Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride and alkyl methacrylates

Radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with methyl methacrylate and allyl methacrylate in the bulk and methanol solution in the presence of azobis-isobutyric acid dinitryle at 70–90°C has been studied. Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with methyl methacrylate or allyl methacrylate in the bulk proceeds with formation of random copolymers enriched in methacrylate units; in the copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidiny chloride with methyl methacrylate in methanol, the copolymerization constants of the monomers become close. The kinetic parameters of the reaction have been studied, the relative activities of the monomers have been determined. It has been found that 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride is copolymerized with allyl methacrylate or methylmethacrylate to form pyrrolidinium structures in the cyclolinear polymer chain. At high degrees of conversion of the copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with allyl methacrylate, the viscosity increases and the side polymer chains are crosslinked by “allyl bonds” to form insoluble copolymers, swelling in benzene and DMSO.     

Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with vinyl acetate

The free-radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with vinyl acetate in bulk and organic solvents has been studied. Copolymerization is shown to produce random copolymers. The kinetic features of the process are examined, and the relative activities of the monomers are estimated. 2,2-Diallyl-1,1,3,3-tetraethylguanidinium chloride is involved in copolymerization with vinyl acetate via both double bonds to give rise to pyrrolidinium structures.     

Copolymerization of <Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone with new allyl monomers

Radical copolymerization of N-vinylpyrrolidone with diallylacylhydrazines, 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride, N-allyl-2-azanorborn-5-ene, and N-allylmaleimide in the bulk and in organic solvents was studied. The kinetic features of the reactions were examined, the structures of the copolymers obtained were determined, and their physicochemical and biological properties were studied.     

Copolymerization of 2,2-Diallyl-1,1,3,3-tetraethylguanidinium chloride with fumaric acid

Radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with fumaric acid in the bulk and in organic solvents was studied. The kinetic relationships of the reaction were examined, and the relative activities of the monomers were determined.     

Nanocomposites of silver and copolymers of 2,2-Diallyl-1,1,3,3-tetraethylguanidinium chloride with vinyl acetate

New water-soluble nanocomposites consisting of silver nanoparticles and copolymers of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with vinyl acetate were prepared. These nanocomposites show promise for the development of new water-soluble antiseptics and biocides.     

Copolymerization of <Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone with 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride

Radical copolymerization of N-vinylpyrrolidone with 2,2-diallyl-l,l,3,3-tetraethylguanidinium chloride in the bulk and in dimethyl sulfoxide was studied. Kinetic parameters of the reaction were examined. The monomer activities were determined.     

Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride and maleic acid

The free-radical copolymerization of 1,1,3,3-tetraethyl-2,2-diallylguanidinium chloride and maleic acid in bulk and organic solvents forms copolymers with a high tendency of monomer units toward alternation. It is shown that 1,1,3,3-tetraethyl-2,2-diallylguanidinium chloride undergoes copolymerization with maleic acid to give rise to pyrrolidinium structures in the cyclolinear polymer chain.     

Rheological behavior of associating ionic polymers based on diallylammonium salts containing single-, twin-, and triple-tailed hydrophobes

The cycloterpolymerizations of N,N-diallyl-(4-octyloxy)benzyl-, N,N-diallyl-(3,5-dioctyloxy)benzyl-, and N,N-diallyl-(3,4,5-trioctyloxy)benzyl-ammonium chloride (0-8 mol%) with hydrophilic monomer N,N-diallyl-N-carboethoxymethylammonium chloride and sulfur dioxide afforded a series of cationic polyelectrolytes (CPE). The CPEs were treated with HCl and NaOH to produce the corresponding pH-responsive cationic acid salts (CAS) and polybetaines (PB), anionic polyelectrolytes (APE) as well as polymers PB/APE containing various proportions of zwitterionic (PB) and anionic fractions (APE) in the polymer chain. Likewise, the cycloterpolymerizations of these single-, twin-, and triple-tailed hydrophobes (0-12 mol%) with hydrophilic monomer diallyldimethylammonium chloride and sulfur dioxide afforded a series of CPE in excellent yields. The polymers were characterized by different techniques including NMR and IR. The solution properties of the series of CPE were investigated by rheological techniques. The studied water soluble polymers showed different rheological behavior depending on their structure (hydrophobe type and content) as well as salinity and pH. The high shear thinning and the formation of networks at low shear would likely promote the use of such polymers in enhanced oil recovery applications.     

Synthesis of guanidine‐containing copolymers and their applications in the sorption of transition metals

2,2‐Diallyl‐1,1,3,3‐tetraethylguanidinium chloride copolymers with N‐substituted maleimides have been prepared by free radical copolymerization. Specific surface area and porosity of the copolymers under investigation have been determined by using the low‐temperature adsorption method. Sorption capacity of the copolymers toward Re(VII), Mo(VI), Ni(II) and Cu(II) ions has been investigated. The influence of treatment time, temperature and pH on sorption of metal ions was studied. Copyright © 2016 John Wiley & Sons, Ltd.     

