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A New Type of Photo-Thermo Staged-Responsive Shape-Memory Polyurethanes Network.

ABSTRACT: In this paper, we developed a photo-thermo staged-responsive shape-memory polymer network which has a unique ability of being spontaneously photo-responsive deformable and thermo-responsive shape recovery. This new type of shape-memory polyurethane network (A-SMPUs) was successfully synthesized with 4,4-azodibenzoic acid (Azoa), hexamethylenediisocyanate (HDI) and polycaprolactone (PCL), followed by chemical cross-linking with glycerol (Gl). The structures, morphology, and shape-memory properties of A-SMPUs have been carefully investigated. The results demonstrate that the A-SMPUs form micro-phase separation structures consisting of a semi-crystallized PCL soft phase and an Azoa amorphous hard phase that could influence the crystallinity of PCL soft phases. The chemical cross-linking provided a stable network and good thermal stability to the A-SMPUs. All A-SMPUs exhibited good triple-shape-memory properties with higher than 97% shape fixity ratio and 95% shape recovery ratio. Additionally, the A-SMPUs with higher Azoa content exhibited interesting photo-thermo two-staged responsiveness. A pre-processed film with orientated Azoa structure exhibited spontaneous curling deformation upon exposing to ultraviolet (UV) light, and curling deformation is constant even under Vis light. Finally, the curling deformation can spontaneously recover to the original shape by applying a thermal stimulus. This work demonstrates new synergistically multi-responsive SMPUs that will have many applications in smart science and technology.

SUBMITTER: Yang J

PROVIDER: S-EPMC6431991 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Photo-Responsive Shape-Memory and Shape-Changing Liquid-Crystal Polymer Networks.

Project description:"Surrounding matters" is a phrase that has become more significant in recent times when discussing polymeric materials. Although regular polymers do respond to external stimuli like softening of material at higher temperatures, that response is gradual and linear in nature. Smart polymers (SPs) or stimuli-responsive polymers (SRPs) behave differently to those external stimuli, as their behavior is more rapid and nonlinear in nature and even a small magnitude of external stimulus can cause noticeable changes in their shape, size, color or conductivity. Of these SRPs, two types of SPs with the ability to actively change can be differentiated: shape-memory polymers and shape-changing polymers. The uniqueness of these materials lies not only in the fast macroscopic changes occurring in their structure but also in that some of these shape changes are reversible. This paper presents a brief review of current progress in the area of light activated shape-memory polymers and shape-changing polymers and their possible field of applications.

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| S-EPMC5787381 | biostudies-literature

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Project description:This work aimed at elucidating the influence of zwitterionic hard segments on the structures and properties of shape memory polyurethanes (SMPUs). A series of zwitterionic SMPUs was successfully prepared with N-methyldiethanolamine (MDEA), 1,3-propanesultone (1,3-PS), 1,6-hexamethylene diisocyanate (HDI) and polyethylene glycol (PEG6000). The influence of MDEA-PS-based zwitterionic hard segment on structure, morphology, thermal property, shape memory property and cytocompatibility were systematically investigated. The results demonstrated that the PEG-based zwitterionic SMPUs (PEG-ZSMPUs) formed phase separation structure consisting of crystalline soft phase and amorphous hard phase. The MDEA-PS zwitterionic segments showed a tendency to form ionic clusters in hard segments, which served as reinforced net points. Shape memory analysis showed that zwitterionic PEG-ZSMPUs containing a high content of zwitterionic segments had thermal-induced shape memory effects. Finally, cytotoxic assays demonstrated that MDEA-PS zwitterionic segment improved the biocompatibility of PEG-ZSMPUs. The zwitterionic PEG-ZSMPUs could thus have a promising application in smart biomedical fields.

| S-EPMC6418923 | biostudies-literature

Block Copolymers of Poly(ω-Pentadecalactone) in Segmented Polyurethanes: Novel Biodegradable Shape Memory Polyurethanes.

