Perfluoroalkyl methacrylates

The properties of the liquid precursors (Table 2) were investigated by wetting experiments on a perfluoroalkyl methacrylate (FC 722 , 3M) covered glass plate (solid surface tension y 12.5 mN/m)[ll]. 

II. Elementorganic polymers and copolymers copolymers of fluorinated olefins [10-21] poly(perfluoroalkyl- methacrylates) and perfluoroalkylmethacrylates copolymers [1-3, 22-34] poly(organosiloxanes) [25, 35] fluorine-containing poly(organo siloxanes) [36] fluorine-containing copolymers with side functional (hydroxy) groups [37, 38], and others [1]. 

Investigation of the kinetics of various FMA on the polymerisation has demonstrated the dependence of the reaction rate constants on the structure of perfluorinated alcohol radical [54]. Data on the molecular properties and structure of perfluoroalkyl methacrylates (CH2=C(R)COOCH2(CF2) X, where R = H, X = H, or X = F m = 2 (4FA), m = 4 (8FA), and m = 6 (12FA) were obtained using determination of dipole moments and Roentgen-phase analysis [55]. 

Table 8.3 Heats of polymerisation of perfluoroalkyl methacrylates, T, PFMA ...

Table 8.6 Some parameters of compolymerisation of perfluoroalkyl methacrylates with MMA and styrene (S) in mixture (Treact = 20 °C, [BPO] = 0.001 mole per mole of monomer mixture) ...

It has also been reported the mechanism on dewetting by increasing temperature of perfluoroalkyl methacrylate as homo- and copolymer with methyl methacrylate films. The following qualitative model has been proposed (Sheiko et al, 1996). As has already been stated, perfluoroalkyl-substituted polymethacrylates have been shown to form ordered structures based on the crystallisation of the perfluoroalkyl side chains and the incompatibility of the fluorinated and the hydrocarbon segments. 

Ishizone, T., Sugiyama, K., Sakano, Y. et al. (1999) Anionic polymerizations of perfluoroalkyl methacrylates and synthesis of well-defined ABC triblock copolymers of methacrylates containing hydrophilic, hydrophobic, and perfluoroalkyl groups. Polymer Jourrud, 31,983 988. 

Many graft copolymers have been made by free radical copolymerization of co-styryl or co-methacryloyloxy macromonomers and various comonomers. Special interest has been devoted to amphiphilic copolymers involving a hydrophilic backbone and hydrophobic grafts, or vice versaf Poly(perfluoroalkyl methacrylate) and poly(stearyl methacrylate) are typical examples of hydrophobic polymers, whereas poly(hydroxyethyl methacrylate) or poly(vinylpyrrolidone) are examples of nonionic hydrophilic chains. Such graft copolymers have found a number of applications as surface modifiers or coatings because of their ability to give intramolecular phase separation (surface accumulation phenomena ). 

Block polymer of perfluoroalkyl methacrylates, lower alkyl methacrylates, and two polyalkylene glycol methacrylates Fluorocarbon acrylate + A/-acrylol-A/-buty-lurethane + Bunte salt (e.g., C7H15CONH CH2CH2S203Na)... 

Based on perfluoroalkyl methacrylates and various matrices, selfocs with A > 0.06-0.08 and high thermal and humidity resistance have been created, which also display excellent optical and mechanical properties that they retain for a long time [46]. 

Yamashita et al.2,99) also investigated the copolymerization of PMMA macromonomers both with a mixture of HEMA and perfluoroalkyl acrylate and with a MMA-methacrylic acid mixture here again, the PMMA grafts originating from the macromonomer play the role of anchoring segments, and surface accumulation of the functional backbone segments is well established. 

In Fig. 3 one finds a variety of functional groups that may be subdivided as follows haloalkyl groups [14-16], saturated esters (acetate [17], and benzoate [18,19]) unsaturated esters (methacrylate [19,20], acrylate [21], cinnamate [20], and others [21]) malonate and related esters [22-24] ethers and oligo(oxyethylenes) [25-28] imides [29,30] alkylsilyloxy groups [31] perfluoroalkyls [32-34] and protected carbohydrate groups [35]. Vinyl ethers with mesogenic (liquid-crystal forming) substituents will be treated separately in Section II. B.2. 

The pendant functions listed in Figure 3 are often useful and of synthetic interest per se. For example, methacrylate and acrylate esters are polymerizable (cross-linking sites) [19-21] the cinnamate is photorespon-sive (for the photo-induced dimerization of its unsaturated groups) [20] oligo(oxyethylene) [25-27] and carbohydrate groups [35] give hydrophilic and water-soluble polymers, whereas perfluoroalkyl moieties [32-34] enhance hydrophobicity. Thus, poly(vinyl ethers) with cinnamate functions... 

Perfluoroalkyl groups are also introduced into block copolymers with methacrylates, acrylates, and styrene (B-46 to B-53), which can be synthesized in scCC>2 or in the bulk.95,315 Amphiphilic block copolymers based on glycopolymer segments (B-54 and B-55) are synthesized by copper-catalyzed polymerizations.321,322 Comonomers with a polyhedral oligomeric silsesquioxane unit afforded hybrid polymers between organic and inorganic components (B-56 and B-57).326... 

Perfluoroalkyl chain surfactants are much poorer wetting agents than alkyl chain surfactants for both paraffin and polymethyl methacrylate surfaces (Pyter, 1982). One explanation may be the mutual phobicity of alkyl and perfluoroalkyl chains, causing perfluoroalkyl chain surfactants to be adsorbed more poorly than alkyl chain surfactants at these solid-aqueous solution interfaces. 

Table 8.2 Some quantum-chemical parameters of perfluoroalkyl (meth)acrylates and methyl methacrylate [22, 49] ...

Perfluoroalkyl vinyl ether copolymer resin, 227 Perfluorooctyl methacrylate, 74 PerlenetetracarboxyUc-bis-benzimidazole, 49 Perylene, 13, 49 Phenol, 141, 241, 257, 286 Phenolphthalein, 258, 263, 284, 286 Phenolsulfonic acid, 241 p-Phenoxybenzenesulfonyl chloride, 248 4-Phenoxybenzophenone, 213 p-Phenoxybenzoyl chloride, 210, 213, 248 Phenoxyethylacrylate, 540 4-(4-Phenoxyphenoxy)benzophenone, 213 p-Phenoxyphenoxybenzoyl chloride, 210, 213... 

MJkg.moC = 18.9, 81.99 mol% butyl methacrylate, perfluoroalkyl = (CF2)s 6CF3 carbon dioxide CO2... 

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