2016 Volume 34 Issue 5

Miniemulsion Cross-linking: A Convenient Route to Hollow Polymeric Nanocapsule with a Liquid Core
Lin Wu , Tao Pang , Ye-bin Guan
2016, 34(5): 523-531  doi: 10.1007/s10118-016-1784-6
[Abstract](550) [FullText HTML] [PDF 0KB](0)
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Miniemulsion stabilized by poly(2-(dimethylamino) ethyl methacrylate)-block-poly(butyl methylacrylate) (PDMAEMA- b-PBMA) diblock copolymers has been used as liquid templates for the synthesis of polymer nanocapsules via quaternization cross-linking of PDMAEMA segments of the copolymer by 1,2-bis(2-iodoethoxy)ethane (BIEE) crosslinkers. PDMAEMA- b-PBMAs here as a stabilizer in miniemulsion with different molecular weights led to a size variation in diameters of nanocapsules, demonstrating the capsules have potential design capability of this technique. The solution behavior of the capsules has been also investigated in this paper.
Facile Fabrication of High-performance Polyimide Nanocomposites with in situ Formed “Impurity-free” Dispersants
Jing-jing Shen , Dong-ge Zhang , Xing Liu , Yu-chang Tang , Yu Lin , Guo-zhang Wu
2016, 34(5): 532-541  doi: 10.1007/s10118-016-1771-y
[Abstract](602) [FullText HTML] [PDF 0KB](0)
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Polyimide/carbon black (PI/CB) nanocomposite films were fabricated via the direct ball-milling method with poly(amic acid) (PAA), the precursor of PI, as an in situ formed impurity-free dispersant. FTIR and Raman spectral results reveal that, besides physical adsorption, chemical grafting of PAA chains onto the CB surface occurs during the ball-milling process. Comparative studies show that introduction of various commercial dispersants improves the dispersion of CB. However, the mixtures exhibit poor reproducibility, unstable electrical properties, and decreased tensile strength; these issues may be attributed to interfacial pollution brought about by differences in the chemical structures of the dispersant and the matrix. The impurity-free dispersant is effective not only in ensuring the uniform dispersion of CB particles but also in enhancing filler-matrix interfacial adhesion. High-molecular weight PAA chains are effective reagents for impurity-free modification and can therefore be used to improve the electrical and mechanical properties of the resultant composite.
Thermal Stability and Thermal Aging of Poly(vinyl chloride)/MgAl Layered Double Hydroxides Composites
Hong-mei Zhang , Shu-hua Zhang , Polite Stewart , Chen-hui Zhu , Wei-jun Liu , Alexander Hexemer , Eric Schaible , Cheng Wang
2016, 34(5): 542-551  doi: 10.1007/s10118-016-1778-4
[Abstract](611) [FullText HTML] [PDF 0KB](0)
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MgAl-LDH (layered double hydroxides) were prepared with CO(NH2)2, NH4Cl and NH3·H2O by the co-precipitation method, respectively. Corresponding composite membranes were prepared by the coating method. LDHs were characterized by WAXS, CO2-TPD and SEM. The morphology of the PVC/LDHs composite membranes were characterized by means of SEM. The thermal stability of the membranes was analyzed by air aging box and TGA-FTIR. The SEM results show that nano-particles can be compatible with poly(vinyl chloride) (PVC) matrix homogeneously by the stirring-ultrasound blend method with two steps. Furthermore, the air aging box results proved that MgAl-CO(NH2)2-LDH has the best effect on thermal stability of PVC. TGA-FTIR results show that MgAl-CO(NH2)2-LDH could adsorb more HCl that resulted from the degradation of PVC and improve the pyrolysis temperature of the first degradation stage by 15 K compared with PVC.
Numerical Study of the Interplay of Monomer-Surface Electrostatic and Non-electrostatic Interactions in the Adsorption of Weak Polyelectrolytes on Oppositely Charged Surfaces
Hai-ming Li , Yu-wei Chen , Yue-jin Zhu , Chao-hui Tong
2016, 34(5): 552-562  doi: 10.1007/s10118-016-1780-x
[Abstract](595) [FullText HTML] [PDF 0KB](0)
Abstract:
The adsorption of weak polybase on oppositely charged planar surfaces has been investigated numerically by using the self-consistent field theory (SCFT). Particular attention was paid to the interplay of monomer-surface electrostatic and non-electrostatic interactions in the adsorption behaviors of weak polybase. In this study, the strength of monomer-surface non-electrostatic interactions was set to be no more than the thermal energy kBT. It was found from the numerical study that in the regime of low surface charge density of the substrate and low pH or high bulk degree of ionization, both the screening-enhanced and screening-reduced salt effects emerge. On the contrary, in the opposite regime, only the screening-reduced salt effect was observed. Moreover, the overall charge neutrality inside the adsorption layer was analyzed. The underlying mechanism governing the adsorption behaviors of weak polybase on oppositely charged surfaces was elucidated.
