Dithiophosphoric Acids for Polymer Functionalization.

Dithiophosphoric acids (DTPAs) are an intriguing class of compounds that are sourced from elemental sulfur and white phosphorus and are prepared from the reaction of phosphorus pentasulfide with alcohols. The electrophilic addition of DTPAs to alkenes and unsaturated olefinic substrates is a known reaction, but has not been applied to polymer synthesis and polymer functionalization. We report on the synthesis and application of DTPAs for the functionalization of challenging poly-enes, namely polyisoprene (PI) and polynorbornene (pNB) prepared by ring-opening metathesis polymerization (ROMP). The high heteroatom content within DTPA moieties impart intriguing bulk properties to poly-ene materials after direct electrophilic addition reactions to the polymer backbone introducing DTPAs as side chain groups. The resulting materials possess both enhanced optical and flame retardant properties vs the poly-ene starting materials. Finally, we demonstrate the ability to prepare crosslinked polydiene films with di-functional DTPAs, where the crosslinking density and thermomechanical properties can be directly tuned by DTPA feed ratios.

Unraveling the rheology of inverse vulcanized polymers.

Multiple relaxation times are used to capture the numerous stress relaxation modes found in bulk polymer melts. Herein, inverse vulcanization is used to synthesize high sulfur content (≥50 wt%) polymers that only need a single relaxation time to describe their stress relaxation. The S-S bonds in these organopolysulfides undergo dissociative bond exchange when exposed to elevated temperatures, making the bond exchange dominate the stress relaxation. Through the introduction of a dimeric norbornadiene crosslinker that improves thermomechanical properties, we show that it is possible for the Maxwell model of viscoelasticity to describe both dissociative covalent adaptable networks and living polymers, which is one of the few experimental realizations of a Maxwellian material. Rheological master curves utilizing time-temperature superposition were constructed using relaxation times as nonarbitrary horizontal shift factors. Despite advances in inverse vulcanization, this is the first complete characterization of the rheological properties of this class of unique polymeric material.

Sequence-defined vinyl sulfonamide click nucleic acids (VS-CNAs) and their assembly into dynamically responsive materials.

Synthetic DNA analogues are of great interest for their application in information storage, therapeutics, and nanostructured materials, yet are often limited in scalability. Vinyl sulfonamide click nucleic acids (VS-CNAs) have been developed to overcome this limitation using the highly efficient thiol-Michael 'click' reaction. Utilizing all four nucleobases, sequence-defined click nucleic acids (CNAs) were synthesized using a simple and scalabale solution-phase approach. Employing a polyethylene glycol (PEG) support, synthesis of the CNA sequence, GATTACA, was achieved in high yields. CNA crosslinked hydrogels were assembled using multiarm PEG-CNAs resulting in materials that dynamically respond to temperature, strain, and competitive sequences.

Copper Ligand and Anion Effects: Controlling the Kinetics of the Photoinitiated Copper(I) Catalyzed Azide-Alkyne Cycloaddition Polymerization.

The kinetics of photoinduced copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations were assessed as a function of copper(II) amine-based ligands. Copper(II) bromide ligated with 1,1,4,7,10,10-hexamethylenetetramine (HMTETA) exhibited the fastest kinetics in both Norrish type(I) and type(II) photoinitiating systems. A characteristic induction period is observed with these polymerizations and is manipulated by adding an external tertiary amine in Norrish Type(II) photoinitating systems or by changing the anion of the copper(II) salt. Halides, specifically bromide and chloride, exhibit the fastest kinetics with the smallest induction period in comparison with organic anions, such as bistriflimide and triflate. The temporal control of the photo-CuAAC polymerization is affected by pre-ligation of the copper catalyst, by the presence of certain anions such as acetate, and by specific ligands such as tetramethylethylenediamine (TMEDA).