A photothermally triggered one-component shape memory polymer material prepared by cross-linking porphyrin-based amphiphilic copolymer self-assemblies.

Photothermally triggered shape memory polymer materials are usually prepared by dispersing photothermally responsive fillers or compounds into shape memory polymer matrixes through physical blending, while the migration and non-biodegradability of the fillers limit their potential applications (e.g., in the biomedical field). Here, we synthesized a new type of porphyrin-based amphiphilic random copolymer bearing a reactive moiety of carbonyl group by co-polymerizing methyl methacrylate (MMA), butyl acrylate (BA), diacetone acrylamide (DAAM), acrylic acid (AA) and double-bonded vinyl porphyrin monomers, followed by induced self-assembly in aqueous solution to give rise to amphiphilic random copolymer nanoparticles. The nanoparticles were further crosslinked by means of adipic dihydrazide (ADH) to fabricate the photothermally triggered one-component shape memory polymer material. Compared with the most-studied multi-phase/multi-component shape memory polymer materials, the porphyrin moiety, playing the role of a photo-to-heat converter, covalently bonded into the polymer structure would certainly make it more homogeneous and more stable in principle.

Photothermal-Triggered Shape Memory Polymer Prepared by Cross-Linking Porphyrin-Loaded Micellar Particles.

In this work, we fabricated porphyrin-loaded shape memory polymer (SMP) film by cross-linking micellar particles prepared by co-assembly of porphyrin compounds and amphiphilic macromolecules formulated by copolymerization of 2-butoxy ethanol (BCS), methyl methacrylate (MMA), butyl acrylate (BA) acrylic acid (AA), and diacetone acrylamide (DAAM). The experimental results revealed that this film was able to respond to the red light in terms of photothermal effect enabled by the porphyrin filler. The photothermal-triggered shape memory behaviors of the film were further examined in detail. It was noteworthy that this material was expected to have potential applications in the biomedical field due to the excellent biocompatibility of the porphyrin filler and the red-light source, which was optimal and safe enough for biomedical treatment.

One-Pot Preparation of Autonomously Self-Healable Elastomeric Hydrogel from Boric Acid and Random Copolymer Bearing Hydroxyl Groups.

Self-healable hydrogels based on the dynamically reversible boronate ester or borate ester bonds are usually prepared by reacting boronic acid or boric acid with diol compounds or polymer-like poly(vinyl alcohol) bearing a hydroxyl group in each monomer unit. Herein, we report a finding that not only facilitates the preparation but also extends the range of self-healable hydrogels of this kind. By simply copolymerizing commercially available N,N-dimethylacrylamide and 2-hydroxyethyl acrylate (8:2 weight ratio) in the presence of boric acid in a one-pot fashion, the resulting random copolymer can gel in aqueous solution at pH = 9, giving rise to a solid hydrogel (tensile strength >0.5 MPa at water content of 30%) that, on the one hand, can autonomously self-heal (near 100% fracture stress recovery within 48 h in air at room temperature) and, on the other hand, shows the characteristics of elastomer (little stress relaxation under loading and small residual deformation after unloading upon repeated 300% elongation cycles). The results reveal that it can be sufficient to have a random copolymer with comonomer units bearing hydroxyl groups for reacting with boric acid to generate dynamically reversible borate ester bonds. This finding thus points out a general, facile, and cost-effective method to obtain and explore new borate ester bond-based self-healable hydrogels.