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1.
The amine salt, N,N-diallyl-N-carboethoxymethylammonium chloride was copolymerized in dimethyl sulfoxide using ammonium persulfate or azo-bis-isobutyronitrile (AIBN) to afford the cationic polyelectrolyte (CPE) having five-membered cyclic structure on the polymeric backbone. The CPE on acidic (HCl) hydrolysis of the pendent ester groups gave the corresponding cationic acid salt (CAS) having the equivalent of chloride salt of N,N-diallylammonio ethanoic acid as monomeric unit. The CAS was converted into an anionic polyelectrolyte (APE) and polybetaine (PB) [having the monomeric unit equivalent of sodium N,N-diallylaminoethanoate and N,N-diallylammonioethanoate] by treatment with two and one equivalent of base, respectively. The solution properties of APE were investigated by potentiometric and viscometric techniques. Basicity constant of the amine functionality in APE is found to be ‘apparent’ and as such follow the modified Henderson-Hasselbalch equation; the protonation of the APE becomes more and more difficult as the degree of protonation (α) of the whole macromolecule increases. The composition and phase diagram of the aqueous two-phase systems of APE and poly(ethyelene glycol) (PEG) has been studied for the first time for this class of ionic polymers. The CAS and PB were found to be virtually insoluble in water.  相似文献   

2.
Yunusa Umar  B.F. Abu-Sharkh 《Polymer》2004,45(11):3651-3661
Sulfur dioxide, N,N-diallyl-N-carboethoxymethylammonium chloride and the hydrophobic monomers N,N-diallyl-N-dodecylammonium chloride or N,N-diallyl-N-octadecylammonium chloride were cyclocopolymerized in dimethyl sulfoxide using azobisisobutyronitrile (AIBN) as the initiator to afford water-soluble cationic polyelectrolyte (CPE) having five-membered cyclic structure on the polymeric backbone. The CPE on acidic (HCl) hydrolysis of the pendent ester groups gave the corresponding cationic acid salt (CAS) which was converted to the anionic polyelectrolyte (APE) by treatment with sodium hydroxide. The solution properties of the CPE and APE containing varying amount of the hydrophobic monomers in the range 0-10 mol% were investigated by viscometric techniques. The polymers showed that concentration (CHA) of less than 1 wt% was required for the manifestation of hydrophobic association, and displayed significant hydrophobic association in salt (NaCl)-free as well as salt-added solutions.  相似文献   

3.
The quaternary ammonium monomer 1,1‐diallyl‐4‐methoxycarbonylpiperidinium chloride was synthesized in good yield. On polymerization in water using t‐butylhydroperoxide as initiator, a cationic polyelectrolyte (CPE) with a five‐membered cyclic structure on the polymeric backbone was obtained. On acid hydrolysis, followed by basification, the CPE gave the corresponding polybetaine (PB). The solution properties of these polymers were investigated by potentiometric and viscometric techniques. The PB demonstrated “antipolyelectrolyte” behavior. The basicity constant of the carboxylate functionality in the polyzwitterionic polymers was ‘apparent’ in a 0.1 N NaCl solution and followed the modified Henderson‐Hasselbalch equation. It was found that as the degree of protonation (α) of the whole macromolecule increases, the protonation of the amine nitrogen becomes increasingly more difficult. Unlike other polyzwitterions/polybetaines, the PB was soluble in salt‐free water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

