Polymerization intercalative

M. G. Kanatzidis, M. Humbbard, L. M. Tonge, T. J. Marks, H. 0. Marcy, C. R. Kannewurf, In situ intercalative polymerization as a route to layered conducting polymer-inorganic matrix microlaminates, polypyrrole and polythiophene in FeOCl, Synthetic Metals, vol. 28, pp. 89-95,1989. 

J. Zhang, L. Wang, A. Wang, Preparation and properties of chitosan-g-poly(acrylic acid)/montmorillonite superabsorbent nanocomposite via In situ intercalative polymerization, Ind. Eng. Chem Res., vol. 46, pp. 2497-2505, 2007. 

In Situ Intercalative Polymerization A variety of polymer nanocomposites have been prepared using this method, that is, PS/graphene, PMMA/expanded graphite, poly(styrene sulfonate) (PSS)/layered double hydroxyl (LDH), PI/LDH, and PET/LDH. 

The main techniques that can be used to prepare polymer/clay nanocomposites are (a) melt mixing the layered clay with polymer, (b) mixing the layered clay with solution of polymer followed by solvent removal, and (c) in situ intercalative polymerization, where the monomer is first intercalated in the clay and subsequently polymerized in situ. 

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. 

Figure 6.1 Structural model for the Intercalated polypyrrole chains within the van der Waals gap of FeOCI. (Reprinted with permission from Solid State Ionics, In situ intercalative polymerization chemistry of FeOCI. Generation and properties of novel, highly conductive Inorganic/organic polymer microlaminates by M. G. Kanatzidis, H. O. Marcy, W. J. McCarthy et al., 594-608, 1-3. Copyright (1989) Elsevier Ltd)...

G. J.-F. Demets and H. E. Toma, Strong electric fields promote oriented intercalative polymerization of pyrrole inside the lamellar matrices of vanadium pentoxide, Electrochim. Comm., 5, 73-77 (2003). 

H. Nakajima and G. Matsubayashi, Intercation/polymerization of the anilinium cation in the VOPO4 interlayer space, Chem. Lett., 22,423-426 (1993). 

C.-G. Wu, D.C. DeGroot, H.O. Marcy, J.L. Schindler, C.R. Kannewurf, Y.-J. liu, W. Hirpo, and M.G. Kanatzidis, Redox intercalative polymerization of aniline in V2O5 xerogel. The postintercalative intralamellar polymer growth in polyaniline/metal oxide nanocomposites is facilitated by molecular oxygen, Chem. Mater., 8, 1992-2004 (1996). 

D.W. Kim, J. Kumar, and A. Blumstein, Ordered assembly of conjugated ionic polyacetylenes within clay nanoplatelets Layer-hy-layer assembly and intercalative polymerization. Applied... 

Okamoto, M., Morita, S., Taguchi, H., Kim, Y. H., Kotaka, T., and Tateyama, H., Synthesis and structure of smectic clay/poly(methyl methacrylate) and clay/polystyrene nanocomposites via in situ intercalative polymerization. Polymer, 41, 3887-3890 (2000). 

Uthirakumar, R, Hahn, Y. B., Nahm, K. S., and Lee, Y.-S., Preparation of polystyrene/ montmoriUonite nanocomposites using a new radical initiator-montmorillonite hybrid via in situ intercalative polymerization, Eur. Polym. J., 40, 2437-2444 (2004). 

Paul, M., Delcourt, C., Alexandre, M., Degee, P., Monteverde, R, Rulmont, A., and Dubois, P. (2005). (Plasticized) Polylactide/(organo-)clay nanocomposites by in situ intercalative polymerization. Macromol. Chem. Phvs.. 206,484-498. 

Table I. (Polymer)xV205 nH20 Materials Prepared by Intercalative Polymerization Reactions of Monomers with V205 nH20.

During intercalative polymerization, the vanadium oxide framework is reduced to form centers. The unpaired electrons in these d centers are fairly localized (small polarons), and hop between the vanadium sites, thus giving the layers a finite thermally activated n-type conductivity. Assuming all the electrons removed by oxidation from the monomers are transferred to V2O5, the degree of reduction of the V2O5 framework should be... 

A novel microwave method for preparing V O /PEDOT nanocomposites has been proposed by Murugan et al. [71], which significantly shortened the reaction time to several minutes. Compared with the conventional 12 h of refluxing for intercalative polymerization, the microwave-assisted oxidation polymerization proceeds rapidly, enabling the expansion of the... 

Several techniques such as intercalation of polymer from solution, in-situ intercalative polymerization, melt intercalation, direct mixture of polymer and particulates, template synthesis, in-situ polymerization and solgel process, are being employed for the preparation of polmer-layered silicate nanocomposites. Among them the most common and important approaches are in-situ polymerization, solution-induced intercalation method, and melt processing method, which are briefly discussed below. 

Preparation of polymer-day nanocomposites by in situ polymerization (sometimes called intercalative polymerization or polymerization compounding) circumvents the enthalpic and entropic barriers that prohibit the intercalation of nonpolar polyolefins into polar clays. Since supported olefin polymerization catalysts are desirable anyway in high-volume polyolefin manufacturing (see Section 5.1.1), the design of clay-supported catalysts to prepare nanocomposites can achieve both goals at once. In the late 1990s, researchers... 

The first polypropylene/clay nanocomposite made by intercalative polymerization was reported by Qi et al. Sodium montmorillonite was ion exchanged with (hexadecyl/ octadecyl)trimethylammonium, then vacuum-dried at llO C. The organoclay was ground... 

Zhang, R, Li, S., Karaki, T., and Adachi, M. 2005. Synthesis of p>olyethylene/montmorillon-ite nanocomposites by in-situ intercalative polymerization. J meseJomn ofj iedPltt/sics 44 658-661. 

He, A. H., Wang, L., Li, J., Dong, J.-Y, and Han, C. C. 2006. Preparation of exfoliated isotactic polypropylene/alkyl-triphenylphosphonium-modified montmorillonite nanocomposites via in situ intercalative polymerization. Polymer 47 1767-1771. 

Dong, J.-Y. and Hu, Y. 2009. Polymerized delamination of clay in polyolefins From efficient intercalative polymerization to product-retrievable nanocomposite preparation. Polymeric Materials Science and Engineering 100 296-297. 

Huang, Y, Yang, K., and Dong, J.-Y. 2007. An in situ matrix functionalization approach to structure stability enhancement in pKjlyethylene/montmorillonite nanocomposites prepared by intercalative polymerization. Polymer 48 4005-4014. 

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