Effect of PEO‐PPO‐PEO copolymer on the mechanical and thermal properties and morphological behavior of biodegradable poly (L‐lactic acid) (PLLA) and poly (butylene succinate‐co‐L‐lactate) (PBSL) blends

A blend of two biodegradable and semi‐crystalline polymers, poly (L‐lactic acid) (PLLA; 70 wt%) and poly (butylene succinate‐co‐L‐lactate) (PBSL; 30 wt%), was prepared in the presence of various polyethylene oxide‐polypropylene oxide‐polyethylene oxide (PEO‐PPO‐PEO) triblock copolymer contents (0.5, 1, 2 wt%). Mechanical, thermal properties, and Fourier transform infrared (FTIR) analysis of the blends were investigated. It was found that the addition of copolymer to PLLA/PBSL improved the fracture toughness of the blends as shown by mode I fracture energies. It was supported by morphological analysis where the brittle deformation behavior of PLLA changed to ductile deformation with the presence of elongated fibril structure in the blend with copolymer system. The glass transition temperature (T_g), melting temperature (T_m) of PLLA, and PBSL shift‐closed together indicated that some compatibility exists in the blends. In short, PEO‐PPO‐PEO could be used as compatibilizer to improve the toughness and compatibility of the PLLA/PBSL blends. Copyright © 2010 John Wiley & Sons, Ltd.     

New super‐tough poly(butylene terephthalate) materials based on compatibilized blends with metallocenic poly(ethylene‐octene) copolymer

New super‐tough poly(butylene terephthalate) (PBT)/poly(ethylene‐octene) copolymer (PEO) blends containing 2 wt% poly(ethylene‐co‐glycidyl methacrylate) (EGMA) as a compatibilizer were obtained by extrusion and injection molding. The blends comprised of an amorphous PBT‐rich phase with some miscibilized EGMA, a pure PEO amorphous phase, and a crystalline PBT phase that was not influenced by the presence of either PEO or EGMA. The blends showed a fine particle size up to 20 wt% PEO content. Super‐tough blends were obtained with PEO contents equal to or higher than 10%. The maximum toughness was very high (above 710 J/m) and was attained with 20% PEO without chemical modification of the commercial components used. Copyright © 2003 John Wiley & Sons, Ltd.     

Two‐way multi‐shape memory properties of peroxide crosslinked ethylene vinyl‐acetate copolymer (EVA)/polycaprolactone (PCL) blends

Rare studies have investigated on the 2‐way shape memory crosslinked blends with multiple shape memory behavior up to date. To consider the merit of commercial cost‐competitive crystalline polymers, ethylene vinyl‐acetate copolymer (EVA) / polycaprolactone (PCL) blends (60/40 and 30/70) were peroxide‐cured to form the 2‐way multi‐shape memory crosslinked blends using a melt‐blending method. Both resins were selected to have a similar controlled crosslinking degree, which allowed us to distinctly evaluate their actuation contributions from the cooling‐induced elongation (crystallization) and from the entropy‐driven elongation during cooling process, respectively. In the 2‐way process for the 60/40 system, 2 respective peaks contributed from the cooling‐induced crystallization of EVA and PCL in the cooling curves based on the strain derivate rates at various temperatures were observed. After the cooling process under the loading stress of 150 kPa, the 2‐step heating‐induced contraction process with increasing temperature started at 54.1°C above the melting temperature of PCL at 52.3°C and EVA at 78.3°C, demonstrating 2‐way multi‐shape memory behavior. The multi‐step behavior was more prominent at higher PCL composition and higher load for the 30/70 system. It was found that the entropy‐driven contribution to the overall actuation magnitude increased with increasing nominal loads due to the increased orientation of molecular networks in the blends. The current approach offers numerous possibilities in preparing 2‐way multi‐shape memory crosslinked blends.     

