The free radical polymerization of styrene (FRPS) is a complex process system with uncertain parameters in its mechanistic model. When the reaction conditions are switched, or the reaction process generates faults, the parameters will change. Therefore, state and parameter estimation (SPE) becomes an important part of the process monitoring and process control for free radical polymerization of styrene. The unscented Kalman filter (UKF) is widely used for nonlinear process systems, but it rarely considers the problem of model parameter uncertainty. UKF can be used for SPE, called UKF-based SPE (UKF-SPE), where the parameters are usually estimated simultaneously as an extension of the state space. However, when the parameters change with system switching, the traditional UKF-SPE cannot detect and track the parameter changes in time, and inaccurate parameters generate modeling errors. To deal with the problem, a UKF-based robust SPE method (UKF-RSPE) for the free radical polymerization of styrene with variable parameters is proposed, introducing a parameter testing criterion based on hypothesis testing and moving windows to directly detect whether the parameters have changed. Based on the detection results, a gradient descent method with adaptive learning rate is used to iteratively update the parameters to speed up the tracking of the parameters and to obtain more accurate parameters and states. Finally, the proposed UKF-based robust SPE is applied to free radical polymerization of styrene in a jacketed continuous stirred tank reactor. The experimental results verify the effectiveness and robustness of the method, which can track the parameters faster and obtain more accurate states.