Synthesis of water‐soluble thermosensitive polymers having phosphonium groups from methacryloyloxyethyl trialkyl phosphonium chlorides–N‐isopropylacrylamide copolymers and their functions

Water‐soluble thermosensitive polymers having phosphonium groups were synthesized by the copolymerization of N‐isopropylacrylamide (NIPAAm) with methacryloyloxyethyl trialkyl phosphonium chlorides (METRs) having varying alkyl lengths. The relative viscosities of the copolymer solutions increased with increasing content of phosphonium groups in the copolymers and decreased with increasing chain length of alkyl chains in the phosphonium groups. However, the copolymers of METR with octyl groups in phosphonium groups (METO) and NIPAAm became water insoluble with increasing contents of METO moieties in the copolymers. The transmittance at 660 nm of the copolymer solutions above the lower critical solution temperature (LCST) decreased gradually with increasing temperature and decreased with increasing chain length of alkyl chains in the phosphonium groups. The transmittance at 660 nm of the copolymer solutions above the LCST was greatly affected by the addition of neutral salts such as KCl. The copolymers of METR with ethyl groups in phosphonium groups and NIPAAm and those of METR with butyl groups in phosphonium groups and NIPAAm had high flocculating abilities against bacterial suspensions. The METO–NIPAAm copolymer was found to have a high antibacterial activity. The flocculating ability and the antibacterial activity of the copolymers were affected by not only the content of phosphonium groups but also the alkyl chain length in the phosphonium groups in the copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 386–393, 2003     

Formation of thermosensitive copolymer beads having phosphinic acid groups and adsorption ability for metal ions

Hydrophilic thermosensitive copolymer beads having phosphinic acid groups were prepared by suspension copolymerization of acryloyloxypropyl n‐octylphosphinic acid (APPO), N‐isopropyl acrylamide (NIPAAm), and tetraethyleneglycol dimethacrylate (4G). The thermosensitivity and the adsorption ability of the copolymer beads for metal ions beads were studied. The APPO‐NIPAAm‐4G copolymer beads were obtained in a good yield by suspension copolymerization of monomers (APPO, NIPAAm, and 4G) dissolved in chloroform, in a saturated Na₂SO₄ aqueous solution in the presence of surfactant and MgCO₃. The APPO‐NIPAAm‐4G copolymer beads had higher adsorption ability for lanthanide metal ions (Eu³⁺, Sm³⁺, Nd³⁺, or La³⁺) than for main transition metal ions (Cu²⁺, Ni²⁺, or Co²⁺). Furthermore, it was also found that the APPO‐NIPAAm‐4G copolymer beads had selective adsorption ability between lanthanide metal ions, and the order of adsorption ability for lanthanide metal ions was as follows: Eu³⁺ > Sm³⁺ > Nd³⁺ > La³⁺. The selective adsorption for these metal ions from their mixed solutions was performed by both a batch method and a column method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 449–460, 2006     

Synthesis of thermosensitive copolymer beads containing pyridinium groups and their antibacterial activity

Thermosensitive 4VP‐NIPAAm‐4G copolymer beads containing pyridyl groups were first prepared by suspension copolymerization of 4‐vinylpyridine (4VP), N‐isopropylacrylamide(NIPAAm), and tetraethylene glycol dimethacrylate (4G; crosslinking reagent) in a saturated Na₂SO₄ aqueous solution in the presence of surfactant and MgCO₃ as dispersants. Then the copolymer beads containing pyridinium groups were obtained by the quaternization of the copolymer beads with various alkyl iodides (CH₃I, C₄H₉I, C₈H₁₇I) in N,N‐dimethylformamide. The 4VP‐NIPAAm‐4G (15 : 97 : 3) copolymer bead and the 4VP‐NIPAAm‐4G copolymer beads quaternized with butyl iodide exhibited high thermosensitivity in water, although the 4VP‐NIPAAm‐4G copolymer beads quaternized with methyl iodide or octyl iodide hardly exhibited thermosensitivity. All the quaternized copolymer beads exhibited antibacterial activity against Escherichia coli (E. coli), although the 4VP‐NIPAAm‐4G copolymer bead did not. In particular, the copolymer bead quaternized with butyl iodide exhibited the highest antibacterial activity against E. coli at 30°C. It was also found that the antibacterial activity of the quaternized 4VP‐NIPAAm‐4G copolymer beads was greatly affected by not only chain length of alkyl groups in alkyl iodides, with which the 4VP‐NIPAAm‐4G copolymer beads were quaternized, but also by temperature of the solutions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Properties of water‐soluble acrylic copolymer/montmorillonite nanocomposites for warp sizing

