Vinylidene cyanide polymers

Y. Inoue, K. Kawaguchi, Y. Maruyatna, Y. S. Jo. and R. Cbujo, C njn.r. atudies on the micTostructure of piezoelectric oopolymcrs of vinylidene cyanide. Polymer S0 698 (1969). P. A. Mtrau and S. A. Heffner, Chain caaformation in poiyfvinylidene cyanide-vinyl ace-ute) Solid state and solution 2D orrd 3D njn.r. studies. Polymer 33 1156 (1992). 

Polymer Solvent. Sulfolane is a solvent for a variety of polymers, including polyacrylonitrile (PAN), poly(vinylidene cyanide), poly(vinyl chloride) (PVC), poly(vinyl fluoride), and polysulfones (124—129). Sulfolane solutions of PAN, poly(vinylidene cyanide), and PVC have been patented for fiber-spinning processes, in which the relatively low solution viscosity, good thermal stability, and comparatively low solvent toxicity of sulfolane are advantageous. Powdered perfluorocarbon copolymers bearing sulfo or carboxy groups have been prepared by precipitation from sulfolane solution with toluene at temperatures below 300°C. Particle sizes of 0.5—100 Jim result. 

The synthesis of anion-exchange resins from acrylonitrile — SDVB copolymer has been reported The copolymer beads are converted to imino ester form by passing dry hydrogen chloride gas into a slurry of the beads in anhydrous methanol at 5 °C. These beads, after washing with anhydrous methanol, are refluxed with a mixture of ethylene diamine and anhydrous methanol. The resin thus synthesized has a capacity of 5 meq/g in Cl" form. Other diamines used for the synthesis of such type of resins are aminoethanolamine, neopentyldiamine, and trimethylenediamine Other monomers which are used for the synthesis of polymer matrices are methyl-acrylonitrile, vinylidene cyanide, cyanoalkyacrylates, and methacrylates, o-, m-, and />-cyanostyrene, 1-cyanobutadiene, 2-cyanobutadiene, methyl, ethyl, propyl,... 

Similar to vinyl derivatives, a number of substituted vinylidene polymers are used in practice. Some of these polymers are part of classes of polymers such as halogenated polyolefins and were discussed separately (see Section 6.3 and 7.5). One example of polymer that can be indicated here is poly(vinylidene cyanide). Its pyrolysis generates a high yield of monomer [42],... 

HAC Hachisuka, H., Tsujita, Y., TaMzawa, A., and Kinoshita, T., CO2 sorption properties and enthalpy relaxation in alternating copoly(vinylidene cyanide-virtyl acetate)s. Polymer, 29, 2050, 1988. 

To develop dielectric polymers with C-CN and C-F groups, the syntheses of poly(vinylidene fluoride)-h-poly(AN, MAN, VCN) (PVDF-h-PMcN) block copolymers (Scheme 20.8), using the iodine transfer polymerization (ITP) of acrylonitrile (AN), methacrylonitrile (MAN), and vinylidene cyanide (VCN), in the presence of PVDF-1, was reported. In a first step, the ITP of vinylidene fluoride (or 1,1-difluoroethylene, VDF) with C6F13I initiated by tcrt-butyl peroxypivalate (TBPPI)... 

Fig. 5 The ratio of the relevant component of the piezoelectric coefficient d and the respective polarization is plotted vs. the reciprocal of the respective elastic modulus Y (i.e., the relevant component of the elastic compliance). From left to right Literature data for inorganic ferroelectrics squares) barium titanate (BaTiOs), lead zirconate titanate (PZT), and lead zirconate niobate (PZN). Ferroelectric polymers triangles) polyamide-11 (PA-11), poly(vinylidene cyanide-vinyl acetate) (P(VDCN-VAc)), polyurea-5, poly(vinylidene fiuoride (PVDF)), poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)), and poly(vinylidene-hexafiuoropropylene) (P(VDF-HFP)). Polymer ferroelectrets circles) cellular polypropylene (cellular-PP) and tubular-channel poly (fluoro-ethylene-propylene) (FEP) (Qiu et al. 2014)...

Application of the concepts obtained in the study of PVDF and its copolymers has been made for other types of novel polymers with similar polar chemical structure. For example, poly(vinylidene cyanide) (PVDCN) and its copolymer with vinyl n-fatty acid ester have ciMmical structures close to that of PVDF F atoms arc displaced by CN groups. These polymers are also attracting attention because of their characteristic electric properties. Odd-numbered members of nylon (nylon 7, nylon 11, etc.) and ferroelectric liquid-crystalline polymers (FLCP) are also the candidates for ferroelectric polymers. These substances are still new. and their structural study has not yet been developed extensively compared with the study of PVDF and its copolymers. 

K. 1108110, M. Kobayashi, M. Kishimoto, and I. So Structure of copolymers of vinylidene cyanide and n-fatty add vinyl ester. Polymer Prepr. Jpn. 43 1273 (1992). 

K. Ihshiro, M. Koteyashi, M. Ktshimoto, and 1. sieo. Crystal structure of vinylidene cyanide Gapolyraers Energy minimizatkm and computer simulation of X-ray diffraction panem. Polymer Prepr. Jpn. 42 1442 (1993). 

S. Ihsaka. N. Inagahi. T. Okutani. and S. Miyaia, Stmcmic and properties of anoiplwus piezoeleclric vinylidene cyanide copolymefs. Polymer 30 1639 (19WX... 

D. Zou, S. Iwauki. T. Ihutnai. S. Saito, M. Kiihiraolo, and I. Seo, Anomaly in dielectric lelaxatioo in alternating copoiymen of vinylidene cyanide and fatty add vinyl ester. Polymer 3J I888 (1990). 

A similar initiation mechanism was demonstrated for the interaction of vinyl ethers with vinylidene cyanide, but in this case both an anionic and cationic homopolymerization took place in the same polymerization flask, an unusual event which was termed "cohabitory polymerization . ° ° Later, Dan Chting 16,119 able to fish some 2+2 cycloaddition products out of the polymer mixture obtained when the vinyl ethers reacted with vinylidene cyanide, thus lending support to a reaction mechanism in which the radical cation-radical anion pair could collapse to form the cyclobutane derivative or separate to initiate polymerization. The fact that a 1 1 alternating copolymer was obtained in the presence of a radical initiator supported the existence of a charge transfer complex. 

Investigations into alternative piezoelectric polymers, both semicrystalline and amorphous, continued into the 1980s, and two of the most significant discoveries are worth a brief mention. Of semicrystalline materials, the odd-membered polyamides (or nylons), particularly nylon-11, were found to exhibit reasonable piezoelectric activity, especially when mechanically oriented [9]. The highest piezoelectricity in an amorphous polymer was discovered in 1980 [10] in a copolymer of vinylidene cyanide and vinyl acetate. 

Four polymers of this structural type have been studied. These are polymethacrylonitrile (PMAN), polyphenylacrylonitrile (PPAN), poly(vinylidene cyanide) (PVCN) and poly-a-chloro acrylonitrile (PCAN). The structures, compared to polyacrylonitrile (PAN, 1), are shown below (2-5). 

It has been shown that repeated distillation heating of a gel-polymer based on vinyl monomers (for example, vinyl acetate-vinylidene cyanide) at 160-180°C alternating with rapid cooling down leads to an increase of the refractive index by 0.33-0.70% [45],... 

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