Synthesis of Varying Length Polyhedral Oligomeric Silsesquioxane Methyl- Methacrylate (POSS-MMA) and its Effect on Viscosity and Polymerization Shrinkage

Download Synthesis of Varying Length Polyhedral Oligomeric Silsesquioxane Methyl- Methacrylate (POSS-MMA) and its Effect on Viscosity and Polymerization Shrinkage

Post on 22-Dec-2015

226 views

Category:

Documents

6 download

Embed Size (px)

TRANSCRIPT

  • Slide 1
  • Synthesis of Varying Length Polyhedral Oligomeric Silsesquioxane Methyl- Methacrylate (POSS-MMA) and its Effect on Viscosity and Polymerization Shrinkage of Neat Dental Resin Formulations Research Mentor: Dr. Paul Buonora California State University Long Beach
  • Slide 2
  • Outline Introduction Materials/Methods Results Conclusions/Summary Future Experiments Acknowledgements
  • Slide 3
  • What are dental restorative materials? A mixture of one to several monomers that are able to polymerize or copolymerize upon light- curing (i.e. composites) Materials usually consisting of methacrylate ester functionalities (i.e. BisGMA/TEGDMA)
  • Slide 4
  • What should these materials be able to do? Should have: high resistance to erosion, degradation, and thermal stresses Retain high tensile and compressive strength, while being biologically inert or bioactive. Should be easily mixed and placed as an unset paste, have short working and setting times, react rapidly, and give color and translucency which match that of the natural tooth
  • Slide 5
  • Drawbacks of current materials High viscosity these materials become difficult for dental clinicians to extract from tubes designed for small scale applications like placement on teeth Large polymerization shrinkage these materials tend to shrink in volume after curing with blue light (foods and liquids can accumulate in these cavities and cause more tooth damage)
  • Slide 6
  • Polyhedral Oligomeric Silsesquioxanes Inorganic-Organic Hybrids Strictly defined inorganic cubic structure of alternating array of silicon and oxygen atoms Eight pendant side chains tethered to cube center Inorganic unreactive center and organic reactive side chains
  • Slide 7
  • POSS Structure * Soluble in methylene chloride
  • Slide 8
  • Why POSS? Provides a new class of monomer having the potential to reduce both viscosity and shrinkage Its defined nano-sized architecture offers a unique opportunity to modify its octameric sites through the addition of organic groups tethered to its vertices Provides a multitude of possibilities for the synthesis of hyperbranched dendrimer systems.
  • Slide 9
  • Materials/Methods Starting Compounds: - POSS - allyloxytrimethylsilane (varying lengths) - BisGMA / TEGDMA Solvents/Reagents/Catalyst: -methylene chloride, toluene, methanol -triethylamine, triphenylphosphine, methacryloyl chloride -Pt(0)-divinyltetramethyldisiloxane [Pt(dvs)]
  • Slide 10
  • Materials/Methods Instruments/Techniques: - Perkin Elmer Paragon 1000 FTIR spectrometer (4 scans) - Eft-90 H1/C13 NMR spectrometer (90 and 400 Mhz) - Standard Thin Layer Chromatography (solvent: 50:50 ethyl acetate/hexane)
  • Slide 11
  • - Brookfield CAP 2000 dynamic mechanical analyzer Materials/Methods - Visible Light Curing Apparatus ( = 460nm)
  • Slide 12
  • The experiment Synthesize POSS-MMA of varying side-chain lengths Incorporate these varying POSS-MMA moieties into a resin matrix forming a constant 40/40/20 (% wt) formulation of BisGMA/TEGDMA/POSS- MMA respectively Assay for pre-polymerization viscosity (poise) and polymerization shrinkage after blue-light curing (equation: % shrinkage = [1-d uncured /d cured ] x 100%) *d = density
  • Slide 13
  • Control POSS-MMA having allyloxytrimethylsilane chains of 3 carbons in length *n indicates the # of carbons present within the parenthesis Viscosity and Polymerization Shrinkage data of other formulations will be compared to values found in control
  • Slide 14
  • Synthesis of POSS-MMA species Step 1: Octasilane-POSS + Allyloxytrimethylsilane Pt(dvs) Octasilane-POSS Octakis[(3- trimethylsiloxypropyl)dimethylsiloxy] -silsesquioxane (POSS-TMSP)
  • Slide 15
  • Synthesis of POSS-MMA species Step 2: POSS-TMSP + Anhydrous Methanol CH 3 OH POSS-TMSP Octakis[3-hydroxypropyldimethylsiloxy) octasilsesquioxane (POSS-HP)
