Triblock copolymers cationic

Symmetric triblock copolymers of the ABA type, where B was PTHF and A poly(2-methyl-2-oxazoline), PMeOx, were prepared by cationic polymerization with trifluoromethanesulfonic anhydride as a difunctional initiator [58]. Subsequent hydrolysis of the PMeOx blocks with HC1 in a methanol/ water mixture resulted in the formation of the corresponding polyethylen-imine blocks (Scheme 20). Samples with relatively low molecular weight distributions were obtained. 

For some applications, it is desirable to lock the micellar structure by cross-Hnking one of the micellar compartments, as discussed previously in Sect. 2.6. Cross-Hnked core-shell-corona micelles have been prepared and investigated by several groups as illustrated by the work of Wooley and Ma [278], who reported the cross-linking of PS-PMA-PAA micelles in aqueous solution by amidation of the PAA shell. Very recently, Wooley et al. prepared toroidal block copolymer micelles from similar PS-PMA-PAA copolymers dissolved in a mixture of water, THF, and 2,2-(ethylenedioxy)diethylamine [279]. Under optimized conditions, the toroidal phase was the predominant structure of the amphiphilic triblock copolymer (Fig. 19). The collapse of the negatively charged cylindrical micelles into toroids was found to be driven by the divalent 2,2-(ethylenedioxy)diethylamine cation. 

Some particularities of the extraction of ions from an aqueous organic phase, and of the phase catalyzed polyetherification will be summarized. These will represent the fundamentals of our work on the synthesis of some novel classes of functional polymers and sequential copolymers. Examples will be provided for the synthesis of functional polymers containing only cyclic imino ethers or both cyclic imino ethers as well as their own cationic initiator attached to the same polymer backbone ABA triblock copolymers and (AB)n alternating block copolymers and a novel class of main chain thermotropic liquid crystalline polymers containing functional chain ends, i.e., polyethers. 

Hoogenboom R, Wiesbrock F, Huang H et al. (2006) Microwave-assisted cationic ringopening polymerization of 2-oxazolines a powerful method for the synthesis of amphiphilic triblock copolymers. Macromolecules 39 4719-4725... 

In summary, nanometer-sized mesoporous silica and alumina spheres with tunable diameters (80 - 900 nm) can be synthesized in organic solvent. Mesoporous silica spheres templated by cationic surfactant (CTAB) have hexagonal array with monodispersed pore size (-2.4 nm), high surface areas (-1020 m2/g), and pore volume (1.02 cm3/g). Mesoporous alumina spheres templated by amphiphilic triblock copolymer show a large disordered mesopore (10.0 nm) and high BET surface area (360 m2/g). 

Since soluble multifunctional initiators are more readily available in cationic polymerization than in the anionic counterpart, ABA type linear triblock copolymers have been almost exclusively prepared using difunctional initiation followed by sequential monomer addition. The preparation and properties of ABA type block copolymer thermoplastic elastomers (TPEs), where the middle segment is PIB, have been reviewed recently [47]. 

Due to the lack of vinyl monomers giving rise to crystalline segment by cationic polymerization, amorphous/crystalline block copolymers have not been prepared by living cationic sequential block copolymerization. Although site-transformation has been utilized extensively for the synthesis of block copolymers, only a few PIB/crystalline block copolymers such as poly(L-lactide-fc-IB-fc-L-lactide) [92], poly(IB-fr- -caprolactone( -CL)) [93] diblock and poly( -CL-fr-IB-fr- -CL) [94] triblock copolymers with relatively short PIB block segment (Mn< 10,000 g/mol) were reported. This is most likely due to difficulties in quantitative end-functionalization of high molecular weight PIB. 

We recently investigated a different route for the synthesis of poly(IB-h-f-CL) diblock and poly( -CL-fo-IB-fo- -CL) triblock copolymers by site-transformation of living cationic polymerization of IB to cationic ring-opening polymerization of -CL via the activated monomer mechanism [95]. 

So far we have discovered very few polymerization techniques for making macromolecules with narrow molar mass distributions and for preparing di-and triblock copolymers. These types of polymers are usually made by anionic or cationic techniques, which require special equipment, ultrapure reagents, and low temperatures. In contrast, most of the commodity polymers in the world such as LDPE, poly(methyl methacrylate), polystyrene, poly(vinyl chloride), vinyl latexes, and so on are prepared by free radical chain polymerization. Free radical polymerizations are relatively safe and easy to perform, even on very large scales, tolerate a wide variety of solvents, including water, and are suitable for a large number of monomers. However, most free radical polymerizations are unsuitable for preparing block copolymers or polymers with narrow molar mass distributions. 

At the Eys/nucleotide ratio of 2, the triblock copolymer formed a micelle with a size and zeta potential of 90 nm and -i- 7 mV. The interaction between the triblock copolymers and pDNA was evaluated and compared to the diblock copolymers using the EtBr exclusion assay. In the case of PEG-PEE, the fluorescence intensity decreased to 20% of the uncondensed naked pDNA at the N/P ratio of two. In contrast, PEG-PAsp(MPA), which has a cationic segment with a lower pKa value, maintained a relatively high fluorescence (> 90%) over a wide range of N/P ratios, suggesting that PEG-PAsp(MPA) lacks the capacity to condense pDNA based on the EtBr assay result. On the other hand, PEG-PAsp(MPA)-PEE exhibited a 80% decrease in fluorescence... 

Planar polymer films (either free-standing or at interfaces) are of particular interest, not only because they are preferred in many applications, but also because they allow for surface studies which could not be performed on vesicles. Langmuir monolayers from a vesicle-forming amphiphilic triblock copolymer were studied towards understanding the polymer interactions with a cation transporting peptide, alamethicin [275]. Planar solid supported block copolymer membranes are... 

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