Tables Fluorinated Acrylic Acids

Four fluorinated acrylates are presented in Table 4 [66, 67, 68, 69] to supplement the vmyl fluoride data Perfluoroacrylic acid [70] and methyl per-fluoroaciylate [69, 70] are both reported m the literature. The cts and trans isomers of fluoroethylenes are readily distinguished by the magnitude of their couphng constants, with trans typically more than 3 times the magnitude of cis... 

The preparation of fluorinated alcohols was carried out in multistep routes according to the reported procedures.1012 The synthesis of acrylic and methacrylic esters as shown in Table 11.1 was carried out in a fluorocarbon solvent such as Freon 113 by the reaction of the respective fluorinated alcohol with acryloyl chloride or methacryloyl chloride and an amine acid acceptor such as triethyla-mine with examples shown in Scheme 1. Other attempts to esterify the fluoroalcohols directly with acrylic acid or acrylic anhydride were not successful.11 Product purification by distillation was not feasible because of the temperature required, but purification by percolation of fluorocarbon solutions through neutral alumina resulted in products of good purity identified by TLC, FTIR, and H-, 13C-, and 19F- FTNMRs. 

Acrylic acid esterified with cross-linked hydroxymethyl polystyrene or Wang resin reacts smoothly with primary or secondary aliphatic amines at room temperature (Entries 1 and 2, Table 10.6). Only sterically demanding amines or amines of low nucleophilicity (anilines, a-amino acid esters) fail to add to polystyrene-bound acrylate. Support-bound acrylamides are less reactive than acrylic esters, and generally require heating to undergo addition with amines (Entries 4 and 5, Table 10.6). a, 3-Unsaturated esters with substituents in the 3-position (e.g. crotonates, Entry 3, Table 10.6) react significantly more slowly with nucleophiles than do acrylates. The examples in Table 10.6 also show that polystyrene-bound esters are rather stable towards aminolysis, and provide for robust attachment even in the presence of high concentrations of amines. Entry 10 in Table 10.6 is an example of the alkylation of a resin-bound amine with an electron-poor alkene to yield a fluorinated peptide mimetic. 

Since fluoroalkyl groups are uniformly acid-strengthening and the order of magnitude of the effect, relative to other haloalkyl groups, is consistent with electronegativities F > Cl, etc., it may be expected that the same situation occurs when fluorine is attached to unsaturated carbon. Inspection of the data in Table 4.5 quickly indicates a more complicated situation because, while fluorine substitution increases the acidity relative to the hydrocarbon analogue, the acidities are lower than the corresponding chlorocarbon compounds in the cases of the acrylic acids and phenols. 

In Table I are summarized the results obtained for different sample Nafion perfluoroethylene membrane (NAF), acrylic acid irradiation grafted polytetrafluoroethylene (PTFE), sulfonated styrene irradiation grafted fluorinated ethylene propylene copolymer (RAI), and sulfonated polysulfone (SPS). 

Table 8.10 Properties of some polymers based on MMA and fluorinated ethers (meth)acrylic acid ... 

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