Novel Copolymers of Vinyl Acetate and Halogen Ring‐Disubstituted 2‐Phenyl‐1,1‐dicyanoethylenes

Abstract

Electrophilic trisubstituted ethylene monomers, halogen ring-disubstituted 2-phenyl-1,1-dicyanoethylenes, RC 6 H 3 CH5 5C(CN) 2 (where R is 2,3-diCl, 2,4-diCl, 2,6-diCl, 3,4-diCl, 3,5-diCl, 2,4-diF, 2,5-diF, 2,6-diF, 3,4-diF, 3,5-diF, 2-Cl, 6-F) were synthesized by piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and malononitrile, and characterized by CHN elemental analysis, IR, 1 H-and 13 C-NMR. Novel copolymers of the ethylenes and vinyl acetate were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 708C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1 H and 13 C-NMR, GPC, DSC, and TGA. High T g of the copolymers, in comparison with that of polyvinyl acetate, indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 220-8008C range.

Novel Copolymers of Styrene and Some Halogen Ring-substituted 2-Phenyl-1,1-dicyanoethylenes

“…In continuation of our studies of the monomer structurereactivity correlation in the radical copolymerization of ring-substituted 2-phenyl-1,1-dicyanoethylene monomers (14,15) we have prepared halogen ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC 6 H 3 CH C(CN) 2 (where R is 2-bromo, 3-bromo, 3-chloro, 2,3-dichloro, 2-chloro-6-fluoro, 2,6-difluoro, 3,4-difluoro, and 3,5-difluoro), and explore the feasibility of their copolymerization with styrene (ST).…”

Hypervalent Iodine(III)-Catalyzed Epoxidation of β-Cyanostyrenes

“…[(2,3-Dichlorophenyl)methylene]propanedinitrile (1e)24 White solid; yield: 1.71 g(7.66 mmol, 77%); mp 160-162 C (Lit 14. mp 159-161 C); R f = 0.2 (EtOAc-hexane 1:49).…”

“…IR (KBr):684, 699, 718, 830, 857, 1011, 1045, 1191, 1377, 1425, 1513, 1573, 1926, 2112, 2258, 2344 cm -1 .1 H NMR (400 MHz, CDCl 3 ):  = 4.84 (s, 1 H, CH), 7.21 (dd, J 1 = 1.6 Hz, J 2 = 7.6 Hz, 1 H, ArH), 7.27 (dt, J 1 = 2.0 Hz, J 2 = 8.4 Hz, 1 H, ArH), 7.31 (dt, J 1 = 1.6 Hz, J 2 = 8.4 Hz, 1 H, ArH), 7.35 (dd, J 1 = 1.6 Hz, J 2 = 7.6 Hz, 1 H, ArH). NMR (100 MHz, CDCl 3 ):  = 40.9, 63.6, 109.7, 111.1, 126.4, 127.1, 127.4, 129.9, 132.2, 133.9.GC-MS: m/z (%) = 206 ([M + ], 8), 204(24), 169(15), 141 (95), 140(25), 139(24), 89 (100), 75(24), 49(25).Anal. Calcd for C 10 H 5 ClN 2 O: C, 58.70; H, 2.46; N, 13.69.…”