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1.
Concentrated solutions of a chitin from squid pens and of two commercial samples of chitosan were successfully prepared by using an ionic liquid 1‐butyl‐3‐methylimidazolium acetate as a solvent. The dynamic viscoelasticity data for the solutions exhibited rubbery plateaus, indicating the existence of entanglement network of chitin and chitosan in the solutions. To characterize the network, the values of the molecular weight between entanglements (Me) for chitin and chitosan in the solutions were determined from the plateau moduli. Then the values of Me in the molten state (Me,melt), a material constant reflecting the inherent nature of polymer species, for chitin and chitosan were estimated to be 1.7 × 103 and 3.0 × 103, respectively. It was found that there was a significant difference in Me,melt between chitin and chitosan. Compared with other polysaccharides such as cellulose and agarose in terms of the number of monosaccharide units between entanglements (Nunit), chitin had significantly smaller Nunit of 8, while chitosan had equivalent Nunit of 19. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2439–2443, 2013  相似文献   

2.
Network formation was monitored by shear storage modulus (G′) during free radical crosslinking polymerization to investigate the effects of pH and ethylenediaminetetraacetic acid (EDTA; a complex agent). Three types of acrylic monomers, acrylic acid (AAc), 2‐acrylamidoglycolic acid (AmGc), and 2‐acrylamido‐2‐methyl propanesulfonic acid (AmPS), were polymerized in the presence of a crosslinking agent. The ratio of crosslinking agent (methylene bis‐acrylamide; MBAAm) to monomer was varied as: 0.583 × 10?3, 1.169 × 10?3, 1.753 × 10?3, and 2.338 × 10?3. G′ of the hydrogel in crosslinking polymerizations of AAc and AmPS was effectively increased by addition of EDTA, which was not the case for the crosslinking polymerization of AmGc. The order of magnitude of G′ differed based on the acidity of monomer. The maximum values of G′ in crosslinking polymerizations of AAc, AmGc, and AmPS were ~20,000 Pa, 6000 Pa, and 400 Pa, respectively. G′ varied linearly with the molecular weight between crosslinks (Mwc). pH and EDTA‐complex affected the rate of intramolecular propagation during crosslinking polymerization. Our results indicated that G′ was primarily affected by the following factors in the order: (1) acidity of monomer, (2) Mwc, and (3) physical interactions induced by pH and EDTA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41026.  相似文献   

3.
Cassava starch‐graft‐poly(acrylamide) superabsorbent polymers (SAPs) with varying absorbencies were synthesized. Weight average molecular weight (Mw) of the hydrolyzed starch‐graft‐copolymers ranged from 1.6 × 106 to 2.8 × 106 g/mol, the largest being shown by the sample with highest percentage grafting. The storage (G′) and loss modulus (G″) of hydrogels were determined as a function of frequency. G″ was larger than G′ for the hydrogels with higher absorbencies and exhibited a liquid‐like behavior. However, hydrogels with lower absorbencies showed a reverse viscoelastic behavior. The viscosity of hydrogels determined using a Brookfield viscometer at different shear rates was found to be larger for the hydrogels with higher absorbencies. The melting temperature (Tm) and enthalpy change of fusion (ΔHf) of the SAPs ranged from 149.7 to 177.7°C and 65 to 494.9 J/g, respectively and showed a positive correlation with grafting parameters and Mw. Heavy metal ion removal capacity of hydrogel followed the order Cu2+ > Pb2+ > Zn2+. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40368.  相似文献   

4.
Dynamic adsorption behavior between Cu2+ ion and water‐insoluble amphoteric starch was investigated. The sorption process occurs in two stages: external mass transport occurs in the early stage and intraparticle diffusion occurs in the long‐term stage. The diffusion rate of Cu2+ ion in both stages is concentration dependent. In the external mass‐transport process, the diffusion coefficient (D1) increases with increasing initial concentration in the low‐ (1 × 10?3‐4 × 10?3M) and high‐concentration regions (6 × 10?3‐10 × 10?3M). The values of adsorption activation energy (kd1) in the low‐ and high‐concentration regions are 15.46–24.67 and ?1.80 to ?11.57 kJ/mol, respectively. In the intraparticle diffusion process, the diffusion coefficient (D2) increases with increasing initial concentration in the low‐concentration region (1 × 10?3‐2 × 10?3M) and decreases with increasing initial concentration in the high‐concentration region (4 × 10?3‐10 × 10?3M). The kd2 values in the low‐ and high‐concentration regions are 9.96–15.30 and ?15.53 to ?10.71 kJ/mol, respectively. These results indicate that the diffusion process is endothermic in the low‐concentration region and is exothermic in the high‐concentration region for both stages. The external mass‐transport process is more concentration dependent than the intraparticle diffusion process in the high‐concentration region, and the dependence of concentration for both processes is about equal in the low‐concentration region. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2849–2855, 2001  相似文献   

