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2019 Volume 37 Issue 5
2019, 37(5):
Abstract:
2019, 37(5): 437-443
doi: 10.1007/s10118-019-2223-2
Abstract:
Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves complex chemical synthesis steps or specific conditions which limits their practical applications. Herein, a new photoresponsive hydrogel is facilely prepared via co-assembly of two simple molecules, Fmoc-Phe-OH and Azp, without chemical synthesis. The co-assembly mechanism, morphology, and photoresponsiveness of (Fmoc-Phe-OH)-Azp hydrogel are investigated by circular dichroism (CD), ultraviolet-visible (UV-Vis), fluorescence, 1H nuclear magnetic resonance (1H-NMR), attenuated total internal reflection Fourier transform Infrared (ATR-FTIR) spectroscopy, and scanning electron microscopy (SEM). Furthermore, the enhanced release of encapsulated sulforhodamine B (SRB) dye molecules can be achieved via UV light irradiation. The enhanced dye release amount can be controlled by manipulating photoirradiation time. This study provides a facile way to prepare photoresponsive hydrogel which holds great potential for controllable drug release.
Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves complex chemical synthesis steps or specific conditions which limits their practical applications. Herein, a new photoresponsive hydrogel is facilely prepared via co-assembly of two simple molecules, Fmoc-Phe-OH and Azp, without chemical synthesis. The co-assembly mechanism, morphology, and photoresponsiveness of (Fmoc-Phe-OH)-Azp hydrogel are investigated by circular dichroism (CD), ultraviolet-visible (UV-Vis), fluorescence, 1H nuclear magnetic resonance (1H-NMR), attenuated total internal reflection Fourier transform Infrared (ATR-FTIR) spectroscopy, and scanning electron microscopy (SEM). Furthermore, the enhanced release of encapsulated sulforhodamine B (SRB) dye molecules can be achieved via UV light irradiation. The enhanced dye release amount can be controlled by manipulating photoirradiation time. This study provides a facile way to prepare photoresponsive hydrogel which holds great potential for controllable drug release.
2019, 37(5): 444-450
doi: 10.1007/s10118-019-2213-4
Abstract:
A novel nanomagnetic organogel was synthesized by in situ emulsion polymerization-crosslinking method using dodecyl methacrylate (DDMA) and styrene (St) as monomers, divinylbenzene (DVB) as a crosslinking agent, azobisisobutyronitrile (AIBN) as an initiator, and Fe3O4 as a nanomagnetic particle. Modification of the network was carried out by inclusion of the multi-walled carbon nanotubes (MWCNT) into the organogel matrix. The structure of the nanocomposite was characterized using FTIR spectroscopy, SEM, TEM, TGA/DTG, VSM, and BET analysis. The effects of various parameters such as the amount of crosslinker, initiator, Fe3O4, and reaction time as well as monomer ratio on the oil absorption of the organogel were studied. The synthesized organogel can absorb about 35.5, 22.1, 29.86, 14.58, 17.6, 15.3, and 13.7 g·g−1 of CHCl3, toluene, CH2Cl2, hexane, crude oil, gasoline, and diesel oil, under the optimized polymerization conditions, respectively. The nanocomposite organogels can be easily separated by a magnetic field after absorption of organic solvents.
A novel nanomagnetic organogel was synthesized by in situ emulsion polymerization-crosslinking method using dodecyl methacrylate (DDMA) and styrene (St) as monomers, divinylbenzene (DVB) as a crosslinking agent, azobisisobutyronitrile (AIBN) as an initiator, and Fe3O4 as a nanomagnetic particle. Modification of the network was carried out by inclusion of the multi-walled carbon nanotubes (MWCNT) into the organogel matrix. The structure of the nanocomposite was characterized using FTIR spectroscopy, SEM, TEM, TGA/DTG, VSM, and BET analysis. The effects of various parameters such as the amount of crosslinker, initiator, Fe3O4, and reaction time as well as monomer ratio on the oil absorption of the organogel were studied. The synthesized organogel can absorb about 35.5, 22.1, 29.86, 14.58, 17.6, 15.3, and 13.7 g·g−1 of CHCl3, toluene, CH2Cl2, hexane, crude oil, gasoline, and diesel oil, under the optimized polymerization conditions, respectively. The nanocomposite organogels can be easily separated by a magnetic field after absorption of organic solvents.
