| The bulk ring-opening copolymerization of octamethylcyclotetrasiloxane (D4) with functional siloxane monomers, such as N-p-aminoethyl-y-aminopropylmethy--ldimethyoxysilane(APAEDMS), can prepare a wide variety of silicones, especially amino-silicone oil series. Amino-silicone oil series have many advantages such as softness, stability and flexibility. Besides these advantages, there are still several advantages in its synthesis process such as environmental friendliness, non-polluting and low-cost. Amino-silicone oil can be used as fabric softening agent not only in light industry, but also in other industries such as electronic industry, mechanical industry etc. Unfortunately few systemic fundamental studies on copolymerization of D4 with APAEDMS were reported in literature by far. Therefore, the study of bulk ring-opening copolymerization is of important theoretical meaning and has an evident application background.In order to develop polymerization product of high quality and environmental protection in the industrial application, the thesis focuses on perfecting polymerization mechanism, providing novel research method in polymerization engineering and extending its applied scope. Moreover, this dissertation chooses the bulk copolymerization of D4 with APAEDMS as specific polymerization system and does relative overall simulative research by using various methods-experiment, theory, Monte Carlo simulation et al, from the macroscopic and microscopic viewpoint. Based on the simulative results above, the dissertation also carries out the industrial application research of amino-silicone oil synthesis via bulk ring-opening copolymerization of D4 with APAEDMS. The thesis includes several aspects as follows:1. The bulk polymerization kinetics and rules of D4 with APAEDMS were firstly investigated with experimental and theoretical methods in the thesis. The polymerization kinetics was investigated in two phases by using three mathematic disposing methods: (1) experimental data fit based on polymerization mechanism, (2) semi-empirical and semi-theoretic data approximate method, (3) optimization algorithm method. The first phase was conventional kinetics simulation. The second phase was the foundation of reaction-diffusion model. The detailed research results are as below:(1). The elemental reactions of bulk copolymerization of D4 with APAEDMS were put forward based on experimental results. The copolymerization mechanism was an anionic chain-reaction mechanism with the characteristic of step polymerization.(2). The kinetic equations of bulk ring-opening copolymerization of D4 with APAEDMS were deduced via optimization algorithm method based on model idea of classical kinetics. The equations were tested by simulating bulk copolymerization of D4 with APAEDMS which acts as the synthesis way of amino-silicone oil softening-agent in industry when the polymerization is in the state of equilibrium. The simulation results show that the experimental data coincides with the calculated data during the prophase of polymerization very well, and some discrepancy in the anaphase of polymerization, but the tendency is consistent.(3). Because of the polymerization character that the polymerization behaviors approach to the general anionic polymerization with the mass ratio of APAEDMS decreasing, the bulk anionic copolymerization kinetics of D4 with APAEDMS was put forward and the application range of the model was indicated.2. According to high viscosity of bulk-copolymerization of D4 with APAEDMS, the multisyphon flow physical model was put forward. Based on the free volume and chemical reaction kinetic theories, a new computational model was established to simulate the multisyphon flow. In the model, the united influences of reaction and diffusion were reviewed and analyzed. The model was applied to simulate bulk copolymerization of D4 with APAEDMS which acts as the synthesis way of amino-silicone oil softening-agent in industry and agreed well with the results even in the anaphase of polymerization.
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