Acrylic copolymer/montmorillonite (MMT) nanocomposites for warp sizing were prepared in the presence of Na⁺‐MMT by the in situ intercalative polymerization of acrylic acid, acrylamide, and methyl acrylate in water solution. The properties of the solution and cast film were tested according to an application in sizing process of the nanocomposite size with various MMT contents. The results indicate that, for an exfoliated structure corresponding to the MMT content increasing to 7 wt %, the performance parameters of solution viscosity, glass‐transition temperature, and tensile strength of the film increased and the moisture sorption, abrasion loss, and elongation at break of the film decreased. When the intercalated structure of MMT was 9 wt %, the gathered MMT layers acted as a common inorganic filler in the copolymer matrix, with limited contribution to the properties of the composite. The adhesion work of the nanocomposite solution was calculated by use of the Young–Dupre relation, which showed maximum values at an MMT content of 3 wt % on the surfaces of both the polyester and cellulose films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A water‐soluble acrylate/sulfonate copolymer. I. Its synthesis and dispersing ability on cement

A new water‐soluble methacrylate/2‐acrylamido‐2‐methylpropane sulfonate copolymer (PMAMP) was synthesized and evaluated as a dispersion agent for cement particles. PMAMP was prepared from methacrylic acid and 2‐acrylamido‐2‐methylpropane sulfonic acid (AMP). The structure of the prepared polymer was verified by its NMR and IR spectra. The dispersing properties of PMAMP were evaluated by a minislump test on cement pastes. The test results indicated that this copolymer could disperse the cement particles and improve the minislump of cement pastes. Compared with a commercial superplasticizer (sulfonated naphthalene formaldehyde condensates), PMAMP performed better in enhancing the fluidity of the cement pastes. The polymer with about 40–50% AMP and a weight‐average molecular weight of about 5 × 10⁴ was most effective in dispersing cement particles and promoting the fluidity of cement pastes. Nevertheless, PMAMP with a higher AMP content or a higher molecular weight appeared to cause less slump loss. This was related to the interaction of this admixture with the cement particles and its adsorption behavior onto the cement particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2490–2496, 2006     

Synthesis of thermosensitive glycopolymers containing D‐glucose residue: Copolymers with N‐isopropylacrylamide

A new glycomonomer, 3‐acrylamido‐3‐deoxy‐1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose, was synthesized from D ‐glucose. This monomer was homopolymerized and copolymerized with N‐isopropylacrylamide in different compositions by free‐radical polymerization. The composition of the copolymer was determined with ¹H‐NMR spectroscopy. On acid hydrolysis, water‐soluble deprotected copolymers were obtained. The protected and deprotected copolymers showed a sharp cloud‐point temperature. A linear correlation was obtained between the lower critical solution temperatures and the concentration of glycomonomer in the copolymers © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel water‐soluble acryloylmorpholine copolymers: Synthesis,characterization, and metal ion binding properties

Poly(4‐acryloylmorpholine), poly(4‐acryloylmorpholine‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) were synthesized by radical polymerization. The water‐soluble polymers obtained, containing tertiary amino, amide, and sulfonic acid groups, were investigated, in view of their metal binding properties, as polychelatogens by using the liquid‐phase polymer‐based retention technique, under different experimental conditions. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), Cd(II), Pb(II), Zn(II), Cr(III), and Al(III). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 180–185, 2006     

