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Polydicyclopentadiene aerogels from first- versus second-generation Grubbs’ catalysts: a molecular versus a nanoscopic perspective

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Abstract

Polydicyclopentadiene (pDCPD) aerogels obtained via ring-opening metathesis polymerization using the first-generation Grubbs’ catalyst (GC-I) are well-shaped monoliths; those obtained from the second-generation Grubbs’ catalyst (GC-II) were severely deformed. At lower densities, materials from either catalyst consisted of entangled nanofibers, turning into random aggregates of nanoparticles as density increased. Nanoscopically, all those microstructures consisted of similar mass-fractal aggregates of secondary particles (by rheology), which in turn are closely packed assemblies of primary particles (by SAXS). Soluble oligomers along gelation were observed only with GC-II (by 1H NMR); nevertheless, all monomers were eventually incorporated in the skeletal framework of both materials (gravimetrically). The extent of cross-linking by olefin addition (via solid-state 13C NMR) was in the same range with both catalysts (19–25 % of pendant cyclopentenes). The only significant difference in the two kinds of aerogels was in the cis versus trans configuration of the polymeric backbone (by IR and solid-state 13C NMR). Deformation of GC-II-derived aerogels has been rectified by filling the empty space among primary particles (about 36 % v/v) with a hard polymer. Those aerogels have the same mechanical properties with those derived from GC-I, meaning that deformation is due to rearrangement at a level below the load-bearing macroporous network. Thus, a self-consistent model for deformation calls for primary particles of mostly trans pDCPD (via GC-I) being more rigid and more difficult to squeeze; thus, higher mass-fractal aggregates of secondary particles do not penetrate into the empty space of one another. Conversely, primary particles of more malleable cis/trans pDCPD (via GC-II) are squeezable, allowing higher aggregates to partially penetrate into one another. This model may also be related to frequently noted drying shrinkage of wet-gels even after converting the pore-filling solvent into a supercritical fluid, whereas all surface tension forces should have been eliminated.

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Notes

  1. It is noted that in our previous study on the gelation of pDCPD with GC-II [24, 25], whereas the goal was to keep the gelation time of different concentration sols constant, the catalyst:DCPD ratio of the lower concentration sols was double than the one used here. It had been observed then that gels with xx ≤ 10 dissolved spontaneously (within 12 h) to free-flowing solutions, which eventually “gelled” again into thixotropic liquids.

  2. Similar observations have been made previously with polyurea aerogels, whereas morphology changes with density from fibrous to particulate; nevertheless, all nanostructures consisted of about same-size primary particles [11].

References

  1. Pierre AC, Pajonk GM (2002) Chemistry of aerogels and their applications. Chem Rev 102:4243–4265

    Article  Google Scholar 

  2. Hüsing N, Schubert U (1998) Aerogels—airy materials: chemistry, structure, and properties. Angew Chem Int Ed 37:22–45

    Article  Google Scholar 

  3. Morris CA, Anderson ML, Stroud RM, Merzhacher CI, Rolison DR (1999) Silica sol as a nanoglue: flexible synthesis of composite aerogels. Science 284:622–624

    Article  Google Scholar 

  4. Leventis N (2007) Three-dimensional core-shell superstructures: mechanically strong aerogels. Acc Chem Res 40:874–884

    Article  Google Scholar 

  5. Leventis N, Lu H (2011) In: Aegerter MA, Leventis N, Koebel M (eds) Aerogels handbook. Springer, New York

    Google Scholar 

  6. Mohite DP, Larimore ZJ, Lu H, Mang JT, Sotiriou-Leventis C, Leventis N (2012) Monolithic hierarchical fractal assemblies of silica nanoparticles with polynorbornene via ROMP: a structure-property correlation from molecular to bulk through nano. Chem Mater 24:3434–3448

    Article  Google Scholar 

  7. Leventis N, Sotiriou-Leventis C, Mohite DP, Larimore ZJ, Mang JT, Churu G, Lu H (2011) Polyimide aerogels by ring-opening metathesis polymerization (ROMP). Chem Mater 23:2250–2261

    Article  Google Scholar 

  8. Chidambareswarapattar C, Xu L, Sotiriou-Leventis C, Leventis N (2013) Robust monolithic multiscale nanoporous polyimides and conversion to isomorphic carbons. RSC Adv 3:26459–26469

    Article  Google Scholar 

  9. Meador MAB, Malow EJ, He ZJ, McCorkle L, Guo H, Nauyen BN (2010) Synthesis and properties of nanoporous polyimide aerogels having a covalently bonded network structure. Polym Prepr 51:265–266

