A Kinetic Monte Carlo Model of Secondary Nucleation of Linear and Short-Branched Polyolefins

We develop a Kinetic Monte Carlo simulation model that extends the Hoffman-Lauritzen (HL) theory for homopolymers to copolymers, by including stems with short chain branches (SCBs), when adsorb onto the crystal growth surface, but block growth over them until they randomly desorb at the rate specified by the HL theory. This simple extension of the HL theory predicts an exponential slowdown in crystalline growth rate with number density of short chain branches. Utilizing established input parameters from the literature, predicted isothermal copolymer growth rates are consistent with the experimental results of Wagner and Phillips across a wide range of crystallization temperatures and SCB levels, without the need for additional adjustable parameters.