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Three-dimensional (3D) bioprinting has emerged as an important technique for fabricating tissue constructs with precise structural and compositional control. However, developing suitable bioinks with biocompatible crosslinking mechanisms remains a significant challenge. This study investigates extrusion-based bioprinting (EBB) using uniaxial or coaxial nozzles with enzymatic crosslinking (EC) to produce 3D tissue constructs in vitro. Initially, low-molecular-weight dextran-tyramine and hyaluronic acid-tyramine (LMW Dex-TA/HA-TA) bioink prepolymers were evaluated. Enzymatically pre-crosslinking these prepolymers, achieved by the addition of horseradish peroxidase and hydrogen peroxide, produced viscous polymer solutions. However, this approach resulted in inconsistent bioprinting outcomes (uniaxial) due to inhomogeneous crosslinking, leading to irreproducible properties and suboptimal shear recovery behavior of the hydrogel inks. To address these challenges, we explored a one-step coaxial bioprinting system consisting of enzymatically crosslinkable high-molecular-weight hyaluronic acid-tyramine conjugates (HMW HA-TA) mixed with horseradish peroxidase (HRP) in the inner core and a mixture of Pluronic F127 and hydrogen peroxide in the outer shell. This configuration resulted in nearly instantaneous gelation by diffusion of the hydrogen peroxide into the core. Stable hydrogel fibers with desirable properties, including appropriate swelling ratios and controlled degradation rates, were obtained. The optimized bioink and printing parameters included 1.3% w/v HMW HA-TA and 5.5 U/mL HRP (bioink, inner core), and 27.5% w/v Pluronic F127 and 0.1% H2O2 (sacrificial ink, outer shell). Additionally, optimal pressures for the inner core and outer shell were 45 and 80 kPa, combined with a printing speed of 300 mm/min and a bed temperature of 30 °C. The extruded HMW HA-TA core filaments, containing bovine primary chondrocytes (BPCs) or 3T3 fibroblasts (3T3 Fs), exhibited good cell viabilities and were successfully cultured for up to seven days. This study serves as a proof-of-concept for the one-step generation of core filaments using a rapidly gelling bioink with an enzymatic crosslinking mechanism, and a coaxial bioprinter nozzle system. The results demonstrate significant potential for developing designed, printed, and organized 3D tissue fiber constructs. [ABSTRACT FROM AUTHOR]

Purpose: This paper aims to investigate the effects on coatings performance in the epoxy silicone resin system owing to the existence of the different chain length of open-chain epoxy monomer. In this paper, [4-Methylphenyl-(4–(2-methylpropyl) phenyl)]iodonium as photoinitiator was added into epoxy silicone resin by ultraviolet (UV)-cured polymerization to investigate the effects on coatings performance owing to the existence of the different chain length of open-chain epoxy monomer. Design/methodology/approach: A simple hydrosilylation reaction was used to synthesize epoxy-based silicone prepolymers by using hydrogen-terminated polydimethylsiloxane, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene and 1,2-epoxy-9-decene as precursors. Findings: The results revealed that the glass transition temperatures (Tg) and hydrophobicity increased with the chain length of open-chain epoxy monomer in the UV curable epoxy-based silicone coatings, and these films had excellent heat resistance, hydrophobicity, antigraffiti and ink removal properties. Research limitations/implications: The cationic photocuring systems are not susceptible to the effect of oxygen inhibition. However, the limitation of cationic light curing process is that it requires a long curing time. Originality/value: The coatings prepared via the UV curing approach can provide superior antismudge effects, and thus they are promising candidates for use in various industries, especially in fields such as antismudge coatings and antigraffiti coatings. [ABSTRACT FROM AUTHOR]

Acrylic pressure‐sensitive adhesives (PSAs) were synthesized using a solvent‐free ultraviolet‐induced polymerization method. The monomers n‐(isobutoxymethyl) acrylamide, 2‐ethylhexyl acrylate, 2‐hydroxyethyl acrylate, and methyl methacrylate and an initiator, hydroxy dimethyl acetophenone, were used to prepare acrylic copolymers as prepolymers. A multifunctional monomer, trimethylolpropane triacrylate, was added to form a semi‐interpenetrating network, leading to an increase in the modulus and elasticity of the prepolymer. This decreased the peel strength, which is suitable for temporary protective films. Rheological data from small‐amplitude oscillatory shear measurements also revealed consistent results suitable for removable PSAs. The plasticizers, such as dioctyl phthalate and dioctyl terephthalate, possessing favorable interactions with the main resins were found to exhibit transparency, clear debonding, and ultralow release, which are essential features for temporary protective films. [ABSTRACT FROM AUTHOR]

Attenuated total reflection Fourier transform infrared (ATR-FTIR) tests were performed on a series of polyurethane prepolymer samples prepared from polymeric methylene diisocyanate (pMDI) and polyether polyol. The absorbance A of the infrared characteristic peak (~ 2 245 cm-1) and the corrected peak area S of isocyanate group (--NCO) were used to linearly fit with the content of--NCO obtained by potentiometric titration, respectively. The results showed that the linear relationship of the latter was better than the former, the correlation coefficients R² were 0.9967 and 0.9856, respectively. According to the working curve between the corrected peak area S and the content of --NCO, the content of --NCO of newly prepared prepolymers were determined. Compared with the potentiometric titration method, the relative error of new working curve was <0.2%, and the relative standard deviation was <0.5%, indicating that the test accuracy is good enough and the method is reliable. As ATR-FTIR is used to determine the --NCO content of polyurethane prepolymer, the sample does not need any pretreatment and volume of samples are tiny. In this way, it does not produce waste liquid and is environmentally friendly. The test results are reliable, and it is convenient for operation and application in industrial production site. [ABSTRACT FROM AUTHOR]

The water extractability and acute aquatic toxicity of seven aliphatic diisocyanate-based prepolymer substances were investigated to determine if lesser reactivity of the aliphatic isocyanate groups, as well as increased ionization potential of the expected (aliphatic amine-terminated) polymeric hydrolysis products, would in- fluence their aquatic behavior compared to that of previously investigated aromatic diisocyanate-based prepolymers. At loading rates of 100 and 1,000 mg/L, only the substances having log Kow ≤9 exhibited more than 1% extractability in water, and a maximum of 66% water extractability was determined for a prepolymer having log Kow = 2.2. For the more hydrophobic prepolymer substances (log Kow values from 18-37), water extractability was negligible. High-resolution mass spectrometric analyses were performed on the water-accommodated fractions (WAF) of the prepolymers, which indicated the occurrence of primary aliphatic amine-terminated polymer species having backbones and functional group equivalent weights aligned to those of the parent prepolymers. Measurements of reduced surface tension and presence of suspended micelles in the WAFs further supported the occurrence of these surface-active cationic polymer species as hydrolysis products of the prepolymers. Despite these characteristics, the water-extractable hydrolysis products were practically nontoxic to Daphnia magna. All of the substances tested exhibited 48-h EL50 values of >1,000 mg/L, with one exception of EL50 = 157 mg/L. The results from this investigation support a grouping of the aliphatic diisocyanatebased prepolymers as a class of water-reactive polymer substances having predictable aquatic exposure and a uniformly low hazard potential, consistent with that previously demonstrated for the aromatic diisocyanatebased prepolymers. [ABSTRACT FROM AUTHOR]

