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2018 Volume 36 Issue 8
2018, 36(8):
Abstract:
2018, 36(8): 897-904
doi: 10.1007/s10118-018-2151-6
Abstract:
We reported the first mussel-inspired alternating copolymer with a high amount of catechol groups (50% molar ratio) through a facile epoxy-amino click reaction between 9,9-bis(4-(2-glycidyloxyethyl)phenyl fluorene (BGEPF) and dopamine (DA). The obtained copolymers were used to prepare carbon/nitrogen-doped α-Fe2O3 nanoparticles through self-assembly, coordination and calcination, which displayed excellent electrochemical performance as anode materials for Li-ion batteries.
We reported the first mussel-inspired alternating copolymer with a high amount of catechol groups (50% molar ratio) through a facile epoxy-amino click reaction between 9,9-bis(4-(2-glycidyloxyethyl)phenyl fluorene (BGEPF) and dopamine (DA). The obtained copolymers were used to prepare carbon/nitrogen-doped α-Fe2O3 nanoparticles through self-assembly, coordination and calcination, which displayed excellent electrochemical performance as anode materials for Li-ion batteries.
2018, 36(8): 905-917
doi: 10.1007/s10118-018-2118-7
Abstract:
Shape memory polymers (SMPs) as one type of the most important smart materials have attracted increasing attention due to their promising application in the field of biomedicine, textiles, aerospace et al. Following a brief intoduction of the conception and classification of SMPs, this review is focused on the progress of shape memory polymers for biomedical applications. The progress includes the early researches based on thermo-induced SMPs, the improvement of the stimulus, the development of shape recovery ways and the expansion of the applications in biomedical field. In addition, future perspectives of SMPs in the field of biomedicine are also discussed.
Shape memory polymers (SMPs) as one type of the most important smart materials have attracted increasing attention due to their promising application in the field of biomedicine, textiles, aerospace et al. Following a brief intoduction of the conception and classification of SMPs, this review is focused on the progress of shape memory polymers for biomedical applications. The progress includes the early researches based on thermo-induced SMPs, the improvement of the stimulus, the development of shape recovery ways and the expansion of the applications in biomedical field. In addition, future perspectives of SMPs in the field of biomedicine are also discussed.
2018, 36(8): 918-924
doi: 10.1007/s10118-018-2110-2
Abstract:
A simple and effective photochemical method was developed for cross-linking of polymer gate dielectrics. Laborious synthetic processes for functionalizing polymer dielectrics with photo-cross-linkable groups were avoided. The photo-cross-linker, BBP-4, was added into host polymers by simple solution blending process, which was capable of abstracting hydrogen atoms from polymers containing active C―H groups upon exposure to ultraviolet (UV) radiation. The cross-linking can be completed with a relatively long wavelength UV light (365 nm). The approach has been applied to methacrylate and styrenic polymers such as commercial poly(methylmethacrylate) (PMMA), poly(iso-butylmethacrylate) (PiBMA) and poly(4-methylstyrene) (PMS). The cross-linked networks enhanced dielectric properties and solvent resistance of the thin films. The bottom-gate organic field-effect transistors (OFETs) through all solution processes on plastic substrate were fabricated. The OFET devices showed low voltage operation and steep subthreshold swing at relatively small gate dielectric capacitance.
A simple and effective photochemical method was developed for cross-linking of polymer gate dielectrics. Laborious synthetic processes for functionalizing polymer dielectrics with photo-cross-linkable groups were avoided. The photo-cross-linker, BBP-4, was added into host polymers by simple solution blending process, which was capable of abstracting hydrogen atoms from polymers containing active C―H groups upon exposure to ultraviolet (UV) radiation. The cross-linking can be completed with a relatively long wavelength UV light (365 nm). The approach has been applied to methacrylate and styrenic polymers such as commercial poly(methylmethacrylate) (PMMA), poly(iso-butylmethacrylate) (PiBMA) and poly(4-methylstyrene) (PMS). The cross-linked networks enhanced dielectric properties and solvent resistance of the thin films. The bottom-gate organic field-effect transistors (OFETs) through all solution processes on plastic substrate were fabricated. The OFET devices showed low voltage operation and steep subthreshold swing at relatively small gate dielectric capacitance.