Multi‐responsive microgel of a water‐soluble monomer via emulsion polymerization

Microgel of a water‐soluble monomer [2‐(N‐morpholino)ethyl methacrylate (MEMA)] was successfully prepared in aqueous media via emulsion polymerization by using a novel water‐soluble block copolymer as stabilizer. Characterization studies confirmed monodisperse spherical morphologies of microgels with a diameter of 280 nm at neutral pH. These microgels exhibited multi‐responsive behavior by responding solution pH, temperature, ionic strength, type of dispersing media, and magnetic particles. It swells well at low pH (<6.0) and at low temperature, but shrinks above pH 6.0, or even more shrinks with salt addition at neutral and basic conditions. In addition, the hydrodynamic diameter of PMEMA microgel was decreased gradually at basic and neutral pH when solution temperature was increased up to the lower critical solution temperature of PMEMA (LCST, 35°C), but microgel diameter did not change much above LCST. Multi‐responsive behavior of PMEMA microgel was investigated by using dynamic light scattering, UV‐Vis spectrophotometer and zeta potentiometer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42072.     

Viscosity behavior and surface and interfacial activities of hydrophobically modified water‐soluble acrylamide/N‐phenyl acrylamide block copolymers

In this study, the viscosity behavior and surface and interfacial activities of associative water‐soluble polymers, which were prepared by an aqueous micellar copolymerization technique from acrylamide and small amounts of N‐phenyl acrylamide (1.5 and 5 mol %), were investigated under various conditions, including the polymer concentration, shear rate, temperature, and salinity. The copolymer solutions exhibited increased viscosity due to intermolecular hydrophobic associations, as the solution viscosity of the copolymers increased sharply with increasing polymer concentration, especially above a critical overlap concentration. An almost shear‐rate‐independent viscosity (Newtonian plateau) was also displayed at high shear rates, and typical non‐Newtonian shear‐thinning behavior was exhibited at low shear rates and high temperatures. Furthermore, the copolymers exhibited high air–water and oil–water interfacial activities, as the surface and interfacial tensions decreased with increasing polymer concentration and salinity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2290–2300, 2003     

Facile preparation and potential application of water‐soluble polymeric temperature/pH probes bearing fluorescein

An unsaturated monomer bearing xanthene groups and allyloxyfluorescein (Al‐Flu), was synthesized from fluorescein and allyl bromide by etherification. The structure of the monomer was confirmed by IR and mass spectroscopy and ¹H‐NMR, and ¹³C‐NMR spectroscopy. With azobisisobutyronitrile as a thermal initiator in tetrahydrofuran under 65–70°C, a copolymer of allyloxyfluorescein and acrylamide [poly(Al‐Flu‐co‐AM)] was obtained and was characterized by the methods of IR spectroscopy, ultraviolet–visible spectroscopy, and differential scanning calorimetry. The experimental results show that the fluorescence spectra of water‐soluble poly(Al‐Flu‐co‐AM) was dependent on the pH and temperature in the solution. Moreover, poly(Al‐Flu‐co‐AM) had an excellent linear response between the relative fluorescence intensity and temperature in the range 0–60°C and had a nonlinear response from pH 0.00 to 12.85 between the relative fluorescence intensity and pH. The pH and temperature sensitivities of the fluorescence could be advantageous for it as a multifunctional material to probe pH and temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Functional water‐soluble polymers: polymer–metal ion removal and biocide properties

Water‐soluble polymers have attracted much interest due to their potential applications in environmental protection engineering to remove harmful pollutants and in biomedicine in the areas of tissue engineering, within‐body implants or other medical devices, artificial organ prostheses, ophthalmology, dentistry, bone repair, and so on. In this review, particular emphasis is given to the ability of water‐soluble polymers with amine, amide, carboxylic acid, hydroxyl and sulfonic acid functional groups to remove metal ions by means of the liquid‐phase polymer‐based retention (LPR) technique that combines the use of water‐soluble polymers and ultrafiltration membranes. The second part is dedicated to showing the potential application of functional water‐soluble polymers and their polymer–metal complexes as biocides for various bacteria. These polymers and polymer–metal complexes show an efficient bactericide activity, especially to Gram‐negative bacteria, Staphylococcus aureus reaching concentrations lower than 4 µg mL^?1. This activity depends on polymer size, type of metal ion, contact time and concentration of polymer and metal ion. The discussion reveals that in the case of the LPR process the efficiency of metal ion removal depends strongly on the type of polymer functional group and the feed pH value. In general, two mechanisms of ion entrapment are suggested: complex formation and electrostatic interaction. In the case of the medical use of water‐soluble polymers and their complexes with metal ions, the review documents the unique bactericide properties of the investigated species. The polymer‐metal ion complexes show a reduced genotoxic activity compared with free metal ions. Copyright © 2009 Society of Chemical Industry     

