Polysulfobetaines and corresponding cationic polymers. IV. Synthesis and aqueous solution properties of cationic poly(MIQSDMAPM)

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.     

Aqueous solution properties of poly(trimethyl acrylamido propyl ammonium iodide) [poly(TMAAI)]

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.     

Poly(sulfobetaine)s and corresponding cationic polymers. XI. Synthesis and aqueous solution properties of a cationic poly(methyl iodide quaternized ethyl vinyl ether/N,N‐dimethylaminopropyl maleamidic acid) copolymer

A copolymer prepared by the copolymerization of ethyl vinyl ether and maleic anhydride underwent amidoacidation with N,N‐dimethylaminopropylamine. The obtained ethyl vinyl ether/dimethylaminopropyl maleamidic acid copolymer was then reacted with methyl iodide to yield poly(methyl iodide quaternized ethyl vinyl ether/N,N′‐dimethylaminopropyl maleamidic acid) (MIQEDMAPMA). The greatest difference from other polyelectrolytes was the carboxylic group on the polymer chain unit of MIQEDMAPMA. Its aqueous solution properties in various salts and at various pH values were studied by measurements of the reduced viscosity and intrinsic viscosity. The reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the types and concentrations of the added salts. The tendency of the salt effect was similar to that of other polyelectrolytes; that is, soft salt anions were more easily bound to the quaternary ammonium (R₄N⁺) of MIQEDMAPMA than hard salt anions. Some salt ions strongly attracted the quaternary ammonium of the cationic polymeric side chain for the agglomeration of the polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2261–2269, 2003     

Poly(sulfobetaine)s and corresponding cationic polymers. VIII. Synthesis and aqueous solution properties of a cationic poly(methyl iodide quaternized styrene–n,n‐dimethylaminopropyl maleamidic acid) copolymer

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     

Poly(sulfobetaine)s and corresponding cationic polymers. VII. Thermal degradation of copolymers derived from poly(acrylamide co-N,N-dimethylaminopropylmaleimide)

The copolymer prepared by copolymerizing acrylamide and maleic anhydride was imidized with N,N-dimethylaminopropylamine. The obtained acrylamide-N,N-dimethylaminopropylmaleimide (ADMAPM) copolymer was then reacted with propane sultone to yield an acrylamide-N,N-dimethylmaleimidopropyl ammoniopropane sulfonate (ADMMAPS) copolymer or then reacted with methyl iodide to yield a poly(methyl iodide quaternized acrylamide-N,N-dimethylaminopropyl maleimide) copolymer [poly(MIQADMAPM)]. The kinetic parameters, such as the reaction order, the activation energy, and the preexponential factor, of the thermal degradation were evaluated from thermal gravimetric curves for these two copolymers. The activation energy and preexponential factor of the poly(ADMMAPS) were higher than those of poly(MIQADMAPM) for Ozawa's method and van Krevelen's method. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 95–103, 1997     

Dilute solution properties of naphthalene-labeled cationic poly(dimethyl sulfate quaternized acrylamide/N,N-dimethylaminopropylmaleimide copolymer)

The properties of a novel cationic, naphthalene-labeled cationic poly(dimethyl sulfate quaternized acrylamide/N,N-dimethylaminopropylmaleimide copolymer), poly-(DSQADMAPM)/NA in aqueous solution are examined in this study, measuring intrinsic viscosity, reduced viscosity, and ionic strength. This cationic poly(DSQADMAPM)/NA’s intrinsic viscosity is dependent on the type and concentration of salt added to the aqueous solution. The intrinsic viscosity behavior of the cationic poly(DSQADMAPM)/NA resulting from the electrostatic repulsive force of the polymer chain is contrasted with polyampholyte. Smaller anions such as F⁻ with a common cation (K⁺) are found to be the most difficult to be bound to the end group, indicating that a higher intrinsic viscosity of the poly(DSQADMAPM)/NA would be in KF salt aqueous solution. Smaller cations such as Li⁺ with a common anion (Cl⁻) are found to be the most difficult to be bound to the quaternary ammonium group, indicating that a higher intrinsic viscosity of the poly(DSQADMAPM)/NA would also be in LiCI salt aqueous solution. Models are proposed to account for the poly(DSQADMAPM)/NA solution viscometrics.     