2018, 36(8): 925-933
doi: 10.1007/s10118-018-2120-0
Abstract:
This work investigates the degradation and properties of a thermoplastically prepared composite comprising a polylactide/ hybrid zinc stearate-silver system. The influence of the zinc stearate-silver system on the properties of the composite is investigated by electron microscopy, differential scanning calorimetry and tensile tests. Furthermore, the antimicrobial activities of the systems are examined. The degradation behaviour of the composites is studied in both abiotic and biotic (composting) environments at an elevated temperature of 58 °C. The results reveal good dispersion of the additive in the PLA matrix, a stabilizing effect exerted by the same on the polylactide matrix during processing, and slight reduction in glass transition temperature. The zinc stearate-silver component also reduces brittleness and extends elongation of the composite. Abiotic hydrolysis is not significantly affected, which is in contrast with pure PLA, although mineralization during the early stage of biodegradation increases noticeably. The composite exhibits antimicrobial activity, even at the lowest dosage of the zinc stearate/silver component (1 wt%). Moreover, Ag and Zn contents were found to be present in the composite during abiotic hydrolysis, which was demonstrated by minimal diffusion of Ag ions from the matrix and very extensive washing of compounds that contained Zn.
This work investigates the degradation and properties of a thermoplastically prepared composite comprising a polylactide/ hybrid zinc stearate-silver system. The influence of the zinc stearate-silver system on the properties of the composite is investigated by electron microscopy, differential scanning calorimetry and tensile tests. Furthermore, the antimicrobial activities of the systems are examined. The degradation behaviour of the composites is studied in both abiotic and biotic (composting) environments at an elevated temperature of 58 °C. The results reveal good dispersion of the additive in the PLA matrix, a stabilizing effect exerted by the same on the polylactide matrix during processing, and slight reduction in glass transition temperature. The zinc stearate-silver component also reduces brittleness and extends elongation of the composite. Abiotic hydrolysis is not significantly affected, which is in contrast with pure PLA, although mineralization during the early stage of biodegradation increases noticeably. The composite exhibits antimicrobial activity, even at the lowest dosage of the zinc stearate/silver component (1 wt%). Moreover, Ag and Zn contents were found to be present in the composite during abiotic hydrolysis, which was demonstrated by minimal diffusion of Ag ions from the matrix and very extensive washing of compounds that contained Zn.
2018, 36(8): 934-942
doi: 10.1007/s10118-018-2104-0
Abstract:
Poly(ethylene oxide) (PEO) was controllably grafted from styrene-b-(ethylene-co-propylene)-b-styrene (SEPS) backbones by combining lithiation of styrenic units and living monomer-activated anionic ring-opening polymerization of ethylene oxide (EO) monomers with the aid of co-initiators triisobutyl aluminum. The as-synthesized SEPS-g-PEO copolymers were characterized by SEC, 1H-NMR, FTIR, SAXS, AFM and DSC. When the branch length is relatively small, increase of PEO fraction leads to the increase of the correlation length between neighboring hard domains, but the degree of correlation reduces. When the branch length is relatively large, the phase-separated structures become random both in terms of size and spatial correlation, and macro-phase separated structures appear. The crystallization behavior of the PEO branches can be effectively inhibited in SEPS-g-PEO, so no significant crystallization takes place until the fraction of PEO branches is 20.1 wt%, which greatly promotes the rapid delivery of hydrophilic drugs in the hot-melting pressure-sensitive adhesives (HMPSAs) based on SEPS-g-PEO. Their cumulative release amount of a model drug could achieve 80%, more than twice the value in the HMPSAs based on linear PEO-containing styrenic block copolymers.
