Polymers based on divalent metal salts of mono(hydroxyethyl) phthalate—a review

Divalent metal salts of mono(hydroxyethyl) phthalate are useful starting materials for synthesis of ionic polymers into which metal is firmly incorporated. This article surveys a series of polymers that have been synthesized by using metal salts. The salts can react with compounds having functional groups capable of reacting with hydroxyl groups. By polyaddition reactions of the salt-diol with diisocyanates in dimethylformamide, metal-containing polyurethanes, polyurethane-ureas, and isocyanurate-type crosslinked polyurethanes are obtained. In polycondensation reactions of the salt-diols with anhydrides, some systems give unsaturated polyesters soluble in styrene. Meanwhile, polyaddition reactions of systems of the salt-anhydride-epoxide give metal-containing polyesters containing ionic links in the main chain. The metal carboxylate groups of the salts catalyze the reactions in this case. The reactions have offered a commercially favorable synthetic route. Through the proper selection of components, various types of metal-containing unsaturated polyesters, cured resins, and cured rubbers are obtained. The effect of introducing metal on their physical and other properties results, and, in addition, generally Mg is more effective than Ca in improving the properties of the polymers.     

Crosslinking of polypropylene glycol with divalent metal salts of mono(hydroxyethyl) phthalate,anhydride, and bisepoxide

Crosslinking of polypropylene glycol with divalent metal salts of mono(hydroxyethyl) phthalate, anhydride, and bisepoxide is investigated. The anhydride and bisepoxide were hexahydrophthalic anhydride and bisphenol A diglycidyl ether. The metal carboxylate groups catalyzed the crosslinking reactions. The Mg carboxylate group showed higher catalytic activities than the Ca carboxylate group. The rubbers containing Mg showed much better physical properties than those containing Ca, due to higher interionic attraction of Mg⁺⁺ and better homogeneity. In addition, tensile strength of the cured rubbers at about the same soft block contents depended largely upon that of the hard block. Resistances to water and chemical attack, stress–relaxation, and thermal behavior are also discussed.     

Crosslinking of poly(ethylene glycol) with divalent metal salts of mono(hydroxyethyl) phthalate,anhydride, and bisepoxide

Poly(ethylene glycol)s (PEG) were crosslinked with divalent metal salts of mono(hydroxyethyl) phthalate, anhydride, and bisepoxide to give metal-containing cured rubbers. As the anhydride, hexahydrophthalic anhydride was used, and bisphenol A diglycidyl ether was the bisepoxide used. As for the physical properties of the cured rubbers obtained, the rubbers containing Mg showed much better physical properties than those containing Ca. In addition, the rubbers with high hard block contents and high overall crosslinking densities exhibited high tensile strength and Shore A hardness, and so did the rubbers having a high degree of crystallinity of the PEG soft block. The occurrence of crystallization became easy as the soft block length became longer and the soft block content became higher, or as the crosslinking density of the hard block became lower. The PEG-based rubbers showed much higher water absorption than the previously reported poly(propylene glycol)-based rubbers, due to the much higher hydrophilicity of the PEG block. Resistance to chemical attack and stress–relaxation are also discussed.     

Crosslinking of hydroxyl-terminated liquid rubber with divalent metal salts of mono(hydroxyethyl) phthalate,anhydrides, and bisepoxide

Crosslinking of hydroxyl-terminated liquid rubber with divalent metal salts of mono(hydroxyethyl) phthalate, anhydrides and bisepoxide was investigated by the diols-anhydridesbisepoxide, reactions. As the anhydride, succinic anhydride and hexahydrophthalic anhydride were used, and bisphenol A diglycidyl ether was the bisepoxide used. The metal carboxylate groups of these metal salts catalyzed the crosslinking reactions and, further, the Mg salt showed higher catalytic activities than the Ca salt. As for the physical properties of the metal-containing cured rubbers obtained, tensile strength and Shore A hardness increased with increase in the metal salt content. In addition, the rubbers containing Mg showed better physical properties than those containing Ca. Meanwhile, elongation showed a maximum with increase in the metal salt content. Resistance; to water and chemical attack, thermal behavior, and stress relaxation are also discussed.     

Synthesis of some new divalent metal salts of mono(hydroxyethyl)phthalate

Summary Divalent metal salts of mono(hydroxyethyl)phthalate (HEP) were considered to be of interest as difunctional ionic monomers and are useful for the preparation of condensation polymers. Recently, Matsuda¹ reported the preparation of Ca, Mg and Zn salts of mono-(hydroxyethyl)phthalate and their polymers^2–7. He prepared these salts by the reaction of HEP with the respective divalent metal oxides. But so far there was no report on the preparation of Pb²⁺ and Mn²⁺ salts of HEP. Since metal dicarboxylates can be obtained by the reaction of organic dibasic acids and metal acetates⁸, Pb²⁺ and Mn²⁺ acetates can similarly react with HEP to give their respective salts at the optimum temperature. We report here the synthesis and characterisation of Pb²⁺ and Mn²⁺ salts of mono(hydroxyethyl)-phthalate (HEP).     

