Fluorinated copolymers with

D.J. Connolly and W.F. Gresham, Fluorocarbon vinyl ether polymers. USP 3,282,875, 1966 P.R. Resnick, Preparation of sulfonic acid containing vinyl ethers, USP 3,560,568 K. Kimoto, H. Miyauchi, J. Ohmura, M. Ebisawa and H. Hane, Novel fluorinated copolymers with tridihydro fluorosulfonyl fluoride pendant groups and preparation thereof. USP 4,329,435. 

The use of more complex systems such as ternary blends allows the functionalization of the surfaces with varies chemical functionalities. For instance a PS matrix was mixed with two block copolymers, a hydrophobic (PS-b-P5FS) and an amphiphilic polystyrene-b-poly[poly(ethylene glycol) methyl ether methacrylate] (PS-6-P(PEGMA)) copolymer [96], The chemical distribution of the resultant surface pattern implies an enrichment of the holes in the amphiphilic copolymer with an external surface mainly functionalized in the fluorinated copolymer with low surface energy (Scheme lO.lg). Other ternary blends combining incompatible copolymers and homopolymers have been reported leading to more complex topographies and chemical distributions [148],... 

Shennper, B.S. and Mathias, LJ. (2004) Synthesis and characterization of statistical and block fluorinated copolymers with linear and star-like architectures via ATRP. European Polymer Journal, 40,651 65. 

Aqueous microemulsion has been used for the copolymerization of VDF and HFP in the presence of IC6F12-I as CTA. This technology, used in conjunction with the addition of diene as cross-linkers (e.g., CH2=CH-(CF2) -CH=CF2), allowed the preparation of fluorinated copolymers with improved performances. 

The remainder of this section is divided into two parts (1) investigations on the activation of fluorinated homopolymers followed by the grafting, and (2) methods starting from the irradiation of fluorinated copolymers, with a subsequent grafting step. This section provides nonexhaustive examples of syntheses, properties, and applications of graft copolymers starting from the activation of PVDF. 

The equimolar copolymer of ethylene and tetrafluoroethylene is isomeric with poly(vinyhdene fluoride) but has a higher melting point (16,17) and a lower dielectric loss (18,19) (see Fluorine compounds, organic-poly(VINYLIDENE fluoride)). A copolymer with the degree of alternation of about 0.88 was used to study the stmcture (20). Its unit cell was determined by x-ray diffraction. Despite irregularities in the chain stmcture and low crystallinity, a unit cell and stmcture was derived that gave a calculated crystalline density of 1.9 g/cm. The unit cell is befleved to be orthorhombic or monoclinic (a = 0.96 nm, b = 0.925 nm, c = 0.50 nm 7 = 96%. 

Uses. Vinyhdene fluoride is used for the manufacture of PVDF and for copolymerization with many fluorinated monomers. One commercially significant use is the manufacture of high performance fluoroelastomers that include copolymers of VDF with hexafluoropropylene (HFP) (62) or chlorotrifluoroethylene (CTFE) (63) and terpolymers with HEP and tetrafluoroethylene (TEE) (64) (see Elastomers, synthetic-fluorocarbon elastomers). There is intense commercial interest in thermoplastic copolymers of VDE with HEP (65,66), CTEE (67), or TEE (68). Less common are copolymers with trifluoroethene (69), 3,3,3-trifluoro-2-trifluoromethylpropene (70), or hexafluoroacetone (71). Thermoplastic terpolymers of VDE, HEP, and TEE are also of interest as coatings and film. A thermoplastic elastomer that has an elastomeric VDE copolymer chain as backbone and a grafted PVDE side chain has been developed (72). 

Many synthetic latices exist (7,8) (see Elastomers, synthetic). They contain butadiene and styrene copolymers (elastomeric), styrene—butadiene copolymers (resinous), butadiene and acrylonitrile copolymers, butadiene with styrene and acrylonitrile, chloroprene copolymers, methacrylate and acrylate ester copolymers, vinyl acetate copolymers, vinyl and vinyUdene chloride copolymers, ethylene copolymers, fluorinated copolymers, acrylamide copolymers, styrene—acrolein copolymers, and pyrrole and pyrrole copolymers. Many of these latices also have carboxylated versions. 

Neumann and coworkers [165] synthesized tetrafluorinated-PPV copolymer 133 and studied its light-emitting properties. However, this material was quite unsuccessful for LED applications increasing the amount of fluorinated comonomer resulted in a dramatic decrease of the PLQY and the turn-on voltage of the devices was above 30 V (which could only be realized in ac mode due to device shorting). The quenching was less pronounced for an analogous copolymer with MEH-PPV (134), which showed an EL efficiency of up to 0.08 cd/A (in ITO/PEDOT/134/Ca diode) [166] (Chart 2.26). 

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. 

An alternative means of reducing the dielectric constant of polyimides is to have a low dielectric constant component dispersed as a second phase within the rigid polyimide matrix. Two key approaches have been pursued to this end. The first involves the preparation of polyimide block copolymers with highly fluorinated coblocks and the second involves the generation of a polyimide foam. The main drawback to the first approach is the solubility of highly fluorinated blocks in organic media which will permit copolymerization with polyimides. This led to the investigation of new semi-fluorinated polymers derived from polyfaryl ethers). 

The processability of fluorine-containing polymers is improved by replacement of one or more of the fluorine atoms. Replacing one of the eight fluorine atoms with a trifluoromethyl group gives a product called FEP or Viton, actually a copolymer of tetrafluoroethylene and hexafluoropropylene (Equation 6.53). Polytrifluoromonochloroethylene (PCTFE, Kel F) (Equation 6.54), in which one fluorine atom has been replaced by a chlorine atom, has a less regular structure and is thus more easily processed. Poly(vinylidene fluoride) (PVDF, Kynar) (Equation 6.55) is also more easily processable but less resistant to solvents and corrosives. 

Commonly accepted practice restricts the term to plastics that serve engineering purposes and can be processed and reprocessed by injection and extrusion methods. This excludes the so-called specialty plastics, eg, fluorocarbon polymers and infusible film products such as Kapton and Upilex polyimide film, and thermosets including phenolics, epoxies, urea—formaldehydes, and silicones, some of which have been termed engineering plastics by other authors (4) (see Elastomers, synthetic-fluorocarbon elastomers Fluorine compounds, organic-tetrafluoroethylene copolymers with ethylene Phenolic resins Epoxy resins Amino resins and plastics). 

A revitalization of interest in the copolymerization of epoxides and C02 can be traced to studies involving discrete zinc complexes. Several well-defined zinc monomeric and dimeric derivatives have been shown to be effective catalysts for the coupling of CHO and C02 to afford copolymers with high degrees of C02 incorporation. These include reports of sterically encumbering Ms-phenoxide derivatives of zinc [24], a highly fluorinated zinc carboxylate [25], and zinc [3-diiminate complexes [26] (see Figure 8.2). 

The thermal stability of fluorocarbon elastomers also depends on their molecular structure. Fully fluorinated copolymers, such as copolymer of TFE and PMVE (Kal-rez), are thermally stable up to temperatures exceeding 300°C (572°E). Moreover, with heat aging this perfluoroelastomer becomes more elastic rather than embrittled. Eluorocarbon elastomers containing hydrogen in their structures (e.g., Viton, Dyneon, and DAI-EL EKM) exhibit a considerably lower thermal stability than the perfluori-nated elastomer. Eor example, the long-term maximum service temperature for FKM... 

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