Skip to main content
SpringerLink
Log in

Long-chain branched polypropylene obtained using an epoxy resin as crosslinking agent

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

A reaction between a linear polypropylene functionalized with maleic anhydride (PPg) and epoxy resin (bisphenol A diglycidyl ether) was carried out on the molten state to generate long-chain branches (LCB) in the molecular structure of the PPg. Concentrations of epoxy resin (ER) of up to 3.15 wt% were employed to obtain different levels of branching. FTIR spectroscopy analysis indicates that during the reaction, anhydride groups in PPg are consumed and new ester groups are formed. The presence of branches was verified using multiple-detection size-exclusion chromatography and rheology. The degree of long-chain branching induced in PPg augments with increasing concentration of ER. Furthermore, the materials modified with higher content of ER display gel-like behavior. The long-chain branched polymers also display thermo-rheological complexity. Thermal characterization studies show that LCBs have a nucleating effect during crystallization and cause the augment of the crystallization activation energy of PPg.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14
Fig. 15

Similar content being viewed by others

References

  1. Gahleitner M (2001) Melt rheology of polyolefins. Prog Polym Sci 26:895–944

    Article  CAS  Google Scholar 

  2. Han CD (2007) Rheology and Processing of Polymeric Materials, Polymer Rheology, vol 1. Oxford University Press, New York

    Google Scholar 

  3. Utracki LA (2002) Polymer blends handbook, vol 1. Kluwer Academic Publisher, Berlin

    Google Scholar 

  4. Lu B, Chung TC (1999) Synthesis of long chain branched polypropylene with relatively well-defined molecular structure. Macromolecules 32:8678–8680. doi:10.1021/ma991010r

    Article  CAS  Google Scholar 

  5. Sugimoto M, Tanaka T, Masubuchi Y, Takimoto JI, Koyama K (1999) Effect of chain structure on the melt rheology of modified polypropylene. J Appl Polym Sci 73:1493–1500. doi:10.1002/(SICI)1097-4628(19990822)73:8<1493:AID-APP18>3.0.CO;2-2

    Article  CAS  Google Scholar 

  6. Lagendijk RP, Hogt AH, Buijtenhuijs A, Gotsis AD (2001) Peroxydicarbonate modification of polypropylene and extensional flow properties. Polymer 42:10035–10043. doi:10.1016/S0032-3861(01)00553-5

    Article  CAS  Google Scholar 

  7. Rätzsch M, Arnold M, Borsig E, Ra M, Bucka H, Reichelt N (2002) Radical reactions on polypropylene in the solid state. Prog Polym 27:1195–1282. doi:10.1016/S0079-6700(02)00006-0

    Article  Google Scholar 

  8. Graebling D (2002) Synthesis of branched polypropylene by a reactive extrusion process. Macromolecules 35:4602–4610. doi:10.1021/ma0109469

    Article  CAS  Google Scholar 

  9. Auhl D, Stange J, Münstedt H, Krause B, Voigt D, Lederer A, Lappan U, Lunkwitz K (2004) Long-chain branched polypropylenes by electron beam irradiation and their rheological properties. Macromolecules 37:9465–9472. doi:10.1021/ma030579w

    Article  CAS  Google Scholar 

  10. Auhl D, Stadler FJ, Münstedt H (2012) Comparison of molecular structure and rheological properties of electron-beam- and gamma-irradiated polypropylene. Macromolecules 45:2057–2065. doi:10.1021/ma202265w

    Article  CAS  Google Scholar 

  11. Gotsis AD, Zeevenhoven BLF, Hogt AH (2004) The effect of long chain branching on the processability of polypropylene in thermoforming. Polym Eng Sci 44:973–982. doi:10.1002/pen.20089

    Article  CAS  Google Scholar 

  12. Paavola S, Saarinen T, Löfgren B, Pitkänen P (2004) Propylene copolymerization with non-conjugated dienes and α-olefins using supported metallocene catalyst. Polymer 45:2099–2110. doi:10.1016/j.polymer.2004.01.053

    Article  CAS  Google Scholar 

  13. Ye Z, AlObaidi F, Zhu S (2004) Synthesis and rheological properties of long-chain-branched isotactic polypropylenes prepared by copolymerization of propylene and nonconjugated dienes. Ind Eng Chem Res 43:2860–2870. doi:10.1021/ie0499660

    Article  CAS  Google Scholar 

  14. Nam GJ, Yoo JH, Lee JW (2005) Effect of long-chain branches of polypropylene on rheological properties and foam-extrusion performances. J Appl Polym Sci 96:1793–1800. doi:10.1002/app.21619

    Article  CAS  Google Scholar 

  15. Krause B, Voigt D, Häußler L, Auhl D, Münstedt H (2006) Characterization of electron beam irradiated polypropylene: influence of irradiation temperature on molecular and rheological properties. J Appl Polym Sci 100:2770–2780. doi:10.1002/app.23453

    Article  CAS  Google Scholar 

  16. Tian J, Yu W, Zhou C (2006) The preparation and rheology characterization of long chain branching polypropylene. Polymer 47:7962–7969. doi:10.1016/j.polymer.2006.09.042

