Polymer head groups

The interactions between nonionic surfactants and nonionic polymers has been much less intensively studied than those for ionic surfactants. The limited number of reports available indicate that there is little evidence to indicate extensive direct surfactant-polymer association in such systems. Considering the size of the hydrophilic groups of most nonionic surfactants, their low erne s, and the absence of significant possibilities for head group-polymer interactions, the apparent absence of substantial interactions is not conceptually difficult to accept. An assertion that binding does not occur under any circumstance, however, would be foolish, given the complexities of polymer and surfactant science in general. 

The acid monolayers adsorb via physical forces [30] however, the interactions between the head group and the surface are very strong [29]. While chemisorption controls the SAMs created from alkylthiols or silanes, it is often preceded by a physical adsorption step [42]. This has been shown quantitatively by FTIR for siloxane polymers chemisorbing to alumina illustrated in Fig. XI-2. The fact that irreversible chemisorption is preceded by physical adsorption explains the utility of equilibrium adsorption models for these processes. 

There are a few exceptions to this general rule. One of the few examples of an effect on polymer stereochemistry was provided by Dais et al.m who found that polymerization of 31 above the cmc initiated by y-irradiation at 25 °C yields polymer composed entirely of syndiolaclic dyads P(m) =0. When the double bond was distant from the polar head group in 32, the tacticity observed was similar to that observed in solution polymerization / ( )-0,18. Polymerization of 31 at higher temperatures (50 °C) initiated by AIBN also showed no sign of tacticity control. The stcrcospccific polymerization of 31 was attributed to organization of the methacrylate moiety on the surface of the micelle. 

It was theorized that cationic initiators containing Si-Cl functions in conjunction with alkylaluminum compounds would lead to polymers with Si-Cl head-groups which subsequently could be useful for the preparation of block copolymers by coupling. The following equations help to visualize this proposition ... 

The key requirements for using Si-Cl functional initiators to produce polymers carrying Si Cl termini by carbenium ion polymerization are i) Si-Cl should be inert toward aUcylaluminum coinitiators, ii) Si-Cl should not react with propagating carbenium ions, in) chain transfer to monomer should be negligible so as to end up with one Si-Cl head-group per polymer chain. 

While these exploratory investigations demonstrate that the original objective, i.e., the synthesis of polyolefins carrying Si-Cl head-groups, is attainable, this objective has not been pursued further because concurrent studies aimed at the synthesis of Si-H termini bearing polymers promised to yield more valuable intermediates with less experimental difficulties. 

An objective in this research was the synthesis of polymers with Si-H head-groups. Thus guided by the results of model experiments (Sect. ILF.) the synthesis of poly(a-methylstyrene)(PaMeSt) with Si-H head-group (HSi-PaMeSt) was undertaken. 

Head-group characterization by quantitative IR spectroscopy indicated 1.0 0.1 Si-H bond per polymer. This key data is evidence for the correctness of the proposition that PaMeSt carrying a Si-H head-group can be obtained by the use of HSi(CH3)2CH2CH29>CH2Cl/Me3Al initiating system. 

Significantly, integration of aromatic protons/Si-H head-group per polymer and demonstrates survival of this bond during polymerization. 

Fig. 31. 2H spectra of a polymer model membrane, cf. Fig. 27b), methyl deuterated at the head group. The spectra are compared for the monomer as well as the polymer lamellar phases at the same temperatures, respectively... 

For instance, the Dow experimental membrane and the recently introduced Hyflon Ion E83 membrane by Solvay-Solexis are "short side chain" (SSC) fluoropolymers, which exhibit increased water uptake, significantly enhanced proton conductivity, and better stability at T > 100°C due to higher glass transition temperatures in comparison to Nafion. The membrane morphology and the basic mechanisms of proton transport are, however, similar for all PFSA ionomers mentioned. The base polymer of Nation, depicted schematically in Figure 6.3, consists of a copolymer of tetrafluoro-ethylene, forming the backbone, and randomly attached pendant side chains of perfluorinated vinyl ethers, terminated by sulfonic acid head groups. °... 

Schematic depiction of the structural evolution of polymer electrolyte membranes. The primary chemical structure of the Nafion-type ionomer on the left with hydrophobic backbone, side chains, and acid head groups evolves into polymeric aggregates with complex interfacial structure (middle). Randomly interconnected phases of these aggregates and water-filled voids between them form the heterogeneous membrane morphology at the macroscopic scale (right).

Variations of R with A suggest a two-step hydration process solvation and formation of disconnected water clusters centered on polar head groups, followed by the formation of a continuous hydrogen-bond network. At low A, Ri depends logarithmically on co, suggesting bidimensional diffusion of protons in the interfacial region between polymer and water. 

The overall objective of these studies is to unravel mechanisms of interfacial PT. This requires identification of collective coordinates (or reaction coordinates) and transition pathways of transferring protons. Differences in activation energies and rates of corresponding mechanism due to distinct polymer constituents, acid head groups, side chain lengths, side chain densities, and levels of hydration have to be examined. Comparison with experimental... 

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