Physical Cross-linking Points Research Articles

Dynamic Non-Covalent Bonds Powering Enhanced Temporary Shape Retention Temperature and Mechanical Robustness in Shape Memory Polyurethane.

Shape memory polyurethane (SMPU) with excellent mechanical properties holds significant application value in engineering. However, achieving high strength and toughness typically relies on hydrogen bonding for energy dissipation, which limits the application of such PUs due to their deformation temperature being below room temperature. Here, we introduce a rigid long-chain polyamide acid with a rich aromatic structure as a chain extender, combined with metal coordination, to develop a shape memory polyurethane with a phase transition temperature of 50 °C and outstanding mechanical performance. The presence of rigid segments of polyamic acid (PAA) and -COOH not only increases the rigidity of the polyurethane chains but also promotes the formation of hydrogen bonds and π-π conjugation, leading to physical cross-linking points and significant microphase separation, resulting in superior mechanical properties for PU-PAA. The dynamic bonding characteristics impart self-healing and solvent recyclability to PU-PAA. The coordination interactions enhance the cross-linking points, enabling PU-PAA-Eu to exhibit excellent shape fixation and recovery rates, as well as fluorescence properties. Additionally, due to the presence of -COOH, PU-PAA demonstrates remarkable adhesion to various metals. This work provides a strategy toward the development of high performance SMPU and holds promising potential for applications such as anticounterfeit coatings.

Super-Tough, Non-Swelling Zwitterionic Hydrogel Sensor Based on the Hofmeister Effect for Potential Motion Monitoring of Marine Animals.

Hydrogel-based electronic devices in aquatic environments have sparked widespread research interest. Nevertheless, the challenge of developing hydrogel electronics underwater has not been profoundly surmounted because of the fragility and swelling of hydrogels in aquatic environments. In this work, a zwitterionic double network hydrogel comprisedof polyvinyl alcohol (PVA), poly(sulfobetaine methacrylate) (PSBMA), and sulfuric acid (H2SO4) demonstrates super-tough and non-swelling performance. The Hofmeister effect of H2SO4 and PSBMA induces the PVA chains to form numerous nanocrystalline domains, which serve as the primary physical crosslinking points and provide effective energy dissipation. H2SO4 induces a strong salting-out effect to facilitate PVA crystallization and the formation of a dense and stable network structure that inhibits swelling. The resulting hydrogel exhibits an ultra-high toughness of 4.61MJm-3, non-swelling, and long-term stability for up to a month in pure water and seawater. Based on this, a hydrogel-based seawater strain sensor has been developed to monitor the underwater movements of marine animal models. Reliable and stable sensing performance ensures real-time collection of underwater motion signals, despite the impacts of water flow and the interference of ions. This study provides a facile approach to designing super-tough and non-swelling hydrogels and further expands the application of underwater electronic devices.

Ag-S coordination strategy for high recovery driving stress in recyclable shape memory polymers

To address the issue of low strength and recovery stress in recyclable shape memory polymer (SMP) materials with dynamic covalent bonds in practical applications, we propose a method based on Ag-S coordination interactions to improve dynamic covalent bonds, thereby preparing recyclable SMP with high recovery stress and large recovery strain. The introduction of in situ reduced silver nanoparticles (AgNPs) in the SMP system play multiple roles, serving as additional physical crosslinking points at the microscale and coordinating with disulfide bonds in the system to construct a multi-level dynamic network structure. This endows the material with exceptional mechanical properties (tensile strength of 25.93 MPa and fracture strain of 1466.83 %) and recovery driving stress (5.59 MPa), while maintaining more than 99 % shape recovery and fixity rate. Furthermore, due to the outstanding photothermal performance of AgNPs, the composite material has acquired remote photothermal driving capabilities. The proposed Ag-S coordination enhancement offers a new approach for SMP materials that achieve both large actuation distance and high recovery stress, holding significant potential for applications in soft robotics and actuators.

