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1.
The parent repeating sequence of elastin, poly(GVGVP), was synthesized using solution phase method and characterized by 13C‐ and 1H‐NMR spectroscopy. In order to study the polymer–polymer interactions between poly(GVGVP) and hydroxyl propyl methyl cellulose (HPMC), the blends were prepared both in aqueous and solid phase and examined using various analytical techniques. The viscometric measurements have been carried out at 24 °C and the interaction parameters such as α, β, µ, and Δ[η]m revealed the miscible nature of the poly(GVGVP)/HPMC blend systems. In addition, Fourier‐transform infrared spectroscopy showed the formation of strong intermolecular hydrogen bond between poly(GVGVP) and HPMC networks. This result was further supported by glass transition temperature (Tg), scanning electron microscopic, and X‐ray diffraction studies. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45283.  相似文献   

2.
The parent repeating sequence of elastin, poly(GVGVP) has been synthesized by solution phase method and characterized by 13C and 1H‐NMR spectroscopy. The poly(GVGVP) and poly(vinyl pyrrolidone) (PVP) interactions have been examined in solution phase by the viscometric method at 24 °C. The interaction parameters such as α, β, µ, and Δ[η]m indicated the miscible nature of poly(GVGVP)/PVP blends. Immiscibility occurred when the quantity of poly(GVGVP) is lesser than 60%. In the solid phase, Fourier transform infrared spectroscopic scrutiny of the thin films of poly(GVGVP)/PVP blends indicated the presence of strong intermolecular interaction such as hydrogen bonds linking the blend components. This result was further supported by glass transition temperature (Tg), scanning electron microscopic, and X‐ray diffraction studies. The blending of poly(GVGVP) with PVP may provide an opportunity to produce new materials for potential biomedical applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46699.  相似文献   

3.
The changes in the dynamic structure during temperature-induced phase transition in D2O/ethanol solutions of poly(vinyl methyl ether) (PVME) were studied using NMR methods. The effect of polymer concentration and ethanol (EtOH) content in D2O/EtOH mixtures on the appearance and extent of the phase separation was determined. Measurements of 1H and 13C spin-spin and spin-lattice relaxations showed the presence of two kinds of EtOH molecules: besides the free EtOH expelled from the PVME mesoglobules there are also EtOH molecules bound in PVME mesoglobules. The existence of two different types of EtOH molecules at temperatures above the phase transition was in solutions with polymer concentration 20 wt% manifested by two well-resolved NMR signals (corresponding to free and bound EtOH) in 13C and 1H NMR spectra. With time the originally bound EtOH is slowly released from globular-like structures. From the point of view of polymer-solvent interactions in the phase-separated PVME solutions both EtOH and water (HDO) molecules show a similar behaviour so indicating that the decisive factor in this behaviour is a polar character of these molecules and hydrogen bonding.  相似文献   

4.
Blends of polyaryletherketones (PAEK), such as polyetheretherketones (PEEK) and polyetherketoneketones (PEKK), with polybenzimidazole (PBI) are of commercial interest due to their improved high‐temperature stability and wear properties. The changes of PBI and its PEEK‐ and PEKK‐blends (50 : 50 wt %) after immersing them in liquid H2O and D2O, and exposing them to D2O steam at elevated temperatures and pressures are investigated by multinuclear solid‐state NMR and IR spectroscopy. Macroscopic morphological and chemical changes on the molecular scale, which take place upon high‐temperature steam‐treatment and the extent and reversibility of moisture uptake have been investigated. Interactions and reactions of water, steam, and aqueous solutions of LiCl and ZnBr2 with the functional groups of the polymer components have been studied using D2O in combination with IR, 1H wideline, 2H, 7Li, and 79Br MAS, as well as 13C and 15N CP/MAS NMR spectroscopy. Different locations and types of water and protons in the blends have been described and PBI has been proven to be mainly responsible for water and salt uptake into the blends. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41421.  相似文献   

5.
Static and dynamic light‐scattering techniques were used to study biodegradable thermoplastic poly(hydroxy ester ether) in N,N‐dimethylacetamide (DMAc). A weight‐average molecular weight MW = 6.4 × 104 g/mol, radius of gyration RG = 9.4 nm, second‐virial coefficient A2 = 1.05 × 10?3 mol mL/g2, translational diffusion coefficient D = 1.34 × 10?7 cm2/s, and hydrodynamic radius RH = 8.3 nm are reported. In addition, the effect of H2O on the polymer chain's conformation and architecture in a DMAc/H2O solution is evaluated. Results suggest that H2O makes the mixed solvent poorer as well as promotes polymer chain branching via intramolecular transesterification. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1737–1745, 2001  相似文献   

