Attenuated total
reflectance infrared spectroscopy (ATR-IR) is
used to directly measure the rates of copper-catalyzed 1,3-dipolar
cycloaddition 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 to predict that the areal density at saturation should
scale as Σsaturation ∼ M
w
–1.2 for good solvents, and experimentally
we find M
w
–0.93±0.04 scaling.