Complex Formation between Isotactic Polymers of R-(+)- and S-(−)-α-Methylbenzyl Methacrylates in Bulk and in Solution

Highly Asymmetric-selective and Stereoselective Polymerization of (RS)-α-Methylbenzyl Methacrylate with Cyclohexyl-magnesium Bromide-Axially Dissymmetric 2,2′-Diamino-6,6′-dimethylbiphenyl System

“…31 Hatada et a/. 32 Figure 4). The polymer obtained at a later stage of the polymerization showed a close similarity in the solubility property to the polymer racemate.…”

Stereocomplex Formation between (+)- and (−)-Poly(menthyl methacrylate) in Bulk

“…A typical example is stereocomplexation between isotactic and syndiotactic poly(methyl methacrylate)s in some solvents and in bulk. 1 • 2 Stereocomplexation can also occur in blends of isotactic polymers with opposite configuration, such as poly( o:-methylbenzyl methacrylate), 3 poly lactide, 4 polyisopropylthiirane, 5 and more recently, alternating copolymers of o:-olefin and carbon monoxide, poly(l,4-ketone)s. 6 One thing we also have to mention here is that blending two polymers of opposite configuration does not always induce the formation of a stereocomplex, such as the case of polymethylthiirane. 7 In this work, we found that stereocomplexation took place in bulk between poly((+ )-menthyl methacrylate) (( + )-PMnMA) and poly((-)-menthyl methacrylate) ((-)-PMnMA), based on the results of differential scanning calorimetry (DSC), X-ray powder diffraction (XRD), as well as a solubility study.…”

“…The difference in solubility strongly implies that a stereocomplex is formed in bulk between ( + )-PMnMA and (-)-PMnMA, just as in the case of poly(o:-methylbenzyl methacrylate). 3 Figure 1 129oC and 127°C, respectively, corresponding to the glass transition. Both parent polymers had no melting point.…”

Stereoregular Polymerization within Template Nanospaces

“…It is surprising that the mass ratio was potentially consistent with the stoichiometry of double stranded 1:2 (it:st) stereocomplexes. [19][20][21][22] Molecular weights of PMMAs simultaneously prepared in solution (M n 2300, M w =M n 4.0) were obviously independent of template it-PMMAs. The aforementioned observations strongly suggest that structural information from polymer chain length templates, which were derived from the double stranded stereocomplex, were successfully transferred to synthesized polymers.…”

“…[2][3][4][5][6][7][8][9] Biomacromolecules have 3-dimensional and higher-order nanostructures which self-assemble in a given environment. Although molecularly regulated structures seem to be restricted to aqueous phase biomacromolecules, similarly regulated nanostructures, which self-assemble in certain organic solvents, are known to form combinations of synthetic polymers such as methacrylate polymers, [10][11][12][13][14][15][16][17][18][19] polyesters, 20,21 and poly(amino acid)s. [22][23][24] Stereocomplexes are formed between structurally well-defined synthetic polymers in certain solvents, or in films with structural fittings between polymer chains or between lateral functional groups with van der Waals contacts. For instance, isotactic (it) and syndiotactic (st) poly(methyl methacrylate)s (PMMAs) artificially form double stranded helical stereocomplexes in polar organic solvents on the basis of structural fitting with van der Waals interactions, [10][11][12][13][14] in which complex it-PMMAs are surrounded by twice the length of st-PMMAs.…”