2019, 37(5): 451-461
doi: 10.1007/s10118-019-2211-6
Abstract:
To prepare chiral monomer with single chiral center and higher stereospecificity, a pair of amino-functionalized chiral 3,4-propylenedioxythiophene (ProDOT) derivatives, chiral (3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)methyl 2-[(tert-butoxycarbonyl)amino]-3-phenylpropanoate (ProDOT-Boc-Phe), were synthesized. Chiral poly[(3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)methyl 2-[(tert-butoxycarbonyl)amino]-3-phenylpropanoate] (PProDOT-Boc-Phe) modified electrodes were synthesized via potentiostatic polymerization of chiral ProDOT-Boc-Phe. Chiral PProDOT-Boc-Phe films displayed good reversible redox activities. The enantioselective recognition between chiral PProDOT-Boc-Phe modified glassy carbon electrodes and DOPA enantiomers was achieved by different electrochemical technologies, including cyclic voltammetry (CV), square wave voltammetry (SWV), and differential pulse voltammetry (DPV). (D)-PProDOT-Boc-Phe and (L)-PProDOT-Boc-Phe showed higher peak current responses toward L-DOPA and D-DOPA, respectively.
To prepare chiral monomer with single chiral center and higher stereospecificity, a pair of amino-functionalized chiral 3,4-propylenedioxythiophene (ProDOT) derivatives, chiral (3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)methyl 2-[(tert-butoxycarbonyl)amino]-3-phenylpropanoate (ProDOT-Boc-Phe), were synthesized. Chiral poly[(3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)methyl 2-[(tert-butoxycarbonyl)amino]-3-phenylpropanoate] (PProDOT-Boc-Phe) modified electrodes were synthesized via potentiostatic polymerization of chiral ProDOT-Boc-Phe. Chiral PProDOT-Boc-Phe films displayed good reversible redox activities. The enantioselective recognition between chiral PProDOT-Boc-Phe modified glassy carbon electrodes and DOPA enantiomers was achieved by different electrochemical technologies, including cyclic voltammetry (CV), square wave voltammetry (SWV), and differential pulse voltammetry (DPV). (D)-PProDOT-Boc-Phe and (L)-PProDOT-Boc-Phe showed higher peak current responses toward L-DOPA and D-DOPA, respectively.
2019, 37(5): 462-470
doi: 10.1007/s10118-019-2198-z
Abstract:
A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of (PhC＝N(C6H3(R1)2-2,6)(C3HN2(R2)2-3,5)MtCl2 (R1 = Me, R2 = H, Mt = Co (1a), Fe (2a); R1 = Me, R2 = Me, Mt = Co (1b), Fe (2b); R1 = iPr, R2 = H, Mt = Co (1c), Fe (2c); R1 = iPr, R2 = Me, Mt = Co (1d), Fe (2d); R1 = iPr, R2 = Ph, Mt = Co (1e), Fe (2e)) were synthesized and thoroughly characterized. Determined by single crystal X-ray diffraction, complexes 1b and 2b revealed dimeric structures, in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride (EASC), all the cobalt complexes displayed high activities in 1,3-butadiene polymerization, affording polybutadienes with predominant cis-1,4 contents (up to 97.0%). Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes, the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex 2a, changing cocatalyst from trialkyl aluminums to methyl aluminoxane (MAO) led to an shift of selectivity from high cis-1,4- to trans-1,4-/1,2- manner. Being activated by MAO, complexes 2a and 2b gave trans-1,4-/1,2- binary polybutadienes, while complexes 2c, 2d, and 2e afforded cis-1,4- enriched polymers.
