Synthesis of Varying Length Polyhedral

Oligomeric Silsesquioxane MethylMethacrylate (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

Outline
Introduction
Materials/Methods
Results
Conclusions/Summary
Future Experiments
Acknowledgements

What are dental restorative materials?

A mixture of one to several monomers that are
able to polymerize or copolymerize upon lightcuring (i.e. composites)
Materials usually consisting of methacrylate
ester functionalities (i.e. BisGMA/TEGDMA)

OH

OH
BisGMA

O
O

TEGDMA

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

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)

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

POSS Structure

O
Si
O

R
Si
O

O Si
O
Si
R
R
Si
O
O
Si
O
R
O
Si
O
Si O
R
R

* Soluble in methylene chloride

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.

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)]

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)

Materials/Methods
- Brookfield CAP 2000
dynamic mechanical analyzer

- Visible Light Curing Apparatus

( = 460nm)

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/POSSMMA respectively

Assay for pre-polymerization viscosity (poise) and

polymerization shrinkage after blue-light curing

(equation: % shrinkage = [1-duncured/dcured] x 100%)
*d = density

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

Synthesis of POSS-MMA species

Step 1: Octasilane-POSS + Allyloxytrimethylsilane
R

O
Si
O

R
Si
O

O Si
O
Si
R
R
Si
O
O
Si
O
R
O
Si
O
Si O
R

R
R

Octasilane-POSS

Pt(dvs)

O
Si
O

R
Si
O

O Si
O
Si
R
R
Si
O
O
Si
O
R
O
Si
O
Si O
R
R

Octakis[(3trimethylsiloxypropyl)dimethylsiloxy]
-silsesquioxane (POSS-TMSP)

Synthesis of POSS-MMA species

Step 2: POSS-TMSP + Anhydrous Methanol
R O
Si
O

R
Si
O

O Si
O
Si
R
R
Si
O
O
Si
O
R
O
Si
O
Si O
R
R

POSS-TMSP

CH3OH

O
Si
O

R
Si
O

O Si
O
Si
R
R
Si
O
O
Si
O
R
O
Si
O
Si O
R

Octakis[3-hydroxypropyldimethylsiloxy)
octasilsesquioxane (POSS-HP)

Synthesis of POSS-MMA species

Step 3: POSS-HP + Methacryloyl Chloride
R

O
Si
O

R
Si
O

O Si
O
Si
R
R
Si
O
O
Si
O
R
O
Si
O
Si O
R
R

POSS-HP

O
Si
O

R
Si
O

O Si
O
Si
R
R
Si
O
O
Si
O
R
O
Si
O
Si O
R

Octakis(methacryloxypropyldimethylsiloxy)
octasilsesquioxane
(POSS-MMA)

Results

*POSS-MMA FTIR Spectra

Results

*POSS-MMA HNMR Spectra

Results
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.
Trials

Viscosity (Poise)

Shrinkage (%)

1.33

15.2

1.34

15.5

1.31

14.9

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
BisGMA/TEGDMA/POSSMMA*3
BisGMA/TEGDMA/POSSMMA*4
BisGMA/TEGDMA/POSSMMA*5
BisGMA/TEGDMA/POSSMMA*6
BisGMA/TEGDMA/POSSMMA*7
BisGMA/TEGDMA/POSSMMA*8
BisGMA/TEGDMA/POSSMMA*9

Viscosity
(Poise)

Polymerization Shrinkage
(%)

1.33

15.1

1.24

13.4

1.12

11.2

0.87

9.6

0.75

7.1

0.73

5.9

0.72

4.3

BisGMA/TEGDMA/POSSMMA*10

0.72

3.8

Results
B)

Viscosity (Poise)

Effect of Methacrylate Chain Length

on Viscosity
1.5
Viscosity
w ith respect
to Chain
Length

1
0.5
0
0

10

15

Carbon Chain Length

Effect of Methacrylate Chain Length on

Polymerization Shrinkage
Polymerization
Shrinkage (%)

A)

20
Shrinkage
w ith respect
to Chain
Length

15
10
5
0
0

10

Carbon Chain

*Plots illustrating the effects of methacrylate chain

length on A) viscosity and B) polymerization shrinkage.

15

Conclusions/Summary
Using allyloxytrimethylsilane yields an efficient
route in the synthesis of POSS-MMA
Incorporation of POSS-MMA into resin matrix
causes decreased viscosity and polymerization
shrinkage (up to a certain point) of neat dental
resin formulations
Viscosity decreased through low weight to volume
ratio
Polymerization shrinkage decreased through
amount and distance of methacrylate bonds
in matrix

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

Acknowledgements
Dr. Buonora
Romina Panoussi/Teresa Phan
Dr. Mason/Dr. Archie
Howard Hughes Medical Institute

References
(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.