Dilute solution properties of cationic poly(dimethyl sulfate quaternized dimethylaminoethyl methacrylate)

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.     

Synthesis and properties of cationic polyacrylamide containing pyridine quaternary salt

The copolymer P(AM‐co‐4VP) of acrylamide (AM) and 4‐vinylpyridine (4VP) was synthesized by radical copolymerization in solution, and then the copolymer was quaternarized using dimethyl sulfate to produce cationic P(AM‐co‐4VP) (CPAV), a cationic polyacrylamide containing quaternary pyridine salt. Two series of CPAV have been synthesized. The structure and composition of the copolymer and the cationic copolymer were characterized by their FTIR, ¹H NMR and ultraviolet spectra Flocculation and corrosion inhibition properties of the cationic copolymer were studied in detail and effects of cationic degree and molecular weight on the flocculation and corrosion inhibition properties were discussed. The results showed that cationic polyacrylamide containing quaternary pyridine salt possesses excellent flocculation, corrosion inhibition and other functions. The higher the degree of cationization, the better are these functions, and the molecular weight also effects the functions significantly. Copyright © 2003 Society of Chemical Industry     

Dilute solution properties of naphthalene-labelled acrylamide/N,N-dimethyl maleimido propyl ammonium propane sulphonate copolymer

The aqueous solution properties of an ampholytic naphthalene-labelled acrylamide/N,N-dimethyl maleimido propyl ammonium propane sulphonate copolymer, poly(ADMMAPS)/NA, are examined in this study by measuring reduced and intrinsic viscosities. The intrinsic viscosity of the poly(ADMMAPS)/NA is related to the type and concentration of the salt added. This behaviour, resulting from the associations of the polymer chains, is in contrast with cationic and anionic polyelectrolytes. Smaller anions, such as F^-, with a common cation (K⁺) are found to be the most difficult to be bound to the sulphonate group, indicating that a lower intrinsic viscosity of the poly(ADMMAPS)/NA would be found in aqueous KF solution. Smaller cations, such as Li⁺, with a common anion (Cl^-) are found to be the most difficult to be bound to the quaternary ammonium group, indicating that a lower intrinsic viscosity of the poly(ADMMAPS)/NA would be found in LiCl salt aqueous solution. Because a naphthalene label was introduced into the polymer, the behaviour of the solution properties of the poly(ADMMAPS)/NA could be clearly defined in term of macroscopic and microscopic analysis. The models proposed in this study can account for the poly(ADMMAPS)/NA solution viscosities. © 1998 SCI.     

Amphibious water‐soluble copolymer. I. Its synthesis and dispersing ability on barium titanate

An amphibious water‐soluble copolymer, polyacrylamide/(α‐N,N‐dimethyl‐N‐acryloyloxyethyl) ammonium ethanate (PAAM/DAAE), was synthesized and used as a dispersion agent for BaTiO₃ particles. PAAM/DAAE was prepared from acrylamide and (α‐N,N‐dimethyl‐N‐acryloyloxyethyl) ammonium ethanate under basic conditions through a free‐radical polymerization. The structure of this copolymer was verified with IR and ¹H‐NMR spectra. The dispersing effects of PAAM/DAAE were examined through the measurement of the viscosity and sedimentation of BaTiO₃ suspensions and the green density. The results indicated that this copolymer could uniformly disperse the particles, reduce the viscosity, stabilize the suspensions, and produce high‐density green compacts. In comparison with a commercial dispersant, the ammonium salt of poly(methylacrylic acid), PAAM/DAAE was clearly more effective. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2232–2239, 2004     

Poly(sulfobetaine)s and corresponding cationic polymers. X. Viscous properties of zwitterionic poly(sulfobetaine) derived from styrene–(N,N‐dimethylaminopropyl maleamidic acid) copolymer in aqueous salt solutions