Preparation of accelerated-wound-healing lignin/dopamine-based nano-Fe3O4 hydrogels in sensing

Flexible conductive hydrogels hold great promise for applications in motion and medical detection. It is difficult to produce conductive hydrogel epidermal sensors in wearable hydrogels with dependable adhesion, sensing, and wound-healing properties. Nano-Fe3O4 was used as physical cross-linking points in the polyacrylamide/polyvinyl alcohol double network (PP) to increase the strain capacity of the hydrogel. The conductive lignin-dopamine (LD) was immobilized on the surface of Fe3O4 particles, and the LD-coated Fe3O4 was then incorporated into the double network hydrogel to create the PP/LD/Fe3O4 hydrogel. This work was done to look into the possibility of using Fe3O4 hydrogels as flexible strain sensors. The addition of LD/Fe3O4 caused the composite hydrogel to strain up to 124 %, with a modulus of elasticity of 21,308 Pa and electrical conductivity as high as 2.3 S•m−1 following the introduction of LD/Fe3O4. Moreover, the PP/LD/Fe3O4 hydrogel's adhesive qualities offered adequate antimicrobial properties and promoted wound healing. These results indicate that the developed electricity-responsive and tissue-adhesive hydrogel dressing offers a candidate to serve as a tissue sealant for wound healing.

Grafting of nonpolar polyisoprene as midblock and polar polylactide as outer block onto cellulose to produce bio-based thermoplastic elastomers

Sustainable cellulose-graft-diblock copolymers (cellulose-graft-polyisoprene-block-polylactide, MCC-g-PI-b-PLLA, MCC was chemically-modified microcrystalline cellulose) were designed and delicately synthesized for the first time by a mild and facile procedure via combining ring-opening polymerization and reversible addition-fragmentation chain transfer polymerization techniques, which conquered the difficulties in synthesis due to the distinct chemical properties among the MCC backbone, PI and PLLA blocks. Two separate glass transition temperatures were detected for MCC-g-PI-b-PLLA copolymers by differential scanning calorimetry, indicative of microphase separation, consistent with small-angle X-ray scattering and atomic force microscopy measurements. The α-form crystals of PLLA outer blocks were revealed by wide-angle X-ray diffraction measurement. The monotonic and step-cyclic tensile tests revealed that the mechanical property could be tuned by changing the molecular mass of PI midblock. The two ends of the soft PI midblock were anchored by rigid cellulose backbone and hard PLLA outer block, respectively, which served as physical crosslinking points. The rigid cellulose backbones brought the PI rubbery domains and PLLA hard domains together to form a whole hierarchical microstructure, endowing the copolymers with distinguished mechanical property. This work provided a feasible approach to producing environmental-friendly cellulose-based copolymers with fully biomass-derived feedstocks, having a profound impact on the development of sustainable polymer-based materials.

Synchronously enhanced breakdown strength and energy storage ability of cellulose acetate flexible films via introducing ultra-low content of carbonized polymer dots

Developing green and environmentally friendly biomass materials for energy storage and application is of great significance to sustainable development. Novel composite films containing cellulose acetate (CA) and carbonized polymer dots (CPDs) are reported herein. The CPDs have strong hydrogen bonding interactions with CA matrix, in which CPDs act as the physical crosslinking points and enhance the entanglement density of the matrix. And the composite films demonstrate a significant enhancement in breakdown strength (Eb), reaching up to 520.58 MV/m with the addition of 0.1 wt% CPDs (1.62 times higher than 321.94 MV/m of pure CA). Furthermore, the discharging energy density (Ud) achieves 2.55 J/cm3 at 450 MV/m, which is 1.36 times higher than that of the pure CA film (1.87 J/cm3 at 400 MV/m) and simultaneously, the energy efficiency (η) is maintained at 73.3 %. The Coulomb-blockade effect induced by the ultra-low content of CPDs effectively inhibiting carrier migration, and the enhanced entanglement density of the matrix improving mechanical properties and reducing polarization loss, mainly contribute to the enhanced dielectric performances. Furthermore, CPDs also improve the mechanical properties of the composite films apparently. This work provides some references for the fabrication of the next generation of environmentally friendly dielectric composite films.

Polybutylene adipate terephthalate/polylactic acid interface enhanced compatibilization and its bead-foaming characteristics

Bead foaming technique is regarded as a highly promising method for preparing foams with complex geometries and high expansion ratios. The biodegradability of poly(butylene adipate-co-terephthalate) (PBAT) has garnered significant attention in the field of foam materials. However, due to inherent disadvantages such as low melt strength and low modulus, PBAT faces challenges during bead foaming. In this study, a small amount of polylactic acid (PLA) was incorporated into PBAT. Utilizing the differential melting points of PLA and PBAT, PLA served as physical cross-linking points. The epoxy-based chain extender ADR4370S was used as a chain extender and compatibilizer. By varying its content, the compatibility and foaming performance of the PBAT/PLA blend were regulated. Finally, the foaming process employed supercritical carbon dioxide (scCO2) impregnation followed by heating to address the hydrolysis issue of the PBAT/PLA blend during bead foaming. The results demonstrated that the introduction of ADR could initiate reactions between its epoxy groups and PBAT and PLA, resulting in grafting and chain extension. When the ADR content reached 0.6 wt%, the cell structure evolved from a bimodal to a uniform cell structure, with a minimum average cell size of 12.3 μm and a maximum foaming ratio of 10.3 times.