Room temperature deformable shape memory composite with fine‐tuned crystallization induced via nanoclay particles

It is known that particular types of semi‐crystalline/elastomer polymer blends exhibit shape memory effects (SME) due to the dispersion of two immiscible phases. In this study, the crystal structure of polylactic acid (PLA)/ thermoplastic polyurethane (TPU) based shape memory polymer (SMP) is altered by incorporating small amounts of montmorillonite (MMT) nanoclay. The results indicate the incorporation of MMT can improve the compatibility of the two different polymers. Moreover, the presence of MMT affects the total crystallinity of the SMP and improves mechanical properties. Lastly, uniaxial stretching deformation can be applied to the SMP at room temperature conditions while maintaining its shape memory properties. With 1 wt % MMT particles, the recovery ratio (Rr) was nearly 95%, which indicated a strong recovery effect. The shape‐fixing ratio (Rf) remained above 95% for all composites due to plastic deformation applied at room temperature. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1197–1206     

Fabrication of well‐defined shape memory graft polymers derived from biomass: An insight into the effect of side chain architecture on shape memory properties

Fully sustainable shape memory polymers (SMPs) derived from ethyl cellulose (EC, derived from cellulose), tetrahydrofurfuryl methacrylate (THFMA, derived from furfural), and lauryl methacrylate (LMA, derived from fatty acids) were prepared via “grafting from” atom transfer radical polymer (ATRP). The “grafting from” ATRP strategy allows to fabricate SMPs with EC as a backbone, and LMA and THFMA copolymer as a side chain. By utilizing the one‐pot and sequential monomer addition approach, two types of SMPs with random/semi‐block side chain architectures were obtained, respectively. Random/semi‐block side chain architecture of SMPs was confirmed by DSC, DMA, SAXS, and TEM. The presence of microphase separation in the SMPs with semi‐block side chain architecture provided two distinct thermal transitions, which was needed for triple‐shape memory behavior. Shape memory study showed that SMPs with semi‐block side chain architecture exhibited excellent triple‐shape memory property, and also had higher shape recovery speed and shape recovery ratio than those with random side chain architecture. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1711–1720     

A Facile Strategy to Fabricate Multishape Memory Polymers with Controllable Mechanical Properties

A facile blending strategy to fabricate multishape memory polymers (SMPs) with only one sort of phase transition material has been reported. In this work, olefin block copolymer (OBC) and styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS), which are both physically crosslinked, are blended with crystalline paraffin together. Due to the different interactions between polymer matrices and paraffin, the paraffin penetrated in OBC and SEBS exhibit separated melting transitions. It is quite interesting that merely paraffin distributed in OBC also shows two distinct melting transitions with enough OBC content in composites. Therefore, excellent quadruple shape memory effect can be achieved with a maximum of three melting transitions. Furthermore, through adjusting the polymer species and content, the mechanical and rheological properties can be conveniently tuned to a great extent. Compared with the reported strategies, this simple and controllable method sheds light on rapid design of multi‐SMPs using inexpensive raw materials, which greatly paves the way for multi‐SMPs from laboratory to factory.

     

Gradient graft copolymers derived from PEO‐based macromonomers

Atom transfer radical polymerization (ATRP) of two poly(ethylene oxide) (PEO) macromonomers, with different polymerization degrees (DP_n) and different end groups, was conducted in solution via the grafting through method. Selection of a PEO methacrylate with a methyl end‐group (PEOMeMA, DP_PEO = 23) and a PEO acrylate end‐capped by a phenyl ring (PEOPhA, DP_PEO = 4) for the copolymerization led to a spontaneous gradient of PEO grafts along the copolymer backbone. Such a composition was formed because of significantly different reactivities of the two PEO macromonomers. The resulting copolymer has PEOMeMA at one end of the polymer chain, gradually changing through hetero‐sequences of PEOPhA at the other chain end. An increase in the initial feed ratio of PEO acrylate reduced the rate of change in the shape of the gradient. Amorphous–crystalline structure in the copolymers was demonstrated by DSC and WAXS. The mechanical measurements of copolymers consisting of an amorphous PEOPhA and crystallizable PEOMeMA segments indicated elastomeric properties in the range of a soft rubber (G′ ～ 10⁴ Pa, G′ ? G″). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1347–1356, 2006     

