Binding of uranyl ion by poly(ethylenimine) containing a salicylate derivative

Three molecules of 5-(bromoacetyl)salicylate ( 1 ) complexed to uranyl UO ion were crosslinked with branchy poly(ethylenimine) (PEI) in DMSO by alkylation of amino groups of PEI with 1, leading to the formation of UO₂(Sal) PEI. Upon demetalation of UO₂(Sal) PEI with HCl, apo(Sal) PEI was obtained. Based on the pH dependence of log K_f for UO₂(Sal) PEI, it was concluded that each uranyl binding site in UO₂(Sal) PEI or apo(Sal) PEI contains three salicylate moieties. In terms of the equilibrium constant for formation of the uranyl complex, apo(Sal) PEI was found to be comparable to or better than the previously reported effective uranophiles. In terms of the rates for the formation of the uranyl complex, however, apo(Sal) PEI was far superior to those other uranophiles. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2935–2942, 1997     

Magnesium chloride supported high mileage catalysts for olefin polymerization. XII. Polymerization of ethylene

Polymerizations of ethylene by the MgCl₂/ethylbenzoate/p-cresol/AlEt₃ TiCl₄-AlEt₃/methyl-p-toluate (CW-catalyst) have been studied. The initially formed active site concentration, [Ti] has a maximum value of 50% of total titanium at 50°C and lower values at other temperatures. The Ti decays rapidly to Ti sites with conc. ca. 10 mol %/mol Ti. The rate constants for four chain transfer processes have been obtained at 50°C: for transfer with AlEt₃, k = 2.1 × 10^?4 s^?1 and k = 4.8 × 10^?4 s^?1; for transfer with monomer, k = 3.6 × 10^?3 (M s)^?1 and K = 8.3 × 10^?3 (M s)^?1; for β-hydride transfer, k = 7.2 × 10^?4 s^?1 and k = 4.9 × 10^?4 s^?1; and transfer with hydrogen, k = 4.0 × 10^?3 torr^1/2 s^? and k = 5.1 × 10^?3 torr^1/2 s^?1. The rate constants for the termination assisted by hydrogen is k = 1.7 (M^1/2 torr^1/2 S)^?1. If monomer is assisting termination as was observed for propylene polymerization, then k = 7.8 (M^3/2 s)^?1. Values of all the rate constants can be higher or lower at other temperatures. Detailed comparisons were made with the results of propylene polymerizations. There are more than four times as many Ti active sites for ethylene polymerization than there are for stereospecific polymerization of propylene; the difference is more than a factor of two for the Ti sites. Certain rate constants are nearly the same for both monomers while others are markedly different. Some of the differences can be explained by stereoelectronic effects.     

Visible light induced free radical promoted cationic polymerization using thioxanthone derivatives

The free radical promoted cationic polymerization cyclohexene oxide (CHO), was achieved by visible light irradiation (λ_inc = 430–490 nm) of methylene chloride solutions containing thioxanthone‐fluorene carboxylic acid (TX‐FLCOOH) or thioxanthone‐carbazole (TX‐C) and cationic salts, such as diphenyliodonium hexafluorophosphate (Ph₂I⁺PF) or silver hexafluorophosphate (Ag⁺PF) in the presence of hydrogen donors. A feasible initiation mechanism involves the photogeneration of ketyl radicals by hydrogen abstraction in the first step. Subsequent oxidation of ketyl radicals by the oxidizing salts yields Bronsted acids capable of initiating the polymerization of CHO. In agreement with the proposed mechanism, the polymerization was completely inhibited by 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy and di‐2,6‐di‐tert‐butylpyridine as radical and acid scavengers, respectively. Additionally polymerization efficiency was directly related to the reduction potential of the cationic salts, that is, Ag⁺PF (E = +0.8 V) was found to be more efficient than Ph₂I⁺PF (E = ?0.2 V). In addition to CHO, vinyl monomers such as isobutyl vinyl ether and N‐vinyl carbazole, and a bisepoxide such as 3,4‐epoxycyclohexyl‐3′,4′‐epoxycyclohexene carboxylate, were polymerized in the presence of TX‐FLCOOH or TX‐C and iodonium salt with high efficiency. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Electrochemical synthesis of PEDOT derivatives bearing imidazolium‐ionic liquid moieties

