Mechanism of chain propagation for the synthesis of polyoxymethylene dimethyl ethers

Polyoxymethylene dimethyl ethers(PODE)were synthesized from the reaction of paraformaldehyde with dimethoxymethane(DMM)over different acid catalysts at different conditions.Products were found to follow the Schulz-Flory distribution law.The chain propagation proceeds through the insertion of an individual segment of CH2O one by one,while the simultaneous insertion of a few CH2O segments or their assembly is unlikely.Due to the restriction of this law,it is difficult to increase the selectivity to the desired products(e.g.,PODE3 4).

Studies on polyoxymethylene dimethyl ethers production from dimethoxymethane and 1,3,5-trioxane over SO_(4)^(2-)/ZrO_(2)-TiO_(2)

Polyoxymethylene dimethyl ethers(OMEs)with physical properties similar to those of diesel has received significant attention as green additives for soot emission suppression.Herein,series of SO_(4)^(2-)/ZrO_(2)-TiO_(2)catalysts were developed for OMEs production from dimethoxymethane(DMM)and1,3,5-trioxane through sequential formaldehyde monomer insertion into C-O bond of DMM.Not Lewis but Bronsted acid sites were identified to be active for the decomposition of 1,3,5-trioxane into formaldehyde unit,however,both of them are effective for the chain propagation of DMM via formaldehyde unit insertion into C-O bond.Kinetic studies indicated each chain growth step exhibited the same parameters and activation barrier on corresponding Bronsted and Lewis acid sites due to the same reaction mechanism and very similar chemical structure of OMEs.Also,the catalytic stability investigation suggested the deactivation behavior was derived from the carbon deposition,and the decay factor could be exponentially correlated with the amount of coke accumulation.

The estimation of lower refractivity uncertainty from radar sea clutter using the Bayesian-MCMC method

The estimation of lower atmospheric refractivity from radar sea clutter（RFC） is a complicated nonlinear optimization problem.This paper deals with the RFC problem in a Bayesian framework.It uses the unbiased Markov Chain Monte Carlo（MCMC） sampling technique,which can provide accurate posterior probability distributions of the estimated refractivity parameters by using an electromagnetic split-step fast Fourier transform terrain parabolic equation propagation model within a Bayesian inversion framework.In contrast to the global optimization algorithm,the Bayesian-MCMC can obtain not only the approximate solutions,but also the probability distributions of the solutions,that is,uncertainty analyses of solutions.The Bayesian-MCMC algorithm is implemented on the simulation radar sea-clutter data and the real radar seaclutter data.Reference data are assumed to be simulation data and refractivity profiles are obtained using a helicopter.The inversion algorithm is assessed（i） by comparing the estimated refractivity profiles from the assumed simulation and the helicopter sounding data;（ii） the one-dimensional（1D） and two-dimensional（2D） posterior probability distribution of solutions.

Nondilute 1,2-Dichloroethane Solution of Poly(9,9-dioctylfluorene-2,7-diyl)：A Study on the Aggregation Process

Molecular aggregates in conjugated polymer（CP） solution can propagate into mesoscale morphology of the relevant film and further dominate the optoelectronic property. Herein, we probed the aggregation behavior of poly（9,9-dioctylfluorene-2,7-diyl）（PFO） and studied its influence on the photophysical property in 1,2-dichloroethane（DCE） solution, where the contents of β-phase or-aggregates increased with prolonged aging time. Thereinto, high quality β-film was fabricated from DCE solution with critical aggregate time of 6 min. The film exhibited excellent surface morphology and characteristic emission of β-phase. Meanwhile, films prepared from aged DCE solutions exhibited high crystallinity, which was promising to obtain higher photoluminance efficiency and charge transport ability simultaneously. Therefore, it is significant to get deep insight into the aggregation behavior of CP, which is involved not only with the solution-processing technology of plastic device, but also with the optoelectronic property of CP.