In this study, ureidopyrimidinone moieties (UPy), capable of physical crosslinking via quadruple hydrogen bonding, were successfully incorporated into UV-curable polyurethane acrylate prepolymers. First, a hydroxyl-terminated unsaturated ester monomer was synthesized and reacted with isophorone diisocyanate to create a hydroxyl-terminated UV-curable urethane oligomer (U–OH). Then, isocyanate-terminated building blocks (UPy moieties and an acrylate-based photosensitive monomer) were synthesized and used in various ratios to functionalize U–OH for the preparation of a series of UV-curable UPy-containing polyurethane acrylate (PUA) resins. The resulting products were structurally characterized using 1H NMR and FTIR spectroscopy. Furthermore, organic–inorganic hybrid nanocomposites were obtained by introducing silane coupling agents into PUA resins using the sol–gel process. A series of UV-curable UPy-containing PUA coatings and hybrid nanocomposites were prepared, and their synergistic effect on coating properties was investigated. The dynamic mechanical analysis revealed that the Tg of the samples increased with increasing UPy content, although the mechanical properties remained largely unaltered, as shown by the stress–strain test. The studies also demonstrated that the hybrid nanocomposites exhibited higher decomposition temperatures and better thermal stability compared to pure PUAs. All the coatings exhibited good transparency in the visible region. An optical microscope was used to investigate the self-healing property by scratching the plexiglass panels with a razor blade. Among the other samples, the coating with the highest percentage of UPy content exhibited the best self-healing ability after heat treatment at 90 °C for 10 min. [ABSTRACT FROM AUTHOR]

Highlights This study focused on the preparation of bamboo flour/Poly (butylene adipate‐co‐terephthalate) (PBAT) composites with high bamboo flour content and high mechanical strength using polyurethane prepolymer as chemical–physical compatibilizer via in‐situ reaction. Additionally, this work explored the effects of different bamboo flour contents and different types of polyurethane prepolymers on the mechanical properties, morphology, thermodynamics, water absorption, and surface wettability of the bamboo flour/PBAT composites. The results showed that PBA‐based polyurethane prepolymer (PBAPU) was an effective compatibilizer, promoting the interfacial adhesion between bamboo flour and PBAT. The strength at break, elongation at break, and impact strength of composites with 50% bamboo flour content reached 19.56 MPa, 25.53%, and 12.8 KJ/m2. With the increase of bamboo flour content, the strength of composites was still higher. The addition of PBAPU enhanced the thermal stability, mechanical properties, water resistance, and hydroscopicity of the bamboo flour/PBAT composites. Furthermore, the compatibilization of PBA‐based polyurethane prepolymer on composites was better than that of PCL‐based polyurethane prepolymer. Overall, we provided an effective strategy for preparing renewable, green, and practical high‐bamboo flour composites. This work successfully prepared bamboo flour/PBAT composites with high bamboo content using an in‐situ melt blending reaction. A new interface structure of physical PBA‐PBA interaction between the PBAPU layer and PBAT matrix improved the compatibilization of the composites. PBAPU as a compatibilizer effectively improved the interface compatibility, thermal stability, and water resistance of Bamboo flour/PBAT blends. Bamboo flour/PBAT composites with high bamboo flour content have excellent mechanical properties. [ABSTRACT FROM AUTHOR]

In this study, a series of hindered urea bond (HUB) containing polyurethane-urea methacrylate prepolymers and a none HUB containing polyurethane methacrylate prepolymer were prepared using isobornyl methacrylate as the reactive diluent via one-pot procedure. The prepolymers were characterized fully by various techniques. Then, their thermosets were fabricated via UV curing in presence of a photo initiator, and their mechanical property and thermal behavior were investigated and compared. Different from the none HUB containing thermoset, the HUB containing thermosets (defined as PUT) could be recycled and reprocessed by hot press under relatively mild conditions with high recovery ratio of mechanical property. Furthermore, zinc oxide (ZnO) nanoparticles were modified with 3-(trimethoxysilyl) propyl methacrylate and the modified ZnO (defined as ZnO-TPM) was dispersed and polymerized into PUT matrix to prepare their nanocomposites. The influence of ZnO-TPM on the mechanical performance of the composites was evaluated, which indicated that the Young's modulus and tensile strength increased gradually to the maximum values at ZnO-TPM content of 1 wt% and then decreased. The composites also displayed good reprocessability with improved recovery ratio compared to the pure PUT sample. In addition, the composite materials exhibited strong UV absorption capacity, implying their potential application in the circumstance where UV-shielding was required. [ABSTRACT FROM AUTHOR]

In this study, a series of crosslinked waterborne polyurethane/acrylate copolymer latexes with different compositions were fabricated via emulsion polymerization using oil-soluble initiator (AIBN) based on a solvent-/emulsifiers-free method. Using the blend of styrene (St), butyl acrylate (BA) and crosslinkers (pentaerythritol triacrylate (PET3A) and pentaerythritol tetraacrylate (PET4A)) instead of acetone as a diluent and modifier, polyurethane prepolymers terminated with hydroxyethyl acrylate composite emulsions were prepared using polypropylene glycol (PPG), toluene diisocyanate (TDI), 2,2-dihydroxymethylpropionic acid (DMPA) and diethylene glycol (DEG) without other solvents. It was found that for all the emulsion polymerization of waterborne polyurethane and acrylates initiated by AIBN, the monomer conversions exceeded 96% when the concentration of AIBN was in the range of 0.5% to 0.9% (w/w) and the optimal reaction temperature was 75 °C. The introduction of St, BA and crosslinkers would form the polymer network, improving the tensile strength, water absorption of the copolymer latex films. Dynamic light scattering analyses showed that the copolymer latexes exhibited a unimodal distribution and showed no precipitates and unstable aggregates. The average particle size distribution was in the range of 131–154 nm. Transmission electron microscopy studies have confirmed the similar results and the latex particles possessed the core–shell morphology structure. [ABSTRACT FROM AUTHOR]

Polyurethane/2-hydoxyethyl methacrylate (PU/2-HEMA) hybrids with the modifying properties of unsaturated polyester resin (UPR) were prepared through two steps of polymerization. In the first step, polyurethane prepolymers (PUA) were prepared with an NCO/OH ratio of 2.2 by a polyaddition reaction based on isophorone diisocyanate (IPDI), polyoxypropylene glycol (PPG 2000), and PPG 2700. In the second step, the hybrid was prepared by adding and mixing different contents of 2-hydroxyethyl methacrylate (2-HEMA) to prepolymer polyurethane (PUA). The effect of PUA and PUA/2-HEMA hybrid on the physicomechanical properties of UPR films was studied, including viscosity, compressive strength, hardness, thixotropy, and gamma radiation resistance. The addition of PUA/2-HEMA hybrids improved the physical and mechanical properties of UPR more than the addition of PUA owing to the existence of functional groups derived from PUA and PUA/2-HEMA, such as NCO, double bonds, and NH, which can establish cross-linking between UPR and PUA, as well as between UPR and PUA/2-HEMA. The findings demonstrate that the mechanical properties improve with dose, indicating cross-linking involving the double bonds of 2-HEMA, NH, C=O, as well as the ether group over oxidative degradation. However, an increase in 2-HEMA content in PUA hybrids increases the gamma radiation resistance, tensile, and compressive strengths demonstrating that cross-linking leads over oxidative degradation. This is attributed to the formation of the polymeric network as a result of cross-linking between PUA and 2-HEMA as indicated in the experimental results shown in Table 3 and Schemes 2 and 3. [ABSTRACT FROM AUTHOR]

