Cyclopentadiene‐functionalized polyketone as self‐cross‐linking thermo‐reversible thermoset with increased softening temperature

Self‐cross‐linkable thermo‐reversible thermosets were obtained by a two‐steps post‐functionalization of aliphatic alternating polyketones yielding two different cyclopentadiene functionalization degree of 9 and 22% (with the respect of initial 1,4‐dicarbonyl units). Thermo‐reversibility was verified by gelation experiments and differential scanning calorimetry (DSC) scans displayed a broad transition varying from 75–100°C till 160°C that can be related to retro‐Diels Alder de‐bonding of the dicyclopentadienyl moieties. The dynamic mechanical thermal (DMTA) analysis showed the complete thermo‐mechanical recovery of the material up to six thermal cycles with a softening temperature around 210°C, thereby ensuring a suitable application window for high‐temperature resistant thermosets. Independently of the exact mechanism at the molecular level and in addition to previous studies which used the same Diels‐Alder diene‐dienophile system, it must be noticed that all prepared materials retained their mechanical behavior during at least six consecutive thermal cycles, thus indicating the re‐workability of the system. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42924.     

Polyether–maleimide‐based crosslinked self‐healing polyurethane with Diels–Alder bonds

The Diels–Alder (DA) reaction is particularly desirable for the preparation of heat‐stimuli self‐healing polymeric materials because of its thermal reversibility, high yield, and minimal side reactions. Some attempts were conducted to synthesize polyether–maleimide‐based crosslinked self‐healing polyurethane with DA bonds (C‐PEMIPU–DA) through the reactions of the prepolymer (polymeric MDI/PBA‐1000) functionalized by furfuryl amine and polyether–maleimide without benzene in this study. The structures of intermediates and C‐PEMIPU–DA were first confirmed by ¹H‐NMR, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Next, the thermal reversibility and the self‐healing performance of C‐PEMIPU–DA were studied by ¹H‐NMR, polarizing optical microscopy, tensile testing, and a sol–gel process. The results show that C‐PEMIPU–DA exhibited interesting properties of thermal reversibility and self‐healing. The polymers could be applied to self‐healing materials or recyclable materials in the fields of the repair of composite structures and aging parts because of their thermosetting properties at room temperature and thermoplasticity at higher temperatures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41944.     

A dual‐induced self‐expandable stent based on biodegradable shape memory polyurethane nanocomposites (PCLAU/Fe3O4) triggered around body temperature

Concerning the occurrence of in‐stent restenosis and stent thrombosis of stent implantation with balloon angioplasty, a dual‐induced self‐expandable stent based on biodegradable shape memory polyurethane nanocomposites (PCLAU/Fe₃O₄) was developed. The stent could maintain its temporary shape at body temperature for a certain period of time while it was able to recover to its permanent shape at the temperature a little above body temperature (around 40 °C) in both a water bath and an alternating magnetic field. The trigger temperature and remote local heating ensured enough operation time and harmless activation without heating the body tissue. The nanocomposites had high fixing ratios above 99% and recovery ratios above 82% at both 37 and 40 °C. Cytotoxicity and in vitro degradation showed the nanocomposites had good biocompatibility and biodegradability. The PCLAU/Fe₃O₄ nanocomposites with dual‐responsive shape memory effects, desirable mechanical properties, biocompatibility, and biodegradability show great potential for vascular stents. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45686.     

A seawater‐assisted self‐healing metal–catechol polyurethane with tunable mechanical properties

Recently, self‐healing polymers have been one of the most intriguing academic fields due to the fact that they can increase their service lives and reduce the amount of waste. Here we designed and synthesized a novel telechelic polyurethane with dopamine (DA) end groups that are coordinated with Ca²⁺ to form dynamic non‐covalent bonds. The tensile stress of the designed polyurethanes increases with increase in the amount of metal cation added, while the strain at break slightly decreases. Rheological tests show that the ionic coordination between Ca²⁺ and catechol can dynamically break and recombine under the stimulation of seawater, endowing the polymer with superior self‐healing properties (up to 84% based on toughness). Therefore, the seawater‐triggered self‐healable, super tough polyurethane presented here is very intriguing as it has many potential applications especially in the marine environment. © 2019 Society of Chemical Industry     

Self‐healing polyurethane nanocomposite films with recoverable surface hydrophobicity