Thermo‐ and pH‐ responsive copolymers: Poly(n‐Isopropylacrylamide‐co‐IAM) copolymers

Poly(N‐isopropylacrylamide) (NIPAAm) is well known as a smart material with good thermal sensitivity and favorable biocompatibility. A series of new smart hydrogels, NIPAAm copolymerized with IAM (itaconamic acid; 4‐amino‐2‐methylene‐4‐oxobutanoic acid), were synthesized through radical solution polymerization in this work. Poly(NIPAAm‐co‐IAM) can respond to the changes of temperature as well as pH value. Such a characteristic is due to the fact that IAM contains not only a hydrophilic acrylic acid moiety but also an acrylamide moiety to be thermal and pH sensitive. The experimental results show that the lower critical solution temperature (LCST) of the copolymer increases as the molar fraction of IAM increases. Moreover, based on the current experimental data, 3 wt % of Poly(NIPAAm‐co‐IAM) aqueous solution in this study exhibits a phase transition temperature (37.8°C) close to the human body temperature in the buffer solution of pH 7 possibly to be useful in drug delivery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42367.     

Synthesis and characterization of novel water‐soluble polyesters for electrical insulation

Polyesters based on poly(alkyl anhydride), aromatic anhydrides, and polyglycols were synthesized by thermal and catalytic condensation polymerization techniques. The polymerization conditions were optimized by the variation of the monomer concentration, reaction temperature, and so on to achieve the desired properties. The reaction was monitored by the measurement of the acid values at different stages of the polymerization reaction. The water solubility of these polyesters was achieved by the termination of the reaction with the addition of ammonia. These polyester resins were characterized with IR and viscosity measurements. The electrical properties of polyester resins coated and cured on glass cloth were measured with the idea of using them as impregnating varnishes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

A water‐soluble self‐doped conducting polypyrrole‐based copolymer

A water‐soluble self‐doped conducting polypyrrole‐based copolymer was synthesized via the grafting of pyrrole onto the p‐aminodiphenylamine moieties of a water‐soluble copolymer. The conductive copolymer exhibited a conductivity as large as 3.4 S/cm. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 86–89, 2001     

Removal of metal ions by water‐soluble polymacromonomers in conjunction with ultrafiltration membrane

The macromonomer polyethylene glycol methylether methacrylate was homo‐ and copolymerized with 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid under three feed monomer ratios. The initiator used was ammonium peroxydisulfate (0.2 mol %). All the polymers were completely soluble in water. The copolymer composition was determined by elemental analysis. The metal ion interaction capability of the three polymers was investigated through the liquid‐phase polymer‐based retention (LPR) technique at different values of pH and filtration factor Z. The highest metal ion retention ability was observed at pH 5.0. The homopolymer showed a high selectivity for Ni(II) ions at pH 3.0. The copolymers (PEGMEM)_1.51‐co‐(APSA)_1.00 and (PEGMEM)_1.00‐co‐(APSA)_1.95 showed a high selectivity for Cr(III) ions at pH 3.0. The maximum retention capacity, in general, was similar for the homo‐ and copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2955–2960, 2004     

Metal ion binding capability of the water‐soluble poly(vinyl phosphonic acid) for mono‐, di‐, and trivalent cations

A water‐soluble polymer containing phosphonic acid groups was investigated as a polychelatogen by using the liquid‐phase polymer‐based retention technique (LPR) under different experimental conditions. The maximum retention capacity of this polymer was determined at different pHs and polymer–metal ion ratios. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), and Cr(III). The maximum retention capacity values of the divalent metal ions were very similar and higher than those for the trivalent cations, indicating that the polymer–metal ion interaction was basically through electrostatic type. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2917–2922, 2004     

Direct formation of emulsions using water‐soluble porous polymers as sacrificial scaffolds