4.
Sulfur dioxide, N,N‐diallyl‐N‐carboethoxymethylammonium chloride, and the hydrophobic monomer N,N‐diallyl‐N‐octadecylammonium chloride were cyclocopolymerized in dimethyl sulfoxide using azobisisobutyronitrile (AIBN) as the initiator to afford water‐soluble cationic polyelectrolytes (CPE) having a five‐membered cyclic structure on the polymeric backbone. The CPE on acidic hydrolysis of the pendent ester groups gave the corresponding cationic acid salts (CAS), which, on treatment with sodium hydroxide, were converted to polybetaines (PB) and anionic polyelectrolytes (APE), as well as polymers PB/APE containing various proportions of zwitterionic (PB) and anionic fractions (APE) in the polymer chain. The solution properties of the CPE, APE, and PB/APE systems containing varying amounts of the hydrophobic monomers in the range 0–4 mol % were investigated by viscometric techniques. Treating the pH‐responsive CAS polymers 4 with different equivalents of NaOH varied the zwitterionic and anionic charge densities in the polymer chain. It was found that the PB/APE polymer with a ratio of 33 : 67 for the zwitterionic and anionic fractions in the polymer chain, respectively, gave the highest viscosity value. The polymers showed that concentration (C*HA) of around 1 g/dL was required for the manifestation of significant hydrophobic associations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1404–1411, 2005  相似文献   

5.
A new class of ionic copolymers containing amine and phosphonate functionalities has been prepared for the first time. N,N-Diallyl-3-(Diethylphosphonato)-methylammonium chloride underwent cyclocopolymerization with SO2 to give a cationic polyelectrolyte (CPE) in very good yields. Likewise, ethyl 3-(N,N-diallylammonio)methanephosphonate/SO2 cyclopolymerization afforded the corresponding polyzwitterion-ester (PZE), which on neutralization with NaOH gave the anionic polyelectrolyte (APE). Both CPE and PZE on hydrolysis of the phosphonate ester functionalities gave the same polyzwitterionic acid (PZA). The pH-responsive PZA on treatment with excess NaOH was converted to dianionic polyelectrolyte (DAPE) which on treatment with 1 equivalent HCl afforded the zwitterionic-anionic polyelectrolyte (ZAPE). Solution properties of the CPE, PZE, DAPE, APE and ZAPE having similar degree of polymerization have been studied in some detail. The apparent basicity constants of the amine group in APE have been determined. An aqueous two-phase system of polyethylene glycol-DAPE-H2O (0.4 N NaCl) has been constructed for its potential application in selective separation of toxic metal ions since polyphosphonates are expected to be effective chelators.  相似文献   

6.
The zwitterionic monomer, 3-(N,N-diallylammonio)propanesulfonate, was copolymerized with sulfur dioxide in dimethyl sulfoxide using azo-bis-isobutyronitrile (AIBN) to afford the polysulfobetaine (PSB) copolymer in excellent yields. The PSB was converted into the corresponding anionic polyelectrolyte (APE) by treatment with 1 equiv. of sodium hydroxide. The solution properties of PSB and APE were investigated by potentiometric and viscometric techniques. The critical (minimum) salt concentrations (CSC) required to promote water solubility for the PSB at 23 °C have been measured. Basicity constant of the amine functionality in APE is found to be ‘apparent’ and as such follow the modified Henderson-Hasselbalch equation. The composition and phase diagram of the aqueous two-phase polymer systems of PSB (treated with 0.60 equiv. sodium hydroxide) and poly(ethyelene glycol) (PEG) in 0.1N KCl has been studied for the first time for this class of PSB copolymer.  相似文献   

7.
Yunusa Umar  Sk. Asrof Ali 《Polymer》2005,46(24):10709-10717
Sulfur dioxide, zwitterionic monomer, 3-(N,N-diallylammonio)propanesulfonate and a hydrophobic monomer N,N-diallyl-N-octadecylammonium chloride were cycloterpolymerized in dimethyl sulfoxide using azobisisobutyronitrile (AIBN) as the initiator to afford water-insoluble polysulfobetaines (PSB) in excellent yields. The PSBs were converted into the corresponding anionic polyelectrolyte (APE) by treatment with 1 equiv. of sodium hydroxide. Treating the pH-responsive PSB polymers with different equivalents of NaOH varied the zwitterionic and anionic charge densities in the polymer chain. The polymer chains with zwitterionic fraction greater than 0.5 were found to be insoluble in water. The solution properties of the APE and PSB/APE systems containing varying amount of the hydrophobic monomers in the range 0-10 mol% were investigated by viscometric techniques. It was found that PSB/APE polymer with a ratio of 33:67 for the zwitterionic and anionic fractions in the polymer chains, respectively, gave the highest viscosity value. The polymer concentration (C*HA) of around 1 g/dl was required for the manifestation of significant hydrophobic associations. The polymer solutions exhibited sharp increase in viscosity with increasing polymer concentrations in salt (NaCl)-free as well as salt-added solutions. The presence of sodium chloride is shown to enhance intermolecular associations in polymers having hydrophobes in the lower mol% range, whereas, intramolecular associations were manifested in polymers containing higher proportions of the hydrophobes.  相似文献   