Hydrogel‐coated polyurethane/urea shape memory polymer foams

Shape memory polymers (SMPs) are a class of responsive polymers that have attracted attention in designing biomedical devices because of their potential to improve minimally invasive surgeries. Use of porous SMPs in vascular grafts has been proposed because porosity aids in transfer of fluids through the graft and growth of vascular tissue. However, porosity also allows blood to leak through grafts so preclotting the materials is necessary. Here hydrogels have been synthesized from acrylic acid and N‐hydroxyethyl acrylamide and coated around a porous SMP produced from lactose functionalized polyurea‐urethanes. The biocompatibility of the polymers used to prepare the cross‐linked shape memory material is demonstrated using an in vitro cell assay. As expected, the hydrogel coating enhanced fluid uptake abilities without hindering the shape memory properties. These results indicate that hydrogels can be used in porous SMP materials without inhibiting the shape recovery of the material. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1389–1395     

Synthesis of poly[(2‐oxo‐1,3‐dioxolane‐ 4‐yl)methyl methacrylate‐co‐styrene] by addition reaction of carbon dioxide and its compatibility with poly(methyl methacrylate) or poly(vinyl chloride)

We investigated the chemical fixation of carbon dioxide (CO ₂) to a copolymer bearing epoxide and the application of the cyclic carbonate group containing copolymer to polymer blends. In the synthesis of poly[(2‐oxo‐1,3‐dioxolane‐4‐yl)methyl methacrylate‐co‐styrene] [poly(DOMA‐co‐St)] from the addition of CO ₂ to poly(glycidyl methacrylate‐co‐styrene) [poly(GMA‐co‐St)], quaternary ammonium salts showed good catalytic activity at mild reaction conditions. The CO ₂ addition reaction followed pseudo first‐order kinetics with the concentration of poly(GMA‐co‐St). In order to expand the applications of the CO ₂ fixed copolymer, polymer blends of this copolymer with poly(methyl methacrylate) (PMMA) or poly(vinyl chloride) (PVC) were cast from N,N′‐dimethylformamide (DMF) solution. Miscibility of blends of poly(DOMA‐co‐St) with PMMA or PVC have been investigated both by differential scanning calorimetry (DSC) and visual inspection of the blends, and the blends were miscible over the whole composition ranges. The miscibility behaviors were also discussed in terms of FT‐IR spectra. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis and properties of shape memory polymers of LLA,TMC, and ε‐CL terpolymers

Biodegradable polylactide (PLA) and its copolymers with shape memory properties have attracted great interests because of their important application prospects in biomedical field. In this study, random poly(L‐lactide‐co‐trimethylene carbonate‐co‐ε‐caprolactone) (LTCL) terpolymers with different molar ratio were synthesized and characterized. Monomer ε‐caprolactone (ε‐CL) was used in this study instead of glycolide in preliminary study of LTG terpolymers to investigate the transition temperature and the shape memory performance. Characterization on crystallization, mechanical properties, shape fixing, and recovery ratios of the terpolymers was conducted to investigate the correlation between crystallization and shape memory performance of LTCL terpolymers. The results are consistent with the formation of crystallized LLA segments, which could act as crosslinks, strengthened the stationary phase within the polymer matrix, and significantly improved the shape memory performance of LTCL terpolymers. For example, LTCL801010 is a crystalline polymer with high shape fixity and shape recovery ratio; its shape recovery temperature is 39°C. LTCL terpolymers with high CL content do not show shape memory performance for the rubbery at room temperature. Based on this study, PLA materials with shape memory property can be designed through the selection of monomers or the adjustment of comonomer ratio. These polymers with recovery temperature close to 37°C are expected to be used in human body such as scaffolds in tissue engineering.     

