New copper(II) complexes of polyampholyte and polyelectrolyte polymers: Solid-state NMR, FTIR, XRPD and thermal analyses

Novel solid copper(II) complexes were obtained from the polyampholyte poly(EGDE-MAA-IM) and the polyelectrolyte poly(EGDE-MAA) polymers with copper salts at different concentration levels.The materials were characterized employing solid-state Nuclear Magnetic Resonance (NMR), Fourier Transform infrared (FTIR), X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC) and thermogravimetry (TG).The reticulation induced by MAA in these materials against the poly(EGDE-IM) gel was analyzed by DSC. The coordination behavior of the carboxylic acid of MAA, compared to that provided by the imidazole ring, was studied through solid-state ¹³C NMR and changes in the FTIR spectra. The non-homogenous character of the doped and undoped materials was analyzed by the glass transition temperature (T_g), 2D ¹H-¹³C WISE NMR and proton spin-lattice relaxation time in the rotating frame (T^H_1ρ). In particular, the T^H_1ρ and T^H₁ values in the complexes decreased with the Cu(II) concentration, showing the high sensitivity of both parameters to the presence of a paramagnetic ion. Finally, the thermogravimetric studies indicated that the presence of the imidazole ring was decisive for the stability of the Cu(II) complexes and for the undoped polymers.     

Metal ion retention properties of water‐insoluble polymers containing carboxylic acid groups

Crosslinked poly(acrylic acid), PAA, and poly(2‐acrylamidoglycolic acid), PAAG, were synthesized by radical polymerization. Both resins contain carboxylic acid groups. PAA at basic pH exists basically as an acrylate anion and PAAG shows three atoms or groups, carboxylic acid, hydroxyl, and amide groups, that can act as ion exchanger or chelating groups. Both resins are studied as adsorbents to trace metal ions from saline aqueous solutions and natural sea water and their properties by Batch equilibrium procedure are compared. The metal ions studied under competitive and noncompetitive conditions were Cu(II), Pb(II), Cd(II), and Ni(II). The effects of pH, time of contact, amount of resin, temperature, and salinity were studied. Resin PAA shows a high affinity (>80%) for Cu(II) and Cd(II) and resin PAAG shows also a high affinity for Ni(II), Pb(II), and Cd(II). By treatment of the metal ion‐loaded resin with 4M HNO₃ it is possible to recover completely the Cu(II) ions from resin PAA and Ni(II) and Pb(II) from resin PAAG. The metal ion retention properties were studied with natural sea water. For those natural sea waters containing Cu(II) and Cd(II), the resins showed a high affinity for Cd(II) ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 697–705, 2006     

Metal ion interaction of water‐soluble copolymers containing carboxylic acid groups in aqueous phase by membrane filtration technique

This article reports the synthesis of poly(N‐maleoylglycine‐co‐itaconic acid) by radical copolymerization under different feed mole ratios and its properties to remove various metal ions, such as Cu(II), Cr(III), Co(II), Zn(II), Ni(II), Pb(II), Cd(II), and Fe(III), in aqueous phase with the liquid‐phase polymer‐based retention(LPR) technique. The interactions of inorganic ions with the hydrophilic water‐soluble polymer were determined as a function of pH and filtration factor. Metal ion retention was found to strongly depend on the pH. Metal ion retention increased as pH and MG content units in the macromolecular backbone increased. The copolymers were characterized by elemental analysis, FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Additionally, intrinsic viscosity, molecular weight, and polydispersity have been determined for the copolymers. Copolymer and polymer–metal complex thermal behavior was studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques under nitrogen atmosphere. The thermal decomposition temperatures (TDT) were influenced by the copolymer composition. The copolymers present lower TDT than the polymer–metal complex with the same copolymer composition. All copolymers present a single T_g, indicating the formation of random copolymers. A slight deviation of the T_g for the copolymers and its complexes can be observed. The copolymer T_g is higher than the T_g value for the polymer–metal complexes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation of copper containing methacrylic polymers and their application for the copper patterns

Copper containing methacrylic polymers were prepared by the polymerization of a copper methacrylate complex (Cu[CH₂C(CH₃)COO](COD), where COD = 1,5-cyclooctadiene) with different methylmethacrylate and methacrylic acid compositions. These polymers were found to be soluble in many organic solvents including THF and chloroform. Copper nano-networks or aggregated nanoparticles were obtained when a THF solution of the polymers was reduced using an aqueous sodium borohydride solution. When a thin film of the polymers coated on a silicon wafer was irradiated with an electron beam, nanoparticles were produced on the irradiated area, while the non-irradiated areas could be washed away with a weak base developer, such as a tetramethylammoniumhydroxyde (TMAH) aqueous solution, to produce a copper pattern through an electron beam lithography process.     