Poly(ethylene oxide) (PEO) was controllably grafted from styrene-b-(ethylene-co-propylene)-b-styrene (SEPS) backbones by combining lithiation of styrenic units and living monomer-activated anionic ring-opening polymerization of ethylene oxide (EO) monomers with the aid of co-initiators triisobutyl aluminum. The as-synthesized SEPS-g-PEO copolymers were characterized by SEC, 1H-NMR, FTIR, SAXS, AFM and DSC. When the branch length is relatively small, increase of PEO fraction leads to the increase of the correlation length between neighboring hard domains, but the degree of correlation reduces. When the branch length is relatively large, the phase-separated structures become random both in terms of size and spatial correlation, and macro-phase separated structures appear. The crystallization behavior of the PEO branches can be effectively inhibited in SEPS-g-PEO, so no significant crystallization takes place until the fraction of PEO branches is 20.1 wt%, which greatly promotes the rapid delivery of hydrophilic drugs in the hot-melting pressure-sensitive adhesives (HMPSAs) based on SEPS-g-PEO. Their cumulative release amount of a model drug could achieve 80%, more than twice the value in the HMPSAs based on linear PEO-containing styrenic block copolymers.
2018, 36(8): 943-952
doi: 10.1007/s10118-018-2097-8
Abstract:
A series of mono- and binuclear Co(II) complexes (Co1–Co7) supported by quinoline-2-imidate ligands were synthesized and thoroughly characterized. Measured by single crystal X-ray crystallography, complexes Co1 and Co3 adopted distorted tetrahedral structures around the cobalt center. Upon activation by ethylaluminium sesquichloride (EASC), these cobalt complexes exhibited high catalytic activity and cis-1,4-selectivity towards 1,3-butadiene polymerization. The effects of ligand environment, polymerization temperature, and cocatalyst types on the polymerization were investigated in detail. Interestingly, the binuclear Co(II) complexes exhibited high thermal stability, and the polymer yields were up to 97.2% even at a high temperature of 70 °C.
A series of mono- and binuclear Co(II) complexes (Co1–Co7) supported by quinoline-2-imidate ligands were synthesized and thoroughly characterized. Measured by single crystal X-ray crystallography, complexes Co1 and Co3 adopted distorted tetrahedral structures around the cobalt center. Upon activation by ethylaluminium sesquichloride (EASC), these cobalt complexes exhibited high catalytic activity and cis-1,4-selectivity towards 1,3-butadiene polymerization. The effects of ligand environment, polymerization temperature, and cocatalyst types on the polymerization were investigated in detail. Interestingly, the binuclear Co(II) complexes exhibited high thermal stability, and the polymer yields were up to 97.2% even at a high temperature of 70 °C.
2018, 36(8): 953-959
doi: 10.1007/s10118-018-2119-6
Abstract:
Transfer printing is a critical procedure for manufacturing stretchable electronics. During such a procedure, stamps are utilized to transfer micro devices from silicon wafers to stretchable polymeric substrates. In addition to conventional silicone rubber stamps, epoxy resin based shape memory stamps have been developed and the transfer yield is thus significantly promoted. However, elastic modulus of the epoxy stamps is too high at both glassy and rubbery states, which may break the brittle micro devices during the adhesion process under mechanical pressure. In this work, we synthesized a copolymer of butyl acrylate (BA) and polycaprolactone diacrylate (PCLDA) as a soft reversible dry adhesive enabling a shape memory capability based on crystalline transition of polycaprolactone (PCL) segments. For the sample containing 40 wt% BA and 60 wt% PCLDA, Young’s modulus was 8.3 and 0.9 MPa respectively below and above the thermal transition temperature, which was much lower than that of the epoxy adhesive. On the other hand, the soft material still provided nearly ideal shape memory fixity and recovery ratios. Subsequently, shape memory surface with cone-shaped microstructure was prepared, which enabled a heating induced strong-to-weak adhesion transition when the microstructure recovered from a pressed temporary morphology to the permanent cone-shaped morphology. Such a soft reversible dry adhesive may contribute to large-scale and automated transfer printing processing.