    Article  CAS  Google Scholar 

  17. Langston JA, Colby RH, Chung TCM, Shimizu F, Suzuki T, Aoki M (2007) Synthesis and characterization of long chain branched isotactic polypropylene via metallocene catalyst and t-reagent. Macromolecules 40:2712–2720. doi:10.1021/ma062111+

    Article  CAS  Google Scholar 

  18. Fina A, Tabuani D, Peijs T, Camino G (2009) POSS grafting on PPgMA by one-step reactive blending. Polymer 50:218–226. doi:10.1016/j.polymer.2008.11.002

    Article  CAS  Google Scholar 

  19. Li S, Xiao M, Wei D, Xiao H, Hu F, Zheng A (2009) The Melt grafting preparation and rheological characterization of long chain branching polypropylene. Polymer 50:6121–6128. doi:10.1016/j.polymer.2009.10.006

    Article  CAS  Google Scholar 

  20. Mabrouk KE, Parent JS, Chaudhary BI, Cong R (2009) Chemical modification of PP architecture: strategies for introducing long-chain branching. Polymer 50:5390–5397. doi:10.1016/j.polymer.2009.09.066

    Article  Google Scholar 

  21. Su F, Huang H (2009) Rheology and thermal behavior of long branching polypropylene prepared by reactive extrusion. J Appl Polym Sci 113:2126–2135. doi:10.1002/app.30061

    Article  CAS  Google Scholar 

  22. Guapacha J, Failla MD, Vallés EM, Quinzani LM (2014) Molecular, rheological, and thermal study of long-chain branched polypropylene obtained by esterification of anhydride grafted polypropylene. J Appl Polym Sci 131:40357. doi:10.1002/app.40357

    Article  Google Scholar 

  23. Hingmann R, Marczinke BL (1994) Shear and elongational flow properties of polypropylene melts. J Rheol 38:573–587. doi:10.1122/1.550475

    Article  CAS  Google Scholar 

  24. Zhang C, Niu H, Dong JY (2012) Fabrication of long chain branched polypropylene using click chemistry. Polym Bull 68:949–959. doi:10.1007/s00289-011-0588-7

    Article  CAS  Google Scholar 

  25. Yoshiga A, Otaguro H, Parra DF, Lima LFCP, Lugao AB (2009) Controlled degradation and crosslinking of polypropylene induced by gamma radiation and acetylene. Polym Bull 63:397–409. doi:10.1007/s00289-009-0102-7

    Article  CAS  Google Scholar 

  26. Oliani WL, Parra DF, Lima LFCP, Lugao AB (2012) Morphological characterization of branched PP under stretching. Polym Bull 68:2121–2130. doi:10.1007/s00289-012-0708-z

    Article  CAS  Google Scholar 

  27. Zhang W, Yang L, Chen P, Zhang H, Lin W, Wang Y (2013) Preparation of long-chain branching polypropylene and investigation on its foamability. Polym Eng Sci 53:1598–1604. doi:10.1002/pen.23416

    Article  CAS  Google Scholar 

  28. Tang H, Dai W, Chen B (2008) A new method for producing high melt strength polypropylene with reactive extrusion. Polym Eng Sci 48:1339–1344. doi:10.1002/pen.21105

    Article  CAS  Google Scholar 

  29. Chaudhary BI, Cong R, Parent JS (2011) Imide-coupled propylene-based polymer and process. Patent US 2011/0009513 A1

  30. Ashcroft WR (1993) Curing agents for epoxy resins. Chemistry and Technology of Epoxy Resins. Springer, The Netherlands, pp 37–71

    Chapter  Google Scholar 

  31. Silverstein R, Webster F (1991) Spectrometric identification of organic compounds, 5th edn. Wiley, New York

    Google Scholar 

  32. Scholte TG, Meijerink NLJ, Schoffeleers HM, Brands AMG (1984) Mark-Houwink equation and GPC calibration linear short-chain branched polyolefins, including polypropylene and ethylene-propylene copolymers. J Appl Polym Sci 29:3763–3782. doi:10.1002/app.1984.070291211

    Article  CAS  Google Scholar 

  33. Zimm BH, StocKmayers WH (1949) The dimensions of chain molecules containing branches and rings. Chem Phys 17:1301–1314. doi:10.1063/1.1747157

    CAS  Google Scholar 

  34. Zimm BH, Kilb RW (1959) Dynamics of branched polymer molecules in dilute solution. J Polym Sci 37:19–42. doi:10.1002/pol.1959.1203713102

    Article  CAS  Google Scholar 

  35. Lecacheux D, Lesec J, Quivoron C (1982) High-temperature coupling of high-speed GPC with continuous viscometry. I. Long-chain branching in polyethylene. J Appl Polym Sci 27:4867–4877. doi:10.1002/app.1982.070271231

    Article  CAS  Google Scholar 

  36. Berry GCJ (1971) Thermodynamic and conformational properties of polystyrene. III dilute solution studies on branched polymers. J Polym Sci Part A-2 9:687–715