It is a great challenge for self‐healing materials to recover their mechanical property and surface hydrophobicity simultaneously after being damaged severely, such as deep and wide surface scratches. In this work, a series of hydrophobic films were prepared by mixing perfluoroalkyl‐loaded SiO₂ nanoparticles with thermally self‐healing polyurethane. The Diels–Alder reaction of furan groups with bismaleimides endowed the polyurethane with self‐healing property, and the introduction of perfluoroalkyl chains gave surface hydrophobicity. When being heated, the low surface energy compounds could gradually move onto the surface to make the surface hydrophobicity recoverable. The self‐healing mechanical property and recoverable hydrophobicity would improve the durability and expand the application of polyurethane nanocomposites as self‐cleaning and self‐healing coatings/surfaces. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46421.     

Multi‐stimuli responsive shape memory polymers synthesized by using reaction‐induced phase separation

Thermo‐induced multishape memory polymers are a growing focus of smart materials because of its promising applications. Multishape memory effect is generally attained by using polymers with broad phase transition and multiphase polymers. The latter is of particular interest for copolymerization and polymer compositing. One requirement has to be fulfilled to achieve multishape memory effect, which is to have two reversible phase transitions. In this study, we report synthesis of polymer composite composed of strong segregated polymers by using reaction‐induced phase separation. We demonstrate the method by using polyurethane (PU) and poly(methacrylic acid) (PMAA). With adjusting the weight ratio, the polymer composites exhibit a phase spectrum from phase separation to miscible composite. The composite with PU/PMAA =3:1 demonstrated triple‐shape memory effect. Based on the results, we argued the effect of segregation on the shape memory effect for polymer composites. With the addition of PMAA, the polymer composite also exhibits pH/water‐induced shape memory effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43534.     

Fast swelling behaviors of thermosensitive poly(N‐isopropylacrylamide‐co‐methacryloxyethyltrimethyl ammonium chloride)/Na2WO4 cationic composite hydrogels

A facile method was explored to synthesize thermosensitive poly[N‐isopropylacrylamide (NIPAM)‐co‐methacryloxyethyltrimethyl ammonium chloride (DMC)]/Na₂WO₄ cationic hydrogels via copolymerization of NIPAM and DMC in the presence of Na₂WO₄. Na₂WO₄ acted as both a physical crosslinking agent and a porogen precursor. The hydrogels were characterized by Fourier transform infrared spectroscopy, energy dispersive X‐ray, thermogravimetry, environmental scanning electron microscopy, and transmission electron microscopy. Effects of various salt solutions, pH solutions on swelling were investigated. Thermosensitivity of the hydrogels were also investigated in various polar solvents at different temperatures. The resultant hydrogel showed a fast swelling rate and good salt tolerance. The hydrogels reached the swelling equilibrium within 10 min. Moreover, the swelling ratio of the hydrogels increased with the increase of the polarity of the solvent. In the water, the swelling ratio decreased with the increasing of temperature, but remained at a high level even at 80 °C since the pore structure weaken the lower critical solution temperature effect of PNIPAM. The swelling ratio increased instead in low polar solvent, while it became negligible in nonpolar solvent with the increasing of temperature. The whole swelling kinetics was fit for Schott's pseudo‐second order model. The hydrogels have a great potential as catalysts and smart materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46375.     

High temperature resistant silane/zirconium‐oxocluster hybrid copolymers containing “free” thiol/ene functionalities in the polymer matrix

Inorganic–organic hybrid copolymers are promising materials where the size of the inorganic/organic domains, the phase continuity and the interface between the domains play an important role in their behavior. Two types of hybrid copolymers composed of 3‐butynoate‐substituted zirconium‐oxoclusters covalently bonded to a (3‐mercaptopropyl)trimethoxysilane or a vinyltrimethoxysilane matrix are investigated in bulk. Their properties are directly correlated with the degree of condensation of the silanes and the alkyne‐3‐mercaptopropyl or alkyne‐vinyl interface. Both copolymers show storage moduli and glass‐transition temperatures (T_gG″) above 130 MPa and 230°C. However, the more impressive results are achieved with the (3‐mercaptopropyl)trimethoxysilane copolymer where a T_gG″ of about 300°C holds over six dynamical mechanical spectroscopy analyses. In addition to their excellent thermo‐mechanical proprieties, the copolymers show unreacted 3‐mercaptopropyl or vinyl groups which could be employed either in direct usage of the materials or for post‐functional modifications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermally and magnetically dual‐responsive mesoporous silica nanospheres: preparation,characterization, and properties for the controlled release of sophoridine