Synthesis and Characterization of D-/L-methionine Grafted PEDOTs for Selective Recognition of 3,4-Dihydroxyphenylalanine Enantiomers
Li-qi Dong , Du-fen Hu , Xue-min Duan , Zhi-peng Wang , Kai-xin Zhang , Xiao-fei Zhu , Hui Sun , You-shan Zhang , Jing-kun Xu
2016, 34(5): 563-577  doi: 10.1007/s10118-016-1772-x
[Abstract](698) [FullText HTML] [PDF 0KB](0)
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Two pairs of amino-acid functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives, namely, poly(N-(tert-butoxycarbonyl)-L-methionyl (3,4-ethylenedioxythiophene-2'-yl)methylamide) (L-PEDOT-Boc-Met) and poly(N-(tert-butoxycarbonyl)-D-methionyl (3,4-ethylenedioxythiophene-2'-yl)methylamide) (D-PEDOT-Boc-Met); poly(L-methionyl (3,4-ethylenedioxythiophene-2'-yl)methylamide) (L-PEDOT-Met) and poly(D-methionyl (3,4-ethylenedioxythiophene-2'-yl)methylamide) (D-PEDOT-Met) were synthesized via chemical oxidative polymerization of corresponding monomers. The structural characterization, spectroscopic properties and thermal stability of these monomers and polymers were systematically explored by FTIR spectra, Raman spectra, XRD spectra, UV-Vis spectra and thermogravimetric analysis. As chiral electrode materials, these polymers were employed to successfully recognize 3,4-dihydroxyphenylalanine (DOPA) enantiomers by cyclic voltammetry (CV) in sulphuric acid solution. The measurement results reveal that the tendency was hetero-chiral interaction between L-PEDOT-Met/PVA/GCE and D-DOPA, D-PEDOT-Met/PVA/GCE and L-DOPA, respectively. Also, the mechanism of chiral discrimination was discussed. All the results implied that the combination of electrochemical molecular recognition technology and chiral PEDOT materials can be a promising approach for chiral recognition and may open new opportunities for facile, biocompatible, sensitive and robust chiral assays in biochemical applications.
The Solvent Quality of Water for Poly(N-isopropylacrylamide) in the Collapsed State: Implications from Single-molecule Studies
Xiang-chao Pang , Bo Cheng , Shu-xun Cui
2016, 34(5): 578-584  doi: 10.1007/s10118-016-1773-9
[Abstract](627) [FullText HTML] [PDF 0KB](0)
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Both of temperature (in water) and composition (in the water/methanol mixed solvent) can induce the coil-to-globule transition of poly(N-isopropylacrylamide) (PNIPAM). The atomic force microscope (AFM) based single molecule force spectroscopy (SMFS) has been exploited to investigate the interactions between the polymer chain and solvent at the single-molecule level. It is found that the single-chain mechanics of PNIPAM show a remarkable dependence on the two external stimuli. A confusing experimental result is that all the force-extension (F-E) curves of unfolding an individual PNIPAM globule present a feature of elastic (monotonically increasing force) stretching but not plateau (constant force) stretching predicted by theory. In this article, we clarify that the presence of the interior solvent molecules in the single-chain globule is the origin of the discrepancy between the F-E curves obtained from theory and experiment. Although both of the external stimuli do tend to lower the solvent quality for PNIPAM, water and the water/methanol mixed solvent will never be the strongly poor solvent for PNIPAM, even at the worst condition.