8.
In this study, the viscoelastic behavior of hydrophobically modified polyelectrolytes obtained from the hydrolysis of cationic acid salts (CAS's) as a function of their zwitterion fraction (x) and anion fraction (z) was studied. The dynamic viscosity (η′) dependence on frequency of polymer solutions of polybetaine/anionic polyelectrolyte (APE) with various compositions of x and z in 0.1N NaCl showed typical shear thinning behavior. η′ of a solution of CAS 4 (M2‐4 (4 mol % hydrophobe)) attained a maximum value in the presence of 1.67 equiv of NaOH (corresponding to an x : z ratio of 33 : 67) and decreased with any further addition of NaOH. We suggest this maximum to be a result of a combined effect of coil expansion and hydrophobic association. The influence of the temperature and concentration on η′ of CAS 4 (M2‐4) treated with 1.67 equiv of NaOH was also investigated. The rheology of CAS 4 (M2‐4) samples treated with 1.67, 1.81, and 2.0 equiv of NaOH suggested a reversible network. However, for APE 7 (M2‐5 (5 mol % hydrophobe)), elastic behavior was dominant, and the formation of highly interconnected three‐dimensional networks was suggested. At lower x : z ratios, the effect of coil expansion due to a higher APE fraction was more than counterbalanced by the lower degree of intermolecular hydrophobic associations, whereas at higher x : z ratios, coil contraction became the predominant effect. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

9.
The cycloterpolymerizations of a newly synthesized dendritic quadruple‐tailed hydrophobic diallylammonium chloride with the hydrophilic monomer N,N‐diallyl‐N‐carboethoxymethylammonium chloride and sulfur dioxide afforded a series of water‐soluble cationic polyelectrolytes (CPEs) containing various proportions (0–1 mol %) of the hydrophobe. At a shear rate of 0.36 s?1 at 30°C, salt‐free water solutions of the CPEs (4 g/dL) containing 0, 0.35, 0.53, 0.65, and 0.93 mol % of the hydrophobe had apparent viscosity values of 140, 1200, 180,000, 308,000, and 858,000 cps, respectively. The study clearly demonstrated an increase in the viscosity values with increasing incorporation of the hydrophobes. The CPEs on acidic hydrolysis of the pendant ester groups gave corresponding pH‐responsive cationic acid salts, which upon treatment with NaOH, were converted to the polybetaines (PBs), anionic polyelectrolytes (APEs), and PB/APEs containing various proportions of PB and APE fractions in the polymer chain. The effects of charge type and charge density on the polymer chain were investigated. Polymer surfactant interactions were investigated with the cationic surfactant cetyltrimethylammonium bromide; a considerable increase in the viscosity values of the CPE was observed in the presence of the surfactant. The superior viscosity behavior for the polymers containing the quadruple‐tailed hydrophobe was attributed to the blocky nature of the comonomer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

