The continuous record of monomer and polymer concentrations, C m and C p , and cumulative weight-average mass, M w , furnished by automatic continuous online monitoring of polymerization reactions (ACOMP) has been harnessed to provide feedback to control reactor monomer flow in order to follow a target trajectory M w,t (t) during linear chain growth free radical polymerization. This was achieved without a detailed kinetic model. Two proportionality parameters to pilot the controller, α and p, result from (i) reaction rate = αC m and (ii) M w,inst = pC m , where M w,inst is instantaneous M w . Using Ansatz values for α and p, the controller periodically recomputes these, based on the ACOMP data stream, in order to follow M w,t (t). A histogram of concentration vs M w,inst estimates the molecular weight distribution width. Invoking an instantaneous distribution provides polydispersities. Results are compared to GPC analysis on end products. The concept of "isomorphic reaction pair" is introduced: two reactions that follow the same trajectory under different reaction variables, e.g., varying T at constant [initiator] and varying [initiator] at T = constant. The controller can be used, as is, for high solids reactions, and extended to copolymerization, including for possible control of composition gradients in controlled radical polymerization.

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Monitoring and control of free radical copolymerization using automatic continuous online monitoring of polymerization reactions (ACOMP) with UV detection has been recently achieved. It is difficult, however, to achieve spectral separation of similar monomers with UV alone. Here, nuclear magnetic resonance (NMR) is coupled to ACOMP for the first time and terpolymerization reactions involving acrylamide (Am), sodium acrylate (Ac), and styrene sulfonate (SS) are monitored, and a first attempt at active composition control is made. The NMR resolves the concentrations of Am and Ac, while the UV resolves SS and the sum of Am and Ac. NMR analysis is performed in water, using signal suppression, to eliminate the need for deuterated solvents. From this, instantaneous fractions of each comonomer in the terpolymer are continuously known, along with weight average molecular weight and intrinsic viscosity, IV. Am and Ac have similar reactivities, whereas the reactivity ratio of SS is much larger. Hence, there is high composition drift in batch polymerization and SS is rapidly consumed, leaving a final copolymer of Am and SS to form. Maintaining constant terpolymer composition is taken as a first step toward active control.

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