Title: Factors that Affect Polymer Brush Formation
Description: The use of polymer brushes (long polymer chains anchored at their end to a surface or an interface) as a robust approach to control surface properties has generated significant interest in recent years. The stretched conformation of polymer brushes results in unique aggregation, phase, and dynamic behaviors, therefore, they have been used to stabilize colloidal particles and applied in numerous innovative biomedical applications: targeted magnetic hyperthermia, targeted drug delivery, and genotyping. The main goal of this thesis is to shed light on the key factors that affect the formation of these brushes in solution on solid surfaces. In Chapter 3, attenuated total reflectance infrared spectroscopy (ATR-IR) is used to directly measure the rates of the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions between alkyne-terminated polystyrene and poly(n-butyl acrylate) and azide-functional substrates in the good solvent DMF. Four regimes of behavior are observed: initially, the reaction rate is diffusion-controlled scaling with t^1/2; in the crossover regime at the onset of chain overlap, the rate scales with ln(t); the rate then accelerates briefly; and finally, in the terminal or penetration-limited regime, the logarithm of areal density scales linearly with time.

Kinetic behavior in the diffusion-limited, crossover, and penetration-limited regimes corresponds well to the predictions of Ligoure and Leibler. The blob model suggests that the acceleration in rate is due to lateral chain contraction during the mushroom to brush transition. A theory is presented which predicts that the areal density at saturation should scale as Σsaturation ∼ MW^1.2 for good solvents, and experimentally we find MW^(−0.93±0.04) scaling. In Chapter 4, the effect of symmetry of the CuAAC reaction is investigated for the reaction of end-functional polystyrene and solid surfaces modified with self-assembled monolayers (SAMs). The polymer grafting density on azide-functional substrates is about two times higher than the polymer density on alkyne-functional surfaces. This asymmetry in the reaction density is caused by the difference in the mobility of the alkyne groups between the two systems. While the reaction stoichiometry requires one alkyne and one azide, the reaction mechanism involves two alkyne groups and one azide group in the formation of a stable triazole ring.

When the alkyne groups are on the surfaces, their mobility is significantly reduced, preventing the formation of the triazole rings and consequently decreasing the amount of polymer grafted. Increasing the alkynes’ mobility by either extending the thickness of the alkyne monolayer or adding free 1-pentyne improves the polymer density on alkyne-functional silica substrates. The presence of free 1-pentyne also increases the polymer density on alkyne-functional wafers containing a preexisting polymer brush. This study shows that the placement of each functional group in the CuAAC reaction is important in surface modification applications. In Chapter 5, a universal model to quantify the amount of tails vs. loops during brush formation of telechelic polymers is proposed. This model involves the synthesis of telechelic polymers bearing a degradable unit in the middle of each chain via ATRP. Several reaction schemes are suggested for the synthesis of the required bi-functional ATRP initiators with degradable units.

The amount of singly (tails) vs. doubly (loops) bound chains is quantified by comparing the brush heights, measured by ellipsometry, before and after degradation.