Polyvinyl chloride (PVC) is a kind of plastic widely used in different industries, and it is a hard and brittle polymer that requires the use of plasticizers to improve processability. Phthalates are small molecule plasticizers of PVC, which are easy to volatilize and migrate while improving the processing properties of PVC. We propose alternatives based on phenolic resin prepolymer modified by cardanol (CPF), which were added to PVC as reactive plasticizer and can improve the processability of PVC. The effects of CPF on the rheological properties and migration resistance of plasticized PVC were studied, and the changes in the physical properties of blends were also discussed. The results showed that the viscosity of PVC melt can be reduced by two orders of magnitude by adding 30 wt% prepolymers at 180°C compared with PVC without CPF, which indicated that CPF can be used to reduce the processing temperature of PVC. The test results of migration resistance showed that the mass loss rate of the blend with 30 wt% prepolymers was less than 1 wt% after curing, however, the mass loss rate of the blend with 30 wt% dioctyl phthalate (DOP) was more than 12% after 5 days of testing. When the PVC/CPF mass ratio was between 60/40-70/30, the maximum values of tensile strength and elastic modulus are 64.4 MPa and 3.2 GPa, respectively, which showed the addition of CPF could significantly improve the tensile strength and elastic modulus of the blend system compared with PVC without CPF. Especially, the thermal stability of CPF is better than that of DOP, CPF exhibits the maximum thermal decomposition temperature (410°C), higher than that of DOP (170°C), which can adapt to higher processing temperature. [ABSTRACT FROM AUTHOR]

Hydrogels have emerged as prototypical stimuli‐responsive materials with potential applications in soft robotics, microfluidics, tissue engineering, and adaptive optics. To leverage the full potential of these materials, fabrication techniques capable of simultaneous control of microstructure, device architecture, and interfacial stability, that is, adhesion of hydrogel components to support substrates, are needed. A universal strategy for the microfabrication of hydrogel‐based devices with robust substrate adhesion amenable to use in liquid environments would enable numerous applications. This manuscript reports a general approach for the facile production of covalently attached, ordered arrays of microscale hydrogels (microgels) on silicone supports. Specifically, silicone‐based templates are used to: i) drive mechanical assembly of prepolymer droplets into well‐defined geometries and morphologies, and ii) present appropriate conjugation moieties to fix gels in place during photoinitiated crosslinking via a "graft from" polymerization scheme. Automated processing enabled rapid microgel array production for characterization, testing, and application. Furthermore, the stimuli‐responsive microlensing properties of these arrays, via contractile modulated refractive index, are demonstrated. This process is directly applicable to the fabrication of adaptive optofluidic systems and can be further applied to advanced functional systems such as soft actuators and robotics, and 3D cell culture technologies. [ABSTRACT FROM AUTHOR]

Waterborne polyurethane (WPU) has gained widespread attention. However, conventional linear WPU emulsions have lower mechanical properties, poor water resistance, and other disadvantages. In this study, polyurethane prepolymers containing branched chains were successfully synthesized by using diphenylmethane diisocyanate (MDI), polytetramethylene ether glycol (PTMG) and castor oil (CO) as the main raw materials. On this basis, epoxy resin was used to further modify the obtained polyurethane prepolymers, which results in an increase in mechanical properties, water resistance, and heat resistance due to the formation of a network cross-linked structure during the film formation. The type and addition amount of epoxy resin were determined by centrifugal stability and particle size of WPU emulsions, water absorption, and mechanical properties of WPU films. The results showed that the prepared epoxy resin–modified WPU (EWPU) emulsions have excellent centrifugal stability. If 7% epoxy resin was added after the polyurethane chain expansion, the corresponding EWPU films have good mechanical properties (the tensile strength of 28.7 MPa and the elongation at break of 379%), water resistance (water absorption of 4.21%), and the thermal stability due to the cross-linked structure in EWPU. This kind of EWPU emulsions may have promising applications in coating material, adhesives, and the textile industry. [ABSTRACT FROM AUTHOR]

In order to improve the poor hydrophobicity and single repair conditions of traditional self-healing polyurethane coatings, prepolymers were synthesized with bio-based polyol castor oil (CO), self-made alkyl aryl modified silicone polyols (Si-OH) and isophorone diisocyanate (IPDI), and 4,4'-dithiodianiline (ODD) was used as chain extender containing dynamic disulfide bond, 4-methylumbelliferone (4-MU), as a bio-based end capping agent with reversible ring structure, was polymerized step by step to prepare a photothermal responsive bio-based superhydrophobic self-healing poly(siloxane-urethane) coating (PUSi). In this paper, the effect of the amount of alkyl aryl modified silicone polyol (Si-OH) on the properties of PUSi was studied. The results showed that PUSi with different alkyl aryl modified silicone polyol additions could achieve self-healing under heating, UV irradiation and infrared light irradiation, and the maximum repair efficiency could reach 91% through optical microscope (OM), 3D profilometer and universal testing machine; The contact angle meter proved that the introduction of alkyl aryl modified silicone polyol greatly improved the hydrophobicity of PUSi, and the maximum water contact angle was 162°. The coating has broad application prospects in the fields of self-cleaning fabrics, super hydrophobic surfaces, special protective clothing and so on. [ABSTRACT FROM AUTHOR]

This publication describes the influence of residue monomers in synthesized pressure-sensitive adhesives based on acrylics on their main properties—tack, peel adhesion, shear strength and shrinkage—in the form of transfer tapes used for joining wooden elements in the furniture industry. The discussed carrier-free adhesive tapes are synthesized via photo-crosslinking and photopolymerization with UV radiation of the photoreactive prepolymers sandwiched between two adhesive siliconized polyester films. The simultaneous crosslinking and polymerization processes carried out under UV lamps placed simultaneously above and below the crosslinked photoreactive polymer layer lead to the production of a carrier-free adhesive film. The preliminary target of these studies was to investigate how the intensity of UV radiation and the time of its exposure affect the viscosity of the photoreactive compositions and the content of unreacted monomers in them. Next, the influence of the crosslinking agent concentration and UV irradiation time on the content of unreacted monomers after the crosslinking process was tested. The last step of the studies was the investigation of the influence of the residue monomer concentration on the application properties of the obtained pressure-sensitive adhesive layers. The typical PSA application properties were tested on the wood samples: tack, peel adhesion, shear strength (cohesion) and shrinkage. [ABSTRACT FROM AUTHOR]

Recently, photocurable coatings are being used frequently. However, it is worth mentioning that the use of photopolymerization has its drawbacks, especially in the case of curing coatings on three-dimensional surfaces and in places that are difficult to access for UV radiation. However, it is possible to develop a system in which UV technology and thermal methods for curing coatings can be combined. Moreover, the obtained resins are derived from low-viscosity epoxy resins or diglycidyl ethers, making them an ideal building material for photopolymerization-based three-dimensional printing techniques. Due to the need to improve this method, a series of epoxy (meth)acrylates containing both epoxy and (meth)acrylate groups were obtained via the addition of acrylic or methacrylic acid to epoxy resin, diglycydylether of bisphenol A epoxy resin (DGEBA), cyclohexane dimethanol diglycidyl ether (CHDMDE) and neopentyl glycol diglycidyl ether (NPDE). The structures of the synthesized copolymers were confirmed through spectroscopic analysis (FTIR) and studied regarding their nonvolatile matter content (NV) and acid values (PAVs), as well as their epoxy equivalent values (EEs). Due to the presence of both epoxy and double carbon–carbon pendant groups, two distinct mechanisms can be applied: cationic and radical. Hence, the obtained resins can be cured using UV radiation with thermally appropriate conditions and initiators. This type of method can be used as a solution to many problems currently encountered in using UV technology, such as failure to cure coatings in underexposed areas as well as deformation of coatings. Synthesized epoxy (meth)acrylate prepolymers were employed to formulate photocurable coating compositions. Furthermore, the curing process and properties of cured coatings were investigated regarding some structural factors and parameters. Among the synthesized materials, the most promising are those based on epoxy resin, characterized by their high glass transition temperature values and satisfactory functional properties. [ABSTRACT FROM AUTHOR]

