A review of shape memory polymers bearing reversible binding groups

Shape memory polymers (SMP) can be deformed to a stable, temporary shape and recovered to their original shape by applying a stimulus. These networks rely on the presence of two types of net points to establish their permanent and temporary shapes. Classical strategies to stabilize temporary shapes rely on cooling below T_g/T_m where macromolecules become pinned in a stressed state. Recovery of the SMP usually involves heating to above the transition temperature where the permanent shape is remembered. Employing reversible binding groups (RBGs) in SMPs has emerged as an alternative strategy for stabilizing temporary shapes or imparting recyclability of the permanent shape. The use of dynamic chemistry often engenders additional functionality such as intrinsic self-healing characteristics or alternative shape recovery triggering strategies. SMPs bearing both supramolecular and covalent RBGs will be reviewed with an emphasis on hydrogen bonding, ionic interactions, metal–ligand coordination, and dynamic covalent exchange and addition reactions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1340–1364     

Porous shape memory polymers: Design and applications

Porous shape memory polymers (SMPs) exhibit geometric and volumetric shape change when actuated by an external stimulus and can be fabricated as foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. These materials have applications in multiple industries such as textiles, biomedical devices, tissue engineering, and aerospace. This review article examines recent developments in porous SMPs, with a focus on fabrication methods, methods of characterization, modes of actuation, and applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1300–1318     

The copolymerization of propylene with higher,linear α‐olefins

Propylene was copolymerized with the linear α‐olefins 1‐octene, 1‐decene, 1‐tetradecene, and 1‐octadecene. The metallocene catalyst Me₂Si(2‐Me Benz[e]Ind)₂ZrCl₂, in conjunction with methylalumoxane as a cocatalyst, was used to synthesize the copolymers. The copolymers were characterized by ¹³C and ¹H NMR with a solvent mixture of 1,2,4‐trichlorobenzene (TCB) and benzene‐d₆ (9/1) at 100 °C. Thermal analyses were carried out to determine the melting and crystallization temperatures, whereas the molecular weights and molecular weight distributions were determined by gel permeation chromatography with TCB at 140 °C. Glass‐transition temperatures were determined with dynamic mechanical analysis. Relationships among the comonomer type and amount of incorporation and the melting/crystallization temperatures, glass‐transition temperature, crystallinity, and molecular weight were established. Moreover, up to 3.5% of the comonomer was incorporated, and there was a decrease in the molecular weight with increased comonomer content. Also, the melting and crystallization temperatures decreased as the comonomer content increased, but this relationship was independent of the comonomer type. In contrast, the values for the glass‐transition temperature also decreased with increased comonomer content, but the extent of the decrease was dependent on the comonomer type. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4110–4118, 2000     

Morphological change of poly (ε‐caprolactone) with a wide range of molecular weight via formation of inclusion complex with α‐cyclodextrin

The effect of molecular weight of poly(ε‐caprolactone) (PCL) on the formation and stability of inclusion complexes (ICs) between α‐cyclodextrin (α‐CD) and PCL was investigated by FTIR, WAXD, and DSC measurements. ICs between α‐CD and PCLs with a wide range of number‐average molecular weight, M_n = 1.21 × 10⁴ – 1.79 × 10⁵, were prepared by mixing the aqueous solution of CD and acetone solution of PCL followed by stirring at 60 °C for 1h and at the room temperature for 1 day. FTIR, WAXD, and DSC measurement showed the PCL chains were included into the α‐CD cavity, and the crystallization of PCL was suppressed in the α‐CD cavity. Stoichiometry and yield of each IC varied with the molecular weight of guest PCL, and the effect of IC formation on the crystallization behaviour of guest polymer decreased with the increase of molecular weight of guest polymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1433–1440, 2005     

Electron microscope study of low molecular weight fractions of linear polyethylene

Electron microscope studies are reported for crystals of linear polyethylene formed in dilute solution from very sharp low molecular weight fractions. Emphasis is placed on molecular weights in the range of 1.1 × 10³ to 15.1 × 10³. The dependence of the crystal habit on the crystallization temperature is very similar to that which has been found for the higher molecular weight species. However, the demarcation temperature for the crystallization of the different morphological forms is very molecular weight-dependent. The conditions under which interfacial dislocation networks form can be clearly defined. The molecular weight must be less than 3000, so that these structures are restricted to very small chain lengths. However, not all crystallization conditions within this allowable molecular weight range yield such dislocations. The formation of interfacial dislocation networks are shown to occur only under very special circumstances. Their occurrence clearly cannot be offered as evidence, as has been done in the past, for a regular, chain-folded interfacial structure.     