Water‐insoluble polymers containing amine,sulfonic acid,and carboxylic acid groups: Synthesis,characterization, and metal‐ion‐retention properties

Crosslinked poly(acryloylmorpholine) and its copolymers poly(acryloyl morpholine‐co‐acrylic acid) and poly(acryloylmorpholine‐co‐2‐acrylamide‐2‐methyl‐1‐propane sulfonic acid) were synthesized by radical polymerization. The resins were completely insoluble in water and were characterized with Fourier transform infrared spectroscopy and thermal analysis. The metal ions Ag(I), Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), Al(III), and Cr(III) were investigated under competitive and noncompetitive conditions by a batch equilibrium procedure. The resin‐metal‐ion equilibrium was achieved before 5 min. The recovery of the resin was investigated at 20°C with different concentrations of HNO₃ and HClO₄. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3266–3274, 2006     

Water remaining properties of nonwoven fabrics treated with the polyurethane polymers containing carboxylic acid group and the thermal and structural characterization of the polymers

Three low‐molecular‐weight polyurethanes (LMWPU) containing various amounts of carboxylic acid were synthesized and applied on the nonwoven fabric for the improvement of water remaining property. The chemical structure of the LMWPUs was confirmed with ¹H‐NMR and ¹³C‐NMR. The molecular weights of those three LMWPUs ranged from 3100 to 4200 g/mol. The results showed that the add‐on values were increased with the increasing of the content of 2,2‐bis(hydroxymethyl)propionic acid in LMWPU at a same resin concentration in padding bath. However, the water remaining values were decreased with the increasing of the content of 2,2‐bis(hydroxymethyl)propionic acid in LMWPU for a given add‐on value. The thermal properties, such as thermo‐degradation and the values of T_g and T_m of the polymers, could not affect the water remaining property of the treated fabrics. The analyses of X‐ray diffraction patterns and polarizing microscope observations showed that LMWPU with higher content of polytetramethyleneglycol had higher amorphous region. This phenomenon clearly supported that the values of water remaining were strongly affected by the amorphous region of the LMWPU polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and heavy metal ion adsorptivity of macroreticular chelating resins containing phosphono and carboxylic acid groups

Macroreticular copolymer beads were prepared by suspension polymerization of 4-vinylbenzyl chloride (VBC), divinylbenzene (DVB) and monomers with carboxylic ester groups like dibutyl maleate (DBM), dibutyl fumarate (DBF) and dibutyl itaconate (DBI) in the presence of toluene as diluent. The copolymer beads were phosphorylated at the chloromethylated phenyl rings with triethyl phosphite and hydrolyzed by an aqueous sodium hydroxide solution; the hydrolysis on the bead surface converted carboxylic ester/phosphonate groups into carboxylic acid/phosphono groups, respectively. The investigations on the metal ion chelation characteristics of the H-form copolymer beads revealed that they have good adsorptivity toward heavy metal ions like Pb²⁺, Cd²⁺ and Cu²⁺, and poor adsorptivity toward ions like Hg²⁺ and UO₂²⁺. The adsorptivity caused by the three carboxylic ester monomer derivatives was in the order DBM > DBI > DBF. Especially, the Na-form copolymer beads neutralized by alkali treatment were very available for the adsorption of all the metal ions under investigation.     