A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of (PhC＝N(C6H3(R1)2-2,6)(C3HN2(R2)2-3,5)MtCl2 (R1 = Me, R2 = H, Mt = Co (1a), Fe (2a); R1 = Me, R2 = Me, Mt = Co (1b), Fe (2b); R1 = iPr, R2 = H, Mt = Co (1c), Fe (2c); R1 = iPr, R2 = Me, Mt = Co (1d), Fe (2d); R1 = iPr, R2 = Ph, Mt = Co (1e), Fe (2e)) were synthesized and thoroughly characterized. Determined by single crystal X-ray diffraction, complexes 1b and 2b revealed dimeric structures, in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride (EASC), all the cobalt complexes displayed high activities in 1,3-butadiene polymerization, affording polybutadienes with predominant cis-1,4 contents (up to 97.0%). Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes, the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex 2a, changing cocatalyst from trialkyl aluminums to methyl aluminoxane (MAO) led to an shift of selectivity from high cis-1,4- to trans-1,4-/1,2- manner. Being activated by MAO, complexes 2a and 2b gave trans-1,4-/1,2- binary polybutadienes, while complexes 2c, 2d, and 2e afforded cis-1,4- enriched polymers.
2019, 37(5): 471-477
doi: 10.1007/s10118-019-2197-0
Abstract:
Binuclear and hexanuclear titanium complexes stabilized by tetradentate [OOOO]4–-type ligand were active in ethylene polymerization in the presence of Et2AlCl/Bu2Mg binary co-catalyst, giving high molecular weight polyethylene. The binuclear complex showed significantly higher catalytic activity and thermal stability in comparison to mononuclear analogue. Ultra high molecular weight polyethylene (UHMWPE) samples were processed by a solid-state uniaxial deformation into high-strength (up to 2.5 GPa) and high-modulus (over 100 GPa) oriented film tapes, which indirectly indicates a low degree of entanglements between the macromolecular chains.
Binuclear and hexanuclear titanium complexes stabilized by tetradentate [OOOO]4–-type ligand were active in ethylene polymerization in the presence of Et2AlCl/Bu2Mg binary co-catalyst, giving high molecular weight polyethylene. The binuclear complex showed significantly higher catalytic activity and thermal stability in comparison to mononuclear analogue. Ultra high molecular weight polyethylene (UHMWPE) samples were processed by a solid-state uniaxial deformation into high-strength (up to 2.5 GPa) and high-modulus (over 100 GPa) oriented film tapes, which indirectly indicates a low degree of entanglements between the macromolecular chains.
2019, 37(5): 478-492
doi: 10.1007/s10118-019-2205-4
Abstract:
A series of polyamic acid copolymers (co-PAAs) with para-hydroxyl groups was synthesized using two diamine monomers, namely p-phenylenediamine (p-PDA) and 5-amino-2-(2-hydroxy-5-aminobenzene)-benzoxazole (m-pHBOA), of different molar ratios through copolymerization with 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) in N,N-dimethyacetamine (DMAc). The co-PAA solutions were used to fabricate fibers by dry-jet wet spinning, and thermal imidization was conducted to obtain polyimide copolymer (co-PI) fibers. The effects of the m-pHBOA moiety on molecular packing and physical properties of the prepared fibers were investigated. Fourier transform infrared (FTIR) spectroscopic results confirmed that intra/intermolecular hydrogen bonds originated from the hydroxyl group and the nitrogen atom of the benzoxazole group and/or the hydroxyl group and the oxygen atom of the carbonyl group of cyclic imide. As-prepared PI fibers displayed homogenous and smooth surface and uniform diameter. The glass transition temperatures (Tgs) of PI fibers were within 311−337 °C. The polyimide fibers showed 5% weight loss temperature (T5%) at above 510 °C in air. Two-dimensional wide-angle X-ray diffraction (WXRD) patterns indicated that the homo-PI and co-PI fibers presented regularly arranged polymer chains along the fiber axial direction. The ordered molecular packing along the transversal direction was destroyed by introducing the m-pHBOA moiety. Moreover, the crystallinity and orientation factors increased with increasing draw ratio. Small-angle X-ray scattering (SAXS) results showed that it is beneficial to reduce defects in the fibers by increasing the draw ratio. The resultant PI fibers exhibited excellent mechanical properties with fracture strength and initial modulus of 2.48 and 89.73 GPa, respectively, when the molar ratio of p-PDA/m-pHBOA was 5/5 and the draw ratio was 3.0.
