Polymer nanocomposites melt intercalation method

This is a highly polar polymer and crystalline due to the presence of amide linkages. To achieve effective intercalation and exfoliation, the nanoclay has to be modified with some functional polar group. Most commonly, amino acid treatment is done for the nanoclays. Nanocomposites have been prepared using in situ polymerization [85] and melt-intercalation methods [113-117]. Crystallization behavior [118-122], mechanical [123,124], thermal, and barrier properties, and kinetic study [125,126] have been carried out. Nylon-based nanocomposites are now being produced commercially. 

Other methods to prepare nanocomposites include a solvent-assisted process, whereby a cosolvent is employed to help carry the monomer into the galleries and is subsequently removed from the polymer system, and direct polymer melt intercalation methods, which involve the direct addition of nanoclays to a polymer melt under shear conditions atelevated temperatures, allowing their direct exfoliationintothepolymer[5]. 

In the melt mixing method, nanoclays are incorporated into the polymer in the molten state. This technique has considerable advantages over either the in situ intercalative polymerization or polymer solution intercalation techniques. Firstly, this method is environmentally benign due to the absence of organic solvents. Secondly, melt processing is compatible with current industrial processes, such as extrusion and injection moulding. The melt intercalation method allows the use of biopolymers that were not suitable for in situ polymerization. This has been the most widely used method in the literature for obtaining PLA/clay nanocomposites. " ... 

A number of methods have frequently been employed in the production of nanocomposite materials. These include solution intercalation, melt intercalation, polymerization, sol-gel, deposition, magnetron sput-tering, laser, ultrasonication, supercritical fluid, etc. In PHA nanocomposite fabrication, solution intercalation and melt intercalation methods are the most widely explored procedures. However, use of in situ intercalative polymerization, supercritical fluids and electrospinning are shown to be promising and emerging techniques. The performance and quality of a nanocomposite depends on how well the nanofillers disperse or blend into the matrix. Therefore, these methods constitute different strategies to improve the composites thermo-mechanical and physico-chemical properties by enhancing efficient interactions between the nanofiller and the polymer matrices. 

To achieve improved dispersibUity of nanoclay fillers within polymer systems, three familiar methods are commonly used, namely, melt intercalation, solution intercalation, and in situ polymerization. The melt-intercalation method is based on the melting point of polymer matrices and is applied by annealing above the melting point of the polymer (Reddy et al., 2013). This method has been chosen by industrial sectors to produce polymer/clay nanocomposites. However, it is not apphcable to the fabrication of biobased polymer/clay nanocomposites based on thermosetting materials such as epoxy and polyester due to their high viscosities (Wypych and Satyanarayana, 2005 Wang et al., 2014). Therefore, the fabrication of biobased thermosetting polymer/clay nanocomposites is mainly based on solution intercalation or in sim polymerization. 

Shafiee M, Ramazani SAA, Danaei M. Investigation of the gas barrier properties of PP/clay nanocomposite films with EVA as a compatibiliser prepared by the melt intercalation method. Polym-Plast Technol Eng 2010 49 991-995. 

From the above discussion, it can be seen that the method adopted to prepare nanocomposites is highly dependent on the nature of the polymer. When the polymers or monomers are water soluble, they can be incorporated into the pristine LDH without any organo-modification due to their good affinity with the LDH. Additionally, the aqueous environment is compatible with the condition for the synthesis of LDH materials. Therefore, water-soluble polymer-LDH nanocomposites can be prepared using some special methods such as in situ synthesis, ion exchange and reconstruction. In the case of water-insoluble polymers and monomers, their nanocomposites are usually prepared in orga-nosolvent (solution intercalation method, exfoliation-absorption method and in situ polymerization method) or molten polymer (melt intercalation method). However, emulsion polymerization and suspension polymerization are methods that allow the incorporation of a water insoluble polymer into an LDH in water. The following sections are devoted to polymer-LDH nanocomposites obtained via emulsion polymerization and suspension polymerization. 

As mentioned in the Introduction, the further property improvement of PBT can be done by the PLS technique, especially by the polymer melt intercalation method. In this session, we discuss on the preparation and characterization of PBT/organic montmorillonite (MMT) (PBT/organoclay) nanocomposites using three kinds of organoclays, each possessing different ammonium cations, in order to see their effects on the morphology of the PBT hybrids. Table 9.2 shows the related structure information of three typical kinds of commercial organoclays produced by Southern Clay, Texas, USA (whose trade names are Cloisite 6A, Cloisite lOA and Cloisite 30B). 

Since the possibility of direct melt intercalation was first demonstrated [11], melt intercalation has become a method of preparation of the intercalated polymer/ layered silicate nanocomposites (PLSNCs). This process involves annealing, statically or under shear, a mixture of the polymer and organically modified layered fillers (OMLFs) above the softening point of the polymer. During annealing, the polymer chains diffused from the bulk polymer melt into the nano-galleries between the layered fillers. 

In the case of mica-type layered silicates it has been recently demonstrated that nanocomposites (both intercalated and delaminated) can be synthesized by direct melt intercalation even with high molecular weight polymers [7-18]. This synthetic method is quite general and is broadly applicable to a range of commodity polymers from essentially non-polar polystyrene, to weakly polar polyethylene terephthalate), to strongly polar nylon. Nanocomposites can, therefore, be processed using currently available techniques such as extrusion, thus lowering the barrier towards commercialization. 

Intercalation of poly(ethylene oxide) into a lithium-ion exchanged clay gives an interesting class of layered silicate nanocomposites that are lithium-ion electrolytes. Componnds have been prepared by intercalation from methanol/water solutions and by melt intercalation. Melt intercalation typically gives samples with higher polymer contents than the solution method and with higher lithium-ion conductivity though the conductivity is probably stiU too low for practical applications. 

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. 

The manufacturing methods for PLA nanocomposites include intercalation of polymer from solution, polymer melt intercalation and intercalation of a suitable monomer and subsequent in situ polymerization. 

Another route is polymer melt intercalation. This method, an environmentally benign one, uses all types of polymers as well as being compatible with practicing polymer industrial processes such as injection molding, being the most popular procedure to prepare nanocomposites for industrial applications. In this method, polymers, and layered hosts are annealed above the softening point of the polymer [73]. 

Polypropylene (PP) is one of the most widely used plastics in large volume. To overcome the disadvantages of PP, such as low toughness and low service temperature, researchers have tried to improve the properties with the addition of nanoparticles that contains p>olar functional groups. An alkylammonium surfactant has been adequate to modify the clay surfaces and promote the formation of nanocomposite structure. Until now, two major methods, i.e., in-situ polymerization( Ma et al., 2001 Pirmavaia, 2000) and melt intercalation ( Manias et al.,2001) have been the techniques to prepare clay/PP nanocomposites. In the former method, the clay is used as a catalyst carrier, propylene monomer intercalates into the interlayer space of the clay and then polymerizes there. The macromolecule chains exfoliate the silicate layers and make them disperse in the polymer matrix evenly. In melt intercalation, PP and organoclay are compounded in the molten state to form nanocomposites. 

Polymer nanocomposites are generally prepared by three methods solution intercalation, in-situ polymerisation or melt compounding. 

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