Cyclopolymerization

Abstract

The background and summary of the events that led to the discovery and confirmation of an unusual and unexpected mode of polymerization of certain vinyl monomers is presented. Originally, the process was described as an alternating intra‐intermolecular chain propagation mechanism. For convenience and because cyclic structures are introduced into the polymer chain, the term cyclopolymerization has been adopted. Early attempts to determine the relationship of cyclopolymerization to stereochemical control and to ladder polymer formation are reviewed. Also, it is pointed out that within 10 years of the introduction of the cyclopolymerization concept, worldwide commercialization of certain cyclopolymers and cyclocopolymers had begun. The extent of the research activity in this area of chemistry and its relationship to commercialization are emphasized. Two areas of research activity that are featured are chirality induction into well‐known polymers and synthesis of conjugated polymers via cyclopolymerization. Both areas are discussed, and suitable examples are included. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3451–3461, 2000

Polymeric pseudo-crown ether for cation recognition via cation template-assisted cyclopolymerization

“…The efficiency and selectivity in the cation recognition by PPEG6DMA was further evaluated in competitive recognition. Thus, in cyclohexanone/ acetone-d 6 (1/1, v/v), the polymer was mixed with an equimolar mixture of Na and another alkali metal cation, and the selectivity was evaluated in monitoring the sodium guest by 23 Na NMR spectroscopy (Fig. 5); obviously, 1 H or 13 C NMR is totally useless in this analysis, because there was little difference in the chemical shift between cyclic PEG units with Na and with another cation.…”

“…and 40 Hz) and with PPEG3MA (a linear pendant counterpart to PPEG6DMA: -0.34 p.p.m. and 135 Hz), again demonstrating the efficient cation binding by 23 Na NMR.…”

“…Cyclopolymerization [23][24][25][26][27][28][29][30][31][32][33][34][35][36] is a chain polymerization of bifunctional monomers via alternating propagation process of intramolecular cyclization and intermolecular addition, to give soluble linear polymers consisting of 'in-chain' cyclic structures. This strategy affords direct and quantitative incorporation of cyclic units into polymers as repeating units, in sharp contrast to the polymerization of monomers bearing a cyclic pendent group 37 or the postfunctionalization of linear polymers 38 .…”

Stereo-controlled synthesis of polyolefins with cycloalkane groups by using late transition metals

“…[7][8][9][10][11] The polymerization of non-conjugated dienes can also be used to synthesize polymers with cycloalkane groups because chain growth is accompanied by monomer ring closure. 12 Early transition metal complexes have been extensively used in cyclopolymerization reactions. [13][14][15][16][17][18][19][20][21][22][23][24] The polymers produced via cyclopolymerization often contain both cis-and trans-isomeric repeating units.…”

The effect of a dithiol spiroorthocarbonate on mechanical properties and shrinkage of a dental resin

“…[6] Also, the inclusion of monomers that undergo cyclopolymerization has been investigated. [7] Another approach is the use of expandable monomers. Bailey reported that bicyclic monomers, like the spiroorthocarbonates (SOCs) and the spiroorthoesters undergo expansion during polymerization.…”