5.
Partially N‐acetylated chitosan was hydrolyzed by the cheap, commercially available, and efficient cellulase. The products, with different molecular weight, were comparatively investigated by GPC, FT‐IR, XRD, and NMR. The results show that the decrease of molecular weight led to transformation of crystal structure and increase of water‐solubility, but the chemical structures of residues were not modified. Superoxide anion radical and hydroxyl radical quenching assay were used for the evaluation of free radical scavenging activity of cellulase‐treated chitosan in vitro. Low molecular weight chitosan (LMWC3, Mw 1.7 × 103) exhibited high scavenging activity against free radical. It scavenged 79.3% superoxide radical at 0.1 mg mL?1. At 2.0 mg mL?1, scavenging percentage of initial chitiosan, LMWC1 (Mw 27.3 × 103), LMWC2 (Mw 5.9 × 103), and LMWC3 (Mw 1.7 × 103) against hydroxyl radical was 14.3%, 33.1%, 47.4%, and 65.9%, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

6.
Polyacrylonitrile was grafted onto kenaf fibers in aqueous media by ceric ion–p-xylene redox system. The graft yield dependence on p-xylene concentration in the range 1.8–45.0 × 10−4M showed a minimum accompanied by an enhanced yield. This suggested the existence of two kinetically distinct grafting reactions associated with two precursor-initiating species, a p-xylyl radical and a diradical. The frequency of graft Fg and the average molecular weight of grafted polymer Mv were inversely related at varying concentrations of p-xylene with values for Mv of up to 5.18 × 104. The effect of ceric ion concentration on Mv showed that the ion is nonterminating at low concentrations in the range 8.3–33.3 × 10−3M. The graft yield showed positive temperature dependence in the region of 30–40°C and a negative one at higher temperatures, resulting in a decrease in the initial rate of graft at 70°C by a factor of 8 compared to its value at 40°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1751–1755, 1999  相似文献   

7.
The viscoelastic properties of poly(n‐butyl acrylate), poly(ethyl acrylate) and poly(methyl acrylate) melts have been studied using samples that varied in both molar mass and the mol% branched repeat units, these properties having been previously determined by gel permeation chromatography and 13C NMR spectroscopy, respectively. Poly(n‐butyl acrylate) was studied most extensively using seven samples; one sample of poly(n‐butyl acrylate), two samples of poly(ethyl acrylate) and one sample of poly(methyl acrylate) were used to study the effect of side‐group size. Storage and loss moduli were measured over a range of frequency (1 × 10?3 to 1 × 102 rad s?1) at temperatures from Tg + 20 °C to Tg + 155 °C and then shifted to form master curves at Tg + 74 °C through use of standard superposition procedures. The plateau regions were not distinct due to the broad molar mass distributions of the polyacrylates. Hence, the upper and lower limits of shear storage modulus from the nominal ‘plateau’ region of the curves for the seven poly(n‐butyl acrylate) samples were used to calculate the chain molar mass between entanglements, Me, which gave the range 13.0 kg mol?1 < Me < 65.0 kg mol?1. The Graessley–Edwards dimensionless interaction density and dimensionless contour length concentration were calculated for poly(n‐butyl acrylate) using the mean value of plateau modulus (1.2 × 105 Pa) and three different methods for estimation of the Kuhn length; the data fitted closely to the Graessley–Edwards universal plot. The Williams–Landel–Ferry C1 and C2 parameters were determined for each of the polyacrylates; the data for the poly(n‐butyl acrylate) samples indicate an overall reduction in C1 and C2 as the degree of branching increases. Although the values of C1 and C2 were different for poly(n‐butyl acrylate), poly(ethyl acrylate) and poly(methyl acrylate), there is no trend for variation with structure. Thus the viscoelastic properties of the polyacrylate melts are similar to those for other polymer melts and, for the samples investigated, the effect of molar mass appears to dominate the effect of branching. © 2001 Society of Chemical Industry  相似文献   