Novel thermally and magnetically dual‐responsive mesoporous silica nanoparticles [magnetic mesoporous silica nanospheres (M‐MSNs)–poly(N‐isopropyl acrylamide) (PNIPAAm)] were developed with magnetic iron oxide (Fe₃O₄) nanoparticles as the core, mesoporous silica nanoparticles as the sandwiched layer, and thermally responsive polymers (PNIPAAm) as the outer shell. M‐MSN–PNIPAAm was initially used to control the release of sophoridine. The characteristics of M‐MSN–PNIPAAm were investigated by transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetry, N₂ adsorption–desorption isotherms, and vibrating specimen magnetometry analyses. The results indicate that the Fe₃O₄ nanoparticles were incorporated into the M‐MSNs, and PNIPAAm was grafted onto the surface of the M‐MSNs via precipitation polymerization. The obtained M‐MSN–PNIPAAm possessed superparamagnetic characteristics with a high surface area (292.44 m²/g), large pore volume (0.246 mL/g), and large mesoporous pore size (2.18 nm). Sophoridine was used as a drug model to investigate the loading and release properties at different temperatures. The results demonstrate that the PNIPAAm layers on the surface of M‐MSN–PNIPAAm effectively regulated the uptake and release of sophoridine. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40477.     

Shape‐memory polyurethane/multiwalled carbon nanotube fibers

Shape‐memory polyurethane/multiwalled carbon nanotube (SMP–MWNT) composites with various multiwalled carbon nanotube (MWNT) contents were synthesized, and the corresponding SMP–MWNT fibers were prepared by melt spinning. The influence of the MWNT content on the spinnability, fracture morphology, thermal and mechanical properties, and shape‐memory behavior of the shape‐memory polymer was studied. The spinning ability of SMP–MWNTs decreased significantly with increasing MWNT content. When the MWNT content reached 8.0 wt %, the fibers could not be produced because of the poor rheological properties of the composites. The melt‐blending, extrusion, and melt‐spinning processes for the shape‐memory fiber (SMF), particularly at low MWNT contents, caused the nanotubes to distribute homogeneously and preferentially align along the drawing direction of the SMF. The crystallization in the SMF was promoted at low MWNT contents because it acted as a nucleation agent. At high MWNT contents, however, the crystallization was hindered because the movement of the polyurethane chains was restricted. The homogeneously distributed and aligned MWNTs preserved the SMF with high tenacity and initial modulus. The recovery ratio and recovery force were also improved because the MWNTs helped to store the internal elastic energy during stretching and fixing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and pH‐responsive performance of silane‐modified poly(methylacrylic acid)

The poly(methylacrylic acid) modified by silane [poly(methylacrylic acid‐co‐vinyl triethoxylsilane) (PMAA)] was prepared via free‐radical polymerization with different mass ratios of methylacrylic acid to vinyl triethoxylsilane (VTES). The swelling performance of the prepared PMAA in different solutions with various pH values, salt species (NaCl and CaCl₂), and concentrations was investigated in detail. The results indicated that the introduction of silane boosted the stability of the obtained PMAA in aqueous solutions in the presence of an increased quantity of VTES additive. Meanwhile, the different swelling ratios of PMAA in various pH solutions showed a high pH responsivity. In addition, we found that when the PMAA underwent a number of swelling–deswelling cycles, it demonstrated the good reversibility properties when the pH value of the swelling medium was changed from 9.0 to 1.4. Moreover, the swelling mechanism of PMAA in different solutions with different pH values was investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40403.     

