Molecular location in a nonaqueous lyotropic liquid crystal polymer

A surfactant bis[2-(10-undecenoyloxycarbonyl)ethyl] (p-vinylbenzoyl) methylammonium chloride formed a lamellar liquid crystal in native form and retained the structure after polymerization. Addition of heptadiene, of glycerylmonomethacrylate, and of both to the surfactant monomer gave an isotropic solution, which was transformed to a lamellar liquid crystal after polymerization. Low angle X-ray diffractometry was used to determine the interlayer spacing and to estimate the location of the added molecules. 1.6-Heptadiene was located between methyl group layers of the surfactant chains with 46 vol % of the molecules penetrating between the hydrocarbon chains of the surfactant. Addition of both the polar and the nonpolar monomer followed by polymerization caused the latter to be expelled from the space in between the chains.     

Solid-state electrolytes based on ionic network polymers

Interpenetrating and semi-interpenetrating polymer networks are synthesized with the use of cationic and anionic ionic monomers: N-[3-(methacryloyloxy)propyl]-N-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide, N-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]-N-methylpyrrolidinium bis(fluorosulfonyl)imide, and (N-butyl-N-methylpyrrolidinium 1-[3-(methacryloyloxy)propylsulfonyl] (trifluoromethanesulfonyl) imide. Their ionic conductivities, electrochemical stabilities, heat resistances, thermal stabilities, and mechanical properties and the swelling of the films in ionic liquid/lithium salt mixtures were studied. The copolymerization of N-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]-N-methylpyrrolidinium bis(fluorosulfonyl)imide and poly(ethylene glycol dimethacrylate) and poly(ethylene glycol methacrylate) in the presence of butadiene-acrylonitrile rubber and a solution of Li(CF₃SO₂)₂N in N-(methoxymethyl)-N-methylpyrrolidinium bis(fluorosulfonyl)imide yielded a solid-state electrolyte with a set of properties optimum among the studied films: an ionic conductivity of 1.3 × 10^?4S/cm (25°C), a tensile strength of 80 kPa, and an elongation at break of 60%.     

α‐Diimine nickel catalyst for copolymerization of hexene and acrylate monomers activated by different cocatalysts

Bulk homopolymerization and copolymerization of 1‐hexene (H) with polar monomers including butyl acrylate (B) and methyl methacrylate (M) in the presence of 1,4‐bis (2,6‐diisopropylphenyl) acenaphthene diimine nickel (II) dibromide catalyst were investigated. Two cocatalysts, including diethyl aluminium chloride (DEAC) and ethyl aluminium sesqui chloride (EASC), were used to activate the catalyst at ambient temperature. In both the homopolymerization and copolymerization of 1‐hexene with polar monomers, the catalyst activity resulted from EASC as cocatalyst was higher than that resulted from DEAC. ¹HNMR analysis was used in order to determine incorporation level of polar monomers and branching density of the synthesized polymers. A highest incorporation level of 13.3% mol was obtained using monomer B in the presence of the cocatalyst EASC. In addition, the influence of polar monomers on molecular weight and molecular weight distribution (PDI) was studied for both the homo‐ and co‐polymerizations of 1‐hexene in the presence of various cocatalysts. A higher molecular weight and narrower PDI were obtained by using the DEAC cocatalyst compared to the EASC cocatalyst. Glass transition temperature (Tg) and melting point (Tm) of the synthesized polymers were found to be dependent on the cocatalyst type and comonomer incorporation level. The addition of dichloromethane solvent into reaction medium showed a positive effect on comonomer incorporation which could not be seen in bulk polymerization. However, the presence of dichloromethane led to decrease the catalyst activity and molecular weight of the polymers.     

Preparation and characterization of azlactone functionalized polymer supports and their application as scavengers

A series of cross-linked porous copolymer supports based on N-(p-vinylbenzoyl)-2-methylalanine (VBM), styrene and divinylbenzene was prepared by aqueous suspension copolymerization in the presence of butan-2-ol used as porogen. The cross-linked copolymer beads were characterized by elemental analysis, scanning electron microscopy (SEM), FT-IR and confocal Raman spectrometries. It was observed that the VBM incorporation was effective and homogeneous within the beads. Those VBM functionalized supports were converted into azlactone functionalized supports using acetic anhydride and their scavenging efficiency towards different amines was measured. It appeared that 90% of benzylamine was quenched after 5 h.     