A styrene–[N,N‐dimethyl (maleamidic acid) propyl ammonium propane sulfonate] (SDMMAAPS) copolymer was synthesized through an amidoacidation reaction of styrene–maleic anhydride (SMA) alternating copolymer with N,N‐dimethylaminopropylamine (ring‐opening reaction), which was then reacted with propane sultone. The effect of various salt solutions on the intrinsic viscosity of this ampholytic ADMMAAPS copolymer was investigated. The results showed that the effect of counter ions on the intrinsic viscosity of SDMMAAPS was not entirely similar to that of other zwitterionic poly(sulfobetaine)s. The greatest difference from other poly(sulfobetaine)s is the carboxylic group on the polymer chain unit of SDMMAAPS. The Huggins constants for SDMMAAPS in aqueous salt solutions, however, were also quite different from those of other sulfobetaine copolymers, such as styrene–N,N‐dimethyl (maleimido propyl) ammonium propane sulfonate] (SDMMAPS) copolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 726–734, 2004     

Amphoteric water‐soluble copolymer for barium titanate slurries. I. Synthesis and dispersing ability

An amphoteric water‐soluble copolymer, polyacrylamide/[α‐N,N‐dimethyl‐N‐(3‐(β‐carboxylate)acrylamino)propyl] ammonium ethanate (PAM/DAE) was synthesized and used as a dispersion agent for BaTiO₃ particles. PAM/DAE was prepared from acrylamide and [α‐N,N‐dimethyl‐N‐(3‐(β‐carboxylate)acrylamino)propyl] ammonium ethanate in a basic condition through a free‐radical polymerization. The structure of this copolymer was verified by IR and ¹H‐NMR spectra. The dispersing effects of PAM/DAE were examined by measuring the viscosity and sedimentation of BaTiO₃ suspensions, and by analyzing the particle size. The results indicate that this copolymer could uniformly disperse the particles, and the resulting suspensions were less viscous, more stabilized, and contained powder with smaller particle size. The dispersing/stabilizing ability of PAM/DAE is close to, or slightly better than, that of a commercial dispersant, ammonium salt of poly(methacrylic acid). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1443–1450, 2005     

Superabsorbent polymeric materials IX: Effect of cationic structure on swelling behavior of crosslinked poly(sodium acrylate‐co‐cationic monomers) in aqueous salt solutions

Two series of xerogels based on sodium acrylate (SA), trimethyl methacrylamidopropyl ammonium iodide (TMMAAI), trimethyl methacryloyloxyethyl ammonium iodide (TMMAI), and N,N′‐methylene‐bis‐acrylamide (NMBA) as a crosslinker were prepared by inverse suspension polymerization. The water absorbency and swelling kinetic behavior for these xerogels in water or various saline solutions were investigated. The results showed that the swelling behaviors of these absorbents are related to their chemical structures, their compositions, and the type of external salt solutions. There would be effective improvement in the water absorbency of these two gel series by copolymerizing SA with a small amount of cationic monomer (TMMAAI or TMMAI). The initial absorption rates in deionized water were found to be faster for TM series gels than for TA series gels. The two series of superabsorbents had a tendency to absorb water in dilute nitrate aqueous solutions in the order: Fe³⁺, Ni²⁺, Ca²⁺, Cu²⁺, and Na⁺ for Fe(NO₃)₃, Ni(NO₃)₂, Ca(NO₃)₂, Cu(NO₃)₂, and NaNO₃ aqueous solution, respectively. The absorbency and initial absorption rate for these gels were related to the gel compositions and salt concentrations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1827–1837, 2001     

Synthesis,characterization, and flocculation properties of poly(acrylamide‐methacryloxyethyltrimethyl ammonium chloride‐methacryloxypropyltrimethoxy silane)