8.
The rheology of polyamic acid (PAA) solutions, precursors of polyimides used in microelectronic device applications, has been investigated by dynamic (oscillatory) shear flow measurements. Frequency dependent storage and loss moduli and dynamic viscosity were measured in the frequency range 10?1 to 103 rad/s at 23°C. The storage modulus G′ (ω) and loss modulus G″ (ω) exhibited quadratic and linear dependence in frequency at low frequencies respectively, the viscoelastic fluid behavior commonly predicted for polymer solutions from many molecular theories. At high frequencies both dynamic moduli become proportional to ω2/3. The results show that PAA solutions are very high loss viscoelastic fluids, judging from the loss tangent values which far exceed unity. It is suggested that dynamic viscoelastic properties could be used to monitor the degree of imidization since there is a gradual change from viscoelastic fluids to soft viscoelastic solids to hard viscoelastic solids as PAA is converted to polyimides. Onset of non-Newtonian flow as shown on the frequency dependent dynamic viscosity was in the range 30 to 200 rad/s. The viscoelastic constants, zero-shear rate viscosity ηo and steady-state compliance Je0, where also determined from the dynamic data and compared to previous steady shear flow results.  相似文献   

9.
The intrinsic viscosities, [η], of nine cellulose samples, with molar masses from 50 × 103 to 1 390 × 103 were determined in the solvents NMMO*H2O (N‐methyl morpholin N‐oxide hydrate) at 80°C and in cuen (copper II‐ethlenediamine) at 25°C. The evaluation of these results with respect to the Kuhn–Mark–Houwink relations shows that the data for NMMO*H2O fall on the usual straight line in the double logarithmic plots only for M ≤ 158 103; the corresponding [η]/M relation reads log ([η]/mL g−1) = –1.465 + 0.735 log M. Beyond that molar mass [η] remains almost constant up to M ≈ 106 and increases again thereafter. In contrast to NMMO*H2O the cellulose solutions in cuen behave normal and the Kuhn–Mark–Houwink relation reads log ([η]/mL g−1) = −1.185 + 0.735 log M. Possible reasons for the dissimilarities of the behavior of cellulose in these two solvents are being discussed. The comparison of three different methods for the determination of [η] from viscosity measurements at different polymer concentrations, c, demonstrates the advantages of plotting the natural logarithm of the relative viscosities as a function of c. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

10.
Aminopropyl‐terminated poly(dimethylsiloxane) (ATPS) with different molecular weights was prepared by base‐catalyzed equilibration of octamethylcyclotetrasiloxane and 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetramethyldisiloxane with different ratios. Their number‐average molecular weights (Mn) were determined by end–group analysis, and intrinsic viscosity ([η]) in toluene was measured with a Ubbelohde viscometer. A relationship between Mn and [η] was obtained for ATPS. For 1.0 × 104 < Mn < 6.0 × 104, it was in accord with [η]toluene,25°C = 5.26 × 10?2 Mn0.587. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 975–978, 2001  相似文献   

11.
Grafting of acrylic acid onto cocoyam starch, Xanthosoma sagittitolium was initiated by ceric ion—N,N′‐dimethylacetamide redox pair in aqueous media. The reaction was characterized by high graft yields of up to 676%, and infrared spectroscopy affirmed the presence of grafted polymer. Graft yield was enhanced by N,N′‐dimethylacetamide (DMAc) in the concentration range, 9.0–36.0 × 10?4M but lower concentrations were more favorable with the ratio of percentage graft, Pg/Pg0, in the presence and absence of DMAc respectively, of up to 1.34 at 9.0 × 10?4M of the latter. Ceric ion was nonterminating of the graft reaction and a 10‐fold increase in its concentration of 4.16 × 10?3M resulted in high efficiency of graft of 50.2% in monomer conversion to grafted polymer. Enhanced homopolymer formation and low efficiency of graft were observed at monomer concentration greater than 0.69M. Long reaction time, greater than 30 min, was unfavorable to the graft reaction and the latter showed negative dependence on temperature in the range, 30–50°C. At 30‐min reaction time, the graft yield at 50°C was not more than 70% of the corresponding value at 30°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