BACKGROUND: Emulsions are traditionally formed from two immiscible liquids by mechanical stirring, homogenization, or ultrasonication. For the use of emulsions, stability during storage and transport has been an issue which needs to be addressed. Here, a novel method is proposed to form emulsions instantly by hand shaking from porous polymeric materials. RESULTS: The porous materials were prepared by a freeze‐drying method and then soaked in an oil phase. The oil was absorbed into the micron‐sized pores. The oil‐soaked composites were then placed in water. The dissolution of polymer led to the formation of emulsions by gentle hand shaking within 2 min. Mineral oil, soy oil with drug molecules, and perfluorodecalin were tested as the model oil phases. In each case, stable emulsions with high ratios of oil to water were formed instantly. CONCLUSIONS: A novel route is reported to produce emulsions instantly by hand shaking from porous polymeric materials. Using this method, emulsions could be formed instantly on the site just before application, thus avoiding the cost and stability concerns during transport and storage of emulsions. The method also has the advantages of easy operation and scale‐up possibility. Copyright © 2010 Society of Chemical Industry     

Synthesis and characterization of a water‐soluble sulfonates copolymer of acrylamide and N‐allylbenzamide as enhanced oil recovery chemical

A novel water‐soluble polymer was prepared by copolymerization and sulfomethylation using acrylamide (AM) and N‐allylbenzamide (NABI) as raw materials under mild conditions. The effects of ratio of AM to NABI, initiator concentration, reaction temperature, pH, and monomer concentration on the copolymerization were studied. The sulfonates copolymer was characterized by infrared (IR) spectroscopy, ¹H NMR spectroscopy, elemental analysis, and atomic force microscopy (AFM). It was found that the sulfonates copolymer could achieve up to 25%, 30% retention rate of the viscosity at a high temperature (120°C) and a vigorous shear condition (1000 s^?1). It was also found that the sulfonates copolymer had moderate salt tolerance (NaCl, CaCl₂, and MgCl₂·6H₂O) and its viscosity could be restored to the original value when the shear rate changed from 170 to 510 s^?1 and 510 to 170 s^?1. At last, the enhanced oil recovery (EOR) of the sulfonates copolymer was tested by core flood, and with up to 10.6% EOR was afforded in presence of 5000 mg/L NaCl brine at 60°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Star poly(2‐ethyl‐2‐oxazoline)s—synthesis and thermosensitivity

A series of star‐shaped poly(2‐ethyl‐2‐oxazoline)s was prepared by cationic polymerization. The polymerization was initiated by dipentaerythrityl hexakis(4‐nitrobenzene sulfonate) and a tosylated hyperbranched polymer of glycidol. The polymerization proceeded in a controlled manner. The star structure of the products was determined by nuclear magnetic resonance. The molar mass distributions that were measured by gel permeation chromatography with multiangle laser light scattering were narrow, and the experimental values of the molar masses were close to those predicted. The very compact structure of the polymers obtained (compared with the linear counterparts) confirmed the star formation. The star poly(2‐ethyl‐2‐oxazoline)s show a phase transition temperature in the range 62–75 °C. Comparison of this phase transition temperature with that of the linear poly(2‐ethyl‐2‐oxazoline)s with the same molar masses indicates the influence of molar mass and topological structure of the macromolecule on temperature behavior. The prepared copolymers are spherical, which might be useful for the controlled transport and release of active compounds. Copyright © 2011 Society of Chemical Industry     

Preparation and anti‐clay‐swelling ability of new water‐soluble cellulose derivatives containing quaternary ammonium groups

New water‐soluble cellulose derivatives containing quaternary ammonium groups were prepared by the heterogeneous reactions of hydroxyethyl cellulose with a quaternary chlorohydrin and characterized by reaction parameters and infrared analyses. The dependence of the heterogeneous reaction on the different affecting factors was studied. The cellulose derivatives obtained were investigated for their property as the water‐soluble polymer for inhibiting the swelling of water‐sensitive clay in oilfields. Based on the kinetic curves for clay hydration swelling, a mathematical model that relates linear clay expansion as a function of hydration rate and hydration equilibrium constant was developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1416–1422, 2001