不同分子量尼龙1010的结晶与熔融

不同分子量尼龙１０１０的结晶与熔融＊朱诚身王经武王友文杨桂萍（郑州大学材料工程系郑州４５００５２）陈玉莫志深（东北师范大学分析测试中心长春１３００２４）（中国科学院长春应用化学研究所长春１３００２２）关键词尼龙１０１０，分子量，结晶，熔融＊１９９４＿...     

Strain stiffening and negative normal stress in alginate hydrogels

Alginate hydrogels are polysaccharide biopolymer networks widely useful in biomedical and food applications. Here, we report nonlinear mechanical responses of ionically crosslinked alginate hydrogels captured using large amplitude oscillatory shear experiments. Gelation was performed in situ in a rheometer and the rheological investigations on these samples captured the strain‐stiffening behavior for these gels as a function of oscillatory strain. In addition, negative normal stress was observed, which has not been reported earlier for any polysaccharide networks. The magnitude of negative normal stress increases with the applied strain amplitude and can exceed that of the shear stress at large‐strain. Fitting a constitutive relationship to the stress‐strain curves reveals that the mode of deformation involves stretching of the alginate chains and bending of both the chains and the junction zones. The contribution of bending increases near saturation of G blocks as Ca²⁺ concentration was increased. The results presented here provide an improved understanding of the deformation behavior of alginate hydrogels and such understanding can be extended to other crosslinked polysaccharide networks. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1767–1775     

Molecular dynamics simulation of poly(3‐hexylthiophene) helical structure In Vacuo and in amorphous polymer surrounding

The stability of poly(3‐hexylthiophene) (P3HT) helical structure has been investigated in vacuo and in amorphous polymer surrounding via molecular dynamics‐based simulations at temperatures below and above the P3HT melting point. The results show that the helical chain remains stable at room temperature both in vacuo and in amorphous surrounding, and promptly loses its structure at elevated temperatures. However, the amorphous surrounding inhibits the destruction of the helix at higher temperatures. In addition, it is shown that the electrostatic interactions do not significantly affect the stability of the helical structure. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2448–2456     

Controlled metal‐free polymerization toward well‐defined thermoresponsive polypeptides by polymerization at low temperature

A controlled metal‐free synthetic methodology toward well‐defined thermoresponsive polypeptides by decreasing the reaction temperature to 0 °C has been developed. Good control over the molecular weight in the polymerization of a trithiocarbonate‐functionalized N‐carboxyanhydride (MES‐l ‐Glu‐NCA) monomer was obtained using n‐hexylamine as the initiator at 0 °C. It yielded homopolypeptide macro‐transfer agent (PMESLG) with narrow molecular weight distribution (PDI < 1.3) and controllable chain length. Detailed ¹H NMR and MALDI‐TOF‐MS analysis clearly confirmed that frequently occurring side‐reactions was absent at 0 °C, and the polymerization was controlled. The resultant PMESLG was applied to mediate the reversible addition‐fragmentation chain transfer (RAFT) polymerization of oligo‐ethylene‐glycol acrylate (OEGA) for the metal‐free synthesis of thermoresponsive polypeptides. These thermoresponsive polypeptides have well‐controlled molecular weight, adopted regular α‐helical conformation, and exhibited a lower critical solution temperature between 23 °C and 55 °C. To the best of our knowledge, there are very few reports about the synthesis of well‐defined thermoresponsive graft polypeptides via NCA polymerization and RAFT. Consequently, this provides a new strategy for the synthesis of promising intelligent material for future biomedical applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2618–2624     

Michael addition for crosslinking of poly(caprolactone)s

Poly(caprolactone) (PCL) networks have received significant attention in the literature because of many emerging potential applications as biodegradable materials. In this study, the Michael addition reaction was used for the first time to synthesize biodegradable networks using crosslinking of acetoacetate‐functionalized PCL (PCL bisAcAc) oligomers with neopentyl glycol diacrylate. Hydroxyl‐terminated PCL telechelic oligomers with number‐average molecular weights ranging from 1000 to 4000 g/mol were quantitatively functionalized with acetoacetate groups using transacetoacetylation. In addition to difunctional PCL oligomers, hydroxyl‐terminated trifunctional star‐shaped PCL oligomers were functionalized with acetoacetate groups. Derivatization of the terminal hydroxyl groups with acetoacetate groups was confirmed using FTIR spectroscopy, ¹H NMR spectroscopy, mass spectrometry, and base titration of hydroxyl end groups. PCL bisAcAc precursors were reacted with neopentyl glycol diacrylate in the presence of an organic base at room temperature. The crosslinking reactions yielded networks with high gel contents (>85%). The thermomechanical properties of the networks were analyzed to investigate the influence of molecular weight between crosslink points. The glass transition and the extent of crystallinity of the PCL networks were dependent on the molecular weight of the PCL segment. Dynamic mechanical analysis indicated that the plateau modulus of the networks was dependent on the molecular weight of PCL, which was related to the crosslink density of the networks. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5437–5447, 2009     