12.
Epoxy resins (bisphenol A type epoxy resins/2‐ethyl‐4‐methylimidazole) consisting of oligomers with different molecular weights were foamed using a temperature‐quench physical foaming method with CO2. The resulting cell morphologies could be classified into four types: non‐foamed structure, cracked structure, star‐shaped structure, and sphere‐shaped structure. The effects of the gel fraction and molecular weight between crosslinks (MC) on the cell morphology were investigated for the preparation of microcellular epoxy foams. MC was calculated by measuring the plateau rubber modulus of the rheological properties and the weight uptake of acetone. By varying the molecular weight of the epoxy oligomers and the cure time, the MC of the epoxy was controlled to modulate the cell morphology. The experiments elucidated the threshold MC value that permits CO2‐bubble nucleation: CO2‐bubble nucleation in the epoxy resin could be induced when the distance between the crosslinking points exceeded the critical size of bubble nucleus. Based on this information, the microcellular epoxy foam was prepared by maintaining MC above 104g mol−1 and the complex modulus above 6 × 108 Pa. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40407.  相似文献   

13.
A high molecular weight poly(ethylene oxide) is gelled by radiation from a 60Co source. At concentrations of 0.25 to 1 wt-%, doses of 4.5 to 7.5 × 104 rad cause gelation. The storage modulus of the gel formed increases linearly with additional dose to a plateau value and then remains constant during further irradiation. The does needed to reach the plateau, Dp in rads, and the plateau modulus Gp in dynes per square centimeter, are related to the concentration c, in weight per cent: Dp = 1.05 × 106c and Gp = 1.75 × 104c2.5. The energy absorbed by the polymer per crosslink formed is about 80 ± 10 kcal/mol. The crosslink density produced by radiation is calculated from the measured modulus by using the theory of rubber elasticity. Both modulus and loss are measured in a special air-bearing, recording torsion pendulum with a coneplate geometry.  相似文献   

14.
Chitosan‐N‐2‐hydroxypropyl trimethyl ammonium chloride (QTS) was prepared by reaction of chitosan with glycidyl trimethylammonium chloride, which was characterized by FTIR. QTS with different molecular weights (Mw 41.55 × 104, 9.02 × 104, 3.57 × 104, and 0.17 × 104) showed biocidal activity on Staphylococcua aureus, Bacillus subtilis, Staphylococcua epidermidis, and Candida albicans. QTS with high molecular weight had high biocidal activity on the gram‐positive bacteria, and the biocidal effect of QTS decreased with decreasing molecular weight from 9.02 × 104 to 0.17 × 104. QTS with Mw 41.55 × 104 exhibits slightly lower biocidal activity on Candida albicans than other QTS samples. However, no remarkable biocidal activity of QTS was found on gram‐negative bacteria Escherichia coli and Pseudomonas aeruginosa at the concentration up to 10 g L?1. Existence of cationic surfactant, amphoteric surfactant, nonionic surfactant, Ca2+ and Mg2+ had no remarkable effect on microbiocidal activity of these QTS samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3851–3856, 2007  相似文献   

15.
The chemical stability of perfluorinated and non‐perfluorinated low temperature fuel cell model compounds (MCs) against attack by hydroxyl radicals, HO, is compared using a competition kinetics approach in aqueous solutions at ambient temperature. HO radicals were generated in situ by UV photolysis of hydrogen peroxide in the electron spin resonance (ESR) resonator. Acetic acid (AA), trifluoroacetic acid (TFAA), methanesulfonic acid (MSA), trifluorosulfonic acid (TFSA), and perfluoro(2‐ethoxyethane)sulfonic acid (PFEESA) were chosen as MCs, while the rate constants of 5,5‐dimethyl‐1‐pyrroline‐N‐oxide (DMPO) and methanol (CH3OH) served as reference for the determination of relative rate constants by means of steady state ESR signal amplitudes. In decreasing order the rate constants are: kMSA = (4.8 ± 0.2) × 107 M–1 s–1, kAA = (4.2 ± 0.3) × 107 M–1 s–1, kPFEESA = (3.7 ± 0.1) × 106 M–1 s–1, kTFAA = (7.9 ± 0.2) × 105 M–1 s–1, and kTFSA < 1.0 × 105 M–1 s–1. Applying these results to perfluorinated fuel cell membranes like Nafion®, the main points of attack by HO are concluded to be the ether groups of the side chains, followed by the remaining carboxyl groups from the manufacturing process of the polymers.  相似文献   

16.
The radiation-induced homopolymerization of acrylonitrile (AN) in dimethylformamide (DMF) has been followed in detail over a range of monomer concentrations. In all cases a short induction period was observed which was equivalent to 1.6 × 104 rad. The initial rates of polymerization for solutions of AN in DMF of mole fraction (×) of 0.33, 0.20, and 0.10 are 1.44 × 10?5, 7.23 × 10?6, and 2.79 × 10?6 mole/dm3rad, respectively. Deviations of the polymerization pathway from the standard unity in monomer dependence are examined in terms of radical production ratios to the monomer and the solvent (ΦMS) and the polymer together with the solvent (Φps), for various mole fractions of AN in DMF. Thus, an indirect route to Gradical(events) is provided together with the corresponding k/kt values.  相似文献   