    Google Scholar 

  10. Leventis N, Chidambareswarapattar C, Mohite DP, Larimore ZJ, Lu H, Sotiriou-Leventis C (2011) Multifunctional porous aramids (aerogels) by efficient reaction of carboxylic acids and isocyanates. J Mater Chem 21:11981–11986

    Article  Google Scholar 

  11. Leventis N, Sotiriou-Leventis C, Chandrasekaran N, Mulik S, Larimore ZJ, Lu H, Churu G, Mang JT (2010) Multifunctional polyurea aerogels from isocyanates and water. A Structure–property case study. Chem Mater 22:6692–6710

    Article  Google Scholar 

  12. Sadekar AG, Mahadik SS, Bang AN, Larimore ZJ, Wisner CA, Bertino MF, Kalkan KA, Mang JT, Sotiriou-Leventis C, Leventis N (2012) From ‘green’ aerogels to porous graphite by emulsion gelation of acrylonitrile. Chem Mater 24:26–47

    Article  Google Scholar 

  13. Chidambareswarapattar C, McCarver PM, Luo H, Lu H, Sotiriou-Leventis C, Leventis N (2013) Fractal multiscale nanoporous polyurethanes: flexible to extremely rigid aerogels from multifunctional small molecules. Chem Mater 25:3205–3224

    Article  Google Scholar 

  14. Mahadik-Khanolkar S, Donthula S, Sotiriou-Leventis C, Leventis N (2014) Polybenzoxazine aerogels. 1. High-yield room-temperature acid-catalyzed synthesis of robust monoliths, oxidative aromatization, and conversion to microporous carbons. Chem Mater 26:1303–1317

    Article  Google Scholar 

  15. Perring M, Long TR, Bowden NB (2010) Epoxidation of the surface of polydicyclopentadiene for the self-assembly of organic monolayers. J Mater Chem 20:8679–8685

    Article  Google Scholar 

  16. Jeong W, Kessler MR (2008) Toughness enhancement in ROMP functionalized carbon nanotube/polydicyclopentadiene composites. Chem Mater 20:7060–7068

    Article  Google Scholar 

  17. http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2005/grubbs-slides.pdf. 26 Aug 2014

  18. Lee JK, Gould GL (2007) Polydicyclopentadiene based aerogel: a new insulation material. J Sol–Gel Sci Technol 44:29–40

    Article  Google Scholar 

  19. Dawedeit C, Kim SH, Braun T, Worsley MA, Stephan AL, Wu KJ, Walton CC, Chernov AA, Satcher JH Jr, Hamza AV, Biener J (2012) Tuning the rheological properties of sols for low-density aerogel coating applications. Soft Matter 8:3518–3521

    Article  Google Scholar 

  20. Kim SH, Worsley MA, Valdez CA, Shin SJ, Dawedeit C, Braun T, Baumann TF, Letts SA, Kucheyev SO, Wu KJJ, Biener J, Satcher JH Jr, Hamza AV (2012) Exploration of the versatility of ring opening metathesis polymerization: an approach for gaining access to low density polymeric aerogels. RSC Adv 2:8672–8680

    Article  Google Scholar 

  21. Fisher RA, Grubbs RH (1992) Ring-opening metathesis polymerization of exo-dicyclopentadiene: reversible crosslinking by a metathesis catalyst. Macromol Chem Macromol Symp 63:271–277

    Article  Google Scholar 

  22. Abadie MJ, Dimonie M, Couve C, Dragutan V (2000) New catalysts for linear polydicyclopentadiene synthesis. Eur Polym J 36:1213–1219

    Article  Google Scholar 

  23. Dragutan V, Dragutan I, Dimonie M, Couve C, Abadie MJ (2002) Catalyst activity and selectivity in ROMP of dicyclopentadiene induced by some tungsten systems. NATO Sci Ser II Math Phys Chem 56:465–476

    Google Scholar 

  24. Mohite DP, Mahadik-Khanolkar S, Luo H, Lu H, Sotiriou-Leventis C, Leventis N (2013) Polydicyclopentadiene aerogels grafted with PMMA: I. Molecular and interparticle crosslinking. Soft Matter 9:1516–1530

    Article  Google Scholar 

  25. Mohite DP, Mahadik-Khanolkar S, Luo H, Lu H, Sotiriou-Leventis C, Leventis N (2013) Polydicyclopentadiene aerogels grafted with PMMA: II. Nanoscopic characterization and origin of macroscopic deformation. Soft Matter 9:1531–1539

