Fluoroacrylate polymers monomers

Traditionally, a fluoropolymer or fluoroplastic is defined as a polymer consisting of carbon (C) and fluorine (F). Sometimes these are referred to as per-fluoropolymers to distinguish them from partially fluorinated polymers, fluoroelastomers, and other polymers that contain fluorine in their chemical structure. For example, fluorosilicone and fluoroacrylate polymers are not referred to as fluoropolymers. The monomers used to make the various fluoropolymers are shown in Figure 9.1. 

Lachinov and co-workers [52] have performed a more detailed study of the kinetics of block radical polymerisation of perfluoroalkylmethacrylates (FMA) in the solid state. The main method of investigation of the kinetics of FMA polymerisation was isothermic calorimetry [58]. Due to the absence of data on the heat effects of their polymerisation in the reference literature, these values were measured [52]. The values of AQ and glass transition point (T ) of polymers formed are shown in Table 8.3. Obviously heat of polymerisation of monomers of the fluoroacrylate sequence is quite close to heat of polymerisation of non-substituted monomers of the AMA sequence [59], and a significant influence of the length of the fluoroalkyl radical on this parameter is absent [52]. In accordance with the Polyani-Semenov rule, the present result makes it possible to consider that chain propagation constant of FMA with the accuracy of the pre-exponential multiplicand being equal to each other [57]. 

Recently, Ye and DeSimone [40] showed that a diblock copolymer of a fluorinated acrylate and a glucose-containing hydrophilic block will support the emulsion polymerization of N-ethyl acrylamide in CO2. Here, the use of a fluorinated azo-initiator that partitions strongly to the CO2 phase (avoiding the monomer droplets) led to the generation of very fine (submicron) particles of polymer. Fluoroacrylates are known to be the most C02-philic materials found to date, and hence their use allows for achievement of the crucial phase behavior conditions shown in Fig. 7.2. 

Various acrylic polymers and copolymers are also utilized as support materials. For instance, a copolymer of a fluoroacrylate monomers was prepared by Bergbreiter and coworkers to form a support material that is selectively soluble in fluorinated solvents [28-32],... 

A fluoropolymer is usually an olefinic polymer, which consists of partially or fully fluorinated olefinic monomers such as vinylidene fluoride (CH = CF ) and tetrafluoroethylene (CF = CF ). These polymers have been discussed in a number of publications (see Further Reading). Specialized fluorinated polymers, including perfluoroethers, fluoroacrylates, and fluorosilicones, are used in significantly smaller volume than olefinic fluoropolymers. These specialized fluoropolymers and others have been described in detail elsewhere [1-3] and are not included in this chapter. 

A good review on fluoropolymers was published in 2009 [85], Fluoropolymers (olefinic) are classified as perfluorinated and partially fluorinated products. The former are homo and copolymers of TFE. The speciality fluorinated polymers include perfluoroethers, fluoroacrylates and fluoro silicones, which are used in significantly smaller volumes than olefinic fluoropolymers. The most important monomers are TFE, VDF, ethylene and CTFE. Figure 11.11 highlights fluoropolymers family tree. 

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