Vinyl ethylene carbonate

Butadiene epoxidation to epoxybutene (EpB ) was practiced at a semiworks scale of 1.4 x 10 metric tons year by Tennessee Eastman [9] between 1997 and 2004 [10]. Epoxybutene is a versatile intermediate [11] that can be used to produce a large variety of different products such as epoxybutane, 1,4-butane diols and alcohols, 1,2-butane diols and alcohols, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran, N-methylpyrrolidone, cyclopropyl carboxyaldehyde (CPCA) derivatives, vinyl ethylene carbonate (addition of CCT to EpB), and 3,4-dihydroxy-l-butene (addition of H2O to EpB). 

SCHEME 4.3 Synthesis of vinyl ethylene carbonate from 3,4-epoxy butene-1 and carbon dioxide. 

Polymers with pendant cyclic carbonate functionality were synthesized via the free radical copolymerization of vinyl ethylene carbonate (4-ethenyl-l,3-dioxolane-2-one, VEC) with other imsaturated monomers. Both solution and emulsion free radical processes were used. In solution copolymerizations, it was found that VEC copolymerizes completely with vinyl ester monomers over a wide compositional range. Conversions of monomer to polymer are quantitative with complete incorporation of VEC into the copolymers. Cyclic carbonate functional latex polymers were prepared by the emulsion copolymerization of VEC with vinyl acetate and butyl acrylate. VEC incorporation was quantitative and did not affect the stability of the latex. When copolymerized with acrylic monomers, however, VEC is not completely incorporated into the copolymer. Sufficient levels can be incorporated to provide adequate cyclic carbonate functionality for subsequent reaction and crosslinking. The unincorporated VEC can be removed using a thin film evaporator. The Tg of VEC copolymers can be modeled over the compositional range studied using either linear or Fox models with extrapolated values of the Tg of VEC homopolymer. 

Limited information exists in the literature, however, on the homo- or copolymerization of vinyl ethylene carbonate, 1 (VEC or 4-ethenyl-l,3-dioxolane-2-one) for the preparation of cyclic carbonate functional polymers. A few comments regarding polymerization of VEC are given in an early patent [9], In the only reported study of the copolymerization behavior of VEC, Asahara, Seno, and Imai described the copolymerization of VEC with vinyl acetate, styrene, and maleic anhydride and determined reactivity ratios [10. Their results indicated that VEC would copolymerize well with vinyl acetate, but in copolymerizations with styrene, little VEC could be incorporated into the copolymer. VEC appeared to copolymerize with maleic anhydride, however the compositions of the copolymers was not reported. Our goal was to further explore the use of VEC in the synthesis of cyclic carbonate functional polymers. 

Besides VC, vinyl ethylene carbonate (VEC), phenylethylene carbonate (PhEC), ° phenylvinylene carbonate (PhVC), catechol carbonate (CC), - ally methyl carbonate (AMC), - allyl ethyl carbonate (AEC), vinyl acetate (VA), and other vinyl compounds, - - acryronitrile (AAN) - and 2-cyanofuran (CN-F), whose chemical structures are given in Fig. 4.10, showed the similar effect and no graphite exfoliation in PC solvent systems. 

Chen, G. Zhuang, G. V Richardson, T. J. Liu, G. Ross, P. N. J. Anodic polymerization of vinyl ethylene carbonate in Li-ion battery electrolyte, Electrochem. Solid-State Lett, 2005, 8, A344-A347. 

Saponifying and decarboxylating a copolymer of a vinyl ester monomer and vinyl ethylene carbonate,... 

Hu Y, Kong W, li H, Huang X, Chen L (2004) Experimental and theoretical studies on reduction mechanism of vinyl ethylene carbonate on graphite anode for lithium ion battraies. Electrochem Commrrn 6 126-131. doi 10.1016/j.elecom.2003.10.024... 

Li J, Yao W, Meng YS, Yang Y (2008) Effects of vinyl ethylene carbonate additive on elevated-temperature performance of cathode material in lithium ion batteries. J Phys Chem C 112 12550-12556. doi 10.1021/jp800336n... 

Sulfonyldipropionitrile, cf. Figure 2.20, is structurally different from commonly used compoimds as additives for an LiMn204 cathode, e.g., tiis(pentafluorophenyl) borane (76), vinyl ethylene carbonate (77), fluoroethylene carbonate (78), hexamethyldisilaz-ane (79), tris(trimethylsilyl) borate (80), or tris(trimethylsilyl) phosphate (81). 

Vinyl-functional alkylene carbonates can also be prepared from the corresponding epoxides in a manner similar to the commercial manufacture of ethylene and PCs via CO2 insertion. The most notable examples of this technology are the syntheses of 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate, VEC) (5, Scheme 24) from 3,4-epoxy-1-butene or 4-phenyl-5-vinyl-l,3-dioxolan-2-one (6, Scheme 24) from analogous aromatic derivative l-phenyl-2-vinyl oxirane. Although the homopolymerization of both vinyl monomers produced polymers in relatively low yield, copolymerizations effectively provided cyclic carbonate-containing copolymers. It was found that VEC can be copolymerized with readily available vinyl monomers, such as styrene, alkyl acrylates and methacrylates, and vinyl esters.With the exception of styrene, the authors found that VEC will undergo free-radical solution or emulsion copolymerization to produce polymeric species with a pendant five-membered alkylene carbonate functionality that can be further cross-linked by reaction with amines. Polymerizations of 4-phenyl-5-vinyl-l,3-dioxolan-2-one also provided cyclic carbonate-containing copolymers. 

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