Network reinforcement silicas

Mark and his co-workers reported the reinforcement of poly(dimethylsiloxane) networks by silica gel particles [1-6]. For example, bis(silanol)-terminated poly-(dimethylsiloxane) was reacted with tetraethoxysilane in the presence of acid-catalyst to produce the reinforced siloxane networks. The reaction proceeded homogeneously. The content of the silica filler can be controlled by the feed ratio of polysiloxane and tetraethoxysilane. 

Mark, J.E., 1985. Bimodal networks and networks reinforced by the in-situ precipitation of silica. Brit. Polym. J. 17, 144. 

Molecular composites in terms of synthesis The reinforcements are also formed by the in-situ reaction in the matrix polymers. Such methods are another way to pursue the limit of molecular dispersion of reinforcing materials. One example is found in the in-situ precipitation of reinforcing silica in polydimethyl siloxane networks with the sol-gel methods [21], Another example is the direct polycondensation of p-aminobenzoic acid or p-hydroxybenzoic acid from their monomers in solutions of polyarylate [22]. Mechanical properties of the cast films indicated increase in modulus and tensile strength at elevated temperatures. 

Wen, J. Mark, J. E., Synthesis, Structure, and Properties of Poly (dimethylsiloxane) Networks Reinforced by In Situ-Precipitated Silica-Titania, Silica-Zirconia, and Silica-Alumina Mixed Oxides. J.Appl. Polym. Sci. 1995,58, 1135-1145. 

Polydimethylsiloxane-Based Networks Reinforced with In Situ Generated Silica. Polym. Eng. Sci. 2011, 51, 78-86. 

Ning, Y.-P. Tang, M.-Y. Jiang, C.-Y. Mark, J. E. Roth, W. C., Particle Sizes of Reinforcing Silica Precipitated into Elastomeric Networks. J.Appl. Polym. Sci. 1984,29, 3209-3212. 

Mark, J. E. Ning, Y.-P., Effects of Ethylamine Catalyst Concentration in the Precipitation of Reinforcing Silica Filler in an Elastomeric Network. Polym. Bull. 1984,12,413-417. 

Some elucidation of the mechanism of elastomer reinforcement is being obtained by precipitating chemically-generated fillers into network structures rather than blending badly agglomerated filler particles into elastomers prior to their cross-linking. This has been done for a variety of fillers, for example, silica by hydrolysis of organosilicates, titania from titanates, alumina from aluminates, etc. [85-87], A typical, and important, reaction is the acid- or base-catalyzed hydrolysis of tetraethylorthosilicate ... 

A series of six stress-strain cycles with a crosshead rate of 600 mm/min was applied to specimens having a parallel length of 25 mm and a cross-section of 1 x 4 mm2 on a tensile testing machine. The samples were continuously stretched in six hysteresis cycles up to 60% of their elongation at break values, as shown in Fig. 47. This procedure is an established one and widely practiced for elastomeric composites reinforced with fillers such as carbon black and silica, which tend to build a strong filler-filler network [83]. 

Network structure and reaction mechanisms in high pressure vulcanisation (HPV) and peroxide vulcanisation of BR was studied by 13C solid-state NMR [43]. Different samples of polybutadiene (51% trans, 38% cis, and 11 % vinyl) were peroxide cured with dicumyl peroxide on a silica carrier and by the HPV conditions of 250 °C and 293 MPa. The 13C NMR spectra from peroxide and HPV cures were compared to a control samples heated to 250 °C for 6 minutes under atmospheric pressure. Although no new isolated strong peaks were detected in either the peroxide or HPV vulcanisations, small increases in both spectra were observed at 29.5, 36.0, 46.5, and 48.0 ppm. These peaks compare favourably with calculated shifts from structures that arise from main chain radical addition to the pendent vinyl groups. These assignments are further reinforced by the observation that the vinyl carbon concentration is substantially reduced during vulcanisation in both peroxide and HPV curing. Two peaks at 39.5 and 42.5 ppm appear only in the peroxide spectrum. Cis-trans isomerisation was absent in both cures. 

IPNs are also attractive for development of materials with enhanced mechanical properties. As PDMS acts as an elastomer, it is of interest to have a thermoplastic second network such as PMMA or polystyrene. Crosslinked PDMS have poor mechanical properties and need to be reinforced with silica. In the IPNs field, they can advantageously be replaced by a second thermoplastic network. On the other hand, if the thermoplastic network is the major component, the PDMS network can confer a partially elastomeric character to the resulting material. Huang et al. [92] studied some sequential IPNs of PDMS and polymethacrylate and varied the ester functionalities the polysiloxane network was swollen with MMA (methyl methacrylate), EMA (ethyl methacrylate) or BuMA (butyl methacrylate). Using DMA the authors determined that the more sterically hindered the substituent, the broader the damping zone of the IPN (Table 2). This damping zone broadness was also found to be dependant on the PDMS content, and atomic force microscopy (AFM) was used to observe the co-continuity of the IPN. 

The tensile strength of cross-linked polysiloxane elastomers is low, but can be markedly improved by reinforcement with a filler. The material of choice is fumed silica with high surface area, which can increase the strength by a factor of 20. It is thought that the silica particles agglomerate to form a three-dimensional network within the siloxane, greatly reinforcing the stmcture. 

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