Adhesives from divalent metal salts of mono(hydroxyethyl)phthalate,anhydrides, and bisepoxides

Systems of divalent metal salts of mono(ydroxyethyl)phthalate-anhydride-bisepoxide were evaluated as adhesives. The bisepoxides, bisphenol A diglycidyl ether (BADG) and hexahydrophthalic acid diglycidyl ester and the anhydrides, maleic anhydride and hexahydrophthalic anhydride (HPA) were used. The adhesive properties of the above metal-containing systems were generally superior to those of the systems not containing metal, due to the polarity effect of metal carboxylate groups. The effect of introducing metal (ionic links) on tensile shear and peel strenghths clearly appeared, especially in the metal salt-HPA-BADG systems.     

Metal-containing cured polyesters from divalent metal salts of mono(hydroxyethyl) phthalate,bisester anhydrides,and monoepoxide

Synthesis of novel metal-containing cured polyesters was investigated by the reaction of divalent metal salts of mono(hydroxyethyl) phthalate–bisester anhydride–monoepoxide. As the bisester anhydride, ethylene glycol bis(trimellitate) dianhydride (ETDA), diethylene glycol bis(trimellitate) dianhydride (DETDA), and polyethylene glycol bis(trimellitate) dianhydride (PETDA) were used. They were prepared from trimellitic anhydride and glycols. Phenyl glycidyl ether was the monoepoxide used. In the reactions, the Mg salt showed considerably higher catalytic activities than the Ca salt. As for the physical properties of the cured resins, heat distortion temperature, Rockwell hardness, and compressive strength decreased in the order ETDA > DETDA > PETDA. Generally, the resins containing Mg showed better physical properties than those containing Ca. Resistance to chemical attack and boiling water, thermal behavior, and electrical resistances are also discussed.     

Synthesis of metal-containing cured resins from divalent metal salts of mono(hydroxyethyl) phthalate,anhydrides, and bisepoxides

Synthesis of novel metal-containing cured resins based on divalent metal salts of mono(hydroxyethyl) phthalate were investigated by the metal salt–anhydride–bisepoxide reactions. As the anhydrides, maleic anhydride (MA) and hexahydrophthalic anhydride (HPA) were used, and hexahydrophthalic acid diglycidyl ester (HPDG), bisphenol A diglycidyl ether (BADG), and ethylene glycol bis(glycidyl phthalate) (EBGP) were the bisepoxides used. The reactions were further studied in model reactions using the Ca salt of monoethyl phthalate. The metal carboxylate groups of the metal salts catalyzed the reactions. The reactivity of the bisepoxides decreased in the order HPDG ? BADG > EBGP, and MA was more reactive than HPA. Some of the metal-containing cured resins obtained showed excellent physical properties. Resistance to chemical attack and boiling water, thermal behavior, and electrical resistance are also discussed.     

Adhesive properties of systems of partially neutralized carboxyl-terminated liquid rubber–anhydride–bisepoxide

Systems of partially neutralized carboxyl-terminated liquid rubber (PNCTLR)-anhydride–bisepoxide were evaluated for adhesive properties. The PNCTLRs were prepared by the partial neutralization with MgO and CaO from a polymer of butadiene (BD) (Hycar CTB 2000X162) and copolymers of BD–acrylonitrile (Hycar CTBN 1300X8 and CTBNX 1300X9). As the bisepoxide, bisphenol A diglycidyl ether was used, and hexahydrophthalic anhydride was the anhydride used. The adhesive properties of the metal-containing systems were superior to those of the reference systems not containing metal, owing to the polarity effect of the metal carboxylate groups. Further, the CTBN- and CTBNX-series systems showed higher tensile shear and peel strengths than the CTB-series systems, owing to the enhanced polarity effect of the nitrile groups.     

Synthesis of polymers by using divalent metal salts of mono(hydroxyethyl) phthalate: Unsaturated polyesters from metal salts,glycol, anhydrides,and epoxides

Syntheses of unsaturated polyesters were investigated by the divalent metal salts of mono(hydroxyethyl) phthalate–ethylene glycol–anhydrides–epoxide reactions. As anhydrides, phthalic anhydride and maleic anhydride were used, and propylene oxide and 1,2-butylene oxide were the epoxides used. The metal carboxylate groups of the above metal salts catalyzed the reaction. Viscosities of styrene solutions of the polyesters obtained showed a tendency to increase with increase in metal content. The styrene solutions could be cured to give metal-containing cured polyester resins. The cured resins were evaluated for physical properties. Generally, Mg was more effective than Ca in improving the physical properties. Further, resistance to chemical attack and boiling water and thermal behavior were also discussed.     