Project description:In this report, the synthesis of poly(ω-pentadecalactone) (PPDL) (co)polymers and their incorporation into polyurethanes (PUs) are reported. Optimal conditions for the ring-opening polymerization (ROP) of ω-pentadecalactone (PDL) using dibutyltin dilaurate catalyst were established. For the synthesis of linear and crosslinked PUs, 50 kDa poly(ε-caprolactone) (PCL) and 1,6-hexamethylenediisocyanate (HDI) were used. The obtained polyurethanes were characterized by Attenuated Total Reflectance Fourier-Transform Infrared spectroscopy (AT-FTIR), differential scanning calorimetry (DSC), and dynamical mechanical analysis (DMA). The DMA of the selected sample showed a rubbery plateau on the storage modulus versus temperature curve predicting shape memory behavior. Indeed, good shape memory performances were obtained with shape fixity (Rf) and shape recovery (Rr) ratios.

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Fabrication of Thermo-Responsive Controllable Shape-Changing Hydrogel.

Project description:Temperature response double network (DN) hydrogels comprising a network formed by polymerization of methacrylic acid (MA) modified PVA, N,N'-methylene bis(acrylamide), N-isopropylacryl amide (NIPAM), and one formed from crystalline polyvinyl alcohol (PVA) are prepared in a 3D printed tailor-made mold. The (PVA-MA)-g-PNIPAAm thermoset intermediate is formed in water by a radical, photo-initiated process, and in the presence of dissolved PVA polymers. A subsequent freezing-thawing sequence induces the crystallization of the PVA network, which forms a second network inside the thermoset NIPAM polymer. The prepared hydrogel is thermoresponsive by the phase transition of PNIPAAm segments (T ≈ 32 °C) and has good mechanical properties (tensile strength 1.23 MPa, compressive strength 1.47 MPa). Thermal cycling between room temperature at 40 or 50 °C shows the product converses from a virgin-state to a steady-state, which most likely involves the reorganization of PVA crystals. The swelling-deswelling cycles remain clear at a length change of about 13%.

| S-EPMC9498808 | biostudies-literature

Norbornene-functionalized methylcellulose as a thermo- and photo-responsive bioink.

Project description:Three-dimensional (3D) bioprinting has emerged as an important tool to fabricate scaffolds with complex structures for tissue engineering and regenerative medicine applications. For extrusion-based 3D bioprinting, the success of printing complex structures relies largely on the properties of bioink. Methylcellulose (MC) has been exploited as a potential bioink for 3D bioprinting due to its temperature-dependent rheological properties. However, MC is highly soluble and has low structural stability at room temperature, making it suboptimal for 3D bioprinting applications. In this study, we report a one-step synthesis protocol for modifying MC with norbornene (MCNB), which serves as a new bioink for 3D bioprinting. MCNB preserves the temperature-dependent reversible sol-gel transition and readily reacts with thiol-bearing linkers through light-mediated step-growth thiol-norbornene photopolymerization. Furthermore, we rendered the otherwise inert MC network bioactive through facile conjugation of integrin-binding ligands (e.g. CRGDS) or via incorporating cell-adhesive and protease-sensitive gelatin-based macromer (e.g. GelNB). The adaptability of the new MCNB-based bioink offers an attractive option for diverse 3D bioprinting applications.

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Shape memory polyurethanes crosslinked with castor oil-based multifunctional polyols.

Project description:As both the industry and academia become more focused on biomass-based smart materials, they are attracting a lot of attention. There has been a significant effort in the field of polyurethane (PU) synthesis to replace polyols used in synthesis with bio-derived polyols. Bio-derived polyols have limited application potential for bio-based PU due to their low functionality. Here, we reported castor oil (CO) based multifunctional polyols prepared by grafting thiols such as 1-mercaptoethanol or α-thioglycerol via a facile thiol-ene click reaction method (coded as COM and COT, respectively). Subsequently, bio-based shape memory polyurethanes (SMPU) crosslinked with prepared polyols were synthesized using a 2-step prepolymer method. By confirming the functionality of the synthesized polyols, it was determined that COT has an OH value of 380 mg KOH/g, which is approximately three times that of CO. The successful synthesis of SMPUs was confirmed through chemical structural analysis. It was also proved that the phase separation between the soft and hard segments was limited due to the increase in crosslinking density. As compared to SMPU crosslinked with CO, the mechanical strength of SMPU crosslinked with COT was improved by 80%, while the elongation was decreased by about 26%. As a result of shape memory behavior analysis, it was confirmed that the outstanding SMPU can be synthesized using CO-based multifunctional polyols.

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