Transfer printing is a critical procedure for manufacturing stretchable electronics. During such a procedure, stamps are utilized to transfer micro devices from silicon wafers to stretchable polymeric substrates. In addition to conventional silicone rubber stamps, epoxy resin based shape memory stamps have been developed and the transfer yield is thus significantly promoted. However, elastic modulus of the epoxy stamps is too high at both glassy and rubbery states, which may break the brittle micro devices during the adhesion process under mechanical pressure. In this work, we synthesized a copolymer of butyl acrylate (BA) and polycaprolactone diacrylate (PCLDA) as a soft reversible dry adhesive enabling a shape memory capability based on crystalline transition of polycaprolactone (PCL) segments. For the sample containing 40 wt% BA and 60 wt% PCLDA, Young’s modulus was 8.3 and 0.9 MPa respectively below and above the thermal transition temperature, which was much lower than that of the epoxy adhesive. On the other hand, the soft material still provided nearly ideal shape memory fixity and recovery ratios. Subsequently, shape memory surface with cone-shaped microstructure was prepared, which enabled a heating induced strong-to-weak adhesion transition when the microstructure recovered from a pressed temporary morphology to the permanent cone-shaped morphology. Such a soft reversible dry adhesive may contribute to large-scale and automated transfer printing processing.
2018, 36(8): 960-969
doi: 10.1007/s10118-018-2108-9
Abstract:
Long-alkyl tail triphenylene (TP) side-chain liquid crystalline polymers (SCLCPs) with different spacer length (P-m-TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers) have been successfully synthesized via free radical polymerization. The differential scanning calorimetry (DSC), polarized light microscopy (POM), ultraviolet-visible spectroscopy (UV-Vis), wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P-m-TP, including steric effect, decoupling effect and π-π stacking effect. The experimental results revealed that P-m-TP (m = 2, 3, 4) formed the columnar phase which was developed by the TP moieties and the main chain as a whole, suggesting that the side-chains had strong steric effect even though the number of spacer length (m) exceeded 4. In addition, the clearing points (Tis) of the polymers were above 300 °C. When m = 6 and 8, the polymers displayed hexagonal columnar phase and exhibited the low Tis (91 and 80 °C respectively), originating from the self-assembly of triphenylene due to the decoupling effect and π-π stacking effect. This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure of TP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.
Long-alkyl tail triphenylene (TP) side-chain liquid crystalline polymers (SCLCPs) with different spacer length (P-m-TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers) have been successfully synthesized via free radical polymerization. The differential scanning calorimetry (DSC), polarized light microscopy (POM), ultraviolet-visible spectroscopy (UV-Vis), wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P-m-TP, including steric effect, decoupling effect and π-π stacking effect. The experimental results revealed that P-m-TP (m = 2, 3, 4) formed the columnar phase which was developed by the TP moieties and the main chain as a whole, suggesting that the side-chains had strong steric effect even though the number of spacer length (m) exceeded 4. In addition, the clearing points (Tis) of the polymers were above 300 °C. When m = 6 and 8, the polymers displayed hexagonal columnar phase and exhibited the low Tis (91 and 80 °C respectively), originating from the self-assembly of triphenylene due to the decoupling effect and π-π stacking effect. This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure of TP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.
