Use of a Third Component

The last main route to produce CNT/polymer composites with well-dispersed CNTs is based on the use of a third component, assisting the optimum incorporation of exfoliated CNTs into the polymer matrix, preferably without altering the intrinsic properties of the CNTs. In most of the cases reported in literature, this third component is a surfactant, but it can also be a conductive polymer, as exemplified in the next paragraph. 

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Medium Boiling Esters. Esterificatioa of ethyl and propyl alcohols, ethylene glycol, and glycerol with various acids, eg, chloro- or bromoacetic, or pymvic, by the use of a third component such as bensene, toluene, hexane, cyclohexane, or carbon tetrachloride to remove the water produced is quite common. Bensene has been used as a co-solvent ia the preparatioa of methyl pymvate from pymvic acid (101). The preparatioa of ethyl lactate is described as an example of the general procedure (102). A mixture of 1 mol 80% lactic acid and 2.3 mol 95% ethyl alcohol is added to a volume of benzene equal to half that of the alcohol (ca 43 mL), and the resulting mixture is refluxed for several hours. When distilled, the overhead condensate separates iato layers. The lower layer is extracted to recover the benzene and alcohol, and the water is discarded. The upper layer is returned to the column for reflux. After all the water is removed from the reaction mixture, the excess of alcohol and benzene is removed by distillation, and the ester is fractionated to isolate the pure ester. 

The treatment of blends as a two phase system opened up an interesting field of modifying the composite properties by the use of a (third component within the interface boundaries, which is termed as compatibilizers [1]. Such modifications are still being extended to the formation of microgel out of the interaction between the two blend partners having a reactive for functionalities. This type of interchain crosslinking does not require any compatibilizer to enhance the blend properties and also allows the blends to be reprocessed by further addition of a curative to achieve still further improved properties [3,4]. Such interchain crosslinking is believed to reduce the viscoelastic mismatch between the blend partners and, thus, facilitates smooth extrusion [5,6]. 

Medium Boiling Esters. Esterification of ethyl and propyl alcohols, ethylene glycol, and glycerol with various acids, e.g.. chloro- or bromoaceiic. or pyruvic, by the use of a third component such as benzene, toluene, hexane, cyclohexane, or carbon tetrachloride to remove the water produced is quite common. 

Most of the other studies, describing methods based on the use of a third component to facilitate the incorporation of CNTs into a polymer matrix, report on the use of surfactants to reach the mentioned goal. The use of surfactant is based on the physics of colloidal systems. Bundles of CNTs are sonicated in the presence of a surfactant in an aqueous medium. During sonication, the provided mechanical energy overcomes the van der Waals interactions in the CNT bundles and leads to CNT exfoliation, as shown in Figure 2.11, whereas, at the same time, surfactant molecules adsorb onto the surface of the CNT walls. The colloidal stability of the dispersion of CNTs with adsorbed surfactant molecules on their surface is guaranteed by electrostatic, and/or steric repulsion. 

Finally, the third main approach is based on the use of a third component, which, most frequently, is a surfactant. The methods inspired by this strategy are mainly based on latex technology. This route to incorporate CNTs into a polymer matrix appears to be very promising, since it allows the production of conductive nanocomposites with a relatively homogeneous dispersion of CNTs into the polymer matrix, low percolation thresholds, as well as good conductivity levels. Furthermore, it is very flexible with respect to the choice of the polymer matrix it can actually be applied to any polymer that can be either synthesized by (mini)emulsion polymerization, or brought into a polymer latex form in an artificial way. 

The equihbrium shown in equation 3 normally ties far to the left. Usually the water formed is removed by azeotropic distillation with excess alcohol or a suitable azeotroping solvent such as benzene, toluene, or various petroleum distillate fractions. The procedure used depends on the specific ester desired. Preparation of methyl borate and ethyl borate is compHcated by the formation of low boiling azeotropes (Table 1) which are the lowest boiling constituents in these systems. Consequently, the ester—alcohol azeotrope must be prepared and then separated in another step. Some of the methods that have been used to separate methyl borate from the azeotrope are extraction with sulfuric acid and distillation of the enriched phase (18), treatment with calcium chloride or lithium chloride (19,20), washing with a hydrocarbon and distillation (21), fractional distillation at 709 kPa (7 atmospheres) (22), and addition of a third component that will form a low boiling methanol azeotrope (23). 

As mentioned previously, ternaiy mixtures can be represented by 125 different residue curve maps or distillation region diagrams. However, feasible distillation sequences using the first approach can be developed for breaking homogeneous binaiy azeotropes by the addition of a third component only for those more restricted systems that do not have a distillation boundaiy connected to the azeotrope and for which one of the original components is a node. For example, from... 

