Polymerization of adsorbed monolayers. III. Preliminary structure studies in dilute solution of the insertion polymers

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Abstract
Insertion poly(methyl acrylate) and poly(methyl methacrylate) were prepared from monomers adsorbed in monolayers on the surface of montmorillonite clay, both in the presence and in the absence of bifunctional crosslinkers (ethylene glycol dimethacrylate and tetramethylene glycol dimethacrylate). The insertion poly(methyl acrylate) and the crosslinked insertion poly(methyl methacrylate) and dilute‐solution properties quite different from conventional polymers of these monomers, the differences including high light‐scattering molecular weights combined with low viscosities, low values of the second virial coefficient, unusually large variations of the Huggins' constant k′ with the time‐temperature history of the solutions, and low sedimentation velocities. These properties suggest that the insertion polymers have compact structures and are consistent with the postulate of sheetlike macromolecules. The dilute‐solution properties of insertion poly(methyl methacrylate) made without crosslinker, unlike those of similarly prepared poly(methyl acrylate), were similar to those of conventional poly(methyl methacrylate). This difference in behavior is attributed to the different tendencies of the two monomers to undergo branching or crosslinking during radical polymerization.