2018, 36(8): 970-978
doi: 10.1007/s10118-018-2142-7
Abstract:
Novel poly(aryl ether sulfone ketone)s (PAESK) were synthesized from bisphenol A (BPA), 9,9′-bis(4-hydroxyphenyl) fluorene (BHPF), 4,4′-dichlorodiphenylsulfone (DCS) and 4,4′-difluorobenzophenone (DFB) via nucleophilic substitution polymerization, which were subsequently used to fabricate ultrafiltration membrane by phase-inversion method for high temperature condensed water treatment. The obtained high molecular weight co-polymers with fluorene group with good solubility and good thermal stability, can be easily cast into flexible, white and non-transparent flat films. The influence of molar ratio of BPA and BHPF on the properties of the prepared co-polymers and membranes was investigated in detail. SEM study of the morphology of the membranes indicated that the prepared membranes possessed homogeneous pores on the top surface and were sponge-like or finger-like in cross-section. Pure water flux of the membranes increased from 71.87 L·m−2·h−1 to 247.65 L·m−2·h−1, while the retention of BSA decreased slightly, and the water contact angle decreased from 82.1° to 55.6° with the PVP concentration from 0 wt% to 10 wt%. With increasing concentration of PVP, the mechanical properties of membranes decreased, while the thermal stability increased. The permeate flux measurement showed that the PAESK membrane had the potential for high temperature condensed water treatment.
Novel poly(aryl ether sulfone ketone)s (PAESK) were synthesized from bisphenol A (BPA), 9,9′-bis(4-hydroxyphenyl) fluorene (BHPF), 4,4′-dichlorodiphenylsulfone (DCS) and 4,4′-difluorobenzophenone (DFB) via nucleophilic substitution polymerization, which were subsequently used to fabricate ultrafiltration membrane by phase-inversion method for high temperature condensed water treatment. The obtained high molecular weight co-polymers with fluorene group with good solubility and good thermal stability, can be easily cast into flexible, white and non-transparent flat films. The influence of molar ratio of BPA and BHPF on the properties of the prepared co-polymers and membranes was investigated in detail. SEM study of the morphology of the membranes indicated that the prepared membranes possessed homogeneous pores on the top surface and were sponge-like or finger-like in cross-section. Pure water flux of the membranes increased from 71.87 L·m−2·h−1 to 247.65 L·m−2·h−1, while the retention of BSA decreased slightly, and the water contact angle decreased from 82.1° to 55.6° with the PVP concentration from 0 wt% to 10 wt%. With increasing concentration of PVP, the mechanical properties of membranes decreased, while the thermal stability increased. The permeate flux measurement showed that the PAESK membrane had the potential for high temperature condensed water treatment.
2018, 36(8): 979-983
doi: 10.1007/s10118-018-2023-0
Abstract:
Pentaerythritol triacrylate (PETA) was successfully grafted onto the plasma-treated isotactic polypropylene (iPP) via the in situ melt processing. The X-ray photoelectron spectroscopy (XPS) results showed that the hydroxyl and carbonyl groups, and peroxides could be generated via plasma treatment. The content of free radical in plasma-treated iPP (PiPP) was measured by 2,2-diphenyl-1-picrylhydrazyl (DPPH). It was found that the resulting peroxides induced the grafting copolymerization of PETA onto iPP, and the grafted PETA promoted the formation of β-crystal in PiPP, which was evidenced by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) measurements, respectively.
Pentaerythritol triacrylate (PETA) was successfully grafted onto the plasma-treated isotactic polypropylene (iPP) via the in situ melt processing. The X-ray photoelectron spectroscopy (XPS) results showed that the hydroxyl and carbonyl groups, and peroxides could be generated via plasma treatment. The content of free radical in plasma-treated iPP (PiPP) was measured by 2,2-diphenyl-1-picrylhydrazyl (DPPH). It was found that the resulting peroxides induced the grafting copolymerization of PETA onto iPP, and the grafted PETA promoted the formation of β-crystal in PiPP, which was evidenced by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) measurements, respectively.