An NIR-responsive hydrogel loaded with polydeoxyribonucleotide nano-vectors for enhanced chronic wound healing

Chronic diabetic wounds are difficult to treat due to imbalanced inflammatory responses, high blood glucose levels, and bacterial infections. Novel therapeutic approaches based on nucleic acid analogues have been proposed, with unique advantages in improving angiogenesis, increasing collagen synthesis, and exerting anti-inflammatory effects. However, the inherent electronegativity of nucleic acids makes them less susceptible to cellular uptake. In this paper, a kind of near infrared (NIR)-responsive nanocomposite hydrogel loaded with nucleic acid vectors was proposed for promoting wound healing. The redox system composed of molybdenum disulphide nanosheets (MoS2 NSs) initiated the copolymerization of quaternized chitosan containing double bonds and N-isopropylacrylamide (NIPAAm) to form the matrix. In addition, MoS2 NSs with photothermal conversion performance endow the nanocomposite hydrogel to have NIR-response property and act as physical crosslinking points in the matrix. Polydeoxyribonucleotides (PDRN), which have the effect of promoting wound healing, were made into nucleic acid vectors, and loaded into the NIR-responsive hydrogel. MoS2 NSs can convert NIR irradiation into heat, causing phase transitions of temperature-sensitive segments that trigger volume contraction of the hydrogel to extrude the nucleic acid vector. Promoting angiogenesis, slowing inflammation, and guiding tissue regeneration were demonstrated in the diabetic wound model treated with the NIR-responsive nanocomposite hydrogel.

Preparation of fully physically crosslinked double-network gel and its fire prevention mechanism

It is important to gain an in-depth understanding of the structure of fire prevention and extinguishing materials during self-heating of coal. In this paper, an Al3+-CMC/PAM-MMT fire prevention and extinguishing gel with double-network was prepared using sodium carboxymethyl cellulose (CMC) and polyacrylamide (PAM) as raw materials, and aluminum citrate (AlCit) and sodium montmorillonite (Na-MMT) as auxiliary materials, by introducing the fully physically crosslinking effect. The optimal amounts of CMC, PAM, AlCit and MMT were determined to be 2 %, 3 %, 8 %, and 3 %, respectively, based on gelation time, stability, and resistance of the gel. The micromorphological image of the double-network gel exhibited a laminar structure of parallel-aligned fibrous networks, where the pores and channels exhibited more complex shapes and became smaller in size, highlighting the superiority of the double-network architecture. The rheological tests showed that the double-network gel had superior structural stability and viscosity under varying shear rates, making it more effective in covering the fire source, enhancing extinguishing efficiency. Additionally, its higher storage and loss moduli indicated stronger elasticity and mechanical properties compared to the single-network gel, emphasizing its advantages in energy storage and recovery. The characterization of active functional groups showed that there was an effective suppression of reactions involving hydroxyl, hydrocarbon, and carbonyl functional groups, during the spontaneous combustion process of coal, following treatment with the gel. Additionally, a proposed mechanism for the gel formation was presented. In the sealing performance test, the pressure-bearing capacity of the double-network gel was approximately twice that of the single-network gel. It indicated that the multi-level structure formed by the gel led to higher density of physical cross-linking points, which provided better sealing performance. Thermogravimetric analysis showed significant decrease in total calorific value and increase in activation energy of coal, after treatment with the gel, rendering it more difficult for spontaneous coal combustion. In the small-scale fire extinguishing performance test, the double network of Al3+-CMC/PAM-MMT gel demonstrated effective suppression of spontaneous combustion of coal and reduced the susceptibility to re-ignition. The fire prevention mechanism of the gel was further explored experimentally.

