment of polyurethanolytic activity of a Pseudomonas putida strain. Environ Sci Pollut Res Int 21:9529–9537

    Article  CAS  Google Scholar 

  11. Zafar U, Nzerem P, Langarica-Fuentes A, Houlden A, Heyworth A, Saiani A, Robson GD (2014) Biodegradation of polyester polyurethane during commercial composting and analysis of associated fungal communities. Bioresour Technol 158:374–377

    Article  CAS  Google Scholar 

  12. Ma Y, Zhuang Z, Ma M, Yang Y, Li W, Dong M, Wu S, Ding T, Guo Z (2019) Solid polyaniline dendrites consisting of high aspect ratio branches self-assembled using sodium lauryl sulfonate as soft templates: synthesis and electrochemical performance. Polymer 182:121808

    Article  Google Scholar 

  13. Ma Y, Ma M, Yin X, Shao Q, Lu N, Feng Y, Lu Y, Wujcik EK, Mai X, Wang C, Guo Z (2018) Tuning polyaniline nanostructures via end group substitutions and their morphology dependent electrochemical performances. Polymer 156:128–135

    Article  CAS  Google Scholar 

  14. Ma Y, Hou C, Zhang H, Zhang Q, Liu H, Wu S, Guo Z (2019) Three-dimensional core-shell Fe3O4/polyaniline coaxial heterogeneous nanonets: preparation and high performance supercapacitor electrodes. Electrochim Acta 315:114–123

    Article  CAS  Google Scholar 

  15. Ma Y, Hou C, Zhang H, Qiao M, Chen Y, Zhang H, Zhang Q, Guo Z (2017) Morphology-dependent electrochemical supercapacitors in multi-dimensional polyaniline nanostructures. J Mater Chem A 5:14041–14052

    Article  CAS  Google Scholar 

  16. Ma M, Li W, Tong Z, Ma Y, Bi Y, Liao Z, Zhou J, Wu G, Li M, Yue J, Song X, Zhang X (2020) NiCo2O4 nanosheets decorated on one-dimensional ZnFe2O4@SiO2@C nanochains with high-performance microwave absorption. J Colloid Interface Sci 578:58–68

    Article  CAS  Google Scholar 

  17. Umare SS, Chandure AS (2008) Synthesis, characterization and biodegradation studies of poly(ester urethane)s. Chem Eng J 142:65–77

    Article  CAS  Google Scholar 

  18. Gómez EF, Luo X, Li C, Michel FC, Li Y (2014) Biodegradability of crude glycerol-based polyurethane foams during composting, anaerobic digestion and soil incubation. Polym Degrad Stab 102:195–203

    Article  Google Scholar 

  19. Mondal S, Hu J (2006) Structural characterization and mass transfer properties of nonporous-segmented polyurethane membrane: influence of the hydrophilic segment content and soft segment melting temperature. J Membr Sci 276:16–22

    Article  CAS  Google Scholar 

Download references


I would like to thank my tutors Yu-Cun Liu and Tao Chai for providing lots of theoretical guidance and useful suggestion.


The authors would like to express their gratitude for the support of Shanxi Province Graduate Innovation Project Funding (2020by105) and the 16th Graduate Science and Technology Project Funding of North University of China (20191659) to this study.

Author information

Authors and Affiliations


Corresponding authors

Correspondence to Yucun Liu, Yong Ma or Chuntai Liu.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wu, K., Liu, Y., Ma, Y. et al. Pretreatment of hydroxy-terminated polybutadiene (HTPB)/toluene diisocyanate (TDI) binder system for biodegradation. Adv Compos Hybrid Mater 4, 96–103 (2021).

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: