Synthesis and Solid-State Properties of PolyC₃ (Co)polymers Containing (CH₂–CH₂–C(COOR)₂) Repeat Units with Densely Packed Fluorocarbon Lateral Chains

Abstract

The synthesis and structural characterization of linear PolyC 3 polymers containing trimethylene-1,1-dicarboxylate structural repeat units, with C 6 F 13 and C 8 F 17 fluorinated side chains is described for the first time, and their properties compared with the traditional polyvinyl structures that display the fluorinated chain on every second rather than on every third carbon alongside the backbone. Homopolymers as well as statistical and block copolymers with npropyl and/or allyl trimethylene-1,1-dicarboxylate blocks have been obtained from PolyC 3 precursors containing diallyl trimethylene-1,1-dicarboxylate units, by reacting C 6 F 13 -C 2 H 4 -SH and C 8 F 17 -C 2 H 4 -SH thiols with the allyl groups using a thiol-ene post-polymerization modification reaction. Solid-state properties have been investigated by DSC for all the (co)polymers and by SAXS/WAXS for the C 8 F 17 homopolymer at several temperatures. The structure of the homopolymer consistently shows a coexistence of two smectic phases at room temperature, which can be identified as SmB and SmC. This coexistence is assumed to arise from the fact that the distances between carboxylic oxygens bonded to the same carbon are very close to the ones between the neighboring carboxylic oxygens alongside the backbone, resulting in two possible ways of packing the pendant fluoroalkyl chains arranged in an hexatic order.

Exploring the Complexation of Counterion in Novel Family of Polyelectrolytes with Unexpected Solubility Behaviour

“…Poly(trimethylene-1,1-dicarboxylate lithium) was synthesized by ring-opening polymerisation followed by hydrolysis of ester and ion exchange reaction as described in previous publications [10,14]. Polyacid was obtained from lithium salt using an ion exchange column loaded with the cation exchange resin Amberlite IR 120 Na.…”

“…The product yield was approximately 40%. Sodium and potassium salts were obtained by addition of excess of respective hydroxide [14]. In further discussion polyacid, lithium, sodium and potassium salts ate noted as H2, Li2, Na2 and K2, respectively.…”

“…Preliminary studies of the PTMDC structure reveal very similar structure for polyacid, sodium and potassium polysalts [14]. Solubility in water decrease as K+> H+>Na+ where sodium salt is almost insoluble.…”

Synthesis of Calamitic Fluorinated Mesogens with Complex Crystallization Behavior

“…Such semi-rigid amphiphilic compounds, known as calamitics, are known to form layered, cylindrical, or cubic superstructures as a function of molecular shape, temperature, humidity, etc. [16][17][18]. For example, Berrod et al [19] suggested original perfluorosulfonic acid molecules that can reproduce the phase-separated morphology of PFSA ionomer membranes used as electrolytes in fuel cells.…”

Molecular Aggregation Structure and Surface Properties of Biomimetic Catechol-Bearing Poly[2-(perfluorooctyl)ethyl acrylate] and Its Application to Superamphiphobic Coatings

“…Due to the high ionization potential and low polarizability of fluorine, fluorinated compounds are known as the most effective materials to provide the ultralow surface free energy required for many applications, such as water and oil repellencies, anticorrosion, antismudge, drag reduction, ice-releasing, and fouling resistance. − Among the fluorinated materials, fluorinated polymers (or fluoropolymers) have been developed as an important branch since the discovery of poly­(tetrafluoroethylene) (PTFE) by Plunkett in 1938. , Fluorinated polymers can be divided into two groups: (I) those where the fluorinated carbons are located in the polymer backbone and (II) those containing fluorinated dangling side groups. In recent years, group (II) has attracted increasing research interest due to the high density of trifluoromethyl (−CF 3 ) terminal groups, tunable linkers between the dangling group and the backbone, and the improved solubility and processability compared with that of group (I). − In particular, the polymers of perfluoroalkyl-substituted acrylates (PFAs) or methacrylates (PFMAs) maintain both the special surface property of fluoropolymers and the good film-forming characteristic of poly­(meth)­acrylates. , …”