Novel poly(3,4‐ethylenedioxythiophene) (PEDOT) polymers bearing imidazolium‐ionic liquid moieties were synthesized by electrochemical polymerizations. For this purpose, new functional monomers were synthesized having an 3,4‐ethylenedioxythiophene (EDOT) unit and an imidazolium‐ionic liquid with different anions such as tetrafluoroborate (BF), bis(trifluoromethane)sulfonimide ((CF₃SO₂)₂N^?), and hexafluorophosphate (PF). Next, polymer films were obtained by electrochemical synthesis in dicholoromethane solutions. Obtained polymers were characterized, revealing the characteristics of PEDOT in terms of electrochemical and spectroelectrochemical properties, FTIR, ¹H NMR, and AFM microscopy. Interestingly, the hydrophobic character of electropolymerized films could be modified depending on the anion type. The hydrophobicity followed the trend PF > (CF₃SO₂)₂N^? > BF > pure PEDOT as determined by water contact angle measurements. Furthermore, the polymers could be dissolved in a range of polar organic solvents such as dimethylformamide, propylene carbonate, and dimethyl sulfoxide making these polymers interesting candidates for wet processing methods. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3010–3021, 2009     

Role of anions in the polymerization of 2,5‐dimethoxyaniline in the presence of poly(styrene sulfonic acid)

Poly(2,5‐dimethoxyaniline) (PDMA)–Ag composites were successfully obtained through the oxidative polymerization of 2,5‐dimethoxyaniline in poly(styrene sulfonic acid) with CH₃SO₃Ag and AgNO₃ as oxidants. In situ ultraviolet–visible spectroscopy results showed that the growth rate of PDMA was strongly affected by CH₃SO and NO. The coupling reaction of PDMA and NO was proposed to explain the lower growth rate of PDMA with AgNO₃ as the oxidant in comparison with CH₃SO₃Ag. X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy were used to validate the proposed coupling reaction through the monitoring of the side products and oxidized state of PDMA. The results showed that there were more side products and lower oxidized states for the composite structure in the presence of NO than in the presence of CH₃SO, and this agreed with the proposal. Transmission electron microscopy showed that the Ag nanoparticles had almost the same size, regardless of the anions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6624–6632, 2006     

Cationic grafting from carbon black. VIII. Cationic ring-opening polymerization and copolymerization of oxepane initiated by acylium perchlorate groups on carbon black

The cationic ring-opening polymerization of oxepane was found to be initiated by carbon black having acylium perchlorate (CO⁺CIO) groups, which were introduced by the reaction of acyl chloride groups with silver perchlorate. It was confirmed that polyoxepane, i.e., poly(oxyhexamethylene), was propagated from CO⁺CIO groups on carbon black and effectively grafted on the surface. The rate of the polymerization and the percentage of grafting of poly(oxyhexamethylene) remarkably increased by the addition of epichlorohydrin (ECH) as a promoter: the percentage of grafting in the presence of ECH increased to about 100% with an increase in conversion. Furthermore, CO⁺CIO groups on carbon black have an ability to initiate the cationic ring-opening copolymerization of oxepane with ECH to give poly(oxepane-co-ECH) with various composition. The ring-opening copolymerization of oxepane with phthalic anhydride was also initiated by CO⁺CIO groups to give polyether ester, i.e., poly(hexamethylene phthalate) containing poly(oxyhexamethylene) sequence. In the copolymerization, polyether or polyether ester was effectively grafted from carbon black based on the propagation of these polymers from CO⁺CIO groups.     