2018, 36(8): 984-990
doi: 10.1007/s10118-018-2111-1
Abstract:
We have investigated the influence of the adsorption process on the dewetting behavior of the linear polystyrene film (LPS), the 3-arm star polystyrene film (3SPS) and the ring polystyrene film (RPS) on the silanized Si substrate. Results show that the adsorption process greatly influences the dewetting behavior of the thin polymer films. On the silanized Si substrate, the 3SPS chains exhibit stronger adsorption compared with the LPS chains and RPS chains; as a result, the wetting layer forms more easily. For LPS films, with the decrease of annealing temperature, the kinetics of polymer film changes from exponential behavior to slip dewetting. As a comparison, the stability of 3SPS and RPS films switches from slip dewetting to unusual dewetting kinetic behavior. The adsorbed nanodroplets on the solid substrate play an important role in the dewetting kinetics by reducing the driving force of dewetting and increase the resistant force of dewetting. Additionally, Brownian dynamics (BD) simulation shows that the absolute values of adsorption energy (ε) gradually increase from linear polymer (−0.3896) to ring polymer (−0.4033) and to star polymer (−0.4264), which is consistent with the results of our adsorption experiments.
We have investigated the influence of the adsorption process on the dewetting behavior of the linear polystyrene film (LPS), the 3-arm star polystyrene film (3SPS) and the ring polystyrene film (RPS) on the silanized Si substrate. Results show that the adsorption process greatly influences the dewetting behavior of the thin polymer films. On the silanized Si substrate, the 3SPS chains exhibit stronger adsorption compared with the LPS chains and RPS chains; as a result, the wetting layer forms more easily. For LPS films, with the decrease of annealing temperature, the kinetics of polymer film changes from exponential behavior to slip dewetting. As a comparison, the stability of 3SPS and RPS films switches from slip dewetting to unusual dewetting kinetic behavior. The adsorbed nanodroplets on the solid substrate play an important role in the dewetting kinetics by reducing the driving force of dewetting and increase the resistant force of dewetting. Additionally, Brownian dynamics (BD) simulation shows that the absolute values of adsorption energy (ε) gradually increase from linear polymer (−0.3896) to ring polymer (−0.4033) and to star polymer (−0.4264), which is consistent with the results of our adsorption experiments.
2018, 36(8): 991-998
doi: 10.1007/s10118-018-2114-y
Abstract:
It has been experimentally shown that epoxide-terminated hyperbranched polyether sulphone (EHBPES) can significantly improve the mechanical properties of traditional diglycidyl ether of bisphenol A/triethylenetetramine (DGEBA/TETA) systems, but the origin of the improvement is still unclear. In this work, we used molecular dynamics (MD) simulations to gain a thorough understanding of the origin of modulus improvement for EHBPES/DGEBA/TETA systems. It is found that the modulus of EHBPES/DGEBA/TETA systems increases with the increase of EHBPES loading. In addition, the crosslinking density, cohesive energy density (CED), and free volume can be used to understand the modulus for EHBPES/DGEBA/TETA systems. It is shown that the highest modulus is achieved at 7 wt% EHBPES loading due to the highest crosslinking density and CED. When EHBPES loading is below 7 wt%, the higher CED and crosslinking density are responsible for the higher modulus. At higher loadings (> 7 wt%), the decreased modulus is closely related to the decreased crosslinking density and increased fractional free volume. It is expected that our results could be of great implications for designing high-performance epoxy materials.
It has been experimentally shown that epoxide-terminated hyperbranched polyether sulphone (EHBPES) can significantly improve the mechanical properties of traditional diglycidyl ether of bisphenol A/triethylenetetramine (DGEBA/TETA) systems, but the origin of the improvement is still unclear. In this work, we used molecular dynamics (MD) simulations to gain a thorough understanding of the origin of modulus improvement for EHBPES/DGEBA/TETA systems. It is found that the modulus of EHBPES/DGEBA/TETA systems increases with the increase of EHBPES loading. In addition, the crosslinking density, cohesive energy density (CED), and free volume can be used to understand the modulus for EHBPES/DGEBA/TETA systems. It is shown that the highest modulus is achieved at 7 wt% EHBPES loading due to the highest crosslinking density and CED. When EHBPES loading is below 7 wt%, the higher CED and crosslinking density are responsible for the higher modulus. At higher loadings (> 7 wt%), the decreased modulus is closely related to the decreased crosslinking density and increased fractional free volume. It is expected that our results could be of great implications for designing high-performance epoxy materials.
