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1.
Lei Chen Hui-Qing Yang Cheng-Yu Jin Zhao-Xu Chen 《International journal of quantum chemistry》2020,120(22):e26366
We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH− group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH− group and the Fukui function condensed on the OH− group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts. 相似文献
2.
Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol‐ene photochemistry
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Victor A. Kusuma Elliot A. Roth William P. Clafshenkel Steven S. Klara Xu Zhou Surendar R. Venna Erik Albenze David R. Luebke Meagan S. Mauter Richard R. Koepsel Alan J. Russell David Hopkinson Hunaid B. Nulwala 《Journal of polymer science. Part A, Polymer chemistry》2015,53(13):1548-1557
Homogenous amphiphilic crosslinked polymer films comprising of poly(ethylene oxide) and polysiloxane were synthesized utilizing thiol‐ene “ click ” photochemistry. A systematic variation in polymer composition was Carried out to obtain high quality films with varied amount of siloxane and poly(ethylene oxide). These films showed improved gas separation performance with high gas permeabilities with good CO2/N2 selectivity. Furthermore, the resulting films were also tested for its biocompatibility, as a carrier media which allow human adult mesenchymal stem cells to retain their capacity for osteoblastic differentiation after transplantation. The obtained crosslinked films were characterized using differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, FTIR, Raman‐IR , and small angle X‐ray scattering. The synthesis ease and commercial availability of the starting materials suggests that these new crosslinked polymer networks could find applications in wide range of applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1548–1557 相似文献
3.
Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants
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Michael A. Brook Frances Lasowski Heather Sheardown 《Journal of polymer science. Part A, Polymer chemistry》2015,53(9):1082-1093
The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093 相似文献
4.
Jie Da Thieo E. Hogen‐Esch 《Journal of polymer science. Part A, Polymer chemistry》2004,42(2):360-373
The synthesis is reported of copolymers of N,N‐dimethylacrylamide (DMA) and methacrylates containing 2,2′‐dihydroperfluorodecanoyl (RF) groups separated from the methacrylate by long polyethylene glycol (PEG) tether groups (between 1000 and 14,000 Da). At concentrations of between 1 and 8 wt % the copolymers with macromonomer contents of 1 mol % or less give gels in organic solvents such as dioxane, THF, or methanol, as well as in water. Given the low molecular weights, this indicates very efficient association of very low numbers of RF groups. Association and gel formation is enormously enhanced in the presence of longer PEG tethers. This is consistent with smaller poly(N,N,‐dimethylacrylamide) (PDMA) intermolecular excluded volume effects that are mediated by the longer PEG tethers and possibly by the incompatibility of PEG and PDMA that may lead to the formation of PEG microdomains. This increases the local concentrations of the RF groups in the PEO domains that are not diluted by the PDMA chains, as would be the case in the absence of PEG tethers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 360–373, 2004 相似文献
5.
G. G. Bandyopadhyay S. S. Bhagawan K. N. Ninan Sabu Thomas 《Journal of Polymer Science.Polymer Physics》2004,42(8):1417-1432
The viscoelastic properties of binary blends of nitrile rubber (NBR) and isotactic polypropylene (PP) of different compositions have been calculated with mean‐field theories developed by Kerner. The phase morphology and geometry have been assumed, and experimental data for the component polymers over a wide temperature range have been used. Hashin's elastic–viscoelastic analogy principle is used in applying Kerner's theory of elastic systems for viscoelastic materials, namely, polymer blends. The two theoretical models used are the discrete particle model (which assumes one component as dispersed inclusions in the matrix of the other) and the polyaggregate model (in which no matrix phase but a cocontinuous structure of the two is postulated). A solution method for the coupled equations of the polyaggregate model, considering Poisson's ratio as a complex parameter, is deduced. The viscoelastic properties are determined in terms of the small‐strain dynamic storage modulus and loss tangent with a Rheovibron DDV viscoelastometer for the blends and the component polymers. Theoretical calculations are compared with the experimental small‐strain dynamic mechanical properties of the blends and their morphological characterizations. Predictions are also compared with the experimental mechanical properties of compatibilized and dynamically cured 70/30 PP/NBR blends. The results computed with the discrete particle model with PP as the matrix compare well with the experimental results for 30/70, 70/30, and 50/50 PP/NBR blends. For 70/30 and 50/50 blends, these predictions are supported by scanning electron microscopy (SEM) investigations. However, for 30/70 blends, the predictions are not in agreement with SEM results, which reveal a cocontinuous blend of the two. Predictions of the discrete particle model are poor with NBR as the matrix for all three volume fractions. A closer agreement of the predicted results for a 70/30 PP/NBR blend and the properties of a 1% maleic anhydride modified PP or 3% phenolic‐modified PP compatibilized 70/30 PP/NBR blend in the lower temperature zone has been observed. This may be explained by improved interfacial adhesion and stable phase morphology. A mixed‐cure dynamically vulcanized system gave a better agreement with the predictions with PP as the matrix than the peroxide, sulfur, and unvulcanized systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1417–1432, 2004 相似文献
6.