Asymmetric Solvents Regulated Crystallization-Limited Electrolytes for All-Climate Lithium Metal Batteries

Electrolytes that can keep liquid state are one of the most important physical metrics to ensure the ions transfer with stable operation of rechargeable lithium-based batteries at a wide temperature window. It is generally accepted that strong polar solvents with high melting points favor the safe operation of batteries above room temperatures but are susceptible to crystallization at low temperatures (≤−40 °C). Here, a crystallization limitation strategy was proposed to handle this issue. We demonstrate that, although the high melting points of ethylene sulfite (ES, −17 °C) and fluoroethylene carbonate (FEC, ≈23 °C), their mixtures can avoid crystallization at low temperatures, which can be attributed to low intermolecular interactions and altered molecular motion dynamics. A suitable ES/FEC ratio (10 % FEC) can balance the bulk and interface transport of ions, enabling LiNi_0.8Mn_0.1Co_0.1O₂||lithium (NCM811||Li) full cells to deliver excellent temperature resilience and cycling stability over a wide temperature range from −50 °C to +70 °C. More than 66 % of the capacity retention was achieved at −50 °C compared to room temperature. The NCM811||Li pouch cells exhibit high cycling stability under realistic conditions (electrolyte weight to cathode capacity ratio (E/C)≤3.5 g Ah⁻¹, negative to positive electrode capacity ratio (N/P)≤1.09) at different temperatures.     

Fracture of model polyurethane elastomeric networks

Fracture properties of model elastomeric networks of polyurethane have been investigated with a double‐edge notch geometry. The networks were synthesized from monodisperse end‐functionalized polypropylene glycol precursors and a trifunctional isocyanate. All reagents were carefully purified and nearly defect‐free ideal networks were prepared at a stoichiometry very close to the theoretical one. Three networks were prepared: an unentangled network of short chains (M_n = 4 kg mol^?1), an entangled network of longer chains (M_n = 8 kg mol^?1) and a bimodal network with 8 kg mol^?1 and 1 kg mol^?1 chains. The presence of entanglements was found to increase significantly the toughness of the rubber, in particular at room temperature, relative to the bimodal networks and to the short chains network. Fracture experiments were carried out at different strain rates and temperatures and showed for all three networks a marked decrease in fracture toughness with increasing temperature and decreasing strain rate which mirrored reasonably well the rate and temperature dependence of tan δ, the dissipative factor. However the proportionality factor between tan δ, and G_IC was very material dependent and the shift factors obtained for the master curves of the viscoelastic properties could not be used to build fracture energy master curves. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Surface mechanical properties of low‐molecular‐weight polystyrene below its glass‐transition temperatures

Lap shear and friction force measurements were carried out on a series of monodisperse polystyrene (PS) films below the corresponding glass‐transition temperatures. It showed that adhesion between the PS/PS interface was possible at the temperature below the bulk T_g, and the lower the molecular weight of PS, the lower the temperature at which the interfacial strength was detectable. The examination of a series of molecular weights indicated both the surface molecular motion and the magnitude of the interfacial strength were dependent on molecular weight and its distribution. And a steep increase of the friction force with increasing the test temperature was observed around 0 ∼ 30 °C. The contact angle of water versus molecular weight measurements also showed a transition at room temperature. The behavior observed in this study was supposed to be due to the increased molecular mobility, and was in good agreement with the measured surface transition temperatures by DSC. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 654–658, 2000     

A study of the dilation of the unit cell of metallocene isotactic poly(propylenes): The monoclinic form

The lattice parameters of a series of monoclinic metallocene poly(propylenes) of constant molecular weight are measured as a function of defect content, that vary between 0.3 and 2.35 total defects per 100 monomeric units. The parameters are also measured as a function of molecular weight for a fixed defect content and as a function of the crystallization temperature. The b axis is found to increase with decreasing isothermal crystallization temperature whereas only small changes are found for samples rapidly crystallized. The a and c axis showed basically no variation with crystallization temperature. The parameters of the unit cell were essentially constant with varying defect content in the poly(propylene) chain. Lack of observed effect on the dilation of the unit cell by increasing defects is a consequence of the rapid crystallization required to ensure formation of monoclinic crystals. The unit cell parameters increased as a mild function of the molecular weight. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2511–2521, 1997     

Enhanced ionic conductivity in PEO/PMMA glassy miscible blends: Role of nano‐confinement of minority component chains