Neural network inspired bionic ordered structure polyaniline gel for wearable sensor

In recent years, remarkable progress has been made in the research and development of traditional conductive polymer gel wearable sensors. However, it is still a challenge to achieve high sensitivity and mechanical strength at the same time due to the influence of the characteristics of conductive material in gels. Herein, inspired by human neural network, a novel biomimetic ordered polyaniline conductive gel is presented with stable conductivity (18.04 S/m), excellent sensitivity (GF of 3.53) under the condition of high elongation (stretching of 400 %-500 %), good mechanical properties, biocompatibility, and anti-freezing performance. This conductive gel is composed of maleic anhydride modified γ-cyclodextrin, polyaniline, and polyacrylamide. Modified γ-cyclodextrin can be firmly fixed on the polyacrylamide skeleton of the gel through chemical bonds. The aniline is evenly distributed in the hydrophobic cavity of modified cyclodextrin through hydrophobic interaction, and an ordered polyaniline network with γ-cyclodextrins as a physical crosslinking point is formed in the gel. This biomimetic ordered structure greatly improves the toughness and conductivity of the polyaniline network, which significantly enhances the sensing ability of polyaniline gels. This work is expected to provide a novel method for improving the mechanical and electrical properties of polyaniline gels and pave an avenue for the uniform dispersion of non-polar substances in polar gels.

Strong and tough conductive hydrogels via an amphiphilic macromolecular crosslinker for flexible strain sensor

The strength and toughness of hydrogel are usually achieved through the synergy of chemical cross-linking and physical cross-linking from multi-component contributions. However, there are few reports on hydrogels that rely on a single component to obtain two cross-linked structures. Herein, we successfully synthesized an amphiphilic macromolecular crosslinker (polyoxyethylene 20 oleyl ether acrylate (O20AC)), and introduced it into a system composed of acrylamide (AAm), sodium chloride (NaCl) and water to prepare the P(AAm-O20AC)/NaCl hydrogel with high strength, outstanding toughness, and excellent good conductivity. Notably, the O20AC possess both crosslinker properties, which not only provide hydrogels with a stable chemical cross-linking network, but also its long hydrophobic chain act as physical crosslinking points to give the hydrogel a new pathway of energy dissipation.Depending on the O20AC crosslinker, the P(AAm-O20AC)/NaCl hydrogels exhibit good strength (tensile stress 714.46 kPa), toughness (elongation at break 3005 %), and fatigue resistance (overlap of hysteresis curves in repeated loading–unloading cycles). Besides, the existence of sodium ions and chloride ions also provides the hydrogel with highly sensitive deformation-dependent conductivity (GF is 5.8 in the 400 %-500 % strain range). Collectively, the strategy of preparing chemical and physical double-crosslinked hydrogels by amphiphilic O20AC will provide a bran-new insights for the development of hydrogel sensing materials.

Sustainable Polymers with High Performance and Infinite Scalability

AbstractOur society has been pursuing high‐performance biodegradable polymers made from facile methods and readily available monomers. Here, we demonstrate a library of enzyme‐degradable polymers with desirable properties from the first reported step polyaddition of diamines, COS, and diacrylates. The polymers contain in‐chain ester and thiourethane groups, which can serve as lipase‐degradation and hydrogen‐bonding physical crosslinking points, respectively, resulting in possible biodegradability as well as upgraded mechanical and thermal properties. Also, the properties of the polymers are scalable due to the versatile method and the wide variety of monomers. We obtain 46 polymers with tunable performance covering high‐Tm crystalline plastics, thermoplastic elastomers, and amorphous plastics by regulating polymer structure. Additionally, the polymerization method is highly efficient, atom‐economical, quantitatively yield, metal‐ and even catalyst‐free. Overall, the polymers are promising green materials given their degradability, simple and modular synthesis, remarkable and tunable properties, and readily available monomers.

Sustainable Polymers with High Performance and Infinite Scalability.

Our society has been pursuing high-performance biodegradable polymers made from facile methods and readily available monomers. Here, we demonstrate a library of enzyme-degradable polymers with desirable properties from the first reported step polyaddition of diamines, COS, and diacrylates. The polymers contain in-chain ester and thiourethane groups, which can serve as lipase-degradation and hydrogen-bonding physical crosslinking points, respectively, resulting in possible biodegradability as well as upgraded mechanical and thermal properties. Also, the properties of the polymers are scalable due to the versatile method and the wide variety of monomers. We obtain 46 polymers with tunable performance covering high-Tm crystalline plastics, thermoplastic elastomers, and amorphous plastics by regulating polymer structure. Additionally, the polymerization method is highly efficient, atom-economical, quantitatively yield, metal- and even catalyst-free. Overall, the polymers are promising green materials given their degradability, simple and modular synthesis, remarkable and tunable properties, and readily available monomers.