Shape memory polymers with interconnected nanopores and high mechanical strength

The fabrication of shape memory polymers with both interconnected nanopores and high mechanical strength is challenging. In this work, porous shape memory polymers (PSMPs) were prepared based on the combination of crystallization and phase separation in a ternary blend of poly(l ‐lactic acid)/polyvinyl acetate/poly(ethylene oxide) (i.e., PLLA/PVAc/PEO). The phase separation between the PLLA and PVAc/PEO resulted in bicontinuous structures in microscale including a PLLA‐rich phase and a mixed PVAc/PEO phase. On one hand, the continuous PLLA‐rich phase contributed to the high mechanical strength and shape memory performance, in which tiny crystals and amorphous matrix of PLLA act as the shape fixed phase and reversible phase, respectively. On the other hand, the crystallization of PEO in the miscible PVAc/PEO blend produced submicrometer bicontinuous structures. The interconnected nanopores have been obtained by selective etching of the PEO. Our strategy opens a new avenue for fabricating PSMPs with both interpenetrated channels and high strength. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 125–130     

A novel approach for preparation of conductive hybrid elastomeric nano‐composites

Since the discovery of carbon nanotubes (CNTs) and intrinsically conductive polymers, such as polyaniline (PANI) some research has focused on the development of novel hybrid materials by combining CNT and PANI to achieve their complementary properties. Electrically conductive elastomer nano‐composites containing CNT and PANI are described in the present investigation. The synthesis procedure includes in‐situ inverse emulsion polymerization of aniline doped with dodecylbenzene sulfonic acid in the presence of CNT and dissolved styrene‐isoprene‐styrene (SIS) block copolymer, followed by a precipitation–filtration step. The synthesis step is carried out under ultrasonication. The resulting uniform SIS/CNT/PANI dispersions are stable for long time durations. The incorporation of CNT/PANI in the SIS elastomeric matrix improves thermal, mechanical and electrical properties of the nano‐composites. The formation of continuous three‐dimensional CNT/PANI network, assumed to be responsible for enhancement of the resulting nano‐composite properties, is observed by HRSEM. A relatively low percolation threshold of 0.4 wt.% CNT was determined. The Young's modulus of the SIS/CNT/PANI significantly increases in the presence of CNT. High electrical conductivity levels were obtained in the ternary component systems. Copyright © 2013 John Wiley & Sons, Ltd.     

Novel Shape‐Memory Polymer Based on Hydrogen Bonding

Summary: Due to a large difference in storage modulus below and above the glass transition temperature, a novel shape‐memory poly[(methyl methacrylate)‐co‐(N‐vinyl‐2‐pyrrolidone)]/poly(ethylene glycol) semi‐interpenetrating polymer networks structure was synthesized, which is stabilized by hydrogen‐bonding interactions. The recovery ratio of these polymers could reach 99%. In such a system the maximum molecular weight of PEG required for the semi‐IPNs formation reaches 1 000.

Transition from the temporary shape (chem) to the permanent shape (four rods) for a shape‐memory P(MMA‐co‐VP)/PEG1000 semi‐IPNs.     

Controlled epoxidation of poly(styrene‐b‐isoprene‐b‐styrene) block copolymer for the development of nanostructured epoxy thermosets

To be used as templates for nanostructured thermosets, a commercial poly(styrene‐b‐isoprene‐b‐styrene) (SIS) block copolymer (BCP) was epoxidized by three different epoxidation procedures. An exhaustive analysis of methodologies using metal catalyzed/hydrogen peroxide, dimethyldioxirane (DMDO), and meta‐chloroperbenzoic acid (m‐CPBA) was performed to obtain reactive BCPs. The DMDO approach was the best strategy to obtain highly epoxidized SIS BCP (85 mol %) without formation of side products. Careful control in BCP epoxidation by metal catalyzed/hydrogen peroxide and m‐CPBA approaches led to a maximum epoxidation degree (ED) of approximately 60 mol % without the formation of side products. The ED by metal catalyzed/hydrogen peroxide strategy could be further increased to 69 mol %, but a significant amount of crosslinking, ring opening, and polymer chain scission reactions were detected by spectroscopic and chromatographic techniques. The miscibility of epoxidized BCPs with diglycidyl ether of bisphenol‐A epoxy system before and after curing was analyzed to develop nanostructured epoxy thermosets. For ED higher than 69 mol %, BCPs were miscible, while those with lower ED presented macrophase separation. Highly epoxidized BCPs obtained by the DMDO methodology were successfully used to obtain ordered nanodomains inside the epoxy matrix, as determined by atomic force microscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

