Amphiphilic, thixotropic additives for extrusion-based 3D printing of silica-reinforced silicone.

The ability to utilize extrusion-based, direct ink write (DIW) 3D printing to create silica-reinforced silicones with complex structures could expand their utility in industrial and biomedical applications. Sylgard 184, a common Pt-cure silicone, lacks the thixotropic behavior necessary for effective printing and its hydrophobicity renders cured structures susceptible to biofouling. Herein, we evaluated the efficacy of various PEO-silane amphiphiles (PEO-SAs) as thixotropic and surface modifying additives in Sylgard 184.

Enhanced Osteogenic Potential of Phosphonated-Siloxane Hydrogel Scaffolds.

In a material-guided approach, instructive scaffolds that leverage potent chemistries may efficiently promote bone regeneration. A siloxane macromer has been previously shown to impart osteoinductivity and bioactivity when included in poly(ethylene glycol) diacrylate (PEG-DA) hydrogel scaffolds. Herein, phosphonated-siloxane macromers were evaluated for enhancing the osteogenic potential of siloxane-containing PEG-DA scaffolds.

Controlled Ring-Opening Metathesis Polymerization with Polyisobutylene-Bound Pyridine-Ligated Ru(II) Catalysts.

This study describes the use of polyisobutylene (PIB) to phase-anchor pyridine ligands that form a phase-separable Grubbs third-generation catalyst. We further show that this complex is useful in ring-opening metathesis polymerization (ROMP) reactions. These PIB-bound pyridine-ligated Grubbs catalysts provide the same benefits of control over polymer chain growth and polydispersity of the product as their low-molecular-weight analogs and reduce Ru leaching in ROMP products from approximately 16% (820 ppm residues) as seen with a similar pyridine-ligated catalyst to a value of approximately 3% (160 ppm residues).

Alternatives for Conventional Alkane Solvents.

The studies described in this paper show that hydrocarbon oligomers are alternatives for low molecular weight alkane solvents. These oligomeric solvents are nontoxic, nonvolatile, and recyclable alternatives to heptane in thermomorphic solvent mixtures that use a polar solvent such as methanol, aqueous ethanol, or DMF or in biphasic mixtures that use acetonitrile. Regardless of which polar solvent is used, hydrocarbon oligomers like poly(α-olefin)s (PAOs) exhibit very low leaching into the polar phase.

Supported Catalysts Useful in Ring-Closing Metathesis, Cross Metathesis, and Ring-Opening Metathesis Polymerization.

Ruthenium and molybdenum catalysts are widely used in synthesis of both small molecules and macromolecules. While major developments have led to new increasingly active catalysts that have high functional group compatibility and stereoselectivity, catalyst/product separation, catalyst recycling, and/or catalyst residue/product separation remain an issue in some applications of these catalysts. This review highlights some of the history of efforts to address these problems, first discussing the problem in the context of reactions like ring-closing metathesis and cross metathesis catalysis used in the synthesis of low molecular weight compounds.

Recoverable Reusable Polyisobutylene (PIB)-Bound Ruthenium Bipyridine (Ru(PIB-bpy)Cl) Photoredox Polymerization Catalysts.

Polyisobutylene (PIB)-bound ruthenium bipyridine [Ru(PIB-bpy)] metal complexes were prepared from PIB ligands formed by alkylation of 4,4'-dimethylbipyridine with polyisobutylene bromide. The product Ru(PIB-bpy)Cl complexes with at least one PIB ligand per bipyridine unit function as soluble recyclable photoredox catalysts in free radical polymerization of acrylate monomers under visible light irradiation at 25 °C with ethyl 2-bromoisobutyrate as the initiator in the presence of diisopropylethylamine. The polyacrylate products contained only about 1 ppm Ru contamination.

Polyethylene as a nonvolatile solid cosolvent phase for catalyst separation and recovery.

The studies described here show that a relatively low molecular weight, narrow polydispersity polyethylene (PE) wax (Polywax) can serve as a nontoxic and nonvolatile alternative to alkane solvents in monophasic catalytic organic reactions where catalysts and products are separated under biphasic conditions. In this application, a polymer that is a solid at room temperature substitutes for a conventional alkane solvent at ca. 80 °C.