Non‐transition metal‐catalyzed living radical polymerization of vinyl chloride initiated with iodoform in water at 25 °C

Non‐transition metal‐catalyzed living radical polymerization (LRP) of vinyl chloride (VC) in water at 25–35 °C is reported. This polymerization is initiated with iodoform and catalyzed by Na₂S₂O₄. In water, S₂O dissociates into SO that mediates the initiation and reactivation steps via a single electron transfer (SET) mechanism. The exchange between dormant and active propagating species also includes the degenerative chain transfer to dormant species (DT). In addition, the SO₂ released from SO during the SET process can add reversibly to poly(vinyl chloride) (PVC) radicals and provide additional transient dormant ～SO radicals. This novel LRP proceeds mostly by a combination of competitive SET and DT mechanisms and, therefore, it is called SET‐DTLRP. Telechelic PVC with a number‐average molecular weight (M_n) = 2,000–55,000, containing two active ～CH₂? CHClI chain ends and a higher syndiotacticity than the commercial PVC were obtained by SET‐DTLRP. This PVC is free of structural defects and exhibits a higher thermal stability than commercial PVC. SET‐DTLRP of VC is carried out under reaction conditions related to those used for its commercial free‐radical polymerization. Consequently, SET‐DTLRP is of technological interest both as an alternative commercial method for the production of PVC with superior properties as well as for the synthesis of new PVC‐based architectures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6267–6282, 2004     

Chiral recognition in molecular and macromolecular pairs of (S)‐ and (R)‐1‐cyano‐2‐methylpropyl‐4′‐ {[4‐(8‐vinyloxyoctyloxy)benzoyl]oxy}biphenyl‐4‐ carboxylate enantiomers

(S)‐1‐Cyano‐2‐methylpropyl‐4′‐{[4‐(8‐vinyloxyoctyloxy)benzoyl]oxy}biphenyl‐ 4‐carboxylate [ (S)‐11 ] and (R)‐1‐cyano‐2‐methylpropyl‐4′‐{[4‐(8‐vinyloxyoctyloxy)benzoyl]oxy}biphenyl‐4‐carboxylate [( R)‐11 ] enantiomers, both greater than 99% enantiomeric excess, and their corresponding homopolymers, poly[ (S)‐11 ] and poly[ (R)‐11 ], with well‐defined molecular weights and narrow molecular weight distributions were synthesized and characterized. The mesomorphic behaviors of (S)‐11 and poly[ (S)‐11 ] are identical to those of (R)‐11 and poly[ (R)‐11 ], respectively. Both (S)‐11 and (R)‐11 exhibit enantiotropic S_A, S, and S_X (unidentified smectic) phases. The corresponding homopolymers exhibit S_A and S phases. The homopolymers with a degree of polymerization (DP) less than 6 also show a crystalline phase, whereas those with a DP greater than 10 exhibit a second S_X phase. Phase diagrams were investigated for four different pairs of enantiomers, (S)‐11 /( R)‐11 , (S)‐11 /poly[ (R)‐11 ], and poly[ (S)‐11 ]/poly[ (R)‐11 ], with similar and dissimilar molecular weights. In all cases, the structural units derived from the enantiomeric components are miscible and, therefore, isomorphic in the S_A and S phases over the entire range of enantiomeric composition. Chiral molecular recognition was observed in the S_A and S_X phases of the monomers but not in the S_A phase of the polymers. In addition, a very unusual chiral molecular recognition effect was detected in the S phase of the monomers below their crystallization temperature and in the S phase of the polymers below their glass‐transition temperature. In the S phase of the monomers above the melting temperature and of the polymers above the glass‐transition temperature, nonideal solution behavior was observed. However, in the S_A phase the monomer–polymer and polymer–polymer mixtures behave as an ideal solution. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3631–3655, 2000     

Primary radical termination and unimolecular termination in the heterogeneous polymerization of acrylamide initiated by a fluorinated azo‐derivative initiator: A kinetic study

Acrylamide was polymerized in acetonitrile at 82 °C with a perfluorinated azo‐derivative initiator. The polymerization proceeded heterogeneously. Varying amounts of initiator and monomer were used. The activation energy was deduced from three experiments carried out at 59, 71, and 82 °C. The following kinetic law, deviating a great deal from the classical law, was obtained: R ∼ [I₂][M](0.05% < [I₂]_o/[M]_o < 1.00%) and R ∼ [I₂][M](1% < [I₂]_o/[M]_o < 7%). These results can be interpreted in light of the contribution of primary radical termination and the emergence of occlusion. The development of a new kinetic relationship allowed us to confirm the existence of both of these termination reactions. The calculation of the k_prt /k_i · k_p ratio was also achieved. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1834–1843, 2000     