A novel hydrophobically modified and cationic flocculant poly(acrylamide‐methacryloxyethyltrimethyl ammonium chloride‐methacryloxypropyltrimethoxy silane) (P(AM‐DMC‐MAPMS)) was synthesized by inverse emulsion polymerization. The molecular structure of hydrophobically cationic polyacrylamide (HCPAM) was characterized by FTIR and ¹H‐NMR. The effects of DMC and MAPMS feed ratio on intrinsic viscosity and solubility were measured. The effects of hydrophobically cationic flocculants on reactive brilliant red X‐3B solution and kaolin suspension were studied. It was found that the introduction of MAPMS could increase the intrinsic viscosities of P(AM‐DMC‐MAPMS) and enhance the flocculation properties to anionic dye solution and kaolin suspension, but reduced their water‐solubility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dilute solution properties of anionic poly(potassium-2-sulphopropylacrylate)

The dilute solution properties of an anionic polyelectrolyte, poly(potassium-2-sulphopropylacrylate) (poly(SPA)) are studied by measurements of intrinsic viscosity, degree of binding, ionic strength and critical micelle concentration. The intrinsic viscosity of this polyelectrolyte is related to the type and concentration of the salt added. The intrinsic viscosity behaviour of an anionic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain is in contrast to that of a polyampholyte. The polyelectrolyte in high concentration of NaCl has a low degree of binding, indicating that the proton ion (H⁺) is relatively difficult to bind to the sulphonate group (SO⁻₃) at the polymer end. An increase in ionic strength causes the pK_a to decrease at the half-neutralization point. The monomer solutions exhibit a plot typical of those observed for detergents, with a break in the curve occurring at the critical micelle concentration. For the polymer solutions, no break in the equivalent conductance curve was found for the concentrations studied.     

Modification of cation exchange membrane by grafted poly(4-vinyl-N-methylpyridinium-iodide)

It is well known that cation exchange membranes, having a very thin layer of a cationic polyelectrolyte on the membrane surface, have preferential permselectivity for monovalent cations in a monovelent-divalent cations system. We studied the relationship between preferential permselectivity and molecular structure of the cationic polyelectrolyte. Grafted poly(4-vinyl-N-methylpyridinium-iodide) was used and was compared with poly(4-vinyl-N-methylpyridiniumiodide). The backbone polymers were poly(styrene-co-p-benzylstyrene) and poly(benzyl), onto which 4-vinylpyridine was grafted by anionic polymerization and then quaternized with CH₃I. The grafted poly(4-vinyl-N-methylpyridinium-iodide) is effective in making the cation exchange membrane preferentially permselevtive for Na⁺ - Ca²⁺ system and is more preferable than poly(4-vinyl-N-methylpyridinium-iodide) in terms of electric resistance of the membrane. However, the relationship between the molecular structure of the cationic polyelectrolyte and the durability of the preferential permselectivity is not clear.     

Dilute solution properties of anionic poly(potassium-2-sulfopropylmethacrylate)

The dilute solution properties of an anionic polyelectrolyte, poly(potassium-2-sulfopropylmethacrylate) [poly(SPM)], are studied by measurements of polymerization rate, intrinsic viscosity, degree of binding, ionic strength, and critical micelle concentration. The polymerization of SPM in 0.5M NaCl aqueous solution proceeded more easily than that of SPM in pure water. The polymerization rate of SPM is found to pass through an extreme value as a function of pH. The intrinsic viscosity of this polyelectrolyte is related to the type and concentration of the salt added. The intrinsic viscosity for anionic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain is in contrast with the polyampholyte. The polyelectrolyte in a high concentration of NaCl has a low degree of binding, indicating that the proton ion (H⁺) is relatively difficult to bind to the sulfonate group (SO⁻₃) at the polymer end. An increase in ionic strength causes the pKa (dissociation constant) to decrease at the half-neutralization point. The monomer solutions exhibit a plot typical of those observed for detergents, with a break in the curve occurring at the critical micelle concentration. For the polymer solutions, no break in the equivalent conductance curve was found for the concentrations studied. The polymer is adapted for use as viscosity-controlling agents in secondary oil recovery operations by water flooding. We have the proposed models to account for the poly(SPM) solution viscometrics. © 1997 John Wiley & Sons, Inc.     