In the previous sections, we indicated how, under certain conditions, pressure may be used to induce immiscibility in liquid and gaseous binary mixtures which at normal pressures are completely miscible. We now want to consider how the introduction of a third component can bring about immiscibility in a binary liquid that is completely miscible in the absence of the third component. Specifically, we are concerned with the case where the added component is a gas in this case, elevated pressures are required in order to dissolve an appreciable amount of the added component in the binary liquid solvent. For the situation to be discussed, it should be clear that phase instability is not a consequence of the effect of pressure on the chemical potentials, as was the case in the previous sections, but results instead from the presence of an additional component which affects the chemical potentials of the components to be separated. High pressure enters into our discussion only indirectly, because we want to use a highly volatile substance for the additional component. 

A factor analysis of the Raman spectra of a set of linear polyethylenes identified the existence of a third component in addition to the pure crystalline and pure amorphous components [78]. The characteristics of the Raman spectrum of the interphase were very similar to that of the crystalline spectrum indicating that the interphase retains a significant degree of order. Using the Raman method, the content of interphase in linear polyethylenes was found to increase with molecular weight [74—76,78]. For molecular weights below... 

The introduction of a third component into the reaction system necessitates the use of copolymer nomenclature which can logically be developed Irom the foregoing rules, as the examples below illustrate. The copolymer derived from reaction of ethylene glycol with a mixture of terephthalic and isophthalic acids would be named ... 

The metastable, 2-D packing motif presented by some Pcs adsorbed on Ag(l 11) has also prompted the utilization of such ensembles as templates for the organization of complementary guest molecules such as fullerenes [193] or corannulenes [194], giving rise to the formation of two-component, 2-D architectures. More recently, a similar approach has been used to prepare a surface-supported, three-component system. In fact, the immersion of an Au substrate into a solution containing both a ZnPc and a Zn porphyrin led to the formation of a highly ordered, 2-D arrangement of both Pc and porphyrin which can act as a bimolecular chessboard toward the supramolecular assembly of a third component (i.e., C6o fullerene) which is selectively trapped in the open spaces (Fig. 25) [195],... 

Equation 11.32 is used to model a single-phase liquid in a ternary system, as well as a ternary substitutional-solid solution formed by the addition of a soluble third component to a binary solid solution. The solubility of a third component might be predicted, for example, if there is mutual solid solubility in all three binary subsets (AB, BC, AC). Note that Eq. 11.32 does not contain ternary interaction terms, which ate usually small in comparison to binary terms. When this assumption cannot, or should not, be made, ternary interaction terms of the form xaXbXcLabc where Labc is an excess ternary interaction parameter, can be included. There has been httle evidence for the need of terms of any higher-order. Phase equilibria calculations are normally based on the assessment of only binary and ternary terms. 

The addition of a third component to the metal-alkyl is a widespread practice with MgCI2 catalysts in order to improve their performance and to control the polymer molecular structure. In ethylene polymerization the addition of modifiers (alkyl-halides, Lewis acids such as A1C13, halogens such as I2, and others) is rather limited and is principally used to modify the MWD (see Table 11 in Ref.53)). On the other hand, the addition of modifiers is almost indispensable to obtain satisfactorily stereoregular propylene polymers. The additives used for this purpose are generally electron donor compounds (Lewis bases) and a wide variety has been described in patent and scientific literature. 

Equations for the KBIs in ternary mixtures are available in matrix form [2]. Explicit equations are obtained here which will allow us to analyze interesting features of ternary mixtures, such as the effect of a third component on the phase behavior of a binary mixture and the effect of a cosolvent (entrainer) on supercritical binary mixtures. Only the former problem is examined in the present paper. The calculations will he carried out for an interesting ternary mixture, namely AA -dimethylformamide-methanol-water, in order to extract information about the intermolecular interactions. In the next section explicit equations for the KB integrals will he derived and applied to the above ternary mixture. Finally, the results obtained will be used to shed some light on the local structure and the intermolecular interactions in the above mixture. 

The definition of compatibility has been differentiated from miscibility since it is concerned with phase-separated polymers and is approached through the attainment of optimum properties for the blend (Bonner and Hope, 1993). Two of the main technologies used to achieve it are the addition of a third component (as discussed above) and reactive blending. The target in using a compatibilizer is the control of the interfacial tension between the components in the melt, translating to interfacial adhesion in the blend after processing. 

Resin beads are synthesized as gel or macroporous materials. The macroporous resins are polymerized in the presence of a third component that is insoluble in the polymer. After this insoluble component is removed, large pores remain that allow the ions to have improved access to the interior pore structure of the beads. Macroporous resins can be useful for large ions like proteins, but they are more expensive, have lower capacity, and are harder to regenerate than the gel resins. However, they are said to be more resistant to thermal and osmotic shock as well as to oxidation and organic fouling than the gel-type resins [4]. 

When triethanolamine is used as a third component in the preliminary chain extension step, at an NC0 0H ratio of 1.5, the resulting product consists of both linear and branched units containing terminal isocyanate groups. Further chain extension, as shown, results in cross-linked structures ... 

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