A series of polyamic acid copolymers (co-PAAs) with para-hydroxyl groups was synthesized using two diamine monomers, namely p-phenylenediamine (p-PDA) and 5-amino-2-(2-hydroxy-5-aminobenzene)-benzoxazole (m-pHBOA), of different molar ratios through copolymerization with 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) in N,N-dimethyacetamine (DMAc). The co-PAA solutions were used to fabricate fibers by dry-jet wet spinning, and thermal imidization was conducted to obtain polyimide copolymer (co-PI) fibers. The effects of the m-pHBOA moiety on molecular packing and physical properties of the prepared fibers were investigated. Fourier transform infrared (FTIR) spectroscopic results confirmed that intra/intermolecular hydrogen bonds originated from the hydroxyl group and the nitrogen atom of the benzoxazole group and/or the hydroxyl group and the oxygen atom of the carbonyl group of cyclic imide. As-prepared PI fibers displayed homogenous and smooth surface and uniform diameter. The glass transition temperatures (Tgs) of PI fibers were within 311−337 °C. The polyimide fibers showed 5% weight loss temperature (T5%) at above 510 °C in air. Two-dimensional wide-angle X-ray diffraction (WXRD) patterns indicated that the homo-PI and co-PI fibers presented regularly arranged polymer chains along the fiber axial direction. The ordered molecular packing along the transversal direction was destroyed by introducing the m-pHBOA moiety. Moreover, the crystallinity and orientation factors increased with increasing draw ratio. Small-angle X-ray scattering (SAXS) results showed that it is beneficial to reduce defects in the fibers by increasing the draw ratio. The resultant PI fibers exhibited excellent mechanical properties with fracture strength and initial modulus of 2.48 and 89.73 GPa, respectively, when the molar ratio of p-PDA/m-pHBOA was 5/5 and the draw ratio was 3.0.
2019, 37(5): 493-499
doi: 10.1007/s10118-019-2194-3
Abstract:
Herein, excellent UV-absorbing poly(vinylidene fluoride) (PVDF) membranes were fabricated through the pre-irradiation induced graft polymerization method. The PVDF chains irradiated with 60Co γ-ray were modified with the polymerizable UV absorber 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (RUVA-93). The influences of irradiation dose and monomer concentration on the prepared PVDF-g-PRUVA-93 membranes were investigated, and the optimal condition was eventually obtained. The chemical structures of the films were studied by 1H-NMR, FTIR, and XRD. UV light transmittance and DSC tests were used to characterize the UV-absorbing performance and thermal property of the PVDF films before and after modification. The results proved that the PRUVA-93 side chains were successfully incorporated into the PVDF main chains and the obtained PVDF-g-PRUVA-93 films possessed remarkable UV-absorbing property. The modified membrane made under the optimized experiment condition could completely block the UV light in the range of 200−387 nm. Additionally, the transmittance of the PVDF-g-PRUVA-93 film could be reduced to 0.04% in 280−320 nm, where the light irradiation could damage polymer materials most seriously.