Polypropylene (PP) was modified with elastomer or CaCO3 particles of two different sizes (1 μm and 50 nm) in various volume fractions. The dispersion morphology and mechanical properties of the two systems were investigated as functions of the particle size and volume fraction of the modifier. The brittle‐to‐tough transition occurred when the matrix ligament thickness was less than the critical ligament thickness, which was about 0.1 μm for the PP used here, being independent of the type of modifier. At the same matrix ligament thickness, the improvement of the toughness was obviously higher with the elastomer rather than with CaCO3, but adding CaCO3 increased the modulus of PP. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1656–1662, 2004 相似文献
7.
The rotation-tunneling spectrum of the second most stable gGg′ conformer of ethylene glycol (1,2-ethanediol) in its ground vibrational state has been studied in selected regions between 77 and 579 GHz. Compared to the study of the more stable aGg′ conformer, a much larger frequency range was studied, resulting in a much extended frequency list covering similar quantum numbers, J?55 and Ka?19. While the input data were reproduced within experimental uncertainties up to moderately high values of J and Ka larger residuals remain at higher quantum numbers. The severe mixing of the states caused by the Coriolis interaction between the two tunneling substates is suggested to provide a considerable part of the explanation. In addition, a Coriolis interaction of the gGg′ ground vibrational state with an excited state of the aGg′ conformer may also contribute. Relative intensities of closely spaced lines have been investigated to determine the signs of the Coriolis constants between the two tunneling substates relative to the dipole moment components and to estimate the magnitudes of the dipole moment components and the energy difference between the gGg′ and the aGg′ conformers. Results of ab initio calculations on the total dipole moment and the vibrational spectrum were needed for these estimates. The current analysis is limited to transitions with quantum numbers J?40 and Ka?6 plus those having J?22 and Ka?17 which could be reproduced within experimental uncertainties. The results are aimed at aiding radioastronomers to search for gGg′ ethylene glycol in comets and in interstellar space. 相似文献
8.
Yong‐Jin Kim Jin‐Woong Kim Jung‐Eun Lee Jee‐Hyun Ryu Junoh Kim Ih‐Seop Chang Kyung‐Do Suh 《Journal of polymer science. Part A, Polymer chemistry》2004,42(22):5627-5635
Mesoporous polymer microspheres with gold (Au) nanoparticles inside their pores were prepared considering their surface functionality and porosity. The Au/polymer composite microspheres prepared were characterized by transmission electron microscope (TEM), X‐ray diffraction (XRD), and Brunauer–Emmett–Teller (BET) techniques. The results showed that the adsorption of Au nanoparticles could be increased by imparting the pore structure and surface‐functional groups into the supporting polymer microspheres (in this study, poly (ethylene glycol dimethacrylate‐co‐acrylonitrile) and poly (EGDMA‐co‐AN) system). Above all, from this study, it was established that the porosity of the polymer microspheres is the most important factor that determines the distribution and adsorption amount of face‐centered cubic (fcc) Au nanoparticles in the final products. Our study showed that the continuous adsorption of Au nanoparticles with the aid of the large surface area and surface interaction sites formed more favorably the Au/polymer composite microspheres. The BET measurements of Au/poly(EGDMA‐co‐AN) composite microspheres reveals that the adsorption of Au nanoparticles into the pores kept the pore structure intact and made it more porous. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5627–5635, 2004 相似文献
9.
10.
Yonggang Shangguan Li Zhao Liyang Tao Qiang Zheng 《Journal of Polymer Science.Polymer Physics》2007,45(13):1704-1712
The effects of preparation method, composition, and thermal condition on formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber (iPP/EPR) blends were studied using modulated differential scanning calorimeter (MDSC), wide angle X‐ray diffraction (WAXD), and phase contrast microscopy (PCM). It was found that the α‐iPP and β‐iPP can simultaneity form in the melt‐blended samples, whereas only α‐iPP exists in the solution‐blended samples. The results show that the formation of β‐iPP in the melt‐blended samples is related to the crystallization temperature and the β‐iPP generally diminishes and finally vanishes when the crystallization temperature moves far from 125 °C. The phenomena that the lower critical temperature of β‐iPP in iPP/EPR obviously increases to 114 °C and the upper critical temperature decreases to 134 °C indicate the narrowing of temperature interval, facilitating the formation of β‐iPP in iPP/EPR. Furthermore, it was found that the amount of β‐iPP in melt‐blended iPP/EPR samples is dependent on the composition and the maximum amount of β‐iPP formed when the composition of iPP/EPR blends is 85:15 in weight. The results through examining the effect of annealing for iPP/EPR samples at melt state indicate that this annealing may eliminate the susceptibility to β‐crystallization of iPP. However, only α‐iPP can be observed in solution‐blended samples subjected to annealing for different time. The PCM images demonstrate that an obvious phase‐separation happens in both melt‐blended and solution‐blended iPP/EPR samples, implying that compared with the disperse degree of EPR in iPP, the preparation method plays a dominant role in formation of β‐iPP. It is suggested that the origin of formation of β‐iPP results from the thermomechanical history of the EPR component in iPP/EPR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1704–1712, 2007 相似文献