6.
1H NMR spectroscopy was used to investigate thermotropic phase transitions in D2O solutions of poly(N-isopropylmethacrylamide) (PIPMAm)/poly(vinyl methyl ether) (PVME) mixtures. In all studied solutions (polymer concentrations c=0.1-10 wt%) two phase transitions were detected at temperatures roughly corresponding to different lower critical solution temperatures of PIPMAm and PVME. While the phase transition of PVME component (located at lower temperatures) is not affected by the presence of PIPMAm in the mixture, the phase transition temperatures of PIPMAm component (located at higher temperatures) are affected by the phase separation of the PVME component. Measurements of 1H spin-spin relaxation of residual water (HDO) molecules revealed that above the phase transition, a certain portion of water molecules is bound to polymer globular structures. A major part of bound water is present in globular structures of predominating polymer component in the mixture.  相似文献   

7.
BACKGROUND: Polymers of phenols and aromatic amines have emerged as new materials in fields such as superconductors, coatings, laminates, photoresists and high‐temperature environments. The stability, kinetics and associated pollution of the thermal decomposition of oligophenols are of interest for the aforementioned fields. RESULTS: A new Schiff base polymer, derived from N,N′‐bis(2‐hydroxy‐3‐methoxyphenylmethylidene)‐2,6‐pyridinediamine, was prepared by oxidative polycondensation. Characterisations using Fourier transform infrared, UV‐visible, 1H NMR and 13C NMR spectroscopy, thermogravimetric/differential thermal analysis, gel permeation chromatography, cyclic voltammetry and conductivity measurements were performed. The number‐average (Mn) and weight‐average molecular weight (Mw) and dispersity (D = Mw/Mn) of the polymer were found to be 61 000 and 94 200 g mol?1 and 1.54, respectively. Apparent activation energies of the thermal decomposition of the polymer were determined using the Tang, Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose and Coats–Redfern methods. The most likely decomposition process was a Dn deceleration type in terms of the Coats–Redfern and master plot results. CONCLUSION: The mechanism of the degradation process can be understood through the use of kinetic parameters obtained from various non‐isothermal methods. Copyright © 2009 Society of Chemical Industry  相似文献   

8.
Amphiphilic thermally sensitive poly(N‐isopropylacrylamide)‐block‐poly(tetramethylene carbonate) block copolymers were synthesized by ring‐opening polymerization of tetramethylene carbonate with hydroxyl‐terminated poly(N‐isopropylacrylamide) (PNiPAAm) as macro‐initiator in the presence of stannous octoate as catalyst. The synthesis involved PNiPAAm bearing a single terminal hydroxyl group prepared by telomerization using 2‐hydroxyethanethiol as a chain‐transfer agent. The copolymers were characterized using 1H NMR and Fourier transform infrared spectroscopy and gel permeation chromatography. Their solutions show reversible changes in optical properties: transparent below the lower critical solution temperature (LCST) and opaque above the LCST. The LCST depends on the polymer composition and the media. Owing to their amphiphilic characteristics, the block copolymers form micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range 1.11–22.9 mg L?1. Increasing the hydrophobic segment length or decreasing the hydrophilic segment length in the amphiphilic diblock copolymers produces lower CMCs. A core‐shell structure of the micelles is evident from 1H NMR analyses of the micelles in D2O. Transmission electron microscopic analyses of micelle morphology show a spherical structure of both blank and drug‐loaded micelles. The blank and drug‐loaded micelles have an average size of less than 130 nm. Observations show high drug‐entrapment efficiency and drug‐loading content for the drug‐loaded micelles. Copyright © 2010 Society of Chemical Industry  相似文献   