10.
A straightforward synthetic strategy to an anionic gemini surfactant having both N-acylamide and carboxylate groups in a molecule has been demonstrated. The surface properties of the anionic gemini surfactant, such as CMC (critical micelle concentration), C20 (the concentration required to reduce the surface tension of the solvent by 20 mN/m), γ CMC (the surface tension at the CMC), CMC (the surface pressure at the CMC), Γ max (the maximum surface excess concentration at the air/aqueous solution interface), A min (the minimum area per surfactant molecule at the air/water interface), and the CMC/C20 ratio (a measure of the tendency to form micelles relative to adsorbtion at the air/water interface), have been studied. The influence of the different concentrations of NaCl on the surface properties of the gemini surfactant has been discussed. The results have shown that the CMC values decreased with an increase in the concentration of NaCl indicating that the Na+ preferentially adsorbs onto the surface of the charged aggregate and facilitates the aggregate growth by suppressing the main impediment of electrostatic repulsion among head groups. Additionally, the values of Γ max are always higher in salt solutions as compared to those in pure water due to their salting out effect. The larger pC20 value indicates that the surfactant adsorbs more efficiently at the air/water interface and reduces surface tension more efficiently. In addition, the geminis in water show little or no break in their specific conductance versus surfactant molar concentration plots. This is attributable to protonation of the carboxylate group and strong Na+ release during micellization.  相似文献   

11.
The aqueous solution properties of a cationic poly(trimethyl acrylamido propyl ammonium iodide) [poly(TMAAI)] were studied by measurements of reduced viscosity, intrinsic viscosity, and flocculation test. The reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the types and concentration of added salt. “Soft” salt anions were more easily bound on the quaternary ammonium (R4N+) of poly(TMAAI) than those of “hard” salt anions. Halide anions are hard anions; consequently, hard cations were more easily attracted to halide anions for reducing the binding degree of halide anion on the quaternary ammonium group (R4N+). Some salt ions were observed to strongly attract the quaternary ammonium of the cationic polymeric side chain for coagulation of the polymers. This effect would make the polymeric aqueous solution become turbid. The intrinsic viscosity behavior for cationic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain is contrasted with polyampholyte. A comparison of various flocculants as to the effect of flocculation was also studied. © 1994 John Wiley & Sons, Inc.  相似文献   

12.
A cationic microgel with quaternized amine groups was prepared and used as a soft template for layer-by-layer (LbL) assemblies. The presence of quaternized amine groups inside the microgels was necessary to prevent rearrangements and subsequent bridging between the coated microgels, which were observed for the precursor microgels containing protonated primary amino groups. Sequentially, negatively charged polyelectrolyte poly(sodium styrene sulfonate) (PSS) and positively charged polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) were added to a suspension of quaternized microgels. This leads to an odd-even effect with respect to particle size and surface charge of the formed microgel–polyelectrolyte complexes (MPECs). MPECs with an even number of layers exhibit positive surface charge due to PDADMAC as the outermost layer and are larger compared to complexes with an odd number of layers, which are negatively charged having PSS in the outermost layer. Taking into account previous results (Macromolecules,2009,42, 1229), these observations show that electrostatic interactions are the major force for the odd-even effect in polyelectrolyte multilayers on microgels: the cationic groups of PDADMAC compete with the cationic moieties of the microgel for binding with the sulfonate groups of PSS. Concomitantly, a fluctuating size of the MPECs is induced by an osmotic pressure modulation within the microgel. In contrast, surface tension effects invoked by a possible varying hydrophilicity of the different terminal layers are negligible.  相似文献   

13.
A cationic poly(methyl iodide quaternized styrene–N,N‐dimethylaminopropylmaleamidic acid) copolymer was synthesized through amidoacidification reaction of styrene‐maleic anhydride copolymer with N,N‐dimethylaminopropylamine (ring‐opening reaction). Its properties in various aqueous salt solutions and pH solutions were studied by measurements of reduced viscosity and intrinsic viscosity. The results indicated that the reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the type and concentration of the added salts and the results also showed a contrary tendency in some salts with monovalent acid groups to polyelectrolyte. At the same time, some salt ions were observed to strongly attract the quaternary ammonium group of the cationic polymeric side chain and resulted in agglomeration of the polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1619–1626, 2001  相似文献   

