Dynamics of living polymers

We study theoretically the dynamics of living polymers which can add and subtract monomer units at their live chain ends. The classic example is ionic living polymerization. In equilibrium, a delicate balance is maintained in which each initiated chain has a very small negative average growth rate (velocity) just sufficient to negate the effect of growth rate fluctuations. This leads to an exponential molecular weight distribution (MWD) with mean . After a small perturbation of relative amplitude , e.g. a small temperature jump, this balance is destroyed: the velocity acquires a boost greatly exceeding its tiny equilibrium value. For the response has 3 stages: (1) Coherent chain growth or shrinkage, leaving a highly non-linear hole or peak in the MWD at small chain lengths. During this episode, lasting time , the MWDs first moment and monomer concentration m relax very close to equilibrium. (2) Hole-filling (or peak decay) after . The absence or surfeit of small chains is erased. (3) Global MWD shape relaxation after . By this time second and higher MWD moments have relaxed. During episodes (2) and (3) the fast variables ( ) are enslaved to the slowly varying number of free initiators (chains of zero length). Thus fast variables are quasi-statically fine-tuned to equilibrium. The outstanding feature of these dynamics is their ultrasensitivity: despite the perturbations linearity, the response is non-linear until the late episode (3). For very small perturbations, , response remains non-linear but with a less dramatic peak or hole during episode (1). Our predictions are in agreement with viscosity measurements on the most widely studied system, -methylstyrene.Received: 23 September 2003PACS: 82.35.-x Polymers: properties; reactions; polymerization - 05.40.-a Fluctuation phenomena, random processes, noise, and Brownian Motion - 87.15.Rn Biomolecules: structure and physical properties; Reactions and kinetics; polymerization