9.
The adsorption and diffusion of ethene/ethane mixtures is explored by 1H and 13C MAS NMR spectroscopy and by the combination of PFG NMR with magic-angle spinning (MAS PFG NMR). Some indication for a preferential adsorption of the molecules close to the methyl-groups of the imidazole-rings was found, however no evidence for structural changes upon adsorption of an ethene/ethane mixture.MAS PFG NMR allows an individual but simultaneous observation of both molecules in adsorbed state and as well as in the gas phase. The intracrystalline MAS PFG NMR diffusivities are in consistent agreement with our previous data obtained by IR microscopy. Our consideration includes the loading dependence and the correlation of self-diffusion with transport diffusion by accounting for the influence of the thermodynamic factor.The diffusion selectivity is determined to Dethene:Dethane = 5.5 at a loading of four molecules per cavity. The higher mobility of ethene can be rationalized by its smaller size compared to ethane. This conclusion is validated by the measured activation energies for diffusion which are considerably higher for ethane. On the other hand, differences in the guest-host interaction between the saturated and non-saturated molecules can be excluded as possible reason for the different diffusivities.  相似文献   

10.
A series of glycopolypeptides with constant main‐chain lengths and various compositions of mannose moieties and biphenyl pendants were synthesized by copper‐mediated 1,3‐dipolar cycloadditions. 1H NMR and Fourier transform IR (FTIR) analysis confirmed the molecular structures of the resulting polypeptides. FTIR analysis characterized the molar contents of the mannose pendants and α‐helical conformations in the solid state. Glycopolypeptides conjugated with tetra‐O‐acetyl‐d ‐(+)‐mannopyranoside showed a reversible upper‐critical‐solution‐temperature‐type (UCST‐type) phase behavior both in MeOH/H2O and EtOH/H2O binary solvent mixtures depending on the weight percentage of alcohols (fw). Incorporation of a low content of biphenyl pendants (≤0.20) can broaden the range of fw at which polymers showed UCST‐type phase behaviors. The UCST‐type transition temperature (Tpt) was highly related to the incorporation of biphenyl pendants, polymer concentrations, and the nature and weight percentage of alcohols. It decreased as the polymer concentration decreased and increased on incorporation of biphenyl groups. © 2016 Society of Chemical Industry  相似文献   

11.
Polymer‐coated SiO2 particles are prepared by precipitation of poly[styrene‐co‐(acrylic acid)] on SiO2 microspheres through an improved phase inversion method. The diffusion resistance of the polymer membrane was considered to be the critical reason for producing tailor‐made polyethylene by catalysts supported on these polymer‐coated particles. This paper employs pulsed field gradient NMR (PFG‐NMR) to distinguish diffusion of n‐hexane in different regimes, i.e., in the space between each particle, the pores in SiO2 and the polymer shell, by their respective diffusion coefficients. By varying the observation time, the time scale of the molecular exchange is discussed. A three‐region ansatz was used to interpret the exchange and diffusion in polymer‐coated SiO2 system, and was compared with results acquired with noncoated particles. At long diffusion times, the mean‐squared displacement, and thus the averaged self‐diffusion coefficient, of hexane in the system of polymer‐coated SiO2 particles is significantly reduced. The PSA membrane is identified as an efficient barrier against molecular exchange between the pores in SiO2 and the intraparticle space. Consistently, the relaxation measurements indicated that the mobility of n‐hexane molecules, especially the rotation of n‐hexane, was limited by the PSA membrane. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40160.  相似文献   

12.
In order to overcome the poor flowability of poly(arylene sulfide sulfone) (PASS), we introduced ether bonds into the polymer main chain. A series poly(arylene ether sulfide sulfone) copolymers (PAESS) containing different proportion of ether bonds were synthesized with 4,4′‐dichlorodiphenyl sulfone (DCDPS), sodium sulfide (Na2xH2O), and 4,4′‐dihydroxydiphenyl ether (DHDPE). The copolymers were characterized by Fourier transform infrared (FTIR), 1H‐nuclear magnetic resonance (NMR), differential scanning calorimetry, dynamic mechanical analysis (DMA), and rheometer. The results of FTIR and 1H‐NMR indicate the copolymers are synthesized successfully. PAESS were found to have excellent thermal properties with glass transition temperature (Tg) of 175.7–219.1 °C and 5% weight lost temperature were all above 420 °C. The tensile and DMA test indicates that these resultant copolymers have good mechanical properties with tensile strength of 60 MPa and storage modulus of 1.5 GPa. From the results of rheology properties testing, we found that the melt stability and melt flowability of PASS were improved distinctly from 25,470 Pa s down to 355 Pa s with the incorporation of ether bonds. That will be quite beneficial to the processing of PASS, especially for the thermoforming of precision products. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46534.  相似文献   