Sustainable ultra-strong polyesteramide elastomers with rapid degradation and high resilience

Degradable polymers typically require prolonged exposure to harsh conditions for degradation, but this extended duration and severe treatment often result in incomplete breakdown, leading to the formation of harmful microplastics that pose significant environmental pollution risks. In this work, degradable alternating polyamide hard segments and soft crystallizable segments were combined by amide groups to design thermoplastic bio-based polyesteramide elastomers (PEAEs) with customizable properties and rapid degradability. The hard segment of the polymer features an alternating arrangement of amide and ester bonds. This arrangement facilitates the formation of small molecule monomers when the ester bond is broken, preventing microplastic contamination that may arise from incomplete degradation of the hard segment. Additionally, the inclusion of side groups in the soft segment disrupts the crystallization, enhancing its susceptibility to solvent penetration and thereby accelerating the degradation rate. After step-cyclic tensile tests, additional physical cross-linking points were formed in PEAEs to enhance their mechanical strength and elasticity. Furthermore, PEAEs demonstrated outstanding processing capabilities, including compounding, extrusion, pelletization, and spinning. This innovative approach introduces fresh design concepts for the industrial application of bio-based degradable polymers, playing a pivotal role in advancing resource conservation and environmental protection.

Construction of porous and hydrophilic polypropylene-based membrane with microphase separation in amorphous region

Polypropylene (PP) membrane with low porosity and poor hydrophilicity limits the performance of lithium-ion batteries. In mechanism, the function of amorphous structure of precursor film on microporous structure of PP membrane is yet unknown. In this work, the porous and hydrophilic PP/reduced hydroxyl-modified polypropylene (PPrOH) membrane was fabricated by blending esterified-PPOH firstly and then hydrolyzing to introduce the hydrogen bond in amorphous region and avoid phase separation. The results showed that the hydrogen bond was successfully introduced into the amorphous region of PP/PPrOH film and led to an increase of physical crosslinking points. Therefore, a large region of microphase separation emerged in the PP/PPrOH membrane after cold stretching, which resulted in a 45.6 % increase of porosity at maximum compared to the PP membrane. Besides, the hydrophilicity of PP/PPrOH membrane was improved with the blend content exceeding 10 wt%. Eventually, the lithium-ion conductivity of PP/PPrOH-10 membrane enhanced by 37.5 % over the base PP membrane. This work provides a novel perspective for preparing hydrophilic PP membrane with high porosity.

High mechanical properties nanocomposite hydrogel achieved based on montmorillonite and tailored microgel suspensions reinforcing polyacryamide networks

Hydrogels have attracted much attention because of their softness and water retention ability, but their poor mechanical properties have severely limited their application in various aspects. Herein, we reported a strategy to fabricate polyacrylamide/montmorillonite nanocomposite hydrogel by introducing montmorillonite via a facile and universal two-step method composed of microgel suspension system and in situ free radical polymerization. Compared with microgel, microgel suspension is simpler to prepare and better dispersed in hydrogels, which it could act as physical crosslinking points, interpenetrate with polyacrylamide networks embedded, and serve as sacrifical bonds to strengthen the hydrogels. Simultaneously, montmorillonite synergistically facilitated the formation of a robust and uniform polymer structure through the interaction of hydrogen bonds and polyacrylamide networks, resulting in significant improvements in mechanical properties. As a result, the satisfactory mechanical properties of the nanocomposite hydrogels are achieved at a relative high water content (80 wt%), including a superior compressive strength (95% deformation) of 37.96 MPa, tensile strength of 311.1 ± 8.2 kPa, elongation at break of 316.5 ± 21.1%, Young's modulus of 165.8 ± 7.5 kPa, and excellent toughness of 644.1 ± 21.8 kJ/m3, respectively. In addition, it was found that the hydrogel had excellent cycle compression stability through 10 cycles of loading and unloading at 80% strain. These new high-performance nanocomposite hydrogels are expected to be used in the fields of structural or load-bearing materials.