    Article  CAS  Google Scholar 

  37. Roovers J, Toporowski P, Martin J (1989) synthesis and characterization of multiarm star polybutadienes. Macromolecules 22:1897–1903. doi:10.1021/ma00194a064

    Article  CAS  Google Scholar 

  38. Wood-Adams P, Dealy JM, de Willem Groot A, Redwine OD (2000) Effect of molecular structure on the linear viscoelastic behavior of polyethylene. Macromolecules 33:7489–7499. doi:10.1021/ma991533z

    Article  CAS  Google Scholar 

  39. Zhang Z, Wan D, Xing H, Tan H, Wang L, Zheng J, An Y, Tang T (2012) A new grafting monomer for synthesizing long chain branched polypropylene through melt radical reaction. Polymer 53:121–129. doi:10.1016/j.polymer.2011.11.033

    Article  CAS  Google Scholar 

  40. Li Y, Yao Z, Chen Z, Qiu S, Zeng C, Cao K (2013) Rheological evidence of physical cross-links and their impact in modified polypropylene. Ind Eng Chem Res 52:7758–7767. doi:10.1021/ie400809z

    Article  CAS  Google Scholar 

  41. Vega JF, Expósito MT, Martínez-Salazar J, Lobón-Poo M, Osío Barcina J, García Martínez A, López M (2011) Molecular architecture and linear viscoelasticity of homogeneous ethylene/styrene copolymers. Rheol Acta 50:207–220. doi:10.1007/s00397-010-0521-2

    Article  CAS  Google Scholar 

  42. Villar MA, Failla MD, Quijada R, Santos Mauler R, Vallés E, Barrera Galland G, Quinzani LM (2001) Rheological characterization of molten ethylene-alfa-olefin copolymers synthesized with Et [Ind] 2 ZrCl 2/MAO catalyst. Polymer 42:9269–9279. doi:10.1016/S0032-3861(01)00458-X

    Article  CAS  Google Scholar 

  43. Wood-Adams P, Costeux S (2001) Thermorheological behavior of polyethylene: effects of microstructure and long chain branching. Macromolecules 34:6281–6290. doi:10.1021/ma0017034

    Article  CAS  Google Scholar 

  44. Keßner U, Münstedt H (2010) Thermorheology as a method to analyze long-chain branched polyethylenes. Polymer 51:507–513. doi:10.1016/j.polymer.2009.11.005

    Article  Google Scholar 

  45. Tian J, Yu W, Zhou C (2007) Crystallization behaviors of linear and long chain branched polypropylene. J Appl Polym Sci 104:3592–3600. doi:10.1080/00222340600870507

    Article  CAS  Google Scholar 

  46. Seo Y, Kim J, Ung K, Chul Y (2000) Study of the crystallization behaviors of polypropylene and maleic anhydride grafted polypropylene. Polymer 41:2639–2646. doi:10.1016/S0032-3861(99)00425-5

    Article  CAS  Google Scholar 

  47. Kang J, Wang B, Peng H, Chen J, Cao Y, Li H, Yang F, Xiang M (2014) Investigation on the structure and crystallization behavior of controlled-rheology polypropylene with different stereo-defect distribution. Polym Bull 71:563–579. doi:10.1007/s00289-013-1077-y

    Article  Google Scholar 

  48. Vyazovkin S (2002) Is the Kissinger equation applicable to the processes that occur on cooling? Macromol Rapid Commun 23:771–775. doi:10.1002/1521-3927(20020901)23:13<771:AID-MARC771>3.0.CO;2-G

    Article  CAS  Google Scholar 

  49. Yang B, Yang M, Wang WJ, Zhu S (2012) Effect of long chain branching on nonisothermal crystallization behavior of polyethylenes synthesized with constrained geometry catalyst. Polym Eng Sci 52:21–34. doi:10.1002/pen.22040

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are grateful for the financial support given by the National Research Council of Argentina (CONICET), the Universidad Nacional del Sur (UNS), the Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT) and the CYTED Project 311RT0417.

Author information

Authors and Affiliations

  1. Planta Piloto de Ingeniería Química (PLAPIQUI), UNS-CONICET-C. C. 717-(8000), Bahía Blanca, Argentina

    Jorge Guapacha, Enrique M. Vallés, Lidia M. Quinzani & Marcelo D. Failla

  2. Departamento de Ingeniería, Universidad Nacional del Sur (UNS), Av. Alem 1253-(8000), Bahía Blanca, Argentina

    Marcelo D. Failla

Authors
  1. Jorge Guapacha
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Enrique M. Vallés
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Lidia M. Quinzani
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Marcelo D. Failla
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Lidia M. Quinzani.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Guapacha, J., Vallés, E.M., Quinzani, L.M. et al. Long-chain branched polypropylene obtained using an epoxy resin as crosslinking agent. Polym. Bull. 74, 2297–2318 (2017). https://doi.org/10.1007/s00289-016-1839-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-016-1839-4

Keywords

Search

Navigation