Relating the heat‐of‐mixing of analog mixtures to the miscibility of hydrogen‐bonding polymers

Abstract

The prediction of polymer/polymer miscibility is addressed using analog calorimetry and molecular modeling. For each polymer, an analog compound representing one or two repeat units was chosen. Heat‐of‐mixing was measured for liquid mixtures of analog compounds and then used in a binary interaction model to predict polymer miscibility. Specifically, we have measured exothermic heats‐of‐mixing for 4‐ethyl phenol, an analog of poly(vinly phenol), with several analogs containing ether, ester, or ketone functional groups. The exothermic heat‐of‐mixing results are consistent with the observed miscibility of poly(vinyl phenol) with polymers containing these functional groups. Using interaction parametes derived from the analog calorimetry in the binary interaction model or using premixes of 4‐ethyl phenol in ethyl benzene, we correctly predict the magnitude and relative order of the fraction of vinyl phenol units in copolymers with styrene required for miscibility with poly(methyl methacrylate), polyacetal, and a polyketone. the miscibility trends for poly(vinyl phenol) blends predicted from analog calorimetry and the binary interaction model are in reasonable agreement with those predicted from the association model of Painter and Coleman, despite the different bases of the two approaches. We have used molecular modeling to complement the analog calorimetry and to assess steric effects on hydrogen‐bonding ability for models of poly(n‐butyl acrylate) and poly(t‐butyl acrylate) with phenol. The modeling results suggest that, in some cases, steric effects and the three‐dimensional structure of the polymer can significantly influence the hydrogen‐bonding ability of polymers relative to their analogs.

Effect of monomer architecture on segmental interaction parameters of binary blends involving copolymers of cyclohexyl methacrylate, methyl methacrylate and styrene derivatives

“…Although quantitatively the values obtained from analog mixtures are quite different to those reported in Tables 2 and 3, qualitative information about the exothermic or endothermic nature of the interactions between polymer repeat units can be obtained from the analog compound mixtures. In fact, reasonable agreement is found between data from copolymer blends and analog mixtures, taking into account that intramolecular connectivity and other macromolecular effects [31,32] are absent in low molecular weight model compound mixtures.…”

Miscibility and phase behavior of poly(D,L-lactide)/poly(p-vinylphenol) blends

“…It has also been found that the interassociation between polymers is affected by the structure of estercontaining polymers. 25,26 In view of the total mis-cibility of PVPh with PPL, 19 PCL, 19 and PHB 22,23 via interassociation, it is of interest to study the miscibility of PDLLA/PVPh blends.…”

Recycling ground tire rubber (GTR) scraps as high‐impact filler of in situ produced polyketone matrix

“…The resulting terpolymer has a lower crystallinity and lower melting point, and it is tougher and more processable . At the same time, PK‐based blends with polypropylene, poly(vinylphenol), polyester, and polyamide have been successfully prepared, showing a good compatibilization level and a generally increasing thermal stability. Composites with calcium carbonates and nanocomposites with layered clay, both organomodified, increased the mechanical performance of PK with particular reference to toughening effects and the flexural strength.…”