Synthesis,Micellar and Surface Properties of Cationic Trisiloxane Surfactants with Different Siloxane Hydrophobic Groups

Three cationic trisiloxane surfactants, 1-methyl-1-[bis(trimethylsiloxy)methyl]silyl-propylpyrrolidinium chloride (Si₃pyCl), 1-methyl-1-[bis(triethylsiloxy)methyl]silyl-propylpyrrolidinium chloride (Et-Si₃pyCl), and 1-methyl-1-[bis(vinyldimethylsiloxy)methyl]silylpropylpyrrolidinium chloride (Vi-Si₃pyCl) were synthesized. The aggregation behavior of the trisiloxane surfactants with different siloxane hydrophobic groups in aqueous solution was investigated by surface tension and electrical conductivity measurements. The structures of hydrophobic groups of the trisiloxane surfactants can obviously influence their surface activities and thermodynamics. All the three cationic trisiloxane surfactants have excellent surface activity. Owing to the steric hindrance of hydrophobic groups, the CMC values increase following the order Et-Si₃PyCl?<?Vi-Si₃PyCl?<?Si₃PyCl. The \(\Delta G_{\text{m}}^{\text{o}}\) values increase in the order Et-Si₃PyCl?>?Vi-Si₃PyCl?>?Si₃PyCl, attributed to the decrease in the hydrophobic effect. The micellization processes of these surfactants are entropy-driven.     

Copolymerization of Ethylene with lO-Undecen-l-ol Using Highly Active Vanadium（III） Precatalysts Bearing Bis（imino）pyrrolyl Ligands

The copolymerizations of ethylene with 10-undecen-1-ol have been investigated using vanadium precatalysts, bis（imino）pyrrolyl vanadium（Ⅲ） complexes 1-3, 2,5-C4H2N（CH=NR）2VCl2（THF）2 [R = C6H5 （1）, 2,6-iPr2C6H3 （2）, C6F5 （3）], and the iminopyrrolyl and b-diketiminate ones for comparison. The polar monomer was pretreated by diethylaluminium chloride （present also as the cocatalyst） before the copolymerization. The monomer reactivity ratios were evaluated using the Fineman-Ross method. The ligand structure considerably influenced the catalytic activity and tolerance towards the polar monomer, the polar monomer incorporation and the molecular weights of the resultant copolymers. The bis（imino）pyrrolyl vanadium complexes exhibited promising catalytic performance for the copolymerization, and a high catalytic activity up to 3.84 kg/mmolv·h with a high comonomer incorporation of 14.0 mol% was achieved by complex 3 under mild conditions.     

Synthesis and properties of soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex particles prepared by seeded emulsion polymerization

In order to obtain functional polymer latex particles with clean surface and with surface carboxyl groups, P(MMA-EA) seed particles with the diameter of 335 nm were first synthesized via soap-free batch emulsion polymerization of methyl methacrylate (MMA) and ethyl acrylate (EA), and then the seeded emulsion copolymerization of MMA, EA and MAA (methacrylic acid) onto the seed particles were performed in the absence of emulsifier. Influences of ingredients and conditions on polymerization, latex particle size (D_p) and its distribution were investigated. Results showed that most of the monomers polymerized onto the seed latex particles in the second step of polymerization by using drop-wise addition method, and D_p increased from 483 nm to 829 nm with the mass ratio of core/shell monomers [C]/[S] decreased from 1:2 to 1:15. It was found that D_p decreased with the increase of MAA and initiator amounts, and the size of the latex particles became uniform with the decrease of MAA amount and with the increase of [C]/[S] value.     

Synthesis of phosphinic acids on the basis of hypophosphites: VI. General methods for synthesis of pseudo-γ-glutamylpeptides

A general method for synthesis of 2-substituted pseudo-γ-glutamylpeptides, namely, [2-(hydroxycarbonyl)ethyl][3-amino-3-(hydroxycarbonyl)propyl]phosphinic acids I which are phosphinic acid analogs of γ-glutamylpeptides. Bis(trimethylsilyl) hypophosphite (IV) formed from ammonium hypophosphite (II) in situ was added to the respective α-substituted acrylate to form bis(trimethylsilyl) [2-R-2-(alkoxycarbonyl)ethyl]-phosphonites V. Treatment of compounds V in situ with excess dibromoethane followed by alcoholysis gave [2-R-2-(alkoxycarbonyl)ethyl](2-bromoethyl)phosphinic acids VI which without isolation were treated with excess triethyl orthoformate. The simultanious esterification and dehydrobromination led to [2-R-2-(alkoxy-carbonyl)ethyl](vinyl)phosphinates III which were isolated and characterized. The Michael addition of diethyl acetamidomalonate to vinylphosphinates III followed by acid hydrolysis of phosphinates VII without their isolation resulted in formation of target [2-R-2-(hydroxycarbonyl)ethyl][3-amino-3-(hydroxycarbonyl)]proly]phosphinic acids-pseudo-γ-glutamylpeptides I. Original Russian Text V.V. Ragulin, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 5, pp. 763–768. For communication V, see [1].     