Patterning of two or more liquids, either homogeneous in each phase or mixed with particles (including biological matter, such as cells and proteins), by controlling their flow dynamics, is relevant to several applications. Examples include dynamic spatial confinement of liquids in microfluidic systems (such as lab-on-a-chip and organ-on-a-chip devices) or structuring of polymers to modulate various properties (such as strength, conductivity, transparency and surface finishing). State-of-the-art strategies use various technologies, including positioners, shakers and acoustic actuators, which often combine limited versatility of mixing with significant inefficiency, energy consumption, and noise, as well as tendency to increase the temperature of the liquids. Here, we describe a new kind of robotic mixers of liquids, based on electro-responsive smart materials (dielectric elastomer actuators). We show for the first time how an efficient soft robotic device can be used to produce, via combinations of rotations and translations, various spatial patterns in liquids and maintain them stable for a few minutes. Moreover, we show that, as compared to a conventional orbital shaker, the new type of robotic device can mix liquids with a higher efficacy (~ 94% relative to ~ 80%, after 8 min of mixing) and with a significantly lower increase of the liquids' temperature (+ 1 °C relative to + 5 °C, after 6 h of mixing). This is especially beneficial when mixing should occur according to controllable spatial features and should involve temperature-sensitive matter (such as biological cells, proteins, pre-polymers and other thermolabile molecules). [ABSTRACT FROM AUTHOR]

The synthesis and characterization of a series of polyurethane ionenes using a non‐isocyanate approach is disclosed. Imidazole‐capped, urethane‐containing prepolymers are prepared by first reacting carbonyl diimidazole (CDI) with several poly(propylene glycol) (PPG) diols with variable molecular weight, followed by subsequent reaction with 3‐aminopropylimidazole (API). Polymerization with 1,4‐dibromomethylbenzene followed by anion exchange resulted in the desired polyurethane ionenes bearing the [NTf2] counteranion as a series of viscous liquids. NMR and FTIR spectroscopy are used to characterize the intermediates and final ionenes, including molecular weight determination by end‐group analysis. A single glass transition temperature (Tg), as determined by differential scanning calorimetry (DSC), is observed for each ionene (−38 to −64 °C) with the Tg decreasing with increasing PPG molecular weight. Thermogravimetric analysis (TGA) indicated a two‐step decomposition for each ionene, with the first being degradation of the PPG segment, followed by the urethane/ionic segment. Microphase separation is observed from x‐ray scattering profiles with Bragg distances that increased with increasing PPG molecular weight. Ionic conductivity is found to be inversely dependent upon DSC Tg at lower temperatures (RT and below); however, at higher temperatures, conductivity appears to be more dependent upon the ability of ionic aggregates caused by phase separation to interact. [ABSTRACT FROM AUTHOR]

The synthesis of isocyanate-terminated polyurethane prepolymers was carried out by reacting toluene diisocyanate (TDI) with an acrylic polyol, PEG-400, and PEG-1000, followed by capping the prepolymers with 2-hydroxyethyl methacrylate (HEMA) to produce polyurethane acrylates. The purpose of this study was to examine how different molecular masses of PEG and HEMA impact the thermal, morphological, and hydrophilic/hydrophobic properties of PUA films. The properties of the polyurethane acrylates were analyzed using various techniques, including DSC, FTIR, TGA, 1H NMR, SEM methods, and water contact angles and gloss tests. The results indicated that microphase separation morphology is prevalent within the PUA containing PEG-1000 and that the hydrophilicity of the PUA film is primarily influenced by the microphase separation behavior. The results revealed that the addition of PEG-400 improved the compatibility of hard and soft segments, leading to a shift toward phase mixing in the microphase separation behavior of PU acrylates. The microphase separation behavior was further studied using FTIR analysis of the C = O stretching vibration, with deconvolution performed using Origin software. The findings provide valuable insights into the structure–property relationships of PU acrylates, which can be utilized to optimize their performance for different applications. [ABSTRACT FROM AUTHOR]

Additive manufacturing technology has significantly impacted contemporary industries due to its ability to generate intricate computer-designed geometries. However, 3D-printed polymer parts often possess limited application potential, primarily because of their weak mechanical attributes. To overcome this drawback, this study formulates liquid crystal/photocurable resins suitable for the stereolithography technique by integrating 4'-pentyl-4-cyanobiphenyl with a photosensitive acrylic resin. This study demonstrates that stereolithography facilitates the precise modulation of the existing liquid crystal morphology within the resin. Furthermore, the orientation of the liquid crystal governs the oriented polymerization of monomers or prepolymers bearing acrylate groups. The products of this 3D printing approach manifest anisotropic behavior. Remarkably, when utilizing liquid crystal/photocurable resins, the resulting 3D-printed objects are approximately twice as robust as those created using commercial resins in terms of their tensile, flexural, and impact properties. This pioneering approach holds promise for realizing autonomously designed structures that remain elusive with present additive manufacturing techniques. Complex computerized geometries can be obtained by additive manufacturing. However, the printing of purely three-dimensional polymer shapes possesses inherent poor mechanical stability. Here, the authors overcome this drawback by the light-driven orientation of liquid crystals to guide the alignment of acrylate prepolymers along the direction parallel to UV light vibrations. [ABSTRACT FROM AUTHOR]

Poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) as a kind of low dielectric polymer has been applied in telecommunications. However, developing PPO based thermosetting resins with good comprehensive properties is highly challenging. Herein, an interpenetrating polymer network (IPN) design strategy for the preparation of methacrylate‐terminated oligo(2,6‐dimethyl‐1,4‐phenylene oxide) (SA9000) based thermosetting resins is presented. Two series of prepolymers are prepared by blending bisphenol A/furfurylamine benzoxazine (B‐f) or bisphenol A/aniline benzoxazine (B‐a) with SA9000. Then the IPN films are fabricated by the programmed temperature rising method with simultaneous polymerization reactions of both SA9000 and benzoxazines. Owing to the intermolecular interactions between SA9000 and benzoxazines, the polymerization peak temperatures of all prepolymers are lower than those of SA9000 and benzoxazines. In comparison with B‐a based films, B‐f/SA9000 films display better miscibility and higher thermal resistances over the entire composition range, due to the strengthened hydrogen bonding and higher cross‐linking density resulting from the presence of furan ring of B‐f. Specifically, B‐f/SA9000 films possess the advantages of low dielectric constants (2.296–2.475) and low‐loss grade dielectric losses (0.00550–0.00683) at 10 GHz. The current work provides a simple and effective path for the fabrication of high‐performance thermosetting PPO resins based on benzoxazine chemistry and IPN structure design. [ABSTRACT FROM AUTHOR]

Polyurethaneimide prepolymer was synthesized using the synthesized chromophore C containing tricyanofuran, hexafluorodianhydride and phenyl diisocyanate as monomers. Polyimide prepolymers were synthesized using fluorinated aromatic diether dianhydride and fluorinated aromatic diamine as monomers. Polyurethaneimide-polyimide (PUI-FPI) copolymers were then synthesized by a polycondensation reaction of the polyimide and polyurethaneimide prepolymers. The electro-optic (EO) PUI-FPI copolymers had a special segment structure and concentrate the advantages of polyurethaneimide and polyimide. The copolymers exhibited good film-forming properties, high glass transition temperature (Tg =196 °C), and high thermal stability (Td up to 358 °C). The copolymers possessed a high EO coefficient (γ33 =72 pm/V) at the 1550 nm wavelength, good long-term electro-poled orientation stability, and low optical propagation loss (1.2–1.4 dB/cm) at 1550 nm. Mach-Zehnder interferometric electro-optic modulators were designed and fabricated using the synthesized copolymer as the waveguide material. The prepared polymer optical waveguide EO modulators showed a good low-frequency electro-optic modulation response. The results showed that the synthesized polyurethaneimide-polyimide copolymers meeted the performance requirements for the preparation of polymeric optical waveguide devices and were suitable as polymeric electro-optic waveguide materials. [ABSTRACT FROM AUTHOR]

