Ring Opening Copolymerization (ROCOP) of boron-containing anhydride with epoxides as a controlled platform to functional polyesters

Vidal, F; Smith, S; Williams, C

Journal article

Ring Opening Copolymerization (ROCOP) of boron-containing anhydride with epoxides as a controlled platform to functional polyesters

Abstract:: Boron-functionalised polymers are used in opto-electronics, biology, and medicine. Methods to produce boron-functionalised and degradable polyesters remain exceedingly rare but relevant where (bio)dissipation is required, for example in self-assembled nanostructures, dynamic polymer networks, and bio-imaging. Here, a boronic ester-phthalic anhydride and various epoxides (cyclohexene oxide, vinyl-cyclohexene oxide, propene oxide, allyl glycidyl ether) undergo controlled ring-opening copolymerizations (ROCOP), catalysed by organometallic complexes [Zn(II)Mg(II) or Al(III)K(I)] or a phosphazene organobase. The polymerizations are well controlled allowing for modulation of the polyester structures (e.g. by epoxide selection, AB or ABA blocks), molar masses (9.4 < Mn < 40 kg/mol) and uptake of boron functionalities (esters, acids, ‘ates’, boroxines, and fluorescent groups) in the polymer. The boronic ester functionalized polymers are amorphous, with high glass transition temperatures (81 < Tg < 224 °C) and good thermal stability (285 < Td < 322 °C). The boronic ester-polyesters are deprotected to yield boronic acid- and borate-polyesters; the ionic polymers are water soluble and degradable under alkaline conditions. Using a hydrophilic macro-initiator in alternating epoxide/anhydride ROCOP, and lactone ring opening polymerization, produces amphiphilic AB and ABC copolyesters. Alternatively, the boron functionalities are subjected to Pd(II)-catalyzed cross-couplings to install fluorescent groups (BODIPY). The utility of this new monomer as a platform to construct specialized polyesters materials is exemplified here in the synthesis of fluorescent spherical nanoparticles that self-assemble in water (Dh = 40 nm). The selective copolymerization, variable structural composition, and adjustable boron loading represent a versatile technology for future explorations of degradable, well-defined and functional polymers.

Publication status:: Published

Peer review status:: Peer reviewed

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APA Style

Vidal, F., Smith, S., & Williams, C. (2023). Ring Opening Copolymerization (ROCOP) of boron-containing anhydride with epoxides as a controlled platform to functional polyesters. Journal of the American Chemical Society, 145(25), 13888–13900.

MLA Style

Vidal, F., et al. “Ring Opening Copolymerization (ROCOP) of Boron-Containing Anhydride with Epoxides as a Controlled Platform to Functional Polyesters.” Journal of the American Chemical Society, vol. 145, no. 25, American Chemical Society, 2023, pp. 13888–900.

Chicago Style

Vidal, F, S Smith, and C Williams. 2023. “Ring Opening Copolymerization (ROCOP) of Boron-Containing Anhydride with Epoxides as a Controlled Platform to Functional Polyesters.” Journal of the American Chemical Society 145 (25): 13888–900.
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