Dynamic Shape Change of Liquid Crystal Polymer Based on An Order‐Order Phase Transition

AbstractLiquid crystal actuators conventionally undergo shape changes across an order‐disorder phase transition between liquid crystal (LC) and isotropic phases. In this study, we introduce an innovative Liquid Crystal Polymer (LCP) actuator harnessing an order‐order LC phase transition mechanism. The LCP film is easily stretchable within the LC phase, facilitated by the π–π stacking of phenyl groups serving as robust physical crosslinking points, and thereby transforms to a stable monodomain structure. The resultant monodomain LCP actuator shows a distinctive reversible dynamic shape change, exhibiting extension followed by contraction along the LC director on cooling. The extension is propelled by the reversible smectic C to smectic A phase transition, and the contraction is attributed to the re‐entry to the smectic C phase from smectic A phase. Thermal annealing temperature determines this peculiar dynamic shape change, which occurs during both heating and cooling processes. This pivotal attribute finds manifestation in gripper and flower‐shaped actuators, adeptly executing grabbing and releasing as well as blooming and closure motions within a single thermal stimulation. In essence, our study introduces an innovative approach to the realm of LCP actuators, ushering in a new avenue for the design and fabrication of versatile and dynamically responsive LCP actuators.

Dynamic Shape Change of Liquid Crystal Polymer Based on An Order-Order Phase Transition.

Liquid crystal actuators conventionally undergo shape changes across an order-disorder phase transition between liquid crystal (LC) and isotropic phases. In this study, we introduce an innovative Liquid Crystal Polymer (LCP) actuator harnessing an order-order LC phase transition mechanism. The LCP film is easily stretchable within the LC phase, facilitated by the π-π stacking of phenyl groups serving as robust physical crosslinking points, and thereby transforms to a stable monodomain structure. The resultant monodomain LCP actuator shows a distinctive reversible dynamic shape change, exhibiting extension followed by contraction along the LC director on cooling. The extension is propelled by the reversible smectic C to smectic A phase transition, and the contraction is attributed to the re-entry to the smectic C phase from smectic A phase. Thermal annealing temperature determines this peculiar dynamic shape change, which occurs during both heating and cooling processes. This pivotal attribute finds manifestation in gripper and flower-shaped actuators, adeptly executing grabbing and releasing as well as blooming and closure motions within a single thermal stimulation. In essence, our study introduces an innovative approach to the realm of LCP actuators, ushering in a new avenue for the design and fabrication of versatile and dynamically responsive LCP actuators.

Mussel-inspired adhesive and anti-swelling hydrogels for underwater strain sensing.

The application of hydrogels in an underwater environment is limited due to their swelling behavior and the existence of a hydration layer. In this study, a hydrogel based on poly(sulfobetaine methacrylate) (PSBMA), tannic acid (TA) and montmorillonite (MMT) was prepared with excellent anti-swelling properties and underwater self-adhesion properties. The PSBMA hydrogel has excellent anti-swelling properties due to the strong electrostatic interaction between charged groups of PSBMA chains. Inspired by marine mussels, tannic acid modified montmorillonite (TA@MMT) was introduced. Natural polyphenol tannic acid, as a catechol donor, provides a large number of catechol groups for hydrogels. Montmorillonite acts as the physical cross-linking point of PSBMA chains through electrostatic interaction to improve the cohesion of the hydrogel. By combining the adhesion mechanism of zwitterions and catechol, the hydrogel maintains adhesion in air and underwater environments. In addition, a strain sensor was prepared based on the PSBMA/TA@MMT hydrogel, which can closely fit the human skin and stably monitor different movements in air and in underwater environments. Through a Bluetooth communication system, long-distance information transmission can be achieved. Therefore, the PSBMA/TA@MMT hydrogel broadens the application prospect of wearable devices in the underwater environment.

Organic-inorganic polyureas with benzyl hindered urea bonds and POSS cages in the main chains: Synthesis, shape memory and reprocessing properties

The organic–inorganic polyureas with benzyl hindered urea bonds (HUBs) and POSS cages as the main-chain structural units were synthesized via the polyaddition of 4,4′-diphenylmethane diisocyanate with α,ω-dibenzyl diamines including α,ω-dibenzylamino-terminated poly(ethylene oxide), N,N’-dibenzylhexamethylene-1,6-diamine and 3,13-dibenzylaminoanilino double decker silsesquioxane. The organic–inorganic PUreas were microphase-separated, in which the POSS cages were self-assembled into the microdomains via POSS-POSS interactions. The POSS microdomains acted as the physical crosslinking points and thus the organic–inorganic PUreas behaved as the crosslinked elastomers; the physical crosslinking remained thermally stable even at elevated temperature as high as 200 °C. In spite of the high thermal stability, the networks can be reprocessed with the plasticity in solids via the dynamic exchange of benzyl HUBs. Due also to the physical crosslinking, the organic–inorganic PUreas possessed the excellent shape memory properties; the original shapes were re-configurable by taking advantage of the benzyl HUBs in the main chains.