13.
The diffusion of sodium polystyrene sulfonate through polycarbonate nanochanels was studied in salt‐free dilute aqueous solution. A stronger molecular weight dependence of diffusion was observed compared to free diffusion in dilute solution. Scaling exponentials relating polymer size to diffusivity were between Flory's theory (DeffN?0.6) and Rouse's model (DeffN?1), revealing a crossover regime from 3‐D diffusion to 1‐D diffusion. Diffusion was less hindered for the polyelectrolyte (Deff/D0), than for a rigid sphere, when the polymer/channel size ratio exceeded 0.2. This is attributed to elongated chains with reduced frictional hindrance. Simulation of the confined diffusion based on an elongated cigar model gave DN?1 ${R_{\rm t}^{2/3}}$ while the experimental results agree with DN?0.94${R_{\rm t}^{ 2/3}}$ . For charged polyelectrolytes, the transition to 1‐D diffusion therefore begins before the polymer radius of gyration exceeds the channel size contrary to model assumptions. We attribute this to the charged nature of the polyelectrolytes causing extended chain conformations. © 2009 American Institute of Chemical Engineers AIChE J, 2010  相似文献   

14.
In this study, tetraethoxysilane (TEOS) and a metallocene polyethylene–octene elastomer (POE) were chosen as the ceramic precursor and the continuous phase, respectively, for the preparation of new hybrids by an in situ sol–gel process. To obtain a better hybrid, a maleic anhydride‐grafted polyethylene–octene elastomer (POE‐g‐MAH), used as the continuous phase, was also investigated. Characterizations of POE‐g‐MAH/SiO2 and POE/SiO2 hybrids were performed by Fourier transform infrared (FTIR) and 29Si solid‐state nuclear magnetic resonance (NMR) spectrometers, a differential scanning calorimeter (DSC), a thermogravimetry analyzer, and an Instron mechanical tester. The results showed that the POE‐g‐MAH/SiO2 hybrid could improve the properties of the POE/SiO2 hybrid because the interfacial force between the polymer matrix and the silica network was changed from hydrogen bonds into covalent Si? O? C bonds through dehydration of hydroxy groups in POE‐g‐MAH with residual silanol groups in the silica network. The existence of covalent Si? O? C bonds was proved by FTIR spectra. For the POE/SiO2 and POE‐g‐MAH/SiO2 hybrids, maximum values of the tensile strength and the glass transition temperature were found at 9 wt % SiO2 since a limited content of silica might be linked with the polymer chains through the covalent bond. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 966–972, 2003  相似文献   

15.
Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF3· Et2O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and1H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (Tg), the DSC data imply that the resulting copolymers have a lower Tg than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10?5 S cm?1 at room temperature and 2.79 × 10?4 S cm?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry  相似文献   

16.
Poly(vinyl alcohol) (PVA) can be dissolved in a nonaqueous medium in the presence of catalytic concentration of ethyl nitrate dimethyl sulfoxide, C2H5ONO2 · DMSO (EN · DMSO). From the PVA solution, poly(vinyl butyral) (PVBu) was prepared by acid‐catalyzed homogeneous acetalization of PVA with butyraldehyde. The formation of PVBu was confirmed by IR and 1H‐NMR spectra. The degree of acetalization of PVBu was found to be 95 mol %, which was verified by 1H‐NMR data and acetylation method. The molecular mass of the polymer was determined by GPC method. The glass transition temperature, Tg, was measured from differential scanning calorimetric (DSC) thermograms. Thermal stabilities were checked by thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). The acetal decomposed in three stages. The corresponding initial decomposition temperatures were found to be 285, 390, and above 500°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1182–1186, 2001  相似文献   

17.
The influences of average degree of polymerization (Dp) and terminal group on thermal and optical properties of high refractive indexed transparent polymers were investigated. In this study, 9,9‐bis[4–(2‐hydroxyethoxy) phenyl] fluorene (BPEF) homo polymer was selected because it has been used as a representative monomer in high refractive index polymers as well as its unique property. BPEF has stable amorphous phase and reacts like a polymer. Its unique reaction allows continuous investigation from monomer to polymer. For hydroxyl‐terminated polymer, the refractive index (nd) decreased with increasing Dp. On the other hand, for a phenolic‐terminated group, nd increased with increasing Dp, and both converged to same value in high Dp region. As for glass transition temperatures (Tg), both terminal group series were increased as Dp increased. Though Tg of hydroxyl‐terminated polymer was higher than that of phenolic‐terminated polymer in the low Dp region, both converged to the same value and the inverse number of Tg had linear correlation against the weight percentage of carbonyl groups (CO), which was calculated by Dp. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45042.  相似文献   