In the present work, the influence of glycerol prepolymers as potential chain extenders in the reactive mixture with post-consumer recycled PET (PET-PCR) was studied, namely: poly(glycerol citrate) (PGC), poly(glycerol succinate) (PGSu) and poly(glycerol citrate-co-succinate) (PGCSu). Mixtures of recycled PET with 2 wt% of glycerol prepolymers or Joncryl ADR®4638, a commercial chain extender, were processed in an internal mixer at 265 °C for 6 min and 60 rpm. The compositions were characterized by viscosimetry, carboxylic end groups (CEG) analysis using the Pohl method, crosslinking degree as the percentage of insoluble gel, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The addition of glycerol prepolymers increased the fluidity in the post-consumer PET resin, consequently, decreasing its viscosity by 33% for PETPCR/PGC, 24% for PET-PCR/PGSu, 44% for PET-PCR/PGCSu and 17% PET-PCR/Joncryl; the molecular weight in the order of 42% for PET-PCR/PGC, 31% for PET-PCR/PGSu, 55% for PETPCR/PGCSu and 23% for PET-PCR/Joncryl and increasing the number of carboxylic end groups. Although they did not show extensive chain crosslinking, the samples were fragile and brittle, thus making the tensile test unfeasible. Thermogravimetry showed that the polyesters were thermally stable up to approximately 350 °C and the sample that presented the lowest thermal stability was the PETPCR/PGCSu corroborating to the highest reduction in the molecular weight recorded. The DSC results showed an almost constant melting and glass transition temperature among the samples, a decrease of 8 °C in the crystallization temperature and an increase in the degree of crystallinity relative to neat PET-PCR, which corroborates to the intrinsic viscosity results. These results indicated that at the concentration and processing conditions used, the potential additives to chain extenders had an opposite effect to the desired one, that is, they reduced the molecular weight of recycled PET and the same effect occurred for the commercial chain extender. However, the additive that showed the greatest potential for use as chain extender was PGSu, which presented results similar to the commercial extender Joncryl ADR®4638, composed of multifunctional epoxy groups. [ABSTRACT FROM AUTHOR]

Copolymerizing poly(lactide) with other materials to obtain better comprehensive performance is a effective way to expand its application range. In this work, the precursors of hydroxyl terminated (poly(L-lactide) [PLLA], poly (e-caprolactone) [PCL], poly(D,L-lactide) [PDLLA]) were prepared, and PLLAPCL-PDLLA copolymer were synthesized by chain extension. The effects of the proportion and molecular weight of each component and the amount of chain extender on crystallization, phase structures, mechanical properties and thermal stabilities of PLLA-PCL-PDLLA copolymer were studied in detail. Based on small-angle X-ray scattering results, the competition between crystallization and microphase separation was regulated by the composition and chain length of prepolymers. As the ratio of PLLA/PDLLA was 1:1, crystallization was prevailing and no obvious peak was observed in SAXS pattern. The tensile test results showed that as the ratio of PLLA/PDLLA increased from 1:1 to 1:5, the elongation at break of the copolymer changed from 1.8% to 343%. By using shorter length of PCL and PLLA segments in chain extension, improvement in strength and flexibility were obtained due to moderate degree of crystallization and microphase separation. This work used biodegradable materials to prepare extraordinary toughness copolymers without losing the biocompatibility, which may provide a feasible method for obtaining high toughness and biodegradable PLA-based materials. [ABSTRACT FROM AUTHOR]

Self-polymerization epoxy/phthalonitrile (APPEN) pre-polymers were studied systematically, and then, gelation time and differential scanning calorimetry (DSC) were employed to investigate their curing behaviors. Taking advantage of orthogonal test analysis, the key factors that affected the co-polymerization of APPEN were defined and the appropriate pre-polymerization conditions were analyzed. A possible curing mechanism of APPEN was proposed. Then, the thermomechanical and mechanical properties of glass-fiber-reinforced APPEN laminates (APPEN/GF) prepared at 180 °C were analyzed to understand the cross-linked and aggregation structures. Fracture surface of the composite laminates was also investigated to reveal the copolymerization degree and the interfacial binding. The results indicated that APPEN/GF composites exhibit outstanding mechanical and thermomechanical properties (flexural strength, 712 MPa, flexural modulus, 38 GPa, and Tg > 185 °C). The thermal stability (T5% > 334 °C and IPDT reached 1482 °C) of APPEN/GF composites was also investigated to further reveal the copolymerization between epoxy resin and aminophthalonitrile, which may be beneficial to the application of epoxy-matrix-based composites in the field of high-performance polymer composites. [ABSTRACT FROM AUTHOR]

Copyright of Polymer Materials Science & Engineering is the property of Sichuan University, Polymer Research Institute and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Self‐healable degradable networks encounter a growing popularity for biomedical applications due to their ability to recover their properties after damage. Self‐healable hydrogels dominate with applications in tissue engineering and drug delivery. On the opposite and despite their potential for medical devices, self‐healable elastomers remain scarce, especially if they must be compatible with fused deposition modeling (FDM) 3D‐printing and self‐heal at physiological temperature under a hydrated state. These unmet challenges are addressed in this work with degradable elastomeric networks based on dynamic imine bonds prepared from multi(aldehyde) and multi(amine) hydrophobic PEG‐PLA star‐shaped copolymers. The star topology of these copolymers is the key feature of the strategy as it allows the design of multifunctional high molecular weights pre‐polymers that ensure an efficient dynamic chemical crosslinking while guaranteeing access to the FDM process generally restricted to thermoplastics. The proposed elastomeric networks combine high self‐healing efficiencies at 37 °C (>97%) with mechanical properties compatible with soft tissues and a linear degradation profile. Their FDM processing to produce self‐healable tubular devices is demonstrated. Finally, their cytocompatibility is assessed and confirm their potential as biodegradable elastomeric networks to be used for the design of self‐healable 3D‐printed devices for biomedical applications. [ABSTRACT FROM AUTHOR]

Polyurethanes are one of most versatile and large class of polymer because of its wide range of applications. The products of polyurethane are innovative and life-enhancing that play a unique role in making the world more sustainable and can help to solve some of the world's biggest challenges. Most of the polyurethane products and components are durable and long lasting due to its unique chemical structure. To a large extent, the characteristics of the polyurethane are determined by the chemical nature of the building blocks and modification by the addition of the components in the backbone chain of the polymer. This review summarises the synthesis of polyurethanes using different polyols and pre-polymers from renewable feedstock and modification by maleic anhydride via different synthetic routes for various industrial applications like paints, adhesives, foam, coatings, inks, leathers, toys, automotive, packaging, dispersions, hydrogels, composites, construction etc. The objective of this review is to provide a comprehensive, informative, valuable and critical summary about the current development in the field of maleic anhydride-based polyurethanes. Generally polyurethane synthesized from Renewable as well as petrochemical sources but Polyurethane from Renewable resources is most explored transformation in polymer chemistry. This review highlights the most recent developments in the role of maleic anhydride in polyurethane synthesis from renewable feedstock/ starting material. [ABSTRACT FROM AUTHOR]

UV-curable silicone prepolymer was synthesized by hydrolytic condensation by tetraethyl orthosilicate (TEOS) and γ-methacryloxypropyltrimethoxysilane (KH 570), which can be quickly 3D-printed by light curing LCD 3D printer. The composition and structure of silicone resin were characterized by FTIR and H NMR spectroscopy, and the UV-curing kinetics of silicone prepolymer was studied by HAAKE torque rheometer and RT-IR spectrum. The influence of different mole ratios of TEOS to KH 570 on silicone prepolymer for rapid UV-curing 3D printing were investigated. The results showed that the silicone prepolymer with excellent comprehensive performance and fast UV-curing 3D printing was successfully prepared. When the ratio of TEOS/KH570 was 5:5, its critical exposure was 4.431 mJ/cm², curing depth was 0.5226 mm, and the 3 D-printed silicone prepolymers showed good comprehensive properties. [ABSTRACT FROM AUTHOR]

