Vinyl ether group functionalization

The UV cure system contains an epoxy or a vinyl ether functionalized PDMS polymer and a photo catalyst [36]. This latter, a diaryliodonium salt is photolyti-cally decomposed to form an active acid that polymerizes the epoxy or vinyl ether groups and crosslinks the network. 

In order to circumvent such a drawback, there has been a recent focus on the design of cleavable lipids whose hydrolysis is catalyzed by the drop in pH.10 This approach exploits acid-labile chemical groups such as acetals, ketals, orthoesters, and vinyl ethers. Such functional groups... 

The chiral anisole derivative 37 has been used in the synthesis of several asymmetric functionalized cyclohexenes (Table 9) [22]. In a reaction sequence similar to that employed with racemic anisole complexes, 37 adds an electrophile and a nucleophile across C4 and C3, respectively, to form the cyclohexadiene complex 38. The vinyl ether group of 38 can then be reduced by the tandem addition of a proton and hydride to C2 and Cl, respectively, affording the alkene complex 39. Direct oxidation of 39 liberates cydohexenes 40 and 41, in which the initial asymmetric auxiliary is still intact. Alternatively, the auxiliary may be cleaved under acidic conditions to afford /y3 -allyl complexes, which can be regioselectively attacked by another nucleophile at Cl. Oxidative decomplexation liberates the cyclohexenes 42-44. HPLC analysis revealed high ee values for the organic products isolated both with and without the initial asymmetric group. 

Figure 3.2 Reaction with vinyl ethers, (top with substituted vinyl ethers. A functional arrow) Nonfunctional termination (methylene group or fragment R is transferred onto the transfer) of a living ROMP with ethyl vinyl polymer chain end. ether, (bottom arrow) Functional termination...

The intramolecular coupling between the hydroxyl functions of the HOVE units of block A and the pendant vinyl ether functions of block C was then achieved in presence of pyridinium para-toluene sulfonic acid salt (PTSA) as catalyst. The reaction between hydroxyl functions and vinyl ether groups yield the rapid formation of acetal links between the A and C sequences, as described in Scheme 21.7. 

For example, perfluoromethyl vinyl ether can be obtained by the reaction with carbonyl fluoride. The dimerization of HFPO followed by pyrolysis, leads to the formation of perfluoropropyl vinyl ether. Moreover, functionally substituted perfluorovinyl ether can be synthesized if corresponding acyl fluoride with a functional group are used. 

Shostakovsky, M.F., B.A. Trofimov, A.S. Atavin, and V.I. Lavrov. 1968. Methods for synthesis of vinyl ethers containing functional groups and heteroatoms. Usp Khim 37 (ll) 2070-2093. 

A long-standing goal in polyolefins is the synthesis of polymers bearing polar functional groups such as acrylate, esters, or vinyl ethers, etc [24,40]. These copolymers might endow polyolefins with useful properties such as adhesiveness, dyeability, paintability, and print-ibility. Advances have recently been made in polymerizing polar monomers with cationic metallocene catalysts... 

An alternative technique to NMR spectroscopy is chromatography. The partially functionalized sample is completely fimctionahzed with a group different from the one present, the product carefully de-polymerized, its structure examined with a chromatographic technique. For example, partially substituted CA was further derivatized with methyl vinyl ether, the product hydrolyzed, the monomers produced examined with gas chromatography [241]. HPLC has been advantageously applied for the determination of substitution pattern for CAs with DS 0.8 to 3.0, by employing the same approach, i.e., further derivatization of the partially derivatized polymer with methyl trifluoroacetate, followed by de-polymerization. The results obtained by this technique compared favorably with those obtained by NMR [242]. 

The Stille coupling reaction is very versatile with respect to the functionality that can be carried in both the halide and the tin reagent. Groups such as ester, nitrile, nitro, cyano, and formyl can be present, which permits applications involving masked functionality. For example, when the coupling reaction is applied to l-alkoxy-2-butenylstannanes, the double-bond shift leads to a vinyl ether that can be hydrolyzed to an aldehyde. 

Applying these methodologies monomers such as isobutylene, vinyl ethers, styrene and styrenic derivatives, oxazolines, N-vinyl carbazole, etc. can be efficiently polymerized leading to well-defined structures. Compared to anionic polymerization cationic polymerization requires less demanding experimental conditions and can be applied at room temperature or higher in many cases, and a wide variety of monomers with pendant functional groups can be used. Despite the recent developments in cationic polymerization the method cannot be used with the same success for the synthesis of well-defined complex copolymeric architectures. 

Fluorinated polymers, especially polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) and perfluorinated alkyl vinyl ethers (PFAVE) as well as other fluorine-containing polymers are well known as materials with unique inertness. However, fluorinated polymers with functional groups are of much more interest because they combine the merits of pefluorinated materials and functional polymers (the terms functional monomer/ polymer will be used in this chapter to mean monomer/polymer containing functional groups, respectively). Such materials can be used, e.g., as ion exchange membranes for chlorine-alkali and fuel cells, gas separation membranes, solid polymeric superacid catalysts and polymeric reagents for various organic reactions, and chemical sensors. Of course, fully fluorinated materials are exceptionally inert, but at the same time are the most complicated to produce. 

Widespread chlorine-containing polymers would include, 1) stable molding material for practical use such as polyvinyl chloride (PVC), polyvinylidene chloride and poly(epichlorohydrin)(PECH) and, 2) reactive polymers capable to introduce additional functional groups via their active chlorines such as chloromethyl polystyrene, poly (3-chloroethyl vinyl-ether) and poly (vinyl chloroacetate). While the latter, especially the chloromethyl polystyrene, has been widely used recently for the synthesis of variety of functional polymers, we should like to talk in this article about the chemical modification of the former, mainly of PVC and PECH, which was developed in our laboratory. 

Shackelford and co-workers studied the 1,2-addition of 2,2-dinitropropanol, 2,2,2-trinitroethanol, and 2-fluoro-2,2-dinitroethanol across the double bonds of vinyl ethers. These reactions are Lewis acid catalyzed because of the weak nucleophilic character of alcohols which contain two or three electron-withdrawing groups on the carbon p to the hydroxy functionality. Base catalysis is precluded since alkaline conditions lead to deformylation with the formation of formaldehyde and the nitronate salt. 

Epoxy-functional polydimethylsiloxane oligomers are another group that can be cured by UV radiation. Epoxysilicone block copolymers exhibit a good photoinitiator miscibility, high cure rate, and compatibility with epoxy and vinyl ether monomers. These block copolymers form flexible films with excellent release properties and are therefore used as release coatings. ... 

M. Sawamoto, T. Enoki, and T. Higashimura, End-functionalized polymers by living cationic polymerization. 1. Mono- and bifunctional poly(vinyl ethers) with terminal malonate or carboxyl groups, Macromolecules, 20(l) l-6, January 1987. 

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