The document describes the synthesis of silane-based copolymers to produce polymer-silica stationary phases for use in high-performance liquid chromatography (HPLC). Phenylmaleimide monomers and their copolymers with alkylalkoxysilanes were synthesized. The copolymers were used to coat silica particles and produce polymer-silica nanocomposite particles for use as HPLC stationary phases. The stationary phases were analyzed using techniques such as HPLC, FTIR, fluorescence, NMR and DSC. The copolymer-coated silica materials showed potential for varied selectivity and stability at high temperatures or in aqueous environments depending on the functional groups used.

1. Silane-based Copolymers as Chromatographic
Stationary Phases1
 Objective: To prepare polymer-silica stationary phases with tunable
properties
 Synthesized Monomer
– Phenylmaleimides
 Synthesized Copolymers
– Phenylmaleimide-Alkylalkoxysilanes
 Prepared Polymer-Silica Material
– Polymer-coated Silica Particles
– Polymer-silica Nanocomposite Particles
 Packed HPLC columns

2. Skill Summary – Preparation1
 Synthesis
– Phenylmaleimides (2 steps)
– Copolymer
• Radical polymerization
• Crosslinker - dimaleimide
– Stationary Phase
• Polymer-coated particles
• Polymer-silica composite particles
 Purification
– Crystallization, Evaporation
 Surface Modification
– Encapping, Polymer coating
 Column Packing

3. Skill Summary - Analysis1
 Analysis
– RP-HPLC
– FTIR
– Fluorescence
– NMR
– DSC
0.016
0.014
0.012
OCH3
0.010
0.008
0.006
0.004
0.002
0.000
-0.002
 Potential Stationary Phase Properties
– Varied Selectivity
OCH3
• Controlled by Maleimide Functional Groups
– High Aqueous Separations
• Polar phases
– High Temp Separations
4000 3500 3000 2500 2000 1500 1000
Absorbance
Wavenumbers (cm-1)
N O
O
+ Si
OCH3
OCH3
N Si OCH3
OCH3
O
O
( )
FTIR-ATR
DSC

4. Publications & Presentations
1) Velamakanni, A., Blackwell, D.L., Yang, D., Sonawane, S., Addagulla, S., Major, J.S. “Synthesis and
Characterization of Functionalized Silane-Based Copolymers for Thermally Robust Polymer-Silica Hybrids.”
Polymer Chemistry. 2010, 1, 916.
2) Blackwell, D.L. and J.S. Major, “Thermally Stable Silane-based Copolymer Stationary Phases for Chemical
Separations”, NSYCC Student Symposium, Boston, Massachusetts, May 2009.
3) Blackwell, D.L. and J.S. Major, “Thermally Stable Silane-based Copolymers Stationary Phases for Chemical
Separations”, HPLC Meeting, Baltimore, Maryland, May 2008. (Poster)
4) Blackwell, D.L. and J.S. Major, “Silane-Based Copolymers as Chromatographic Stationary Phases”, Pittcon
Meeting, New Orleans, Louisiana, March 2008. (Poster)
5) Blackwell, D.L. and J.S. Major, “Thermally Stable Silane-based Copolymers as Chromatographic Stationary
Phases”, EAS Meeting, Somerset, New Jersey, November 2007.
6) Blackwell, D.L. and J.S. Major, “Polymer and Polymer-Nanocomposites as Chromatographic Stationary
Phases”, ACS National Meeting, Boston, Massachusetts, August 2007. (Poster)
7) Blackwell, D.L. and J.S. Major, “Chemical Separations Using Silane-Based Copolymers Stationary Phases”,
EAS Meeting, Somerset, New Jersey, November 2006.