Nano-titanium dioxides (nano-TiO2) surface modified with isopropyl tri(dioctylpyrophosphate) titanate (NDZ-201), a titanate coupling agent, and 3-glycidoxypropyltrimethoxysilane (KH-560), a silane coupling agent, were separately mixed with bisphenol A epoxy resin (DEGBA) prepolymer and then cured using a UV-normal temperature synergistic curing process. Then, the isothermal curing process of the system was investigated by differential scanning calorimetry (DSC). The relationship between the organization structures, mechanical properties, and heat resistance properties of the cured composites and material formulation was studied, and the DSC results showed that the addition of nano-TiO2 reduced the curing reaction rate constant k1 and increased the k2 of the prepolymer, while the activation energy of the curing reaction after UV irradiation Ea1 decreased, and the activation energy in the middle and later periods Ea2 increased. The characterization results of the composite material showed that nano-TiO2 as a scattering agent reduced the photoinitiation efficiency of UV light, and due to its obvious agglomeration tendency in the epoxy resin, the mechanical properties of the composite material were poor. The dispersibility of the coupling-agent-modified nano-TiO2 in the epoxy resin was greatly enhanced, and the mechanical and heat resistance properties of the composite material improved remarkably. The comparison results of the two coupling agents showed that NDZ-201 had better performance in increasing the impact strength by 6.8% (minimum value, the same below) and the maximum thermal decomposition rate temperature by 4.88 °C of the composite, while KH-560 improved the tensile strength by 7.3% and the glass transition temperature (Tg) by 3.34 °C of the composite. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Materials Science & Engineering (1673-2812) is the property of Journal of Materials Science & Engineering Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The dependence of the polymerization and optical damage thresholds in multi-photon polymerization (MPP) lithography was studied using a broadly-tunable laser system with group delay dispersion (GDD) control. The order of non-linearity and the light–matter interaction mechanisms were investigated using the resolution bridges method for non-photosensitized SZ2080TM and photosensitized SZ2080TM + IRG369 prepolymers. Energy deposition, voxel dimension growth, and the size of the dynamic fabrication window (DFW) were measured in the 700–1300 nm wavelength range at three different pulse durations measured at the sample – 100, 200 and 300 fs. Polymerization was observed at all wavelengths and pulse durations without significant differences in the achieved minimal spatial dimension (< 300 nm). This was achieved despite the broad range of excitation wavelengths used which spanned two- and three-photon absorption bands, and the differences in the absorption spectra of the prepolymers. The lateral and longitudinal voxel growth dynamics revealed an abrupt change in the power dependence of polymerization and a significant variation of the DFW – from 1 at 1250 nm to 29 at 700 nm. This result can be interpreted as a consequence of a change in the instantaneous refractive index and a lowering of the polymerization but not the damage threshold. The optimization of energy delivery to the material by a wavelength-tunable laser source with pulse duration control was experimentally validated. These findings are uncovering the complexity of polymerization mechanisms and are useful in further development of MPP technology. [ABSTRACT FROM AUTHOR]

The development of degradable polymeric materials such as degradable polyurethane or polyurea has been much highlighted for resource conservation and environmental protection. Herein, a facile strategy of constructing mechanically strong and tough poly(urea‐urethane) (PUU) thermosets that can be degraded under mild conditions by using triple boron‐urethane bonds (TBUB) as cross‐linkers is demonstrated. By tailoring the molecular weight of the soft segment of the prepolymers, the mechanical performance can be finely controlled. Based on the cross‐linking of TBUB units and hydrogen‐binding interactions between TBUB linkages, the as‐prepared PUU thermosets have excellent mechanical strength of ≈40.2 MPa and toughness of ≈304.9 MJ m−3. Typically, the PBUU900 strip can lift a barbell with 60 000 times its own weight, showing excellent load‐bearing capacity. Meanwhile, owing to the covalent cross‐linking of TBUB units, all the PUU thermosets show initial decomposition temperatures over 290 °C, which are comparable to those of the traditional thermosets. Moreover, the TBUB cross‐linked PUU thermosets can be easily degraded in a mild acid solution. The small pieces of the PBUU sample can be fully decomposed in 1 m HCl/THF solution for 3.5 h at room temperature. [ABSTRACT FROM AUTHOR]

Neoprene rubber (CR) plasticized with low viscosity benzoxazine prepolymers (CRDBz and CRTBz) are fabricated by a novel process using co-curing mechanism. In this study, the influence of these prepolymers on the mechanical properties and processing behavior of CR has been investigated. It was found that the oscillating torques of DBz, TBz and DOP are 1.27 μN·m, 0.99μN·m and 0.50μN·m at 60 ℃, respectively. Tg decreased with increased DBz and TBz loadings of 5, 10, 15 phr, when the addition amount of DBz and TBz is 10 phr, the glass transition temperature (Tg) of CRDBZ10 and CRTBz10 is -41.70 ℃ and -40.44 ℃, respectively, lower than that of CR, -31.68 ℃. Compared with CR vulcanized rubber, the tensile strength of CRDBz10 and CRTBz10 was increased by 46.2% and 85.7%, respectively, and the elongation at break was increased by about 65.8%% for CRDBz10 and by about 44.4% for CRTBz10. Scanning electron microscope analysis (SEM) provides evidence that adding benzoxazine prepolymer has obvious plasticizing effect. The results of the ageing in ASTM-3 oil (100 ℃ × 72 h) indicated that prepolymers of DBz and TBz had both plasticizing and enhancing effects in CR materials. [ABSTRACT FROM AUTHOR]

Copyright of Materials & Technologies / Materiali in Tehnologije is the property of Institute of Metals & Technology and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

A series of UV-curable urethane (meth)acrylates were obtained by copolymerization of the Diels–Alder adduct (HODA), isophorone diisocyanate, PEG1000, and various hydroxy (meth)acrylates. The aim of the present work was to determine the influence of the chemical structure of the introduced (meth)acrylic groups, i.e., hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate, on the UV-curing process and self-healing properties of cured coatings. The chemical structure of prepolymers was characterized by FTIR and NMR spectroscopy, whereas the UV-curing process was monitored in real time using FTIR and photo-DSC. In turn, the self-healing properties were characterized in relation to the thermally reversible mechanism, which was tested using the following methods: an FTIR spectroscope equipped with a heating attachment; DSC and TG apparatus; and an optical microscope equipped with a stage with programmable heating. The result of comprehensive research on the self-healing of photocurable coatings in the context of the presence of various photoreactive groups and the course of the curing process allows one to control the self-healing process by reducing the effective healing temperature. The self-healing properties, taken together with the fast UV curing of the coatings and excellent properties of cured coatings, make the material attractive for a variety of applications, in particular in cases where coatings are not repaired, e.g., for economic reasons or when it is not possible, such as in flexible electronic screens, car paint film, and aircraft interior finishes. [ABSTRACT FROM AUTHOR]

The reaction of diols with isocyanates, leading to mono-functional and di-functional prepolymers may be investigated using various characterization methods which show the overall conversion of isocyanate monomers. On the other hand, matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) polymer characterization can be employed to identify the monomer units, the end-group functionalities, molecular weight averages, and to determine the copolymer sequence. Herein, we focus on prepolymer synthesis using isophorone diisocyanate (IPDI), a widely used diisocyanate for prepolymers preparation, especially in waterborne polyurethane materials. Thus, the reaction between polyethylene glycol diol and IPDI was in-depth investigated by mass spectrometry to determine the influence of the reaction parameters on the prepolymer's structure. The relative content of the different functional oligomer species at given reaction times was determined in the reaction mixture. More specifically, the offline analysis revealed the influence of reaction parameters such as reaction temperature, the concentration of reactants, and the amount of dibutyltin dilaurate catalyst. The established MALDI MS analysis involved measurements of samples, first, directly collected from the reaction mixture and secondly, following derivatization with methanol. The obtained results revealed the effects of reaction parameters on the functionalization reaction with isocyanates, allowing to achieve a better reaction control. [ABSTRACT FROM AUTHOR]