Synthesis and characterizations of well‐defined branched polymers with AB2 branches by combination of RAFT polymerization and ROP as well as ATRP

A well‐defined branched copolymer with PLLA‐b‐PS₂ branches was prepared by combination of reversible addition‐fragmentation transfer (RAFT) polymerization, ring‐opening polymerization (ROP), and atom transfer radical polymerization (ATRP). The RAFT copolymerization of methyl acrylate (MA) and hydroxyethyl acrylate (HEA) yielded poly(MA‐co‐HEA), which was used as macro initiator in the successive ROP polymerization of LLA. After divergent reaction of poly(MA‐co‐HEA)‐g‐PLLAOH with divergent agent, the macro initiator, poly(MA‐co‐HEA)‐g‐PLLABr₂ was formed in high conversion. The following ATRP of styrene (St) produced the target polymer, poly(MA‐co‐HEA)‐g‐(PLLA‐b‐PS₂). The structures, molecular weight, and molecular weight distribution of the intermediates and the target polymers obtained from every step were confirmed by their ¹H NMR and GPC measurements. DSC results show one T = 3 °C for the poly(MA‐co‐HEA), T = ?5 °C, T= 122 °C, and T = 157 °C for the branched copolymers (poly(MA‐co‐HEA)‐g‐PLLA), and T = 51 °C, T = 116 °C, and T = 162 °C for poly(MA‐co‐HEA)‐g‐(PLLA‐b‐PS₂). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 549–560, 2006     

Magnesium chloride-supported high-mileage catalysts for olefin polymerization XI. Determinations of poly(decene-1) molecular weight chain dimension and thermal transitions

Decene-1 was polymerized with the CW catalyst and fractionated by precipitation technique. Light-scattering and viscometric measurements on these fractions established the relationship [η] = 5.19 × 10^?3 M . The unperturbed mean square end-to-end distance is (〈R〉/M)^1/2 = (6.17 ± 0.34) × 10^?9. Light-scattering data is consistent with a relatively stiff molecule with length of L = 1.75 × 10^?5 cm for poly(decene-1) with MW = 397,000. Its mean square radius of gyration 〈R〉 is 2.79 × 10^?11 cm.² The ratio of L²/〈R〉 = 11 is close to the theoretical ratio of 12 for this kind of macromolecule.     

Effects of salts and copolymer composition on the lower critical solution temperature of poly(methyl 2‐acetamidoacrylate‐co‐methyl methacrylate) solutions

Copolymerizations of methyl 2‐acetamidoacrylate (MAA) with methyl methacrylate (MMA) were carried out at 60 °C in chloroform. Copolymers containing MAA units in the range of 83–90 mol % exhibited a lower critical solution temperature (LCST), although homopolymers of MAA and MMA did not. The LCST of polymer solutions decreased with (1) an increase in the concentration of the copolymer, (2) a decrease in the MAA content in the copolymer, and (3) an increase in the concentration of salts added. The effectiveness of anionic species for reducing the LCST is NO < Cl^? < SO < SO. Divalent anion is more effective for lowering the LCST than monovalent anion. However, there is no difference between cationic species in the salting‐out effect. Sodium carbonate and sodium phosphate had a salting‐in effect. Salting‐out coefficients were evaluated from the relationship between the logarithm of solubility of the copolymers and the salt concentration. Salting‐out coefficients of the copolymer depended not on the composition of the copolymers but on the salt added. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1945–1951, 2002     

Kinetics of crosslinking reactions. 2. Reaction rates of intermolecular and intramolecular crosslinkings by using a soluble microgel

Soluble microgels with several pendant vinyl groups were synthesised by radical copolymerization of methyl methacrylate (MMA) with p-divinyl benzene (p-DVB). The competitive reactions of intermolecular and intramolecular crosslinkings of these microgels were carried out at 40°C in the presence of 1-buten-3-ol as a degradative chain transfer agent. The rate constant of intermolecular crosslinking (k) was estimated by GPC (gel permeation chromatography) analysis on the polymer produced from intermolecular propagation between bimolecules. The k depended strongly on the internal structure of microgels. Network formation was discussd inclusive of informations for the rate constant of intramolecular crosslinking (k).     