Preparation and adsorption properties of the chelating resins containing carboxylic,sulfonic, and imidazole groups

The crosslinked poly(1‐vinylimidazole‐co‐acrylic acid), P(VIm‐co‐AA), and poly(1‐vinylimidazole‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) P(VIm‐co‐APSA) were synthesized by radical polymerization and tested as adsorbents under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) by batch equilibrium procedure. The resin–metal ion equilibrium was achieved before 1 h. The resin P(VIm‐co‐AA) showed a maximum retention capacity (MRC) value for Pb(II) at pH 3 and Hg(II) at pH 1 of 1.1 and 1.2 mEq/g, respectively, and the resin P(VIm‐co‐AA) showed at pH 3 the following MRC values: Hg(II) (1.5 mEq/g), Cd(II) (1.9 mEq/g), Zn(II) (2.7 mEq/g), and Cr(III) (2.8 mEq/g). The recovery of the resin was investigated at 25°C with 1 M and 4 M HNO₃ and 1 M and 4 M HClO₄. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2852–2856, 2003     

Resins containing amino and carboxylic acid groups. Synthesis,characterization, and metal ion retention properties

The crosslinked poly[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide], P(MAPDSA), and poly[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide‐co‐acrylic acid], P(MAPDSA‐co‐AA), were synthesized by radical polymerization. The resins were completely insoluble in water. Due to the lower metal ion retention of P(MAPDSA), the metal ions investigated under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) ions by batch and column equilibrium procedures were carried out only for P(MAPDA‐co‐AA), particularly for Hg(II). The resin–Hg(II) ion equilibrium was achieved before 15 min. The resin showed a maximum retention capacity value for Hg(II) at pH 2 of 1.89 meq/g. The resin showed a high selectivity to Hg(II) ions. The recovery of the resin was investigated at 25°C with different concentrations of HNO₃ and HClO₄. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 525–530, 2005     

Copolymers of N-vinylcarbazole with monomers containing carboxylic acid groups or carboxylic anhydride groups. II. Photoconductivity and composition

Copolymers of N-vinylcarbazole containing olefinic monomers that possess carboxylic acid or anhydride functionality have been produced. The photoconductive properties of the copolymers were measured. Fluorimetry has been used to relate this photoconductivity to the copolymer composition. Photoconductivity was greatest in copolymers containing high percentages of vinylcarbazole. It is suggested that this is due to block copolymer formation, since the development of such blocks allows greater interchromophore overlap than would be possible with alternating copolymers, which exhibit low photoconductivity.     

Synthesis and characterization of coordination polymers of polyesters with pendant amino groups

Oligomeric polyester, namely, poly(tetramethylene aspartate) (PTMA), was synthesized from D ,L -aspartic acid and 1,4-butanediol by a melt-condensation technique. Polyester–metal complexes were synthesized by the reaction of PTMA with hydrated acetates of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Mg(II), Ca(II), Pb(II), and Ce(IV) in DMSO. The polyester–metal complexes were characterized by elemental analysis, IR spectral studies, magnetic susceptibility measurements, and thermogravimetry. The metal ions were found to be six-coordinated with two water molecules as additional ligands besides oxygen and nitrogen atoms of polyester repeating units. Thermogravimetric analysis (TGA) showed that coordination polymers are thermally more stable than is polyester. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 751–759, 1998     

The influence of the ion-exchange groups nature and the degree of chemical activation by silver on the process of copper electrodeposition into the ion exchanger

The electrodeposition of copper into ion-exchange materials with different ionogenic groups is studied. We have worked out that the discharge of copper counterions in an ion-exchange matrix is characterized by a cathodic overvoltage that is higher than the overvoltage of the same process on a graphite substrate by 0.08 V, which is most probably connected with a limited mobility of counterions localized at ionogenic groups. It has been observed microscopically that the process of deposition begins at the graphite substrate/ion exchanger interface and passes into the volume of a polymeric matrix with the filling of nanodimensional pores by copper. Preliminary doping of the ion exchanger by silver leads to the jump of the deposition current of copper counterions that is caused by the appearance of sufficient electron conductivity of the doped polymeric matrix. The data of the local X-ray spectral microanalysis confirm the regular deposition of copper into the volume of an ion exchanger grain doped by silver.     