14.
The copolymer prepared by copolymerizing with acrylamide and maleic anhydride was imidized with N,N-dimethylaminopropylamine. The obtained acrylamide–N,N-dimethylaminopropylmaleimide (ADMAPM) copolymer was then reacted with methyl iodide to yield a poly(methyl iodide quaternized acrylamide–N,N-dimethylaminopropylmaleimide) copolymer [poly(MIQADMAPM)]. Its aqueous solution properties were studied by measurements of reduced viscosity, intrinsic viscosity, and flocculation test in this study. The reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the types and concentration of the added salt. “Soft” salt anions were more easily bound to the quaternary ammonium cation (R4N+) of poly(MIQADMAPM) than were “hard” salt anions. Halide anions are hard anions; consequently, hard cations were more easily attracted to halide anions and reduced the binding degree of halide anion on the quaternary ammonium group (R4N+). The intrinsic viscosity behavior for cationic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain was contrasted with polyampholyte. The effect of various flocculants on flocculation in different pH values was accessed in this study. © 1996 John Wiley & Sons, Inc.  相似文献   

15.
Nicholas B. Wyatt 《Polymer》2011,52(11):2437-5850
The viscosity of several polyelectrolytes is measured in both salt free solutions and solutions in the high salt limit. At low polymer concentrations, the zero shear rate viscosity decreases as much as 100-fold upon addition of a monovalent salt, namely NaCl. However, as polymer concentration increases, the viscosity difference between polymer in salt free and in monovalent salt solution diminishes. Further, the zero shear rate viscosity becomes independent of added monovalent salt at the critical polyelectrolyte concentration cD. Above cD, the addition of monovalent salt increases the zero shear rate viscosity of the entangled polyelectrolyte solutions. The viscosity increase agrees with viscosity scaling theory for polyelectrolytes in the entangled regime. Polyelectrolytes exhibiting an increase in viscosity above cD in the presence of monovalent salt include three natural anionic polyelectrolytes (xanthan, carrageenan, welan), one synthetic anionic polyelectrolyte (hydrolyzed polyacrylamide), and one natural cationic polyelectrolyte (chitosan). Generally, these polyelectrolytes are relatively high molecular weight (>1 M Dalton), which makes cD experimentally accessible (e.g., cD = 0.2 wt% for xanthan). The magnitude of the viscosity increase is as high as 300% for xanthan and nearly independent of monovalent salt concentration in the high salt limit. The increase in viscosity in monovalent salt solution and magnitude of cD appear to be heavily influenced by the molecular characteristics of the polymers such as monomer weight, molecular structure, and chain conformation.  相似文献   

16.
A cationic poly(methyl iodide quaternized styrene-dimethylaminopropylmaleimide) copolymer [poly(MIQSDMAPM)] was synthesized by imidizing styrene-maleic anhydride (SMA) copolymer. Its aqueous solution properties were studied by measurements of reduced viscosity, intrinsic viscosity, and a flocculation test. The reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the types and concentration of the added salt. “Soft” salt anions were more easily bound to the quaternary ammonium cation (R4N+) of poly(MIQSDMAPM) than “hard” salt anions. Halide anions are hard anions; consequently, hard cations were more easily atracted to halide anions, and reduced binding degree of halide anion on the quaternary ammonium group (R4N+). Some salt ions were observed to strongly attract the quaternary ammonium group of the cationic polymeric side chain and resulted in agglomeration of the polymers. A comparison of various flocculants as to the effect of flocculation was made in this study. © 1996 John Wiley & Sons, Inc.  相似文献   