Heterogeneous surface saponification of suspension‐polymerized monodisperse poly(vinyl acetate) microspheres using various ions

Poly(vinyl alcohol) (PVA)/poly(vinyl acetate) (PVAc) microspheres with a skin/core structure were prepared through the heterogeneous surface saponification of PVAc microspheres suspension‐polymerized. The PVA skin formed through the heterogeneous saponification was hydrogel swellable in water. In addition, to obtain monodisperse PVA/PVAc microspheres having various skin/core ratios and morphologies, the ion‐specificities to the heterogeneous saponification were investigated using SO, Cl^?, NO, Br^?, and I^? for anions and Li⁺, Na⁺, and K⁺ for cations, respectively. The ions were not specific significantly to the rate of the heterogeneous saponification, while were related to the degree of saponification (DS). DSs had different values between by weight loss (DS_w) and by proton nuclear magnetic resonance spectroscopy (DS_NMR) measurements. The order of DS_ws was SO < Cl^? < NO < Br^? < I^? for anions and K⁺ < Na⁺ < Li⁺ for cations, and that of DS_NMRs, I^? < Br^? < NO < Cl^? < SO for anions and Li⁺ < Na⁺ < K⁺ for cations. The differences in values between DS_ws and DS_NMRs were caused by the dissolution of PVA skin and were significantly decreased for SO. The peaks at melting temperature of PVA were sharp and their areas were large for ions deswelling PVA skins.     

Narrowly dispersed micrometer‐sized composite spheres based on diazonium–polystyrene

Diazonium group–substituted polystyrene (PS–N) micrometer‐sized spheres with narrow distribution were prepared from highly crosslinked polystyrene particles. Then a composite sphere was prepared with the micro‐PS–N sphere as core and submicrometer‐sized poly(styrene‐methyl methacrylate‐acrylic acid) [P(S‐MMA‐AA)] colloids or nanometer‐sized SiO₂ particles as shell via columbic interaction. The ionic linkages between the core and shell convert to covalent bonds in the thermal treatment process. As a result, the composite sphere becomes very stable toward polar solvents as well as toward ultrasonic treatment. A hollow SiO₂ micrometer‐sized sphere then was achieved by removing the core under sintering conditions (700 °C). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4284–4288, 2004     

Electropolymerization of benzene and biphenyl in organic media: Influence of different parameters (solvent,water, acidity,salt) on the formation of polyparaphenylene films (PPP)

The electrosynthesis of polyparaphenylene films (PPP) by oxidation of benzene or biphenyl on a Pt electrode was studied in different organic media. Film formation was possible only if the solvent had acidic properties according to the Lewis concept, and if the water content of this medium was less than 5 × 10^?2M. Addition of an excess of P₂O₅ or CuCl₂ into the medium increased the acidity and improved the adherence and the homogeneity of the films considerably. PPP films were electroactive and conductive if the electrolysis was carried out in the presence of salts containing BF, SbF, PF anions; they were insulating with perchlorate salts. IR analysis of these polymers showed highly crosslinked structures and the chains were constituted of about 10 para coupled phenyl moieties.     