FT‐IR Studies of Plasticization of Propylene Carbonate and Ethylene Carbonate in PEO‐NaSCN Polymer Electrolytes

The FT‐IR spectra of poly(ethylene oxide) (PEO)‐based gel polymer electrolytes (GPEs), PEO‐NaSCN‐propylene carbonate (PC) and PEO‐NaSCN‐ethylene carbonate (EC), were measured at room temperature. Along with the FT‐IR spectra of NaSCN‐PC, PEO‐PC, and PEO‐EC, the interactions in the GPEs and the plasticizations of PC and EC are revealed. It is shown that the coordination of ether oxygen in PEO with NaSCN is the preferential solvation, whereas the interactions of PC and EC with NaSCN are relatively weak in the GPEs. However, both PC and EC play an important role in inhibiting the formation of crystalline complexes and high ionic aggregations, in addition to the ability of transformation of PEO from crystal to amorphism. It is further observed that EC exhibits the stronger ability to transform PEO crystalline into amorphism than PC when the plasticizer content in PEO is more than 25%, and also the far stronger ability to decompose the crystalline complexes, in particular, in polymer electrolytes with high salt content.     

Preparation and characterization of poly(ethylene oxide)‐loaded hydroxypropyl‐β‐cyclodextrin nanofibers

Hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) is a modified β‐cyclodextrin (β‐CD) derivative, which is toxicologically harmless to mammals and other animals. HP‐β‐CD is electrospun from an aqueous solution by blending with a non‐toxic, biocompatible, synthetic polymer poly(ethylene oxide) (PEO). Aqueous solutions containing different HP‐β‐CD/PEO blends (50:50–80:20) with variable concentrations (4 wt%–12 wt%) were used. Scanning electron microscope was used to investigate the morphology of the fibers, and Fourier transform infrared spectroscopy analysis confirmed the presence of HP‐β‐CD in the fiber. Uniform nanofibers with an average diameter of 264, 244, and 236 nm were obtained from 8 wt% solution of 50:50, 60:40, and 70:30 HP‐β‐CD/PEO, respectively. The average diameter of the fiber was decreased with increasing of HP‐β‐CD/PEO ratio. However, a higher proportion of HP‐β‐CD in the spinning solution increased beads in the fibers. The polymer concentration had no significant effect on the fiber diameter. The most uniform fibers with the narrowest diameter distribution were obtained from the 8 wt% of 50:50 solution. Copyright © 2015 John Wiley & Sons, Ltd.     

Phase behavior,crystallization, and nanostructures in thermoset blends of epoxy resin and amphiphilic star‐shaped block copolymers

This article reports thermoset blends of bisphenol A‐type epoxy resin (ER) and two amphiphilic four‐arm star‐shaped diblock copolymers based on hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(propylene oxide) (PPO). 4,4′‐Methylenedianiline (MDA) was used as a curing agent. The first star‐shaped diblock copolymer with 70 wt % ethylene oxide (EO), denoted as (PPO‐PEO)₄, consists of four PPO‐PEO diblock arms with PPO blocks attached on an ethylenediamine core; the second one with 40 wt % EO, denoted as (PEO‐PPO)₄, contains four PEO‐PPO diblock arms with PEO blocks attached on an ethylenediamine core. The phase behavior, crystallization, and nanoscale structures were investigated by differential scanning calorimetry, transmission electron microscopy, and small‐angle X‐ray scattering. It was found that the MDA‐cured ER/(PPO‐PEO)₄ blends are not macroscopically phase‐separated over the entire blend composition range. There exist, however, two microphases in the ER/(PPO‐PEO)₄ blends. The PPO blocks form a separated microphase, whereas the ER and the PEO blocks, which are miscible, form another microphase. The ER/(PPO‐PEO)₄ blends show composition‐dependent nanostructures on the order of 10?30 nm. The 80/20 ER/(PPO‐PEO)₄ blend displays spherical PPO micelles uniformly dispersed in a continuous ER‐rich matrix. The 60/40 ER/(PPO‐PEO)₄ blend displays a combined morphology of worm‐like micelles and spherical micelles with characteristic of a bicontinuous microphase structure. Macroscopic phase separation took place in the MDA‐cured ER/(PEO‐PPO)₄ blends. The MDA‐cured ER/(PEO‐PPO)₄ blends with (PEO‐PPO)₄ content up to 50 wt % exhibit phase‐separated structures on the order of 0.5–1 μm. This can be considered to be due to the different EO content and block sequence of the (PEO‐PPO)₄ copolymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 975–985, 2006     