    Article  Google Scholar 

  26. Aldridge M, Shankar C, Zhen C, Sui L, Kieffer J, Caruso M, Moore J (2010) Combined experimental and simulation study of the cure kinetics of DCPD. J Compos Mater 45:1827–1835

    Article  Google Scholar 

  27. Wilson GO, Caruso MM, Reimer MT, White SR, Sottos NR, Moore JS (2008) Evaluation of ruthenium catalysts for ring-opening metathesis polymerization-based self-healing applications. Chem Mater 20:3288–3297

    Article  Google Scholar 

  28. Rule JD, Moore JS (2002) ROMP reactivity of endo- and exo-dicyclopentadiene. Macromolecules 35:7878–7882

    Article  Google Scholar 

  29. Yang G, Lee JK (2014) Curing kinetics and mechanical properties of endo-dicyclopentadiene synthesized using different Grubbs’ catalysts. Ind Eng Chem Res 53:3001–3011

    Article  Google Scholar 

  30. Davidson TA, Wagener KB, Priddy DB (1996) Polymerization of dicyclopentadiene: a tale of two mechanisms. Macromolecules 29:786–788

    Article  Google Scholar 

  31. Davidson TA, Wagener KB (1998) The polymerization of dicyclopentadiene: an investigation of mechanism. J Mol Catal A: Chem 133:67–74

    Article  Google Scholar 

  32. Dzik WI, Zhang XP, de Bruin B (2011) Redox noninnocence of carbene ligands: carbene radicals in (catalytic) C–C bond formation. Inorg Chem 50:9896–9903

    Article  Google Scholar 

  33. Amir-Ebrahimi V, Corry DA, Hamilton JG, Thompson JM, Rooney JJ (2000) Characteristics of RuCl2(CHPh)(PCy3)2 as a catalyst for ring-opening metathesis polymerization. Macromolecules 33:717–724

    Article  Google Scholar 

  34. Schaubroeck D, Brughmans S, Vercaemst C, Schaubroeck J, Verpoort F (2006) Qualitative FT-Raman investigation of the ring opening metathesis polymerization of dicyclopentadiene. J Mol Catal A: Chem 254:180–185

    Article  Google Scholar 

  35. Ding F, Monsaert S, Drozdzak R, Dragutan I, Dragutan V, Sun Y, Gao E, Voort PVD, Verpoort F (2009) First FT-Raman and 1H NMR comparative investigations in ring opening metathesis polymerization. Vib Spectrosc 51:147–151

    Article  Google Scholar 

  36. Kim S-Y, Choi D-G, Yang S-M (2002) Rheological analysis of the gelation behavior of tetraethylorthosilane/vinyltriethoxysilane hybrid solutions. Korean J Chem Eng 19:190–196

    Article  Google Scholar 

  37. Raghavan SR, Chen LA, McDowell C, Khan SA, Hwang R, White S (1996) Rheological study of crosslinking and gelation in chlorobutyl elastomer systems. Polymer 37:5869–5875

    Article  Google Scholar 

  38. Muthukumar M (1989) Screening effect on viscoelasticity near the gel point. Macromolecules 22:4656–4658

    Article  Google Scholar 

  39. Kolb M, Botet R, Jullien R (1983) Scaling of kinetically growing clusters. Phys Rev Lett 51:1123–1126

    Article  Google Scholar 

  40. Yang Y-S, Lafontaine E, Mortaigne B (1996) NMR characterization of dicyclopentadiene resins and polydicyclopentadienes. J Appl Polym Sci 60:2419–2435

    Article  Google Scholar 

  41. Vargas J, Martínez A, Santiago AA, Tlenkopatchev MA, Gaviño R, Aguilar-Vega MJ (2009) The effect of fluorine atoms on gas transport properties of new polynorbornene dicarboximides. Fluor Chem 130:162–168

    Article  Google Scholar 

  42. Díaz K, Vargas J, Del Castillo LF, Tlenkopatchev MA, Aguilar-Vega M (2005) Polynorbornene dicarboximides with cyclic pendant groups: synthesis and gas transport properties. Macromol Chem Phys 206:2316–2322

    Article  Google Scholar 

  43. Lu X, Caps R, Fricke J, Alviso CT, Pekala RW (1995) Correlation between structure and thermal conductivity of organic aerogels. J Non Cryst Solids 188:226–234