Evaluation of two‐center,three‐ and four‐electron integrals over Slater‐type orbitals in elliptical coordinates

An algorithm for evaluation of two‐center, three‐electron integrals with the correlation factors of the type rr and rrr as well as four‐electron integrals with the correlation factors rrr and rrr in the Slater basis is presented. This problem has been solved here in elliptical coordinates, using the generalized and modified form of the Neumann expansion of the interelectronic distance function r for k ≥ ?1. Some numerical results are also included. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Lactide polymerization activity of alkoxide,phenoxide, and amide derivatives of yttrium(III) arylamidinates

In quest of new, single‐site catalysts for cyclic ester polymerizations, a series of mononuclear yttrium(III) complexes of N,N′‐bis(trimethylsilyl)benzamidinate ([L^TMS]⁻) and hindered N,N′‐bis‐(2,6‐dialkylaryl)toluamidinates ([L^Et]⁻, aryl = Et₂C₆H₃, and [L^iPr]⁻, aryl = ⁱPr₂C₆H₃) were synthesized and characterized by X‐ray diffraction: LY(μ‐Cl)₂Li(TMEDA) ( 1 ), LY(OC₆H₂^tBu₂Me) ( 2 ), LY(OC₆H₃Me₂)₂Li(THF)₄ ( 3 ), LY(μ‐O^tBu)₂Li(THF) ( 4 ), L^iPrY[N(SiMe₂H)₂]₂(THF) ( 5 ), LY(THF)(Cl)(μ‐Cl)Li(THF)₃ ( 6 ), and LY[N(SiMe₂H)₂] ( 7 ). Coordination numbers ranging from five to seven were observed, and they appeared to be controlled by the steric bulk of the supporting amidinate and alkoxide, phenoxide, or amide coligands. Complexes 2 – 5 and 7 are active catalysts for the polymerization of D,L ‐lactide (e.g., with 2 and added benzyl alcohol, 1000 equiv of D,L ‐lactide were polymerized at room temperature in less than 1 h, with polydispersities less than 1.5). The neutral complexes 2 , 5 , and 7 were more effective than the anionic complexes 3 and 4 . In addition, the presence of the more hindered amidinate ligands [L^Et]⁻ and [L^iPr]⁻ on yttrium‐amides slowed the polymerizations ( 7 < 5 < Y[N(SiMe₂H)₂]₃). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 284–293, 2001     

Depolymerization kinetics of di(4‐tert‐butyl cyclohexyl) itaconate and Mark‐Houwink‐Kuhn‐Sakurada parameters of di(4‐tert‐butyl cyclohexyl) itaconate and di‐n‐butyl itaconate

Multipulse pulsed laser polymerization coupled with size exclusion chromatography (MP‐PLP‐SEC) has been employed to study the depropagation kinetics of the sterically demanding 1,1‐disubstituted monomer di(4‐tert‐butylcyclohexyl) itaconate (DBCHI). The effective rate coefficient of propagation, k, was determined for a solution of monomer in anisole at concentrations, c, 0.72 and 0.88 mol L^?1 in the temperature range 0 ≤ T ≤ 70 °C. The resulting Arrhenius plot (i.e., ln k vs. 1/RT) displayed a subtle curvature in the higher temperature regime and was analyzed in the linear part to yield the activation parameters of the forward reaction. In the temperature region where no depropagation was observed (0 ≤ T ≤ 50 °C), the following Arrhenius parameters for k_p were obtained (DBCHI, E_p = 35.5 ± 1.2 kJ mol^?1, ln A_p = 14.8 ± 0.5 L mol^?1 s^?1). In addition, the k data was analyzed in the depropagatation regime for DBCHI, resulting in estimates for the associated entropy (?ΔS = 150 J mol^?1 K^?1) of polymerization. With decreasing monomer concentration and increasing temperature, it is increasingly more difficult to obtain well structured molecular weight distributions. The Mark Houwink Kuhn Sakurada (MHKS) parameters for di‐n‐butyl itaconate (DBI) and DBCHI were determined using a triple detection GPC system incorporating online viscometry and multi‐angle laser light scattering in THF at 40 °C. The MHKS for poly‐DBI and poly‐DBCHI in the molecular weight range 35–256 kDa and 36.5–250 kDa, respectively, were determined to be K_DBI = 24.9 (10³ mL g^?1), α_DBI = 0.58, K_DBCHI = 12.8 (10³ mL g^?1), and α_DBCHI = 0.63. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1931–1943, 2007