We used all-atom Molecular Dynamics (MD) computer simulations to study the formation of pre-polymers between the four nucleotides in RNA (AMP, UMP, CMP, GMP) in the presence of different substrates that could have been present in a prebiotic environment. Pre-polymers are C 3 ′ – C 5 ′ hydrogen-bonded nucleotides that have been suggested to be the precursors of phosphodiester-bonded RNA polymers. We simulated wet–dry cycles by successively removing water molecules from the simulations, from ~60 to 3 water molecules per nucleotide. The nine substrates in this study include three clay minerals, one mica, one phosphate mineral, one silica, and two metal oxides. The substrates differ in their surface charge and ability to form hydrogen bonds with the nucleotides. From the MD simulations, we quantify the interactions between different nucleotides, and between nucleotides and substrates. For comparison, we included graphite as an inert substrate, which is not charged and cannot form hydrogen bonds. We also simulated the dehydration of a nucleotide-only system, which mimics the drying of small droplets. The number of hydrogen bonds between nucleotides and nucleotides and substrates was found to increase significantly when water molecules were removed from the systems. The largest number of C 3 ′ – C 5 ′ hydrogen bonds between nucleotides occurred in the graphite and nucleotide-only systems. While the surface of the substrates led to an organization and periodic arrangement of the nucleotides, none of the substrates was found to be a catalyst for pre-polymer formation, neither at full hydration, nor when dehydrated. While confinement and dehydration seem to be the main drivers for hydrogen bond formation, substrate interactions reduced the interactions between nucleotides in all cases. Our findings suggest that small supersaturated water droplets that could have been produced by geysers or springs on the primitive Earth may play an important role in non-enzymatic RNA polymerization. [ABSTRACT FROM AUTHOR]

Encapsulation of water-soluble bioactive compounds for enabling specific accumulation in tumor locations, while avoiding premature clearance and/or degradation in the bloodstream, is one of the main hallmarks in nanomedicine, especially that of NIR fluorescent probes for cancer theragnosis. The herein reported technology furnishes water-dispersible double-walled polyurethane-polyurea hybrid nanocapsules (NCs) loaded with indocyanine green (ICG-NCs), using a versatile and highly efficient one-pot and industrially scalable synthetic process based on the use of two different prepolymers to set up the NCs walls. Flow cytometry and confocal microscopy confirmed that both ICG-loaded NCs internalized in monocyte-derived dendritic cells (moDCs). The in vivo analysis of xenograft A375 mouse melanoma model revealed that amphoteric functionalization of NCs' surface promotes the selective accumulation of ICG-NCs in tumor tissues, making them promising agents for a less-invasive theragnosis of cancer. [ABSTRACT FROM AUTHOR]

In response to environmental concerns and restrictions on isocyanate-based materials, researchers and the coatings industry are focused on developing eco-friendly isocyanate-free polyurethanes. This article introduces a novel class of environmentally-friendly, initiator/catalyst-free, UVcurable, self-healing non-isocyanate polyurethanes (NIPUs) synthesized from bio-based carbonated soybean oil (CSO) and non-toxic coumarin. The synthesis of these polymers is based on using a photo-reactive coumarin that undergoes a reversible [2 + 2] cycloaddition upon exposure to the wavelength of UV light. UV-curable three coumarin-terminated isocyanate-free polyurethane prepolymers were synthesized using CSO and three different amines and epoxy coumarin. Subsequently, a set of cross-linked NIPU polymers were obtained with exposure of 365 nm UV irradiation. The photo-reversible nature of these polymers was investigated in response to various wavelengths of UV radiation. Additionally, their self-healing ability and the thermal and mechanical properties of NIPU coatings were studied using optical microscopy, thermogravimetric analysis, differential scanning calorimetry, and a universal testing machine. The outcomes demonstrate that this polyurethane has the potential to provide a sustainable alternative to isocyanate-based materials. Two examples of stimulated healing are given, that of healing a scratch and the other being the healing of a sample that has been mechanically stressed to failure in a tensile mode. [ABSTRACT FROM AUTHOR]

For cleaning tests, which are important in many industrial processes, there are no test contaminations with which geometry‐independent homogeneous films can be produced. Polymer films can fill this gap when they are able to mimic the properties of reference contaminants. For this purpose, acrylic acid (AA) copolymers are prepared by conventional atom transfer radical copolymerization and subsequent acidolysis of the tert‐butyl acrylate (tBA) prepolymers. In this way polarity and adhesion can be adjusted by the amount of carboxy groups in the polymer. Dynamic contact angle measurements show that the advancing contact angle of acrylic acid/methyl(meth)acrylate statistical copolymer layers increase with decreasing carboxy group content. Cleaning experiments show accordingly that the amount of residual polymer of coatings made from these polymers is dependent on the absolute number of adhesive carboxy groups in the polymer. Therefore, for an adaption of the polymer layers to hydrophilic reference contaminants it is necessary to incorporate additional hydrophilic monomer components into the polymers, which lead to lower contact angles but also stronger adhesion of the layers. Hence, it is shown that the chosen polymer concept is delivering the leverages to adjust the properties of appropriate test contaminants. [ABSTRACT FROM AUTHOR]

As described herein, a simple one-step hydrosilylation reaction was employed to synthesize alicyclic epoxy silicone prepolymers by using poly(dimethylsiloxane-co-methylhydrosiloxane) (PDMS-PHMS) with different hydrogen contents and 4-vinyl-1-cyclohexene-1,2 epoxide (VCHO) as precursors. The structures of the synthesized epoxy polysiloxane oligomer was characterized by Fourier-transform infrared (FTIR) and proton nuclear magnetic resonance (1H-NMR) spectroscopy techniques, thus confirming the successful synthesis of the prepolymers. With the addition of an appropriate amount of cationic photoinitiator, the epoxy polysiloxane prepolymers undergo cationic polymerization under ultraviolet light irradiation and were quickly cured to yield series of epoxy polysiloxane resin films. The performances of these cured films were tested and characterized by various techniques such as UV transmittance, thermal weight loss analysis, and contact angle and pencil hardness measurements. The results revealed that the surfaces of these films were uniform and transparent, and these films had excellent heat resistance, acid resistance, hydrophobicity, and ink removal properties. In addition, the influence of the cycloaliphatic epoxy monomer content on the curing behavior and network performance is explored. This study reveals that the curing rate increases as the amount of grafted cycloaliphatic epoxy monomer is increased and that a denser crosslinking network provides the resultant film. Finally, the photocurable silicone material investigated herein is simple to prepare and has excellent performance, and has potential applications in the field of anti-smudge coatings. [ABSTRACT FROM AUTHOR]