Influence of Sodium Dodecyl Sulfate on the Phase Transition of Thermoresponsive Hyperbranched Polymer in Water
Hua-ji Liu , Yue-yue Xu , Yu Chen
2016, 34(5): 585-593  doi: 10.1007/s10118-016-1779-3
[Abstract](646) [FullText HTML] [PDF 0KB](0)
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The influence of sodium dodecyl sulfate (SDS) on the cloud point temperature (Tcp) of the aqueous solution of thermoresponsive hyperbranched polyethylenimine derivative HPEI-IBAm was studied systematically. When pH was below 8.5, HPEI-IBAm was positively-charged. Initially, the Tcp of HPEI-IBAm decreased significantly, followed by an obvious increase with the increase of SDS concentration. The lower the pH was, the higher the SDS concentration was required to achieve the minimum Tcp. When pH was above 8.5, HPEI-IBAm was neutral and raising the SDS concentration led to the gradual increase of Tcp. Compared to linear poly(N-isopropyl acrylamide) (PNIPAm), the Tcp of the current hyperbranched HPEI-IBAm was more sensitive to SDS. The thermoresponsive HPEI-IBAm/SDS complex was used as host to accommodate the non-polar pyrene in water. The lowest SDS concentration for effectively enhancing the solubility of pyrene in water was around 6.4 mmol·L-1. When HPEI-IBAm was present, the SDS concentration threshhold was decreased to about 0.31 mmol·L-1. Fluorescence technique with pyrene as the hydrophobic probe demonstrated that the SDS concentration of 7.2 mmol·L-1 was required to form the hydrophobic domain to accommodate pyrene guests without HPEI-IBAm, while only 0.2 mmol·L-1 of SDS was required in the presence of HPEI-IBAm.
Novel Terpolymers of Poly(p-dioxanone-co-trimethylene carbonate-co-L-phenylalanine): Synthesis, Characterization, Thermal Properties and Copolymerization Mechanism
Li-nan Li , Cheng-dong Xiong , Dong-liang Chen
2016, 34(5): 594-605  doi: 10.1007/s10118-016-1777-5
[Abstract](645) [FullText HTML] [PDF 0KB](0)
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In order to exploit the biological functions of materials, a series of new random terpolymers were synthesized by the ring-opening polymerization of p-dioxanone, trimethylene carbonate, and L-phenylalanine N-carboxyanhydride (L-Phe-NCA) in the presence of stannous octoate. The terpolymers were characterized by 1H-NMR, 13C-NMR, FTIR, and gel permeation chromatography. The effects of the reactant ratio, catalyst dosage, reaction temperature and time on the copolymerization were investigated, and were found to regulate the composition of the terpolymer. Increases in the reaction temperature, polymerization time, L-Phe-NCA monomer amount, and catalyst content generated a product with a slightly decreased molecular weight. The crystallinity of the terpolymer was investigated by differential scanning calorimetry and polarized optical microscopy. A reasonable mechanism for the polymerization was proposed based on the obtained results.
Characterization of Structural Knot Distributions in UHMWPE Fibers
Hao-jun Xu , Min-fang An , You Lv , Zong-bao Wang , Qun Gu
2016, 34(5): 606-615  doi: 10.1007/s10118-016-1774-8
[Abstract](701) [FullText HTML] [PDF 0KB](0)
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Microbeam wide-angle X-ray diffraction (WAXD) experiments were carried out at different structural knot positions of SIOC and M4 fibers of ultra-high molecular weight polyethylene (UHMWPE). The optical microscope images revealed that SIOC fiber had bamboo-like structural knots, and M4 fiber had chaotic distribution of structural knots. WAXD patterns showed the monoclinic unit cell in the whole M4 fiber, but different lamellar orientations in the bamboo joint of SIOC fiber. In addition, small-angle X-ray scattering (SAXS) patterns confirmed that the SIOC fiber contained uniform distribution of shish structures, and differential scanning calorimetry (DSC) measurements showed that its less branched and short chains benefited the orthorhombic-hexagonal phase transformation.
Polyurethanes Made from Bile Acids
N. Levaray , X.X. Zhu
2016, 34(5): 616-622  doi: 10.1007/s10118-016-1776-6
[Abstract](651) [FullText HTML] [PDF 0KB](0)
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New polyurethanes based on bile acids were synthesized from alcohol derivatives of cholic and lithocholic acids and hexamethylene diisocyanate, in an effort to improve the biocompatibility and biodegradability of polyurethanes through the use of natural compounds. The hydrogen bonding in the polymers is confirmed by IR spectral analysis. The glass transition temperatures of the polymers are in the range of 82-138 ℃ and degradation temperatures in the range of 267-298 ℃ as studied by thermal analyses. Thermogravimetric studies indicate that the comonomers are of equimolar amounts in the polyurethanes derived from both bile acids.