Preparation and adsorption properties of resins containing amine,sulfonic acid,and carboxylic acid moieties

Completely water‐insoluble resins containing amine, carboxylic acid, and sulfonic acid as ligand groups were synthesized by radical polymerization in solution. The yield was higher than 97%. The resins were characterized by FTIR spectroscopy and thermal analysis. The metal ion retention properties at different pH values were investigated by a batch method. Metal ions studied were: Cu(II), Cd(II), Zn(II), Hg(II), Pb(II), and Cr(III). The metal ion binding ability depended strongly on the pH. The retention properties were also tested under competitive conditions. Elution of the metal ion was investigated in acid medium at different concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 700–705, 2003     

Swelling properties of copolymers of styrene and divinylbenzene containing sulfonic and carboxylic acid groups

Copolymers of styrene, divinylbenzene, and acrylic acid that have undergone sulfonation exhibited good water absorbency properties. Removal of the lower molecular weight fraction in the surface region of the copolymer particles by toluene extraction before sulfonation has further increased the water swelling capacity of the sulfonated copolymers. The extent of swelling of the UV‐irradiated copolymer could be related to the ratio of divinylbenzene to styrene. The less crosslinked copolymers were shown to absorb more water. The incorporation of more carboxylate groups in the copolymer could further increase its swelling capacity. Without UV irradiation, the carboxylate containing copolymer was found to absorb more water than the sulfonated copolymer. UV irradiation has induced more effective crosslinking in the carboxylate containing copolymer, hence impairing its water absorbency. By replacing styrene and divinylbenzene partially with butyl acrylate, whereby the amount of crosslinking was reduced, the copolymer was able to absorb water 110 times of its dry weight. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of water‐insoluble functional copolymers containing amide,amine, and carboxylic acid groups and their metal‐ion‐uptake properties

The crosslinked poly[N‐(3‐dimethylamino)propylmethacrylamide] [P(NDAPA)] and poly[N‐(3‐dimethylamino)propylmethacrylamide‐co‐acrylic acid] [P(NDAPA‐co‐AA)] were synthesized by radical polymerization. The resins were completely insoluble in water. The metal‐ion‐uptake properties were studied by a batch equilibrium procedure for the following metal ions: silver(I), copper(II), cadmium(II), zinc(II), lead(II), mercury(II), chromium(III), and aluminum(III). The P(NDAPA‐co‐AA) resin showed a lower metal‐ion affinity than P(NDAPA), except for Hg(II), which was retained at 71% at pH 2. At pH 5, the resin showed a higher affinity for Pb(II) (80%) and Cu(II) (60%), but its affinity was very low for Zn(II) and Cr(III). The polymer ligand–metal‐ion equilibrium was achieved during the first 20 min. By changing the pH, we found it possible to remove between 60 and 70% of Cd(II) and Zn(II) ions with (1M, 4M) HClO₄ and (1M, 4M) HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5232–5239, 2006     

Structures and photoluminescence of coordination polymers assembled from bifunctional ligand containing both tetrazole and imidazole groups

Three new coordination polymers, namely, {[Cu₂(IPT)(SO₄)(OH)(H₂O)]·H₂O}_n (HIPT = 5-(4-(1H-imidazol-1-yl)phenyl)- 1H-tetrazolate, 1), {[Cd₂(IPT)(NPA)(OH)]·H₂O}_n (H₂NPA = 5-nitroisophthalic acid, 2), and {[Zn₂(IPT)(IDC)(H₂O)]·3H₂O}_n (H₃IDC = 1H-imidazole-4,5-dicarboxylic acid, 3), were assembled from a bifunctional organic ligand containing both tetrazole and imidazole groups with/without the aid of carboxylate coligands. Compound 1 possesses 2D structure built by 1D [Cu₂(IPT)(SO₄)(OH)]_n secondary building blocks and IPT⁻ linkers. The 2D networks are linked into 3D supramolecular framework via water chains in helical conformation. Compound 2 displays 3D pillar-layer framework with 2D layers based on tetranuclear Cd(II) SBUs and NPA^2 − pillars. Compound 3 exhibits a 3D framework constructed from the interconnection of 1D [Zn-IDC]_n chains and binuclear Zn₂(IPT)₂ rings. The thermal stabilities of porous compound 3 and luminescent properties of compounds 2 and 3 have also been studied in detail. They exhibit intense solid-state fluorescent emissions at room temperature.     