Hybrid copolymerization of cyclic and vinyl monomers

In this work,we report the hybrid copolymerization of various cyclic monomers and vinyl monomers.Our studies demonstrate that 1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino) phophoranyliden-amino]-2 5,5-catenadi(phosphazene) (t-BuP 4) can catalyze the hybrid copolymerization of caprolactone (CL),lactide (LA) or cyclic carbonate ester with acrylate or methyl acrylate.However,the polymerization of cyclosiloxane with vinyl monomers yields two corresponding homopolymers,and the polymerization of lactone with acrylonitrile (AN) produces only polyacrylonitrile.Clearly,the extent of matching of activity between a monomer and an active center determines whether or not there is hybrid copolymerization.     

Bis[2-(4-pyridyl)ethyl](2-cyanoethyl)phosphine Oxide: Synthesis and Reactions with 1,4-Dihalobutanes

Russian Journal of General Chemistry - Bis[2-(4-pyridyl)ethyl]phosphine reacts with acrylonitrile under mild conditions to form bis[2-(4- pyridyl)ethyl](2-cyanoethyl)phosphine which is readily...     

Synthesis and radical polymerization of vinyl monomers having oxazolidone moiety

Oxazolidone group-containing vinyl monomers, 4-(2-oxo-3-oxazolidinyl)methylstyrene (OS) and 4-[2-(2-oxo-3-oxazolidinyl)ethoxy]methylstyrene (OES), were synthesized and their polymerization and copolymerization behaviors with styrene (St), p-methoxystyrene (PMS), and m-hydroxystyrene (MHS) were investigated. OS was prepared in 70% yield by the reaction of 2-oxazolidone with p-chloromethylstyrene in the presence of sodium hydride. OES was obtained by the similar reaction of p-chloromethylstyrene with N-hydroxyethyl-2-oxazolidone which was prepared by the reaction of 2-oxazolidone with ethylenecarbonate. Homopolymerization of OS and OES afforded mainly gelled polymers, but also soluble polymers on high dilution. In the copolymerization with styrene derivatives, an alternating nature was suggested from the copolymerization parameters obtained by either the nonlinear least-squares analysis method or the Fineman–Ross method. The alternating copolymerizability decreased in the following order: MHS > PMS > St. Q?e values of OS and OES were calculated and demonstrated that OS and OES behaved as stronger electron-accepting monomers in the copolymerization with MHS than in those with St and PMS. The copolymerization behavior of OS (OES) with MHS was compared with those of 4-(2-oxo-1-pyrrolidinyl)methylstyrene (PS) and 4-[2-(2-oxo-1-pyrrolidinyl)ethoxy]methylstyrene (PES). From an IR study examining the shift of carbonyl absorption by addition of MHS, the interaction which contributed to the increase of the alternating copolymerizability in the copolymerization of OS (OES) with MHS was concluded to be based on hydrogen bonding. © 1993 John Wiley & Sons, Inc.     

Nucleotides. Part XXVII Bis[2-(p-nitrophenyl)ethyl] Phosphorochloridate,a New Versatile Phosphorylating Agent in Nucleotide Chemistry

A new, versatile phosphorylating agent, bis[2-(p-nitrophenyl)ethyl] phosphorochloridate ( 3 ), has been prepared and is used for 3′- and/or 5′-phosphorylations of nucleosides. The resulting bis[2-(p-nitrophenyl)ethyl] phosphotriesters are versatile synthons in oligonucleotide synthesis leading finally to 3′- and/or 5′-terminated monophosphates in excellent yields.     

Investigation of the selective reduction of isatin derivatives. Synthesis of α-hydroxyacetophenone derivatives and ethyl spiro-3,3-(ethylenedioxy)-2-hydroxyindoline carboxylates

The product from the reduction of ethyl spiro-3,3-(ethylenedioxy)-2-oxindole carboxylates (1) using borohydride salts has been found to be dependant upon both solvent and metal ion. With polar solvents and lithium bromide/sodium borohydride, spiro-3,3-(ethylenedioxy)-2-hydroxyindole carboxylates (2) are obtained in high yields whilst [2-(2-hydroxymethyl-[1,3]dioxolan-2-yl)-phenyl]-carbamic acid ethyl esters (3) are obtained using sodium borohydride in less polar solvents.     

Synthesis and characterization of acetylene-terminated aromatic amide resin precursors

A series of 10 acetylene-terminated aromatic amide monomers was synthesized by the triethylamine-promoted reaction of bis[p-(m-chlorocarbonylphenoxy)phenyl] sulfone or bis[p-(m-chlorocarbonylphenoxyl)phenyl]ketone with o- or p-ethynyl- and o- or p-trimethylsilylethynylaniline. Yields were essentially quantitative. Structures were verified by infrared and nuclear magnetic resonance spectroscopy and mass spectral data. Thermal characteristics of the monomers were investigated by means of differential scanning calorimetry and thermogravimetric analysis. The initial glass transition temperatures were generally well below the onset of cure which occurred in the 160–225°C range for the terminal ethynyl monomers and in the 260–295°C range for their trimethylsilylethynyl analogs. Onset of decomposition in air for the resinified terminal ethynyl monomers took place in the 400–485°C range, while resins from the trimethylsilylethynyl monomers underwent breakdown at substantially lower temperatures.     