AC impedance spectroscopy was used to investigate the ionic conductivity of solution cast poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends doped with lithium perchlorate. At low PEO contents (below overlap weight fraction w^*), ionic conductivities are almost low. This could be due to nearly distant PEO chains in blend, which means ion transportation cannot be performed adequately. However, at weight fractions well above w^*, a significant increase in ionic conductivity was observed. This enhanced ionic conductivity mimics the PEO segmental relaxation in rigid PMMA matrix, which can be attributed to the accelerated motions of confined PEO chains in PMMA matrix. At PEO content higher than 20 wt % the conductivity measured at room temperature drops due to crystallization of PEO. However by increasing temperature to temperatures well above the melting point of PEO, a sudden increase of conductivity was observed which was attributed to phase transition from crystalline to amorphous state. The results indicate that some PEO/PMMA blends with well enough PEO content, which are structurally solid, can be considered as an interesting candidate for usage as solid‐state electrolytes in Lithium batteries. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2065–2071, 2010     

Ring‐opening copolymerization of ethylene carbonate and ε‐caprolactone catalyzed by neodymium tris(2,6‐di‐tert‐butyl‐4‐methylphenolate): Synthesis,characterization, and dynamic mechanic analysis

The ring‐opening copolymerization of ethylene carbonate (EC) with ε‐caprolactone (CL) was carried out using neodymium tris(2,6‐di‐tert‐butyl‐4‐methylphenolate) as a single‐component catalyst. Copolymers containing up to 22.0% EC contents with high molecular weights (up to 23.97 × 10⁴) and moderate molecular weight distributions (between 1.66 and 2.03) were synthesized at room temperature. Compared with homopoly(ε‐caprolactone), the copolymers with EC units exhibited increased glass transition temperatures (?35.6 °C), reduced melting temperatures (44.5 °C), and greatly enhanced elongation percentage at break (2383%) based on dynamic mechanic analysis. The crystallinities of the copolymers decreased with the increasing EC molar percentage in the products. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4050–4055, 2008     

Molecular weight dependency of crystallization and melting behavior of β‐nucleated isotactic polypropylene

Compounds of isotactic polypropylene (iPP) and β‐nucleating agent were used to investigate the relationship between the development of β phase and molecular weight in iPP under quiescent crystallization conditions by using wide angle X‐ray diffraction and differential scanning calorimetry techniques. In all cases, the dependency of the formation of β phase in iPP on molecular weight of iPP at a defined crystallization temperature range was found. The iPP with high molecular weight possessed a wide range of crystallization temperature in inducing rich β phase. However, poor or even no β phase was obtained for the samples with low molecular weight in the same range. In addition, an upper critical crystallization temperature of producing dominant β phase was found at 125 °C. Beyond this temperature, a phenomenon of prevailing α phase became obvious. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1301–1308     

RAFT polymerization of alternating styrene‐pentafluorostyrene copolymers

Reversible addition‐fragmentation chain‐transfer (RAFT) polymerization was used to control the alternating copolymerization of styrene and 2,3,4,5,6‐pentaflurostyrene. The RAFT polymerization yields a high degree of control over the molecular weight of the polymers and does not significantly influence the reactivity ratios of the monomers. The controlled free‐radical polymerization could be initiated using AIBN at elevated temperatures or using a redox couple (benzoyl peroxide/N,N‐dimethylaniline) at room temperature, while maintaining control over molecular weight and dispersity. The influence of temperature and solvent on the molecular weight distribution and reactivity ratios were investigated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1555–1559     

Crystallization and melting of fractions of branched polyethylene

Effects of the molecular weight on the crystallization behaviour of branched polyethylene become observable if isothermal crystallization is studied at temperatures near to the melting end. Crystallinities decrease with decreasing molecular weight. Thicknesses of lamellae grown during isothermal crystallization are independent of the molecular weight. They depend only on temperature. Compared to the effect of the branches polydispersity gives only a minor contribution to the broadening of the crystallization and melting range of low density polyethylene.     

Breathable rubbery skin protectors: Design,synthesis, characterization,and properties of cyanoacrylated silicone rubber networks

We extended our investigations of rubbery wound closure adhesives and created novel flexible networks by crosslinking cyanoacrylated silicone rubbers (i.e., commercial methylhydrosiloxane‐dimethylsiloxane copolymers, PMHS‐co‐PDMS) with N,N‐dimethyl‐p‐toluidine in tetrahydrofuran and hexamethyldisiloxane solvents at room temperature. Cyanoacrylation was achieved by hydrosilating (anthracene‐protected) allyl cyanoacrylate with PMHS‐co‐PDMS. Steric hindrance and the molecular weight of the copolymer strongly affect the extent of hydrosilation. The rate of crosslinking is proportional with the number of cyanoacrylate groups in the copolymer and networks form in seconds with appropriate amounts of initiator. Networks on porcine skin yield well‐adhering flexible optically‐transparent colorless conformal coatings of good “feel” appropriate for clinically useful non‐occlusive “breathable” skin or wound protectors. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1367‐1372