Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27695, United States.
J Am Chem Soc. 2011 Nov 9;133(44):17567-9. doi: 10.1021/ja2081636. Epub 2011 Oct 12.
We employ Monte Carlo computer simulations to investigate the simultaneous controlled radical polymerization in solution and from a flat surface. The bulk polymers grow at faster rates and possess narrower molecular weight distribution than polymers initiated from flat, impenetrable surfaces. The rate of surface-initiated polymerization depends on the density of initiator sites. Our results provide evidence that the assumption that the molecular weight of surface-initiated polymers is equal to that of polymers grown in bulk, invoked often in determining the grafting density of surface-bound polymers, is generally invalid.
我们采用蒙特卡罗计算机模拟的方法研究了溶液中和平面表面上自由基聚合的同步控制。本体聚合物的生长速率较快，分子量分布较窄，而从平面、不可渗透的表面引发的聚合物则相反。表面引发聚合的速率取决于引发剂位点的密度。我们的结果表明，通常用于确定表面结合聚合物接枝密度的假设，即表面引发聚合物的分子量等于本体聚合物的分子量，通常是无效的。