Studies on polyurethanes and polyurethane–ureas derived from divalent metal salts of mono(hydroxybutyl) hexolate

Divalent metal salts of mono(hydroxybutyl)hexolate [M(HBH)₂), M=Ca²⁺, Mn²⁺or Pb²⁺] were synthesized by the reaction of 1,4‐butanediol, 5,6,7,8,10,10‐hexachloro‐3a,4,4a,5,8,8a,9,9a‐octahydro‐5,8‐methanonaphtho‐[2,3‐C]‐furan‐1,3‐dione and divalent metal acetates. Hexamethylene bis [N′‐(1‐hydroxy‐2‐methyl‐prop‐2‐yl)urea] (HBHMPU) and tolylene 2,4‐bis[N ′‐(1‐hydroxy‐2‐methyl‐prop‐2‐yl)urea] (TBHMPU) were synthesized by reacting 2‐amino‐2‐methyl‐propan‐1‐ol with hexamethylene diisocyanate (HMDI) and tolylene 2,4‐diisocyanate (TDI), respectively, in toluene solvent. Flame‐retardant metal‐containing polyurethanes were synthesized by the solution polymerization of HMDI with M(HBH)₂ and the polyurethane–ureas by reacting HMDI with 1:1 mixture of M(HBH)₂ and HBHMPU or TBHMPU, respectively, in DMSO as solvent. The polymers have been characterized by elemental analysis, solubility, viscosity and IR and ¹H NMR spectroscopy. The thermal stability of the polymers has been studied by thermogravimetry. The flame‐retardant property of the polymers has been investigated by measuring limiting oxygen index values. © 2000 Society of Chemical Industry     

Preparation and copolymerization of divalent metal salts of ethylene glycol–methacrylate–phthalate

Divalent metal salts of ethylene glycol–methacrylate–phthalate (EMP) were prepared by the reaction of EMP and divalent metal ions in aqueous solution. The divalent metal salts obtained, except for the Pb salt, have melting points which decrease in the order of Ca > Ba > Mg > Zn > Cd salt. The Zn and Cd salts are fairly soluble in most organic solvents. Therefore, the Zn salt and Cd salt were selected for the copolymerization with MMA, styrene (St), and hydroxyethyl methacrylate (HEMA). In the copolymerization, the rates of copolymerization increased markedly as the concentration of metal salts increased. Moreover, the systems containing MMA copolymerized more rapidly than those containing St. As for the physical properties of the copolymers obtained, compressive strength and Rockwell hardness were improved by introducing metal salts into the polymers; and heat distortion temperature and tensile and flexural strengths were also improved by selecting the most suitable concentration of metal salts according to the species of metal salts and vinyl monomers. The TGA and the boiling water resistance of the copolymers were also discussed.     

Preparation and copolymerization of divalent metal salts of ethylene glycol–methacrylate–maleate

Divalent metal salts of ethylene glycol–methacrylate–maleate (EMM) were prepared by the reaction of EMM and divalent metal ions. The divalent metal salts obtained, except for the Ba salt, have melting points which decrease in the order Pb > Ca > Cd > Mg > Zn. The Mg and Ca salts were selected for the copolymerization with MMA, styrene (St), and hydroxyethyl methacrylate. In the copolymerization, the rates of copolymerization increased markedly as the concentration of metal salts increased. Moreover, the systems containing MMA copolymerized more rapidly than those containing St. As for the physical properties of the copolymers obtained, heat distortion temperature, compressive strength, and Rockwell hardness were improved by introducing metal salts into the polymers, and tensile, flexural, and impact strengths are also able to be improved by selecting the most suitable concentration of metal salts according to the species of metal salts and vinyl monomers. Generally, Mg is more effective than Ca in improving the physical properties of the copolymers. Moreover, TGA and boiling water resistance of the copolymers are also discussed.     

Poly(styrene‐alt‐maleic acid)–metal complexes with divalent metal ions. synthesis,characterization, and physical properties

Polymer–metal complexes of the alternating copolymer styrene and maleic acid with Cu(II), Co(II), Ni(II), and Zn(II) were synthesized and characterized by elemental analysis, infrarred and electronic spectra, and thermogravimetry. In addition, magnetic measurements were performed and the electrical conductivity was studied at different temperatures. Semiempirical calculations at the PM 3 level were carried out to elucidate the geometrical arrangement of the polychelates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1310–1315, 2001     

Time–temperature–transformation (TTT) cure diagrams: Relationship between Tg and the temperature and time of cure for epoxy systems

A procedure is provided for estimating the time to full cure vs. isothermal cure temperature for vitrified epoxy systems. An equation relating the glass transition temperature of vitrified epoxy systems to the time and temperature of cure is developed.     

