Perfectly AB-alternating copolymers via alternating diene metathesis polymerization: one-step synthesis, characterization and properties

Abstract

Perfectly alternating copolymers with functional phosphate groups were synthesized via reacting diacrylates with terminal dienes using alternating diene metathesis polymerization, showing a controllable polymerization characteristic which was evidenced by changing the relative stoichiometry of the two monomers. The compositional analysis and the sequence structural information of the polymers obtained from 1 H NMR spectra demonstrated that the resulting copolymers possessed strictly alternating structure. In addition, the thermal and flame-retardant properties of the alternating copolymers were investigated, indicating favorable thermal degradation and flame retardancy which is an important feature for future applications. This special combination of the benefits of metathesis polymerization and phosphorus chemistry is a highly versatile system for materials in many applications.

Functional Precision Polymers via Stereo‐ and Regioselective Polymerization Using Group 6 Metal Alkylidene and Group 6 and 8 Metal Alkylidene N‐Heterocyclic Carbene Complexes

“…Using alternating ADMET, referred to as ALTMET, AB‐alternating copolymers are accessible. Taking advantage of the different reactivity of diacrylates and terminal dienes, copolymers, for example, with alternating sequences of phosphate groups and esters in the main chain are available …”

Synthesis of Cis,syndiotactic A-alt-B Copolymers from Two Enantiomerically Pure Trans-2,3-Disubstituted-5,6-Norbornenes

“…In these cases alternation is greatly assisted by the fact that one partner (CO or CO 2 ) does not itself polymerize. A few alternating AB copolymers have been formed through ring-opening metathesis polymerization (ROMP) of cyclic olefin monomers, − but in these circumstances both A and B usually can be homopolymerized and the stereochemistry of the CC bond in the polymer is not fixed. One exception is the alternating AB copolymer which has all trans CC bonds and <5% AA errors formed from a norbornene-like monomer ( B ) that is slow to homopolymerize and cyclooctene or cycloheptene ( A ).…”