Preparation and assessment of a self‐healing material based on microcapsules filled with ethyl phenylacetate

A self‐healing material was developed on the basis of a biological system. The self‐healing epoxy resin, which incorporated microcapsules filled with ethyl phenylacetate (EPA), was investigated. The microcapsules were prepared by an in situ polymerization method. The microcapsule‐formation process was monitored by optical microscopy, and the surface morphology was observed by scanning electron microscopy (SEM). The self‐healing performance of the epoxy resin was assessed by manual and in situ healing experiments. We investigated the effects of the healing time, amount of EPA, and degree of curing of matrix on the healing performance by manually injecting EPA into the crack plane. The maximum healing efficiency was obtained within 24 h. The swelling curve was overlaid onto the healed load plot; this indicated that crack healing was achieved as a result of solvent diffusion. The healing load reached the maximum value when the amount of EPA was 0.5 μL and was capable of filling the crack volume. Moreover, the healing performance was related to the degree of swelling. The in situ healing efficiency was dependent on the microcapsule concentration. The fracture toughness could be fully restored when the microcapsule concentration was 10%. Finally, the crack interface was analyzed with SEM. The results show that the fracture line was difficult to detect, and this suggested complete crack healing by EPA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43430.     

Thermoresponsive crosslinked isocyanate‐free polyurethanes by Diels‐Alder polymerization

This new study is a continuation of our previous work on thermocleavable nonisocyanate polyurethanes (NIPUs), but it is focused on crosslinked networks. Two systems are studied: the first system involves a dicyclocarbonate adduct with a PPO‐bicyclocarbonate and a triamine as crosslinker. The second system involves a tetracyclocarbonate DA adduct as crosslinker with the same PPO‐bicyclocarbonate and a difunctional amine. Firstly, Diels‐Alder adducts are synthesized and characterized. Then they are copolymerized to yield two types of cleavable polymer networks. The thermal behavior of synthesized polymers is fully characterized. Finally, by SEC, it was demonstrated that the obtained NIPU polymer chains are sliced up by rDA reaction. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44408.     

Facile synthesis of functional copolymers with pendant vinyl groups by using asymmetrical divinyl monomers

Polymers bearing pendant vinyl groups have attracted significant attraction because they can be further modified for required applications, but their syntheses are still a big challenge. Herein, allyl methacrylate was catalyzed using a phosphazene base to homopolymerize or copolymerize with 2‐(N, N‐dimethylamino) ethyl methacrylate, affording vinyl functional polymers, which were further successfully tailored by the thiol–ene coupling reaction. The result showed that both the homopolymerizations and copolymerizations could proceed at room temperature with very high monomer conversions. The contents of pendant double bonds in the copolymers were approximately equal to the monomer feeds, but the LCST of the statistical copolymers linearly decreased with increasing AMA content. This strategy offered a new scalable and facile strategy for vinyl functional polymers, would have a wide practical application in many fields. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42758.     

Synthesis of end‐functionalized poly(N‐isopropyl acrylamide) with zinc porphyrin and its photocatalytic activity under visible light

A series of well‐defined linear poly(N‐isopropyl acrylamide) with an asymmetrical zinc(II) porphyrin (ZnPor–PAM) end group was synthesized by atom transfer radical polymerization, wherein 5,10,15,20‐tetra(p‐bromopropanoyloxyethylphenyl) zinc porphyrin tripropionate was used as the initiator and CuBr/tris(2‐dimeoethyl)amine was used as the catalyst system. The structure of the ZnPor–PAM was characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. In addition, the polydispersity index (PDI) obtained by gel permeation chromatography indicated that the molecular weight distribution was narrow; thus, the polymerization was well controlled (1.05 < PDI < 1.21). Because of the incorporation of hydrophobic porphyrin, the lower critical solution temperature of ZnPor–PAM was lower than that of the N‐isopropyl acrylamide homopolymer. Most interestingly, the ZnPor–PAM possessed remarkable photocatalytic activity for the oxidative degradation of methylene blue in the presence of hydrogen peroxide under visible‐light radiation. Moreover, ZnPor–PAM could be reused through the uncomplicated procedure, which exploited the thermoresponsive properties of ZnPor–PAM without any significant loss in activity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40523.     

Thermally activated shape memory behavior of melt‐mixed polyurethane/cellulose nanocrystal composites

Building blocks made from renewable sources attract increasing attention for the design of new polymer systems. Recently, in this particular context, cellulose nanocrystals (CNCs) have gained great interest in both academic research and industry, mainly on account of their ability to reinforce range of polymer matrices and afford nanocomposites with attractive mechanical properties. The limited thermal stability of conventionally produced cellulose nanocrystals (CNCs) has, however, so far limited the range of polymers that could be used as basis for melt‐processed CNC nanocomposites. We herein show that a commercially accessible nanocrystal source, a particular grade of microcrystalline cellulose (MCC), can easily be converted into thermally stable CNCs by ultrasonication in phosphoric acid. A scalable melt‐mixing process was used to produce nanocomposites of these CNCs with a thermoplastic polyurethane (TPU) elastomer. A significant improvement of the room temperature storage modulus from 40 MPa (neat polymer) to 120 MPa (10% w/w CNC) was observed. The introduction of CNCs not only increased the stiffness of the polymer matrix, but also improved the shape memory properties of the nanocomposite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45033.     