Synthesis,characterization, and metal ions adsorption properties of chitosan–calixarenes (I)

Calixarene‐modified chitosans (CTS–CA‐I and CTS–CA‐II) were first synthesized by the reaction of chitosan (CTS‐NH₂) with 1,3‐bis‐chloroethoxyethoxy‐2,4‐dihydroxy‐p‐tert‐butylcalix[4]arene (CA‐I) or its benzoyl derivative (CA‐II). Their structures were characterized by infrared and X‐ray diffraction spectroscopy and scanning electron microscopy (SEM). The adsorption of Ni²⁺, Cd²⁺, Cu²⁺, Pd²⁺, Ag⁺, and Hg²⁺ by CTS–CA‐I and CTS–CA‐II was studied and the thermodynamic parameter of two calixarene‐modified chitosans toward Hg²⁺ was deduced. The adsorption properties of CTS–CA‐I and CTS–CA‐II were greatly varied compared with that CTS‐NH₂, especially with the adsorption capacity toward Ag⁺ and Hg²⁺, because of the presence of the calixarene moiety. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1139–1144, 2003     

Metal‐chelating properties of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) membranes

Metal‐chelating membranes have advantages as adsorbents in comparison with conventional beads because they are not compressible and they eliminate internal diffusion limitations. The aim of this study was to explore in detail the performance of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) [poly(HEMA–MAH)] membranes for the removal of three toxic heavy‐metal ions—Cd(II), Pb(II), and Hg(II)—from aquatic systems. The poly(HEMA–MAH) membranes were characterized with scanning electron microscopy and ¹H‐NMR spectroscopy. The adsorption capacity of the poly(HEMA–MAH) membranes for the selected heavy‐metal ions from aqueous media containing different amounts of these ions (30–500 mg/L) and at different pH values (3.0–7.0) was investigated. The adsorption capacity of the membranes increased with time during the first 60 min and then leveled off toward the equilibrium adsorption. The maximum amounts of the heavy‐metal ions adsorbed were 8.2, 31.5, and 23.2 mg/g for Cd(II), Pb(II), and Hg(II), respectively. The competitive adsorption of the metal ions was also studied. When the metal ions competed, the adsorbed amounts were 2.9 mg of Cd(II)/g, 14.8 mg of Pb(II)/g, and 9.4 mg of Hg(II)/g. The poly(HEMA–MAH) membranes could be regenerated via washing with a solution of nitric acid (0.01M). The desorption ratio was as high as 97%. These membranes were suitable for repeated use for more than three adsorption/desorption cycles with negligible loss in the adsorption capacity. The stability constants for the metal‐ion/2‐methacryloylamidohistidine complexes were calculated to be 3.47 × 10⁶, 7.75 × 10⁷, and 2.01 × 10⁷ L/mol for Cd(II), Pb(II), and Hg(II) ions, respectively, with the Ruzic method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1213–1219, 2005     

Thermal properties of poly(maleic anhydride‐alt‐acrylic acid) in the presence of certain metal chlorides

Polychelates were synthesized by the addition of aqueous solutions of copper(II), cadmium(II), and nickel(II) chlorides to aqueous solutions of poly(maleic anhydride‐alt‐acrylic acid) [poly(MA‐alt‐AA)] in different pH media. The thermal properties of poly(MA‐alt‐AA) and its metal complexes were investigated with thermogravimetry and differential scanning calorimetry (DSC) measurements. The polychelates showed higher thermal stability than poly(MA‐alt‐AA). The thermogravimetry of the polymer–metal complexes revealed variations of the thermal stability by complexation with metal ions. The relative thermal stabilities of the systems under investigation were as follows: poly(MA‐alt‐AA)–Cd(II) > poly(MA‐alt‐AA)–Cu(II) > poly(MA‐alt‐AA)–Ni(II) > poly(MA‐alt‐AA). The effects of pH on the complexation and gravimetric analysis of the polychelates were also studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3926–3930, 2006     

全氟羧酸二价盐及全氟羧酸/三价金属盐混合体系表面活性研究

合成一系列全氟辛酸二价盐(M(PFOA)_2,M~(2+)=Mg~(2+),Ca~(2+),Sr~(2+),Ba~(2+))和全氟丁酸二价盐(M(PFBA)_2),并测定其在水、二甲基亚砜(DMSO)和乙二醇(EG)中的表面张力,同时测定了全氟辛酸(PFOA)和全氟丁酸(PFBA)分别与三价金属盐(LaCl_3和FeCl_3)组成的混合物在水溶液中的表面张力。结果表明,与相应的钾盐相比,M(PFOA)_2和M(PFBA)_2具有更高的表面活性,而全氟羧酸(PFOA或PFBA)与三价金属盐的混合物未见表面活性显著提高。M(PFOA)_2可作为降低PFOA盐使用量的重要方法加以应用。