17.
Poly(acrylic acid) was grafted onto methylcellulose in aqueous media by a potassium permanganate‐p‐xylene redox pair. Within the concentration range from 0.93 × 10?3 to 9.33 × 10?3M, p‐xylene, the graft copolymerization reaction exhibited minimum and maximum graft yields and was associated with two precursor‐initiating species, a p‐xylyl radical and its diradical derivative. The efficiency of the graft was low, not higher than 12.9% at a p‐xylene concentration of 0.93 × 10?3M and suggested the dominance of a competitive homopolymerization reaction under homogeneous conditions. The effect of permanganate on the graft yield was normal and optimal at 135% graft yield, corresponding to a concentration of the latter of 33.3 × 10?3M over the range from 8.3 × 10?3 to 66.7 × 10?3M. The conversion in graft yield showed a negative dependence on temperature in the range 30–60°C and suggested a preponderance of high activation energy transfer reaction processes. The calculated composite activation energy for the graft copolymerization was 7.6 kcal/mol. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 278–281, 2004  相似文献   

18.
ZnO/TiO2 composite ceramics have been prepared by solid‐state reaction technique at 900°C. The X‐ray diffraction results revealed the formation of secondary phases referred to as spinel Zn2TiO4 and hexagonal ZnTiO3. The structural analysis showed that all the composites that have been prepared have a polycrystalline nature and a hexagonal wurtzite structure. The complex modulus (M) and electric impedance of the samples have been investigated by broadband dielectric spectroscopy in a wide range of temperature (40°C‐110°C) and frequency (0.1 Hz to 10 MHz). The modulus plots (M′′, M′) illustrate the presence of non‐Debye type of relaxations attributed to the effects of interfacial and dipolar polarizations. The real and the imaginary parts of the impedance are well fitted to equivalent circuit models. At high temperatures, Z″max varies from 0.03 × 106 to 4.9 × 106 Ω when the TiO2 doping concentration increases from 1 to 7 wt%. From the obtained results, the secondary phase ZnTiO3 plays an important role in the electrical properties.  相似文献   

19.
The effect of the number and size of polystyrene particles and the concentration of ammonium persulfate used as the initiator on the micellar crosslinking polymerization of acrylic acid was studied by real‐time monitoring of the storage modulus (G ′), the damping factor (tanδ), and the ratio of the complex modulus (G*) to the maximum G* (G*max) during 1 h of polymerization. The molar ratio (5.83 × 10?4) of N,N′‐methylenebis‐acrylamide to acrylic acid was fixed. Polystyrene particles were prepared by emulsifier‐free emulsion polymerization. The diameter of the particles ranged from 233 to 696 nm. The results show that crosslinking polymerization was most effective when 1.31 × 1012 particles were incorporated into the system, while crosslinking polymerization was less effective in the particle‐filled system than in the unfilled polymerization system if the particle number was 50% lower or higher. Crosslinking was also more effective with the use of uncrosslinked firmer and larger particles at the fixed particle number, except for the anomalous behavior observed with 696 nm polystyrene particles. Increasing the feed concentration of the initiator resulted in more efficient crosslinking up to a limiting concentration of 0.765 mg mL?1 (the molar ratio of initiator to monomer was 8.52 × 10?4). When this initiator concentration was doubled, the rate of increase of G ′ in the deceleration phase was slower after the network was formed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42851.  相似文献   

20.
An amphoteric water‐soluble copolymer, that is, polyacrylamide/(α‐N,N‐dimethyl‐N‐acryloyloxyethyl)ammonium ethanate (PAAM/DAAE) was synthesized and it showed the ability to disperse BaTiO3 (BT) particles in aqueous solutions. In this work, the effect of molecular weight of this polymer on the dispersing properties was further examined. The results indicate that the effectiveness of three polymer samples with different molecular weights in the dispersion of BT particles is P2 (Mw = 1.1 × 105) > P1 (Mw = 1.2 × 104) > P3 (Mw = 3.0 × 105). Apparently, P2 is most effective in dispersing the particles, reducing the viscosity of the suspensions, and obtaining highest green and sintered densities. This is attributed to the highest adsorption of this polymer onto BT powder, and causes strongest electrostatic and steric repulsions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 886–891, 2006  相似文献   

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