18.
We report the experimental demonstration of a novel and environmentally benign supercritical carbon dioxide (ScCO2) technique that yields an optically active, side chain liquid crystalline polycarbonate in a single‐step reaction. The obtained polymer is worthwhile, since it is highly stereoregular and can find applications in an enlarged mesomorphic temperature range compared to its acrylic analogues. The synthesized materials were characterized by IR, 1H‐NMR, and 13C‐NMR, while the thermal properties were measured by DSC. Polarized optical micrograph and wide angle X‐ray diffraction were used for the mesogenic property characterization of the copolymer. The transfer chirality from the backbone to the mesophase is demonstrated on the optical microscopy textures. Being consistent with the 13C‐NMR, X‐ray implies an ordered polymeric structure. The DSC analysis of the copolymer indicates that the Ti (the clearing point temperature) value does not change dramatically, whereas a pronounced decrease in Tg (the glass transition temperature) value is observed from that of its acrylic analogues. Hence, the obtained polymer exhibits another practical benefit by widening the mesomorphic temperature range. This study is the insightful combination of material processing and chemical design that elucidates the advantages of ScCO2 application, in terms of liquid crystallinity and the tacticity of the obtained polymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1915–1921, 2006  相似文献   

19.
In this study, we conveniently obtained Ag(0)–polymer nanocomposites by reacting AgNO3 with commercial poly(vinyl acetate) (PVAc) in the absence of a special reducing agent. The formation of Ag(0) metal was detected after formic acid (HCOOH) was added to a PVAc–AgNO3 complex system, and some of the acetate groups of the PVAc backbone were hydrolyzed to form hydroxyl groups (OH) under the catalytic effect of the reduced Ag(O) metal. Here, the structure of the partially hydrolyzed PVAc backbone was represented as PVOH‐PVAc. X‐ray diffraction spectra showed that the Ag(0) metal generated in this method was in the form of Ag crystals. The structure of the Ag(0)–polymer was analyzed by 1H‐NMR and 13C‐NMR spectroscopy. The micellization of the Ag(0)–polymer was also investigated by the addition of an inducing solvent to the formic acid solution of Ag(0)–polymer. The image showed that the morphology of the Ag micelles in the H2O‐induced solvent was a Ag corona with a Ag shell, and that in the p‐xylene induced solvent showed a Ag cluster core structure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1457–1464, 2006  相似文献   

20.
Vanillin (4‐hydroxy‐3‐methoxy benzaldehyde) and 5‐formylamino salicylic acid microbicides were reacted with polyoxyalkylene‐montmorillonite (D230–2000‐MMT) nanocomposites. The microstructure of these Schiff base nanocomposites was characterized by TEM and XRD. D230–2000‐MMT nanocomposites were prepared by an ion exchange process of sodium montmorillonite (Na‐MMT) and NH3 + groups in polyoxyalkylene amine hydrochloride with three different molecular masses of D230, D400, and D2000. Wide‐angle X‐ray diffraction confirms the intercalation of the polymer between the silicate layers. Electrostatic interaction between the positively charged NH3 + groups and the negatively charged surface of MMT was observed. The nanocomposites were tested for antimicrobial activity against the Gram‐negative bacteria (Escherichia coli NCIM 2065), Gram‐positive bacteria (Bacillus subtillus ATCC), and fungi (Candida albicans SC5314 and Cryptococcus neoformans). The D2000‐MMT/vanillin Schiff base nanocomposite strongly inhibited the growth of all microorganisms that can be used in different applications. The amount of loaded polymer and the structure of the nanocomposite play an important role in inhibiting the bacterial and fungal strains. It is found that the Schiff base nanocomposite affect the morphology, oxygen consumption, and the release of cytoplasmic constituents such as potassium (K+), sodium (Na+), and calcium (Ca2+) ions leading to death of the cells. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers  相似文献   

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