Light Polarization‐Controlled Shape‐Memory Polymer/Gold Nanorod Composite

It is demonstrated that light polarization can be used to control photothermal effect‐based shape‐memory polymers (SMPs). Gold nanorods (AuNRs) are embedded in poly(vinyl alcohol) (PVA) and aligned by stretching the composite film. By changing the polarization direction of the incident laser at 785 nm with respect to the film stretching direction, the magnitude of the longitudinal surface plasmon resonance of AuNRs can be varied continuously, which determines the amount of heat generated upon laser exposure and thus the local temperature rise in the composite relative to the glass transition of the PVA matrix. Consequently, the temporary‐to‐permanent shape recovery process of the composite can be made to occur to different extents by tuning the polarization of laser while keeping all other conditions unchanged. This finding enhances the toolbox for controlling light‐triggered SMPs.

     

Proton conducting grafted/crosslinked membranes prepared from poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) copolymer

Poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) (P(VDF‐co‐CTFE)) backbone was grafted with crosslinkable chains of poly(hydroxyl ethyl acrylate) (PHEA) and proton conducting chains of poly(styrene sulfonic acid) (PSSA) to produce amphiphilic P(VDF‐co‐CTFE)‐g‐P(HEA‐co‐SSA) graft copolymer via atom transfer radical polymerization (ATRP). Successful synthesis and microphase‐separated structure of the copolymer were confirmed by ¹H NMR, FT‐IR spectroscopy, and TEM analysis. Furthermore, this graft copolymer was thermally crosslinked with sulfosuccinic acid (SA) to produce grafted/crosslinked membranes. Ion exchange capacity (IEC) increased continuously with increasing SA contents but the water uptake increased up to 6 wt% of SA concentration, above which it decreased monotonically. The membrane also exhibited a maximum proton conductivity of 0.062 S/cm at 6 wt% of SA concentration, resulting from competitive effect between the increase of ionic groups and the degree of crosslinking. XRD patterns also revealed that the crystalline structures of P(VDF‐co‐CTFE) disrupted upon graft polymerization and crosslinking. These membranes exhibited good thermal stability at least up to 250°C, as revealed by TGA. Copyright © 2009 John Wiley & Sons, Ltd.     

Structure–property relationships of fatty acid swollen,crosslinked natural rubber shape memory polymers

This article investigates shape memory polymers (SMPs) fabricated by swelling sulfur crosslinked natural rubber with four different molten fatty acids: lauric, myristic, palmitic, and stearic acid. As inexpensive additives, they allow commodity natural rubber to be directly converted to SMPs. The shape memory properties are investigated as a function of wt% fatty acid, the choice of fatty acid, and the applied load during shape memory programming. It is found that increasing the wt% acid improves the shape fixity up to ca. 97% at ≥50 wt% fatty acid, at which point the recovery starts to decline with increasing wt% acid due to network failure during shape programming. The shape fixity is found to depend on the yield stress and modulus of the fatty acid network, which both increase with increasing wt% acid. The choice of fatty acid also varies the trigger temperature for shape memory, which scales with the melting point of the fatty acid. Serendipitously, it is found that alignment of the fatty acid crystals during programming produces stiffer networks whose modulus increase with applied load, which counterbalances the higher elastic energy stored in the rubber network to produce lower sensitivity of the shape fixity to the applied load. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 673–687