    Article  Google Scholar 

  44. Fricke J (1988) Aerogels—highly tenuous solids with fascinating properties. J Non Cryst Solids 100:169–173

    Article  Google Scholar 

  45. Gross J, Fricke J (1995) Scaling of elastic properties in highly porous nanostructured aerogels. Nanostruct Mater 6:905–908

    Article  Google Scholar 

  46. Katti A, Shimpi N, Roy S, Lu H, Fabrizio EF, Dass A, Capadona LA, Leventis N (2006) Chemical, physical, and mechanical characterization of isocyanate cross-linked amine-modified silica aerogels. Chem Mater 18:285–296

    Article  Google Scholar 

  47. Leventis N, Sotiriou-Leventis C, Mulik S, Dass A, Schnobrich J, Hobbs A, Fabrizio EF, Luo H, Churu G, Zhang Y, Lu H (2008) Polymer nanoencapsulated mesoporous vanadia with unusual ductility at cryogenic temperatures. J Mater Chem 18:2475–2482

    Article  Google Scholar 

  48. Luo H, Churu G, Schnobrich J, Hobbs A, Fabrizio EF, Dass A, Mulik S, Sotiriou- Leventis C, Lu H, Leventis N (2008) Synthesis and characterization of the physical, chemical and mechanical properties of isocyanate-crosslinked vanadia aerogels. J Sol–Gel Sci Technol 48:113–134

    Article  Google Scholar 

  49. Beaucage G (1995) Approximations leading to a unified exponential/power-law approach to small-angle scattering. J Appl Crystallogr 28:717–728

    Article  Google Scholar 

  50. Beaucage G (1996) Small-angle scattering from polymeric mass fractals of arbitrary mass-fractal dimension. J Appl Crystallogr 29:134–146

    Article  Google Scholar 

  51. Hamilton G, Ivin KJ, Rooney JJ (1998) Ring-opening polymerization of endo and exo-dicyclopentadiene and their 7,8-dihydro derivatives. J Mol Catal 36:115–125

    Article  Google Scholar 

  52. Feder J (1988) Fractals. Plenum Press, New York

    Book  Google Scholar 

  53. Lee DG, Bonner JS, Garton LS, Ernest AN, Autenrieth RL (2000) Modeling coagulation kinetics incorporating fractal theories: a fractal rectilinear approach. Water Res 34:1987–2000

    Article  Google Scholar 

  54. Schrock RR (2009) Recent advances in high oxidation state Mo and W imido alkylidene chemistry. Chem Rev 109:3211–3226

    Article  Google Scholar 

  55. Schrock RR (2011) Synthesis of stereoregular ROMP polymers using molybdenum and tungsten imido alkylidene initiators. Dalton Trans 40:7484–7495

    Article  Google Scholar 

  56. Saragas N, Floros G, Paraskevopoulou P, Psaroudakis N, Koinis S, Pitsikalis M, Mertis K (2009) Polymerization of terminal alkynes with a triply bonded ditungsten halo-complex. J Mol Catal A: Chem 303:124–131

    Article  Google Scholar 

  57. Adams RD, Cotton FA (eds) (1999) Catalysis by Di- and polynuclear metal cluster complexes. Wiley VCH, New York

    Google Scholar 

  58. Floros G, Saragas N, Paraskevopoulou P, Psaroudakis N, Koinis S, Pitsikalis M, Hadjichristidis N, Mertis K (2012) Ring opening metathesis polymerization of norbornene and derivatives by the triply bonded ditungsten complex Na[W2(µ-Cl)3Cl4(THF)2] (THF)3. Polymers 4:1657–1673

    Article  Google Scholar 

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Acknowledgments

This study was funded by the Army Research Office (W911NF-14-1-0369) and BASF Polyurethanes GmbH (0039509).

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The authors declare that they have no conflict of interest.

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Authors and Affiliations

  1. Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, 65409, USA

    Abhishek Bang, Dhairyashil Mohite, Adnan Malik Saeed, Nicholas Leventis & Chariklia Sotiriou-Leventis

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  1. Abhishek Bang
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  2. Dhairyashil Mohite
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Correspondence to Nicholas Leventis or Chariklia Sotiriou-Leventis.

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Bang, A., Mohite, D., Saeed, A.M. et al. Polydicyclopentadiene aerogels from first- versus second-generation Grubbs’ catalysts: a molecular versus a nanoscopic perspective. J Sol-Gel Sci Technol 75, 460–474 (2015). https://doi.org/10.1007/s10971-015-3718-0

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