  • Slide 16
  • Synthesis of POSS-MMA species Step 3: POSS-HP + Methacryloyl Chloride POSS-HP Octakis(methacryloxypropyldimethylsiloxy) octasilsesquioxane (POSS-MMA)
  • Slide 17
  • *POSS-MMA FTIR Spectra Results
  • Slide 18
  • *POSS-MMA HNMR Spectra Results
  • Slide 19
  • Table 1. Viscosity (poise) and % Polymerization Shrinkage of 40/40/20 ratio of BisGMA/TEGDMA/POSS-MMA oligomer. Trials were conducted on control mixtures containing allyloxytrimethylsilane species 3 carbons in length. TrialsViscosity (Poise)Shrinkage (%) 11.3315.2 21.3415.5 31.3114.9
  • Slide 20
  • Results Table 2. Description of the Resins Formulated, Pre-polymerization Viscosity, and Polymerization Shrinkage. All ratios of BisGMA/TEGDMA/POSS-MMA mixtures have a 40/40/20 ratio according to percent weight (wt%). Numbers following an asterisk indicate the carbon length of POSS-MMA side chain groups. Description of Resin Formulations Viscosity (Poise) Polymerization Shrinkage (%) BisGMA/TEGDMA/POSS- MMA*3 1.3315.1 BisGMA/TEGDMA/POSS- MMA*4 1.2413.4 BisGMA/TEGDMA/POSS- MMA*5 1.1211.2 BisGMA/TEGDMA/POSS- MMA*6 0.879.6 BisGMA/TEGDMA/POSS- MMA*7 0.757.1 BisGMA/TEGDMA/POSS- MMA*8 0.735.9 BisGMA/TEGDMA/POSS- MMA*9 0.724.3 BisGMA/TEGDMA/POSS- MMA*10 0.723.8
  • Slide 21
  • Results *Plots illustrating the effects of methacrylate chain length on A) viscosity and B) polymerization shrinkage. A)B)
  • Slide 22
  • Conclusions/Summary Incorporation of POSS-MMA into resin matrix causes decreased viscosity and polymerization shrinkage (up to a certain point) of neat dental resin formulations Using allyloxytrimethylsilane yields an efficient route in the synthesis of POSS-MMA Viscosity decreased through low weight to volume ratio Polymerization shrinkage decreased through amount and distance of methacrylate bonds in matrix
  • Slide 23
  • Future Experiments Study how incorporating POSS-MMA affects other physical/mechanical properties Study other silsesquioxane compounds (i.e. cyclic version) Other novel di- and tri- methacrylate monomers
  • Slide 24
  • Acknowledgements Dr. Buonora Romina Panoussi/Teresa Phan Dr. Mason/Dr. Archie Howard Hughes Medical Institute
  • Slide 25
  • (1) Bowen, R. L.; Barton Jr., J. A.; Mullineaux, A. L. National Bureau of Standards Special Publication, 1972, 354, 93. (2) Fortin, D. D.M.D.; Vargas, M. D.D.S. Journal of the American Dental Association, 2001, 131, 26S. (3) Mahler, D. National Bureau of Standards Special Publication, 1972, 354, 177. (4) Nicholson, J. W; Anstice, M. H. Journal of Chemical Education, 1999, 76, 1497. (5) Lovell, L. G.; Stansbury, J. W.; Syrpes D. C.; Bowman, C. N. Macromolecules, 1999, 32(12), 3913. (6) Muh, E.; Marquardt, J.; Klee, J. E.; Frey, H.; Mulhaupt, R. Macromolecules, 2001, 34(17), 5778. (7) Gao, F.; Tong, Y.; Schricker, S. R.; Culbertson, B. M. Polymers for Advanced Technologies, 2001, 12, 355. (8) Moszner, N.; Salz, U. Progress in Polymer Science, 2001, 26, 535. (9) Li, G. Z.; Wang, L.; Toghiani, H.; Daulton, T. L.; Koyama, K.; Pittman, C. U. Macromolecules, 2001, 34, 8686. (10) Sellinger, A.; Laine, R. Macromolecules, 1996, 29, 2327. (11) Zhang, C.; Laine, R. M. Journal of the American Chemical Society, 2000, 122, 6979. (12) Costa, R. O. R.; Vasconcelos, W. L.; Tamaki, R.; Laine, R. M. Macromolecules, 2001, 34, 5398. (13) Hong, B.; Thoms, T. P. S.; Murfee, H. J.; Lebrun, M. J. Inorganic Chemistry, 1997, 36, 6146. (14) Wan, Q.; Rumpf, D.; Schricker, S. R.; Mariotti, A.; Culbertson, B. M. Biomacromolecules, 2001, 2, 217. (15) Choi, J.; Harcup, J.; Yee, A. F.; Zhu, Q.; Laine, R. M. Journal of the American Chemical Society, 2001, 123, 11420. (16) Zhang, C.; Babonneau, F.; Bonhomme, C.; Laine, R. M.; Soles, C. L.; Hristov, H. A.; Yee, A. F. Journal of the American Chemical Society, 1998, 120(33), 8380. (17) Szuromi, E.; Berka, M.; Borbely, J. Macromolecules, 2000, 33(11), 3993. (18) Sellinger, A.; Laine, R. Chem. Mater., 1996, 8, 1592-1593. (19) Haddad, T.S.; Lichtenhan, J.D. Macromolecules, 1996, 29, 7302-7304. (20) Zhang, C.; Bunning, T.J.; Laine, R.M. Chem. Mater., 2001, 13(10), 3653-3662. (21) Gao, F.; Schricker, S. R.; Tong, Y.; Culbertson, B. M. Polymer Preprints, 2002, 43(1), 621. References

Recommended

View more >