Intercalation polystyrene-clay

H.-W. Wang, K.-C. Chang, H.-C.h Chu, S.-J.Liou, and J.-M. Yeh, Significant decreased dielectric constant and loss of polystyrene-clay nanocomposite materials by using long-chain intercalation agent. Journal of Applied Polymer Science, 92 (2004), 2402-10. 

Wang ° used two different organic modifications of the montmorillonite, one contains a styryl monomer on the ammonium ion while the other contains no double bond. A double bond that may be involved in the polymerization reaction is present in the cation of the clay. Polystyrene-clay nanocomposite has been prepared by bulk, solution, suspension, and emulsion polymerization as well as by melt blending. The organic modification as well as the mode of preparation may determine whether the composite is either exfoliated or intercalated. Exfoliation is more likely to occur if the ammonium ion contains a double bond... 

Kamal, M. Uribe Calderon, Jorge. Polystyrene/clay nanocomposites by melt intercalation, vfnfec 64 357-361 (2006)... 

Poly(styrene-fc-butadiene) copolymer-clay nanocomposites were prepared from dioctadecyldimethyl ammonium-exchanged MMT via direct melt intercalation [91]. While the identical mixing of copolymer with pristine montmorillonite showed no intercalation, the organoclay expanded from 41 to 46 A, indicating a monolayer intercalation. The nanocomposites showed an increase in storage modulus with increasing loading. In addition, the Tg for the polystyrene block domain increased with clay content, whereas the polybutadiene block Tg remained nearly constant. 

In the case of LASIP with clay nanoparticles, polystyrene was grafted using a DPE coinitiator. The montmorillonite clay surface and intergallery interfaces were intercalated with 1,1-diphenylethylene (DPE) modified to be an organic cation as shown in Fig. 4. Its intercalation was confirmed by a series of characterization methods including X-ray diffraction (XRD), FT-IR spectroscopy, TGA, and XPS. The results showed a complete replacement of... 

In the work of Wilkie et al.,55,56 oligomers of styrene, vinylbenzyl chloride, and diphenyl vinyl-benzylphosphate and diphenyl vinylphenylphosphate (DPVPP) have been prepared and reacted with an amine and then ion-exchanged onto clay. The resulting modified DPVPP clays have been melted blended with polystyrene and the flammability was evaluated. XRD and TEM observations proved the existence of intercalated nanocomposite structures. Cone calorimeter tests have shown a substantial reduction in the PHRR of about 70% in comparison with pure PS. According to the authors, this reduction was higher than the maximum reduction usually obtained with PS nanocomposites. Other vinylphosphate modified clay nanocomposites were also elaborated. The reduction in PHRR was greater with higher phosphorus content than for DPVPP. Consequently, the reduction in PHRR seemed attributed to both the presence of the clay and to the presence of phosphorus. 

Layered clay nano composites have been prepared by melt intercalation for a variety of polymers, including polystyrene [221], nylon-6 [222], ethylene-vinyl acetate copolymers [223], polypropylene [224], polyimide [225], poly(styrene-fo-butadiene) [226], and PEO [227],... 

Besides melt intercalation, described above, in situ intercalative polymerization of E-caprolactone (e-CL) has also been used [231] to prepare polycaprolactone (PCL)-based nanocomposites. The in situ intercalative polymerization, or monomer exfoliation, method was pioneered by Toyota Motor Company to create nylon-6/clay nanocomposites. The method involves in-reactor processing of e-CL and MMT, which has been ion-exchanged with the hydrochloride salt of aminolauric acid (12-aminodecanoic acid). Nanocomposite materials from polymers such as polystyrene, polyacrylates or methacrylates, styrene-butadiene rubber, polyester, polyurethane, and epoxy are amenable to the monomer approach. 

Hwang et al. [113] synthesized via in situ polymerization high-impact polystyrene (HlPS)/organically modifled montmorillonite (organoclay) nanocomposites. X-ray diffraction and TEM experiments revealed that intercalation of polymer chains into silicate layers was achieved, and the addition of nanoclay led to an increase in the size of the robber domain in the composites. In comparison with neat HIPS, they found that the HIPS/organoclay nanocomposites exhibited improved thermal stabiHly as well as an increase in both the complex viscosity and storage modulus, and they may have been influenced by a competition between the incorporation of clay and the decrease in the molecular weight of the polymer matrix. 

This system does not increase the carbon monoxide or soot produced during the combustion, as many commercial FRs do [233]. Other polymer silicate nanocomposites based on a variety of polymers, such as polystyrene, epoxy and polyesters, have been prepared recently by melt intercalation [236]. A direct synthesis of PVA-clay (hectorite) complexes in water solution (hydrothermal crystallization) was reported [237]. It was assumed that the driving force of this phenomenon, at least kinetically, can be described in terms of a simple diffusion reaction of polymers/monomers into clay-layered structures. 

Figure 16.24 shows the schematic representation of dispersed clay particles in a polymer matrix. Conventionally dispersed clay has aggregated layers in face-to-face form. Intercalated clay composites have one or more layers of polymer inserted into the clay host gallery. Exfoliated polymer/clay nanocomposites have low clay content (lower than intercalated clay composites which have clay content -50%). It was found that 1 wt% exfoliated clay such as hectorite, montmorillonite, or fluorohectorite increases the tensile modulus of epoxy resin by 50-65%. Montmorillonite was used in a two stage process of nanocomposite formation. In the first step, montmorillonite was intercalated with vinyl monomer and then used in the second step to insert polystyrene by in situ polymerization. 

The authors observed that the inclusion complex of CPC with cyclodextrin decomposed at higher temperatures then the pure CPC. A decomposition temperature of 284 °C was observed for this complex, compared to 220 °C for pure CPC. This confirmed the attainment of better thermal stability of the pyridinium modification by complexing with cyclodextrin. The thermal behavior of the polystyrene nanocomposites synthesized using both CPC and the inclusion complex of CPC with cyclodextrin has been demonstrated in Figure 1.18 and is compared with that of the pure polymer. Both the nanocomposites had better thermal stability than the pure polymer however, the thermal performance of inclusion complex-intercalated clay nanocomposites was better than that of the CPC-intercalated clay nanocomposites. The temperature at 5% weight loss was observed to be 33 °C higher for the inclusion complex-intercalated clay nanocomposites as compared to the pure polymer, whereas this increase was 18 °C for the CPC-intercalated clay nanocomposites. 

Nanocomposites of syndiotactic polystyrene (sPS) employing MMT-hexadecyltributylphosphonium [40, 41] and high-impact polystyrene (H1PS)/MMT-hexadecyltriphenylphosphonium [42] were prepared by melt-blending and in situ coordination-insertion polymerization. Partially exfoliated or intercalated materials were obtained in all cases, and a decrease of crystallinity of sPS was observed. However, the presence of clay did not have a strong influence on the sPS thermal transitions. Thermal decomposition of the material was slowed and mechanieal properties were improved in the presence of low organoclay content. Intercalated HIPS nanocomposites were obtained, with improved thermal and flame retardant properties compared to pure HIPS (Figure 3.8). 

Other thermally stable surfactants have been used in the preparation of organoclays to produce PS nanocomposites [57]. Triphenylhexadecylstibonium trifluoromethylsulfonate (Table 3.4) was prepared with sodium montmorillonite to prepare polystyrene nanocomposites by bulk polymerization. The organoclay was not uniformly distributed throughout the polymer matrix, but there was evidence of polymer intercalation and a small amount of clay exfoliation (Figure 3.13). The nanocomposite showed enhanced thermal stability. 

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