Herein, excellent UV-absorbing poly(vinylidene fluoride) (PVDF) membranes were fabricated through the pre-irradiation induced graft polymerization method. The PVDF chains irradiated with 60Co γ-ray were modified with the polymerizable UV absorber 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (RUVA-93). The influences of irradiation dose and monomer concentration on the prepared PVDF-g-PRUVA-93 membranes were investigated, and the optimal condition was eventually obtained. The chemical structures of the films were studied by 1H-NMR, FTIR, and XRD. UV light transmittance and DSC tests were used to characterize the UV-absorbing performance and thermal property of the PVDF films before and after modification. The results proved that the PRUVA-93 side chains were successfully incorporated into the PVDF main chains and the obtained PVDF-g-PRUVA-93 films possessed remarkable UV-absorbing property. The modified membrane made under the optimized experiment condition could completely block the UV light in the range of 200−387 nm. Additionally, the transmittance of the PVDF-g-PRUVA-93 film could be reduced to 0.04% in 280−320 nm, where the light irradiation could damage polymer materials most seriously.
2019, 37(5): 500-508
doi: 10.1007/s10118-019-2210-7
Abstract:
In this study, monoglycidyl silyl etherated eugenol (GSE) was synthesized as reactive epoxy diluent, and the chemical structure of GSE, intermediates, and products were characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H-NMR). GSE existed as a potential bio-based reactive diluent for petroleum-based epoxy resin. The curing kinetics of EP/HHPA/GSE system was studied by non-isothermal DSC method. The kinetics parameters were calculated by using the Kissinger model, Crane model, Ozawa model, and β-T (temperature-heating rate) extrapolation, respectively. In addition, the effects of GSE on the thermo-mechanical properties and thermal stability of EP/HHPA/GSE systems were studied, indicating that GSE can effectively improve the toughness and thermal decomposition temperature of the epoxy system.
In this study, monoglycidyl silyl etherated eugenol (GSE) was synthesized as reactive epoxy diluent, and the chemical structure of GSE, intermediates, and products were characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H-NMR). GSE existed as a potential bio-based reactive diluent for petroleum-based epoxy resin. The curing kinetics of EP/HHPA/GSE system was studied by non-isothermal DSC method. The kinetics parameters were calculated by using the Kissinger model, Crane model, Ozawa model, and β-T (temperature-heating rate) extrapolation, respectively. In addition, the effects of GSE on the thermo-mechanical properties and thermal stability of EP/HHPA/GSE systems were studied, indicating that GSE can effectively improve the toughness and thermal decomposition temperature of the epoxy system.
2019, 37(5): 509-517
doi: 10.1007/s10118-019-2220-5
Abstract:
Electrically conductive and flame-retardant maleic anhydride grafted high-density polyethylene (MA-HDPE) nanocomposites with satisfactory mechanical properties are fabricated by melt compounding MA-HDPE with polyethyleneimine (PEI)-modified reduced graphene oxide (PEI@RGO) as the conductive nanofiller and brominated polystyrene (BPS) as the flame retardant. The modification with PEI significantly improves the interfacial compatibility and dispersion of the RGO sheets in the MA-HDPE matrix, leading to electrically conductive nanocomposites with enhanced mechanical properties. Furthermore, the addition of 25 wt% of BPS makes the nanocomposite flame-retardant with a UL-94 V-0 rating. Thus, the multifunctional RGO/MA-HDPE nanocomposites with good electrical, flame-retardant, and mechanical properties would have potential applications in construction and pipeline fields.
Electrically conductive and flame-retardant maleic anhydride grafted high-density polyethylene (MA-HDPE) nanocomposites with satisfactory mechanical properties are fabricated by melt compounding MA-HDPE with polyethyleneimine (PEI)-modified reduced graphene oxide (PEI@RGO) as the conductive nanofiller and brominated polystyrene (BPS) as the flame retardant. The modification with PEI significantly improves the interfacial compatibility and dispersion of the RGO sheets in the MA-HDPE matrix, leading to electrically conductive nanocomposites with enhanced mechanical properties. Furthermore, the addition of 25 wt% of BPS makes the nanocomposite flame-retardant with a UL-94 V-0 rating. Thus, the multifunctional RGO/MA-HDPE nanocomposites with good electrical, flame-retardant, and mechanical properties would have potential applications in construction and pipeline fields.
