Polymers with ether pendant groups

An important advantage of the use of such added nucleophiles is that it allows controlled/living cationic polymerization of alkyl vinyl ethers to proceed at +50 to +70°C [101,103], relatively high temperatures at which conventional cationic polymerizations fail to produce polymers but result in ill-defined oligomers only, due to frequent chain transfer and other side reactions. Recently, initiators with functionalized pendant groups [137] and multifunctional initiators [ 138—140] have been developed for the living cationic polymerizations with added nucleophiles. 

Another important role of the pendant-functionalized vinyl ethers is that they can be precursors of initiators for living cationic polymerization of other vinyl ether and styrene derivatives, from which polymers with terminal functional groups can be prepared (see Section IV). 

Y. Liu, Y. Zhang, S. Guan, L. Li, Z. Jiang, Synthesis and properties of soluble fluorinated poly(ether imide)s with different pendant groups. Polymer 49 (25) (2008) 5439-5445. 

Linear alkane solutions of 60a (n = 300, M = 3.1 x 10", Mw/Mn = 1.15) showed highly sensitive UCST-type phase separation irrespective of the solvent [222]. Interestingly, the cloud point temperature of 60a increased linearly with the number of carbon atoms in the alkane, which is in reasonable agreement with the Flory-Huggins theory. Similar phase separation occurred for poly(vinyl ether)s with various pendant groups, such as alkyl (in alcohols and esters), ester (in alcohols and toluene), and silyloxy groups (in alcohols). The combination of polymer and solvent was the decisive factor in sensitive phase separation. Nonpolar polymers underwent phase separation in polar solvent, and polar ones became thermosensitive in nonpolar media. 

To date, much effort has been undertaken to develop new alternatives. For example, sulfonated aromatic polymers, i.e., polymers with the sulfonic acid groups directly attached to the main chain or carrying short pendant side chains with terminal sulfonic acid units, attract increasing interest because of their chemical and thermal stability, and the ease of the sulfonation procedure. Some of the proposed polymers are sulfonated polysulfone (SPSU) [134] sulfonated poly(phenylene oxide) (SPPO) [135] sulfonated poly-(ether ether ketone) (SPEEK) [136] poly(phenylquinoxaline) (PPQ) [137] and poly(benzeneimidazole) (PBI) [138],... 

PMA is a tough leathery resin with a low Tg and a solubility parameter of 10.5 H. In polymers of alkyl acrylates the solubility parameter decreases as the size of the alkyl group increases. The flexibility also increases with the size of the pendant groups but because of side chain crystallization this tendency is reversed when the alkyl group has more than ten carbon atoms. Polyalkyi acrylates are readily hydrolyzed by alkalis to produce salts of polyacrylic acid. The copolymer of ethyl acrylate (95%) and chloroethyl vinyl ether (5%) is a commercial oil-resistant elastomer. 

This article reports on the synthesis of photosensitive polymers with pendant cinnamic ester moieties and suitable photosensitizer groups by cationic copolymerizations of 2-(cinnamoyloxy)ethyl vinyl ether (CEVE) (12) with other vinyl ethers containing photosensitizer groups, and by cationic polymerization of 2-chloroethyl vinyl ether (CVE) followed by substitution reactions of the resulting poly (2-chloroethyl vinyl ether) (PCVE) with salts of photosensitizer compounds and potassium cinnamate using a phase transfer catalyst in an aprotic polar solvent. The photochemical reactivity of the obtained polymers was also investigated. 

Poly(methylsilylene-/>-phenylene)s carrying Si-linked benzocrown ether and ethoxy pendant groups 86 (parameters x and y are associated with the benzo crown vs. ethoxy ratio present in the polymer) showed ionochromic behavior, and responded selectively to alkali and alkaline earth metal ions in the emission spectra, depending on the crown ether ring size. These polymers also display solvatochromic properties by changing the solvent polarity in the absence of metal ions <2006OM2225>. 

By the use of the polymer-linking method with 20a, a variety of starshaped poly(vinyl ethers) have been synthesized (Scheme 12) [208-212]. A focus of these syntheses is to introduce polar functional groups, such as hydroxyl and carboxyl, into the multiarmed architectures. These functionalized star polymers include star block (23a,23b) [209,210], heteroarm (24) [211], and core-functionalized (25) [212] star polymers. Scheme 12 also shows the route for the amphiphilic star block polymers (23b) where each arm consists of an AB-block copolymer of 1BVE and HOVE [209] or a vinyl ether with a pendant carboxyl group [210], Thus, this is an expanded version of triarmed and tetraarmed amphiphilic block copolymers obtained by the multifunctional initiation (Section VI.B.2) and the multifunctional termination (Section VI.B.3). Note that, as in the previously discussed cases, the hydrophilic arm segments may be placed either the inner or the outer layers of the arms. 

Pittman et al. [29] described the simultaneous aldol condensation and the hydrogenation of the condensation product in a one-pot process with a perfluorinated aliphatic ether polymer with pendant sulfonic acid groups as the acid catalyst and Pd as the hydrogenation catalyst. Taking acetone and hydrogen as the educt components the aim was to obtain 4-methyl-2-pentanone for given reaction conditions. 

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