Preparation and metal ion adsorption properties of the resin containing sulfonic acid groups

In this study, we explored a new ion exchange material synthesized by radical polymerization of styrene and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid by using 2,2′‐azo‐isobutyronitrile (1 mol %) and divinylbenzene (0.5 mol %) as initiator and crosslinking reagents, respectively. The resin was obtained from a large excess (90%) of styrene in the feed. The yield was 72.3%. The resin was completely insoluble in water and characterized by elemental analysis, FTIR spectroscopy, scanning electron microscopy, and thermal analysis. The metal ion retention capability was investigated for Ag(I), Hg(II), Cd(II), Zn(II), Pb(II), and Cr(III). The effect of pH, time, and resin/metal ion mol ratio on the metal ion retention was studied. Selectivity of the resins from a mixture of metal ions and the maximum retention capacity at optimum pH were also determined. The recovery of the resin by using 1 and 4 M HClO₄ and HNO₃ demonstrated that it is possible to recover the resin above 80%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1230–1235, 2003     

Synthesis and characterization of resins with ligands containing guanidinine derivatives. Cu(II) sorption and coordination properties

A new modification direction of acrylonitrile, vinyl acetate and divinylbenzene terpolymers (A, B) are presented. The aminolysis of nitrile groups of the terpolymers using ethylenediamine or hydroxylamine hydrochloride was a first stage of the modification. The resulting amine groups reacted with dicyandiamide (DCDA), cyanamide (CA) and sodium dicyanimide (SDC) in order to obtain the biguanidyl, guanidyl or nitrilguanidyl derivatives in the polymer side chain, respectively. The properties of all obtained resin such as water regain, nitrogen content, amine and carboxyl group concentration and sorption properties towards Cu(II) from nitric acid solutions were determined. The studies of IR spectra of all the resins were performed. Structures of ligand complexes with Cu(II) were studied using electron paramagnetic resonance spectroscopy.     

A novel route for the preparation of hybrid zwitterionic membranes containing both sulfonic and carboxylic acid groups

A novel route for the preparation of hybrid zwitterionic membranes containing both sulfonic and carboxylic acid groups is reported. Based on this synthetic methodology, a series of membranes were synthesized via sol–gel reaction, zwitterionization process, and the oxidization of the  SH group. FTIR spectra confirmed the corresponding reactions. The properties of these prepared membranes were characterized by ion-exchange capacity (IEC), water content, and pure water flux, etc. The anion-exchange capacity (AIEC), total cation-exchange capacity (CIEC_total), and the CIEC of the sulfonic groups (CIEC_sulf) of the membranes coated for 1–3 times were in the range of 0.017–0.12, 0.1–0.53, and 0.029–0.14 mmol g⁻¹, respectively. The measurement of water content showed that it was independent of pH values whether for the membranes coated once or twice. Pure water flux revealed a downward trend with the increased coating times. The surface SEM images of the produced membranes exhibited that these membranes' textures could be affected highly by the curing temperature, and excessively higher curing temperature would lead the membranes to brittle and chasm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

含有磺酸和羧酸基团的水性聚氨酯的研究

以聚氧化丙烯二醇(N210)和2,4-甲苯二异氰酸酯(TDI)为原料,通过逐步加聚反应,合成了聚氨酯预聚体;再以羧酸型亲水扩链剂二羟甲基丙酸(DMPA)和自制的磺酸型亲水扩链剂1,2-二羟基-3-丙磺酸钠(DHPA),通过扩链反应,制备了兼有磺酸盐和羧酸盐的水性聚氨酯乳液,烘干制胶膜,并对胶膜进行了红外光谱的表征以及耐水性能和力学性能的测试和分析;测定了乳液的固含量,重点研究了R值,亲水基团含量(DMPA和DHPA在预聚体中的百分含量)和DHPA在亲水基团中的含量对胶膜力学性能的影响。研究结果表明,通过逐步加聚和扩链反应,可成功地制得固含量高达70％的,兼有磺酸和羧酸的水性聚氨酯乳液;且当R值(NCO／OH)为2,亲水基团含量为5％,DHPA在亲水基团中的含量为20％时,胶膜的综合力学性能优良(断裂伸长率高达2 135％)。