Autonomic self‐healing of poly(vinyl butyral)

The self‐healing behavior of poly(vinyl butyral) (PVB) is evaluated below the glass transition temperature T_g. It is found that PVB shows autonomic self‐healing even at room temperature, although T_g is around at 76°C. Furthermore, a large amount of water is found to be adsorbed on the surface of the film. This is attributed to the surface localization of hydroxyl group in PVB, which is confirmed by X‐ray photoelectron spectroscopy. Since the surface is plasticized by water, the scar applied by a razor blade is healed even in the glassy state of the bulk. Moreover, the healing efficiency is enhanced at high humidity condition, owing to the pronounced plasticizing effect by water. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42008.     

Concentration effect on aggregation and dissolution behavior of poly(N‐isopropylacrylamide) in water

The concentration effect on aggregation and dissolution behavior of poly(N‐isopropylacrylamide) (PNIPAM) in water was studied. Three concentration regimes with different phase behavior were identified by differential scanning calorimetry (DSC). Further optical, light‐scattering, and rheological studies indicated that the appearance of different regimes arose from their corresponding solution structures below lower critical solution temperature (LCST): free chains and small clusters in regime I, large clusters in regime II, and a gel‐like network in regime III. Different solution structures below LCST led to different phase‐separated patterns formed above LCST: colloidal particles in regime I, large precipitate in regime II, and the sponge‐like solid in regime III, which was well understood based on the overlapping parameter P. Different phase‐separated patterns therefore resulted in different remixing behavior as observed by DSC. This work suggests that the swelling and collapse behavior of PNIPAM based hydrogels was controlled through the design of their phase‐separated patterns, and therefore provided a way to develop high performance thermo‐sensitive materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41669.     

Synthesis and characterization of temperature‐responsive poly(vinyl alcohol)‐based copolymers

A poly(vinyl alcohol) (PVA)/sodium acrylate (AANa) copolymer was synthesized to improve the water solubility of PVA at the ambient temperature. Furthermore, a series of temperature‐responsive acetalyzed poly(vinyl alcohol) (APVA)‐co‐AANa samples of various chain lengths, degrees of acetalysis (DAs), and comonomer contents were prepared via an acid‐catalysis process. Fourier transform infrared and ¹H‐NMR techniques were used to analyze the compositions of the copolymers. The measurement of the turbidity change for APVA‐co‐AANa aqueous solutions at different temperatures revealed that the lower critical solution temperature (LCST) of the copolymers could be tailored through the control of the molecular weight of the starting PVA‐co‐AANa, DA, and comonomer ratios. Lower LCSTs were observed for APVA‐co‐AANa with a longer chain length, a higher DA, and fewer acrylic acid segments. In addition, the LCSTs of the APVA‐co‐AANa aqueous solutions appeared to be salt‐sensitive. The LCSTs decreased as the concentration of NaCl increased. Moreover, atomic force microscopy images of APVA‐co‐AANa around the LCST also proved the temperature sensitivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrorheological behavior of side‐chain polysiloxane containing 3‐(4‐amidophenyl) sydnone moieties

Side‐chain polysiloxane containing 3‐(4‐amidophenyl) sydnone moieties at terminal and aliphatic spacer has been synthesized and its structure was confirmed by FTIR and ¹H‐NMR. Low mass molar weight sydnone exhibited electrorheological effect, which was enhanced by electron‐donor substituted group at phenyl, but weakened by electron‐acceptor substituted group. By introducing sydnone into polysiloxane, the polymer displays the higher electrorheological effect due to the increased interaction between sydnone molecules. The oxide states of sydnone affect the electrorheological effect as well as the color of the product. Moreover, the temperature is higher than the glass transfer temperature of the polymer; the electrorheological fluids show a very large leakage current. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2523–2528, 2004