Polyhedral oligomeric silsesquioxane (POSS) is added to poly(hydroxyurethane) (PHU) prepolymers to create hybrid PHUs (HPHUs) with enhanced mechanical and thermal properties. These hybrid materials were then further functionalized with 3‐Isocyanatopropyl(trimethoxy) silane (IPTMS) via the pendent hydroxyl bonds within the backbone of the polymers to obtain a final cured film comparable to conventional polyurethanes (PU), using less isocyanate‐functional material. The incorporation of POSS into PHU prepolymers to obtain HPHUs was supported by gel permeation chromatography, fourier tranform infrared spectroscopy (FTIR) and nuclear magnetic resonance analysis. Furthermore, the thermal degradation of the HPHUs was significantly improved with increasing POSS concentration compared to their PHU counterparts as the degradation temperatures at 50% weight loss increased from 263°C for the PHU to 341°C for the HPHU. Gel content tests in tetrahydrofuran (THF), water, and toluene were performed and gel contents of 87%–99% in THF were observed for the cured films. Water swelling, and contact angle tests confirmed that the POSS‐modified films exhibited hydrophobic behavior. Finally, mechanical properties of the cured films were investigated. The Young's modulus and tensile strength were improved with increasing POSS concentration (from 2.0 to 3.1 MPa and from 0.82 to 1.32 MPa, respectively) and elongations at break up to 41.6% were observed. When compared to a conventional PU sealant, the HPHU achieved a tensile strength that was two‐fold greater and a comparable elongation at break (increasing from 24.8% to as high as 41.6%). [ABSTRACT FROM AUTHOR]

The mechanical properties of HTPE binders have been systemically studied through combining the microstructure molecular simulations with macroscopic experiments. In this study, the crosslinking structures of HTPE binders were established by a computational procedure. Based on the optimized crosslinking models, the mechanical properties and the glass transition temperatures (Tg) of HTPE/N-100, HTPE/HDI, HTPE/TDI, and HTPE/IPDI binder systems were simulated; specifically, the Tg were 245.758 K, 244.573 K, 254.877 K, and 240.588 K, respectively. Then the bond-length distributions, conformation properties, cohesive energy densities, and fraction free volume were investigated to analyze how the microstructures of the crosslinking models influenced the mechanical properties of HTPE binders. Simultaneously, FTIR-ATR spectra analysis of HTPE binders proved that the special peaks, such as -NH and -NCO, could be seen in the crosslinking polyurethane structures synthesized between prepolymers and curing agents. The dynamic mechanical analysis was carried out, and it found that the Tg of HTPE/N-100, HTPE/HDI, HTPE/TDI, and HTPE/IPDI binder systems were −68.18 °C, −68.63 °C, −65.67 °C, and −68.66 °C, respectively. In addition, the uniaxial tension verified that both the ultimate stress and Young's modulus of HTPE binder systems declined with the rising temperatures, while the strains at break presented a fluctuant variation. When it was closer to glass temperatures, especially −40 °C, the mechanical properties of HTPE binders were more prominent. The morphology of the fractured surface revealed that the failure modes of HTPE binders were mainly intermolecular slipping and molecular chain breakage. In a word, the experimental results were prospectively satisfied using the simulations, which confirmed the accuracy of the crosslinking models between prepolymers and curing agents. This study could provide a scientific option for the HTPE binder systems and guide the design of polyurethanes for composite solid propellant applications. [ABSTRACT FROM AUTHOR]

A series of difunctional epoxy methacrylate resins (EAs) containing at least one epoxy and at least one methacrylate group were synthesized by means of an addition reaction between epoxy-terminated diglycidyl ethers and methacrylic acid. In order to investigate the impact of polymer architecture on the course of addition reactions and further coating properties, several different types of diglycidyl ethers, i.e., linear, containing aliphatic or aromatic rings, with a short or polymeric backbone, were employed in the synthesis. The carboxyl–epoxide addition esterification reactions have been found to, in a relatively straightforward manner, control the extent of acrylation depending on the substrate feed ratio and reaction time. The structure of obtained pre-polymers was evaluated by FT-IR and NMR methods. At the same time, the extent of addition reactions was validated via quantitative analysis, including non-volatile matter content (NV), acid value (PAVs), and epoxy equivalent value (EE) analysis. The modification was carried out in a manner likely to create a compound with one epoxy and one carbon–carbon pendant group. Hence, due to the presence of both functionalities, it is possible to crosslink compositions based on synthesized EAs via two distinct mechanisms: (i) cationic polymerization or (ii) free-radical polymerization. Synthesized epoxy methacrylate pre-polymers were further employed for use in formulate photocurable coating compositions by the cationic or radical process. Furthermore, the photopolymerization behavior and properties of cured coatings were explored regarding some structural factors and parameters. The investigated polymeric materials cure in a short time to obtain coatings with good properties, which is why they can be successfully used to produce protective and decorative coatings for many industries. [ABSTRACT FROM AUTHOR]

Polyurethane acrylate prepolymers with different contents of HIPIH and HIH were synthesized via reacting excessive isophorone diisocyanate (IPDI) with poly(propylene glycol) (PPG) and then end-capping with 2-hydroxypropyl methacrylate (HPMA) in isobornyl methacrylate (IBOMA). After the addition of the photoinitiator PI 1173, the resulting prepolymer resins were irradiated by UV light to form cured materials. The structures of the prepolymers were confirmed by 1H NMR, FT-IR, and GPC. SEM analyses proved that no obvious phase separation was observed within the cured sample. As the content of HIH increased, the viscosity of the prepolymers increased slightly. In addition, the gel content, solvent resistance, Shore hardness, Young's modulus, and the tensile strength of the cured films increased, whereas the elongation at break decreased gradually. The volume shrinkage of the cured samples ranged between 4.5% and 4.8%. DMA analyses showed that the Tgs of the cured samples increased as more HIH structures existed. TGA analyses revealed that the cured samples had high thermal stability. This solvent-free fabrication process was simple, convenient, and controllable. By simply regulating the contents of HIPIH and HIH in the prepolymers, the performances of the cured materials could be adjusted to a wide range. [ABSTRACT FROM AUTHOR]

Swollen, surface‐attached hydrogel layers in sliding contact exhibit unusual friction properties. To study this phenomenon, hydrogel layers covalently bonded to solid substrates are generated by CH insertion crosslinking. Brief UV irradiation of thin layers of photoreactive prepolymers leads to simultaneous crosslinking of the polymer chains and attachment of the network to the substrate. As the surface‐attached hydrogel layers can only swell perpendicular to the surface, and the polymer subchains on the two sides of the friction pair cannot interpenetrate for entropic reasons, adhesion in such friction pairs is negligible. In this work, the tribological behavior of surface‐attached hydrogel pairs is investigated as a function of load and sliding velocity. It is observed that for very thin films, the indentation and accordingly the friction is a strong function of the film thickness and the role of the chain confinement on the lubrication of surface‐attached hydrogels is discussed. A model for the friction mechanism of such systems is developed. [ABSTRACT FROM AUTHOR]

Research on biobased thermoset resins has been overlooked when compared with the rapid progress on biobased thermoplastics. The objective of this work was to develop unsaturated polyester prepolymers based on building blocks derived from renewable raw materials, namely, biobased isosorbide, 1,3‐propanediol, and fumaric acid, with petroleum‐derived phthalic anhydride. The prepolymers developed herein behaved as low‐molecular weight macromolecules (oligoesters), with Mn varying between 1.2 and 1.5 kDa, but achieved a high bio‐content of up to 87.1 wt%. The prepolymers were incorporated into reactive diluents comprising a blend of 2‐hydroxyethyl methacrylate and styrene, formulated to be eco‐friendlier and less toxic than typical styrene‐only incorporation approach, thus resulting in resins with viscosities between 750 and 950 cP. These resins are suitable for use in various fiber‐reinforced polymer production techniques, such as manual lamination, vacuum infusion, and pultrusion, having the benefit of presenting over 50 wt% of bio‐content in some formulations. Moreover, the crosslinked polyester resins (thermosets) exhibit comparable mechanical and thermomechanical behavior to their petrochemical‐based counterparts, with modulus of elasticity and tensile strength of up to 3.9 GPa and 62.1 MPa, respectively, and glass transition temperatures of up to 106°C, making them greener alternatives for high‐performance structural applications. [ABSTRACT FROM AUTHOR]