Structure of ethyl 3-(4-tolyl)hydrazono-2,4-dioxopentanoates

As a result of one-pot three-component condensation of acetone with diethyl oxalate and p-tolyl diazonium chloride of ethyl 3-(4-tolyl)hydrazono-2,4-dioxopentanoates p-tolyl diazonium diethyloxalate and chloride, ethyl ether of 3-(4-tolyl)hydrazono-2,4-dioxopentanoic acid is obtained. The structure of the synthesized compound is studied.     

Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with N-substituted maleimides

The free-radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with N-phenyl- and N-p-carboxyphenylmaleimide is studied in bulk and in organic solvents. It is shown that copolymerization proceeds to form copolymers with a high tendency toward alternation of monomer units. The kinetic laws of the reaction are investigated, and the relative activities of the monomers are determined. It is found that 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride is involved in copolymerization with N-substituted maleimides to give rise to pyrrolidinium structures. This work was supported by the Russian Foundation for Basic Research (project no. 09-03-00220) and the by the Presidium of the Russian Academy of Sciences through the program Development of Methods of Synthesis of Chemical Substances and the Creation of Novel Materials.     

Synthesis and properties of tocopherol-containing polymeric vesicle systems

Two different tocopherol-containing amphiphilic monomers, [ [ (tocopheryloxy)-carbonyl ]-methyl ] [ 2-(methacryloyloxy)ethyl ]dimethyl-ammonium chloride(3a) and [[ (tocopheryloxy)penta(ethoxy)carbonyl ]methyl ]2-(methacryloyloxy)ethyl]dimethylammonium chloride(3b), were synthesized and polymerized. The formation of polymeric closed vesicles having diameters ranging from 200 to 5200 Å was confirmed by electron micrographs, entrapment of [¹⁴C]sucrose, permeability measurements and gel filtration. The polymeric vesicles showed reduced permeability and enhanced thermodynamic stability. Antioxidative activities were determined by the thiocyanate method confirming that polymeric tocopherols also exhibited significant activities.     

COPOLYMERIZATION OF 1-OCTENE WITH STYRENE BY RARE EARTH COORDINATION CATALYSTS

The copolymerization of l-octene with styrene catalyzed by rare earth coordination catalysts has been studied for the first time. Some features and kinetic behavior are described. The overall activation energy of the copolymerization was 22.2 KJ/mol and the copolymerization rate could be expressed as R_p=K_p [Nd] [M]~2. (=1.68×10~(-3) L~2/mol~2. S, 50℃, [Oct]/[St]=1). The catalytic activity of various rare earth elements in Ln (naph)_3 for the copolymerization was compared and shows the following sequence: Dy, Y, Yb>Ho>Sm, Gd, Nd>Pr>Ce>La>Tm. Both monomers of l-octene and styrene in the copolymerization by Nd (naph)_3-AlEt_3 have the tendency of constant proportion copolymerization. The structure of the copolymers was studied by ~1H-NMR.     

Poly(1,3,4-oxadiazole-ether-imide)s and their polydimethylsiloxane-containing copolymers

Poly(1,3,4-oxadiazole-ether-imide)s were prepared by thermal imidization of poly(amic-acid) intermediates resulting from the solution polycondensation reaction of a bis(ether-anhydride), namely 2,2′-bis-[(3,4-dicarboxyphenoxy)phenyl]-1,4-phenylenediisopropylidene dianhydride, with different aromatic diamines containing 1,3,4-oxadiazole ring, such as 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis[p-(4-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2-(4-dimethylaminophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole. Poly(1,3,4-oxadiazole-ether-imide)-polydimethylsiloxane copolymers were prepared by polycondensation reaction of the same bis(ether-anhydride) with equimolar quantities of an aromatic diamine having 1,3,4-oxadiazole ring and a bis(aminopropyl)polydimethylsiloxane oligomer of controlled molecular weight. A solution imidization procedure was used to convert quantitatively the poly(amic-acid) intermediates to the corresponding polyimides. All the polymers were easily soluble in polar organic solvents such as N-methylpyrrolidone and N,N-dimethylacetamide. The polymers showed good thermal stability with decomposition temperature being above 400 °C. Solutions of some polymers in N-methylpyrrolidone exhibited blue fluorescence, having maximum emission wavelength in the range of 370-412 nm.