Vinylidene cyanide copolymers

Travis Vinyl acetate/vinylidene cyanide copolymer Hoechst/Celanese... 

It has been shown52 that under similar conditions reduction of the nitrile groups in cellulose ethyl cyanate and of those in the copolymer of vinylidene cyanide with vinyl acetate, proceed simultaneously in two directions with the formation of aldehyde and amine groups. g+ g ... 

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. 

New terpolymers of vinyl acetate with ethylene and carbon monoxide have been prepared and their uses as additives to improve the curing and flexibility of coating resins, eg, nitrocellulose, asphalt, phenolics, and polystyrene, have been described (130—132). Vinyl acetate and vinylidene cyanide form highly alternating copolymers. 

Darvan Vinylidene cyanide-vinyl acetate copolymer Celanese... 

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,... 

Darvatt . Vinylidene cyanide-vinyl acetate copolymer Parian Travis. Methylenemalononitrile copolymer with vinyl acetate contg about equal parts of each component. Polymerization of vinylidene cyanide with vinyl acetate Gilbert et al. J. Am. Chem. Soc. 78, 1669 (1956) Gilbert, Miller, U.S. pat. 2,615,866 and Sayre, U.S. pat. 2,975,-158 (1952, 1961, hoth to B. F. Goodrich). Review R W. Moncrieff, Man-Made Fibres (John Wiley, New York, 4th ed., 1963) pp 488-494. Approximate structure ... 

Only a small percent of styrene copolymers reported in the literature achieved industrial importance. Some of the interesting copolymers of styrene that were reported but not utilized commercially are copolymers with various unsaturated nitriles. This includes vinylidene cyanide, fumaronitrile, malononitrile, methacrylonitrile, acrylonitrile, and cinnamonitrile [292]. Often, copolymerization of styrene with nitriles yields copolymers with higher heat distortion temperature, higher tensiles, better craze resistance, and higher percent elongation. 

Poly(vinyl acetate) grades that are resistant to hydrolysis are obtained by copolymerization with vinyl stearate and vinyl pivalate (vinyl ester of trimethyl acetic acid), since the saponification rate is reduced by the bulkier side groups. Pure poly(vinyl pivalate) has too high a glass-transition temperature (78°C) for most poly(vinyl ester) applications. Copolymerization with vinylidene cyanide yields a fiber with a feel similar to Cashmere wool. Other copolymers are produced with olefins (see Section 25.2.1.5) and vinyl chloride (see Section 25.7.5.5)... 

Vinylidene cyanide/4-acetoxy, a-acetoxy styrene copolymer 21.48 11.25 7.16 21.89 [149]... 

Vinylidene cyanide/4-chloro-styrene copolymer (Rohm and Haas) 16.98 12.07 8.18 22.38 [149]... 

Azumai, Y, Kishimoto, M., Seo, I., and Sato, H., Enhanced SHG power using periodic poling of vinylidene cyanide/vinyl acetate copolymer, IEEE J. Quantum Electron., 30, 1924-1933 (1994). 

Random copolymers based on acrylonitrile and methacrylonitrile with ethyl a-acetoxyacrylate [69] were synthesized by radical copolymerization. The microstructure of the resulting copolymers was characterized by C NMR spectroscopy, and some reactivity ratios could be assessed. In addition, copolymers based on methyl vinylidene cyanide (MVCN) and vinyl acetate [70], styrene [71], or substituted styrene also exhibit interesting dielectric behavior [72]. 

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)... 

Monomers with electron-rich double bonds produce one-to-one copolymers with monomers having electron-poor double bonds in reaction systems that also contain certain Lewis acids. These latter are halides or alkyl halides of nontransition metal elements, including AlCb, ZnCh, SnCL, BF3, AI(CH2CH3)Cl2, alkyl boron halides, and other compounds. The acceptor monomer generally has a cyano or carbonyl group conjugated to a vinyl double bond. Examples are acrylic and methacrylic acids and their esters, acrylonitrile, vinyl ketones, maleic anydride, fumaric esters, vinylidene cyanide, sulfur dioxide, and carbon monoxide. The variety of donor molecules is large and includes various olefins, styrene, isoprene, vinyl halides and esters, vinylidene halides, and allyl monomers [30]. 

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). 

T. Mirugi, A. Yamaguchi. and T. Ogihara. X-ray study on the fiber prepared from vinylidene cyanide/vinyl acetate copolymer. Sea-i Cakkaiski 74 1197 (1961X... 

T. T. tWhng and Y. lUuse, Fcnoelectriclike dielectric behavior in the piezoelcctiic amorphoui copolymer of vinylidene cyanide and vinyl acetate, J. AppL Pkys. 62 3466 (1967). 

Y. S. Jo. M. Sakiirai. Y. Inoiie, R. Cbujo, S. Ihsaka. and S. h4iyau, Solveol-depeadeot coformatioos and piezoelectricity of the copolymer of vinylidene cyanide and vinyl acetate. Pofymer 28 1583 (1987). 

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. 

---