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Preparation of silica-PS composite particles and their application in PET
Authors:Wu Tianbin
Institution:State Key Laboratory of Heavy Oil Processing, Faculty of Chemical Engineering, China University of Petroleum, 18 Fuxue Road, Changping, 102249 Beijing, PR China
Abstract:To investigate how the superfine particles disperse in the polymers, the paper presented the preparation of monodisperse silica particles by Stöber method, and then grafted by γ-methacrylic propyl trimethoxysilane (MPS) as a coupling agent. Using these modified particles, the more stable silica-PS superfine composite particles with higher monodispersity than these of previous reports are prepared and reported through dispersion polymerization (DP) method, whose morphology is investigated with transmission electron microscope (TEM). Their high stability is provided from the bonding of Cdouble bond; length as m-dashC groups of MPS to the silanol groups on the surface of silica particles from FTIR.Using this DP process, the influence of different size grafted silica particles on the morphology, polystyrene (PS) encapsulation behavior and the distribution in these composite particles have been investigated. When the grafted silica size is in nanoscale or less than 54 nm, the spherical shape of neither silica particles nor their composite particles is regular, but they can homogeneously disperse in polystyrene. As the size (dn) of grafted silica particles increase to submicrometer (or 100 nm < dn < 1000 nm), their coefficient variance of size distribution (Cv) ranges from only 9.0% to 1.5%. These obtained particles are completely encapsulated by PS with more regular shape, and have their Cv below 7%. When the size of silica particles reaches 380 nm, their Cv obviously reduces to 2.5%, and specially, the number of grafted silica particles approaches to one in each of the composite particles. But, when the silica size reaches 602 nm, PS can hardly encapsulate grafted silica particles and free silica particles appear in reactive system.Furthermore, using the silica particles of 380 nm, a series of core-shell structured superfine composite particles of 640-1100 nm with Cv lower than 11% are obtained. Under the set conditions, the preparing factors on these composite particles using 380 nm grafted silica particles is discussed, and the best reaction condition for the well-dispersed and regular periphery silica-PS composite particles is optimized as, the additions amounts of PVP, styrene, AIBN, grafted SiO2 and H2O are 0.23 mmol L−1, 0.60 mol L−1, 6.10 mmol L−1, 0.10 mol L−1 and 5.50 mL, respectively. Under this case, the composite particles can be prepared with Cv below 8%.At last, these composite particles are mixed with poly(ethylene terephthalate) (PET) to investigate their nucleation effect. Results show that all different size particles can promote PET’s crystallization and enhance the crystallization rate, and PET’s crystallization temperature (Tmc) is obviously enhanced from 193 to 205 °C through differential scanning calorimetry (DSC). It is strongly suggested that different silica size level all play nucleation role in PET, and thus explain the nucleation effect of multiscale inorganic particles.
Keywords:Dispersion polymerization  Composite particles  Morphology  Polystyrene  Encapsulation  Crystallization
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