2019, 37(5): 518-526
doi: 10.1007/s10118-019-2214-3
Abstract:
By extending the virtual conformational element of the polymer chain, a dynamic end-to-end (ETE) vector was presented to describe the chain’s instantaneous morphology based on the spring-bead theory. A feasible viscoelastic model was proposed to describe the rheological behavior of the isothermal thermoplastic polymer materials, based on the molecular kinetics, thermodynamics, and continuum mechanics method. The model is simplified as the generalized Newton’s law. Its integral formula with similar form to the K-BKZ model was also derived. Rheological experiments were carried out with the isotactic polypropylene material. The experimental results reveal that the viscoelastic model exhibits a three-stage rheological characteristic. There is a distinct high-elastic rheological region in the middle stage, reflecting the pseudoplastic fluids properties. Compared with the Ostwald-de Waele power law model, the viscoelastic model shows a better agreement with the rheological practices.
By extending the virtual conformational element of the polymer chain, a dynamic end-to-end (ETE) vector was presented to describe the chain’s instantaneous morphology based on the spring-bead theory. A feasible viscoelastic model was proposed to describe the rheological behavior of the isothermal thermoplastic polymer materials, based on the molecular kinetics, thermodynamics, and continuum mechanics method. The model is simplified as the generalized Newton’s law. Its integral formula with similar form to the K-BKZ model was also derived. Rheological experiments were carried out with the isotactic polypropylene material. The experimental results reveal that the viscoelastic model exhibits a three-stage rheological characteristic. There is a distinct high-elastic rheological region in the middle stage, reflecting the pseudoplastic fluids properties. Compared with the Ostwald-de Waele power law model, the viscoelastic model shows a better agreement with the rheological practices.
2019, 37(5): 527-534
doi: 10.1007/s10118-019-2195-2
Abstract:
Free volume is an extremely important intrinsic defect in polymers. Structurally, free volume is the randomly distributed holes in the polymer molecular chain segments. In proton exchange membrane fuel cells, free volume is also the space needed for the directional conduction of protons. Irradiation by α particles to grafting sulfonated poly(vinylidene fluoride) (PVDF) is one of the methods to produce proton exchange membrane with good proton channel rate. Positron annihilation lifetime spectroscopy was used to study the free volume size at different absorbed dose levels from 0.13 MGy to 0.65 MGy. Measurement method of positron annihilation lifetime spectroscopy for PVDF based on 44Ti positron source was developed. For low dose irradiation at 0.26 MGy, a decrease in free volume and practically unchanged crystallinity were observed. Further increase of absorbed dose range from 0.26 MGy to 0.39 MGy led to an increasing crystallinity with the same free volume level. For the absorbed dose from 0.39 MGy to 0.65 MGy, crystallinity was decreased but free volume remained almost constant.
Free volume is an extremely important intrinsic defect in polymers. Structurally, free volume is the randomly distributed holes in the polymer molecular chain segments. In proton exchange membrane fuel cells, free volume is also the space needed for the directional conduction of protons. Irradiation by α particles to grafting sulfonated poly(vinylidene fluoride) (PVDF) is one of the methods to produce proton exchange membrane with good proton channel rate. Positron annihilation lifetime spectroscopy was used to study the free volume size at different absorbed dose levels from 0.13 MGy to 0.65 MGy. Measurement method of positron annihilation lifetime spectroscopy for PVDF based on 44Ti positron source was developed. For low dose irradiation at 0.26 MGy, a decrease in free volume and practically unchanged crystallinity were observed. Further increase of absorbed dose range from 0.26 MGy to 0.39 MGy led to an increasing crystallinity with the same free volume level. For the absorbed dose from 0.39 MGy to 0.65 MGy, crystallinity was decreased but free volume remained almost constant.