17.
Zwitterion (Z) monomer 3‐[diallyl{3‐(diethoxyphosphoryl)propyl}ammonio]propane‐1‐sulfonate underwent cyclocopolymerization with sulfur dioxide to give a new alternating copolymer poly(Z‐alt‐SO2) in excellent yield (ca 90%). The polyzwitterion (±) (PZ) (i.e. poly(Z‐alt‐SO2), bearing a diethylphosphonate as well as a sulfonate functionality in each repeat unit, upon ester hydrolysis gave its corresponding pH‐responsive polyzwitterionic acid (±) (PZA). The pH‐induced equilibrations (+) cationic polyelectrolyte ? (±) PZA ? polyzwitterion/anion (± ?) (PZAN) ? polyzwitterion/dianion (± =) (PZDAN) permitted us to examine the effects of charge types and their densities on the interesting solubility and viscosity behaviours. The apparent protonation constants of the basic functionalities &tbond;N±PO32? in (± =) PZDAN and &tbond;N±PO3H1? in (± ?) PZAN in salt‐free water and 0.1 mol L?1 NaCl were determined using potentiometric titrations. (±) PZA at a meagre concentration of 20 ppm was found to be an effective antiscalant to inhibit the precipitation of CaSO4 from its supersaturated solution: after 500 and 800 min, the respective scale inhibitions of 86 and 98% indicated its potential use as an effective antiscalant in reverse osmosis plant. © 2014 Society of Chemical Industry  相似文献   

18.
The dilute solution properties of a cationic polyelectrolyte, poly(dimethyl sulfate quaternized dimethylaminoethyl methacrylate) [poly(DMAEM · C2H6SO4)], are studied by measurements of intrinsic viscosity, degree of binding, and flocculation application. The intrinsic viscosity of this polyelectrolyte is related to the type and concentration of added salt. The intrinsic viscosity behavior for cationic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain is contrasted with polyampholyte. The polyelectrolyte in the presence of KCl has a lower degree of binding, indicating that the proton ion (H+) is relatively difficult to bind to the CH3SO4? at the polymer end. The polymerization of DMAEM · C2H6SO4 in 0.5M KCl aqueous solution proceeded more easily than that of DMAEM · C2H6SO4 in pure water. The polymerization rate of DMAEM · C2H6SO4 is found to pass through an extreme value as a function of pH. Optimum flocculation, corresponding to the complete removal of turbidity in the supernatant, is achieved. Beyond the optimum flocculation, high polymer dosages redisperse the bentonite suspensions.  相似文献   

19.
The cationic monomer N,N‐diallyl‐3‐(diethylphosphonato)propylammonium chloride was cyclo‐copolymerized with sulfur dioxide in dimethylsulfoxide using azoisobutyronitrile as initiator to afford a cationic polyelectrolyte (CPE) having a (diethylphosphonato)propyl pendent moiety. The CPE on acidic hydrolysis of the diester groups gave pH‐responsive polyzwitterionic acid (PZA) which on treatment with one and two equivalents of NaOH gave zwitterionic/anionic polyelectrolyte (ZAPE) and dianionic polyelectrolyte (DAPE), respectively. The solution properties of CPE, PZA, ZAPE and DAPE were investigated in detail using a viscometric technique. For comparison, the solution properties of the polymers were correlated with those of the structurally similar polyzwitterion prepared from copolymerization of the corresponding zwitterionic monomer ethyl‐3‐(N,N‐diallylammonio)propanephosphonate and sulfur dioxide. Evaluation of antiscaling properties using concentrated brine solutions revealed that DAPE at a meagre concentration of 10 ppm is very effective in inhibiting the formation of calcium sulfate scale, and as such can be used effectively as an antiscalant in reverse osmosis plants. © 2013 Society of Chemical Industry  相似文献   

20.
The transport properties of polyelectrolytes with N‐alkyl‐N,N‐dimethyl‐N‐(2‐hydroxypropyl)ammonium chloride pendent groups (alkyl = octyl, dodecyl, or cetyl) randomly distributed along a polysaccharide backbone (dextran) in solutions were studied with viscometry and conductometry. This investigation mainly considered the influence of the side‐chain length and the solvent polarity on the polyelectrolyte behavior in salt‐free aqueous solutions. The viscometric data indicated that all the copolymers exhibited polyelectrolyte behavior, and they were plotted in terms of the Rao equation. The viscosity of the polycation with dodecyl as alkyl substituent was also measured in solvent mixtures of water and methanol. The conductometric behavior of these cationic polysaccharides was found to be influenced by the alkyl side‐chain length and the solvent polarity. A nonlinear dependence of the equivalent conductivity on the dielectric constant of the solvent was observed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

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