两性絮凝剂P(AM-co-IA-co-DAC-co-DMC)的合成及絮凝性能

两性聚丙烯酰胺处理污水用量少,毒性低,pH适用范围广,绿色环保。采用水分散聚合方法合成了两性聚丙烯酰胺P(AM-co-IA-co-DAC-co-DMC),以1%的高岭土悬浮液模拟废水,考察絮凝剂用量、特性粘数、体系pH值、温度以及阴阳离子单体配比对絮凝效果的影响。结果表明,当阳、阴离子单体摩尔比为3∶1,特性粘数为3.16 dL/g,用量为3 mg/L时,絮凝效果好,常温下透过率达到98.7%。两性聚丙烯酰胺分子链上的正、负两种电荷基团同时发挥电中和作用和架桥作用,絮凝效果受pH变化的影响较小,明显优于阳、阴离子型聚丙烯酰胺。     

Quaternarized cationic poly[(vinyl chloride)-co-(vinyl chloroacetate)] binary copolymer as non-migration antibacterial additive in PVC matrix

Antibacterial polyvinyl chloride (PVC) materials have drawn considerable attention since their wide application in medical devices. The objective of this study is to develop a novel quaternary ammonium cationic vinyl chloride copolymer, which can be potentially used as antibacterial additive in PVC matrix. Initially, the low average-number molecular weight poly[(vinyl chloride)-co-(vinyl chloroacetate)] (PVC-co-PVCA) is synthesized by precipitation copolymerization. Subsequently, quaternary ammonium cationic moieties with different lengths of alkyl chains are introduced into the copolymers via quaternization reaction between alkyl-dimethyl tertiary amines with acyl chloride groups. The successful synthesis of PVC-co-PVCA and quaternarized copolymers are carefully confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance (1H NMR), and x-ray photoelectron spectroscopy. The antibacterial behaviors of the quaternarized copolymers and its blends with PVC are investigated. The results reveal that all the PVC blends containing at least 5% by weight of quaternarized copolymer have superior bacteriostasis ratio (>99.6%) against both Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus) due to the incorporation of quaternary ammonium groups. Meanwhile, the cationic copolymer exhibits excellent antifouling and much lower migration rate (<0.4%). These interesting consequences endow the quaternarized copolymers as alternative antibacterial agents possess a great deal of potential for use in PVC materials.     

Synthesis and characterization of fluorocarbon‐modified poly(N‐isopropylacrylamide)

Poly(N‐isopropylacrylamide) copolymers (PNIPAMs) containing pendent perfluoroalkyl (R_F) or dodecyl groups have been synthesized by copolymerization of NIPAM with small amounts of R_R‐acrylates or ‐methacrylates containing a sulfonamido moiety between the acrylate and R_F groups or with dodecyl acrylate. Evidence for strong intermolecular hydrophobic association of the fluorocarbon groups is provided by large viscosity increases with copolymer concentration and upon addition of NaCl and surfactants. These interactions appear to be much stronger than that of the corresponding copolymers of poly(N,N‐dimethylacrylamide) with similar comonomer contents. Hydrophobic association between the R_F groups is found to be much stronger than that of the corresponding dodecyl groups. The viscosity of some of the copolymer solutions, particularly in the presence of perfluorocarbon surfactants, was unusually temperature sensitive, decreasing by a factor of at least 1000 upon increasing the temperature from 10 to 20 °C. This large decrease is most probably related to the collapse of the copolymer coils near the lower critical solution temperature. This is in sharp contrast to the corresponding polyacrylamide or poly(N,N‐dimethylacrylamide) R_F‐acrylate copolymers that show viscosity increases with increasing temperature in the 40–60 °C range. The NIPIAM copolymers were also found to be different from the acrylamide or N,N‐dimethylacrylamide perfluorocarbon acrylate copolymers in that they were found to be Newtonian at a low R_F content but dilatant at a higher comonomer content. © 2000 Society of Chemical Industry