Dynamics of Attractive Vesicles in Shear Flow
Zhen-yu Deng , Dong Zhang , Lin-xi Zhang
2016, 34(5): 623-636  doi: 10.1007/s10118-016-1785-5
[Abstract](646) [FullText HTML] [PDF 0KB](0)
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A nonequilibrium molecular dynamics (NEMD) method is employed to study the dynamics of two identical vesicles with attractive interactions immersed in shear flow. The dynamics behaviors of attractive vesicles depend on the attractive interactions and the shear rates simultaneously. There are four motion types for attractive vesicles in shear flow: a coupled-tumbling (CTB) motion, a coupled-trembling (CTR) motion, a collision/rotation mixture (CRM) motion and a separated-tank-treading (STT) motion, which are determined by the competition between the shear flow and the attractive interactions. Furthermore, the dynamics behavior of an individual vesicle shows three main motion types such as tumbling, trembling and tank-treading motions, and relies mainly on the shear rates. Meanwhile, comparisons with rigid vesicles for the dynamics behaviors are made, and the collision/rotation mixture (M) motion isn't observed for rigid vesicles.
Hydrogels of Chemically Cross-linked and Organ-metallic Complexed Interpenetrating PEG Networks
Meng-jiao Dong , Shun-li Liu , Lin-hua Tan , Lian Cen , Guo-dong Fu
2016, 34(5): 637-648  doi: 10.1007/s10118-016-1783-7
[Abstract](605) [FullText HTML] [PDF 0KB](0)
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The aim of the present work was to prepare a well-defined hydrogel of chemically cross-linked and organ-metallic complexed interpenetrating PEG networks. The hydrogel was synthesized via the reaction of copper(I)-catalyzed 1, 3-dipolar azide-alkyne cycloaddition (CuAAC) with poly(ethylene glycol)-dopamine (PEG-DA) (“Click Chemistry”) followed by complexation with Fe3+ ions to crosslink the polymeric network. The chemical composition and morphology of the resulting hydrogels were characterized by Fourier transform infrared spectroscopy (FTIR), 1H-NMR and scanning electron microscopy (SEM). Swelling ratio, mechanical strength, conductivity, and degradation behaviors of the hydrogels were also studied. The effect of the polymer chain length on properties of hydrogels was explored. The compressive strength of hydrogels could reach as high as 13.1 MPa with a conductivity of 2.2×10-5 S·cm-1. The hydrogels also exhibited excellent thermal stability even at a temperature of 300 ℃, whereas degradation of the hydrogel after 7 weeks was observed under a physiological condition. In addition, the hydrogel exhibited a good biocompatibility based on its in vivo performance through an in vivo subcutaneous implantation model. No inflammation and no obvious abnormality of the surrounding tissue were observed when the hydrogel was subcutaneously implanted for 2 weeks. This work is a step towards creating a new pathway to synthesize hydrogels of interpenetrating networks which could be of important applications in the future research.
Improving Ferro-and Piezo-Electric Properties of Hydrogenized Poly(vinylidene fluoride-trifluoroethylene) Films by Annealing at Elevated Temperatures
Wang Jian , Zhong Li , Yuan Yan , Xiao Wang , Yun-chuan Xie , Zhi-cheng Zhang
2016, 34(5): 649-658  doi: 10.1007/s10118-016-1782-8
[Abstract](705) [FullText HTML] [PDF 0KB](0)
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After annealing the solution cast P(VDF-TrFE) films at elevated temperatures, which were synthesized via a full hydrogenation process from P(VDF-CTFE) with a composition of VDF/TrFE=80/20 (mol%), a series of P(VDF-TrFE) films were fabricated in present work. The crystalline and ferroelectric phases of the films were carefully characterized and their dielectric, ferroelectric and piezoelectric properties were systematically investigated. The improved crystalline and ferroelectric phases in the films induced by annealing at elevated temperatures are responsible for the significant improved electric properties of the films. The optimized annealing temperature is found to be 130 ℃ and the best performance including the highest dielectric constant of 12.5 at 1 kHz, the largest maximum polarization of 11.21 μC/cm2 and remnant polarization of 7.22 μC/cm2, the lowest coercive electric field of 56 MV/m, and the highest piezoelectric coefficient of-25 pC/N is observed.
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