Water-soluble polymer derivatives of cholesterol

New cholesterol-containing water-soluble polymers based on N-methacryloyl aminoglucose and N-vinylpyrrolidone are synthesized by free-radical copolymerization and polymer-analogous transformations. Binary and ternary copolymers of various composition containing N-allylamine and N,N,N-trimethylaminoethyl methacrylate methyl sulfate units and cholesterol residues are prepared. Luminescently labeled copolymers of the same composition are obtained. Effects of the nature of polymers and the amount of cholesterol in them on the intramolecular mobility of macromolecules in solution are studied with polarized luminescence. When 2–4 mol % of cholesterol residues are incorporated into the copolymer, the intramolecular mobility of macromolecules decreases, thus indicating formation of intramolecular compact structures via interaction of nonpolar cholesterol groups. In copolymers containing charged groups, these structures are looser than those in neutral copolymers. It is shown that macromolecules of cholesterol-containing polymers of various types can interact with each other. 1 This work was supported by the Russian Foundation for Basic Research (project no. 08-03-00324) and the Council for Grants of the President of the Russian Federation for Support of Leading Institutes of Higher Education (NSh-4391.2008.3).     

Effect of solvent nature on free-radical copolymerization of N,N-diallyl-N,N-dimethylammonium chloride and maleic acid

The free-radical copolymerization of N,N-diallyl-N,N-dimethylammonium chloride with maleic acid in DMSO proceeds to yield statistical copolymers. When the reaction is carried out in methanol, the copolymers of constant compositions (N,N-diallyl-N,N-dimethylammonium chloride: maleic acid = 2: 1) are formed over a wide range of comonomer ratios in the starting mixture. The formation of alternating copolymers in this case may be attributed to formation of donor-acceptor complexes between the comonomers in the methanol solution, as evidenced by UV spectrophotometry. The kinetic features of the process have been investigated, and the relative activities of the monomers have been assessed. ¹³C NMR studies have demonstrated that, regardless of the solvent nature, both double bonds of N,N-diallyl-N,N-dimethylammonium chloride are involved in copolymerization via intermolecular cyclization accompanied by formation of pyrrolidinium structures.     

Stereoelective radical copolymerization of (RS)-α-methylbenzyl vinyl ether with (S)-(-)- or (R)-(+)-N-(α-methylbenzyl)maleimide

Racemic α-methylbenzyl vinyl ether was copolymerized with optically active (S)-(-)- or (R)-(+)-N-(α-methylbenzyl)maleimide using 2,2′-azobisisobutyronitrile in order to examine the possibility of stereoelective radical polymerization of vinyl-type racemic monomers. The resulting copolymers were found to have almost alternating sequences of the two kinds of monomeric units. The non-polymerized α-methylbenzyl vinyl ether, recovered from the copolymerization system, showed an optical activity of opposite sign to the optically active comonomer used, indicating clearly that the co-polymerization process is stereoelective. It was confirmed that α-methylbenzyl vinyl ether preferentially incorporated in the copolymer has the same absolute configuration as the optically active N-substituted maleimide.     

Free-Radical copolymerization of N-vinylsuccinimide with butyl acrylate in the presence of zinc chloride and aluminum chloride

The free-radical copolymerization of N-vinylsuccinimide with butyl acrylate performed in dimethyl sulfoxide and benzyl alcohol in the presence of zinc chloride and aluminum chloride as complexing agents is studied. Under the given conditions, the reactivity ratios are determined. It is shown that zinc chloride influences the electron-density distribution only in butyl acrylate molecules. It is found that benzyl alcohol retards the total rate of polymerization. The character of the monomer-unit distribution in copolymer macromolecules is described.     

Asymmetric synthesis of enantio-enriched acyclic α-amino alkylstannanes and rearrangement behavior of carbanions thereof

An efficient stereocontrolled synthesis of enantio-enriched N-Boc-N-allyl-α-amino alkylstannanes and N,N-diallylic α-amino alkylstannanes starting from enantio-enriched α-hydroxy alkylstannane has been developed. The aza-Wittig rearrangement of enantio-defined N,N-diallyl-α-amino alkyllithium, generated by tin-lithium exchange, is shown to proceed predominantly with inversion of configuration at the Li-bearing carbon terminus.     

Radical copolymerization of N,N-Diallyl-N,N-dimethylammonium chloride and fumaric acid

The copolymerization of N,N-diallyl-N,N-dimethylammonium chloride and fumaric acid under conditions of radical initiation is studied. The reaction yields copolymers that exhibit a random distribution of comonomer units in the macrochain. Fumaric acid is highly active in the copolymerization of the above system. A significant effect on the relative activity of the comonomers is exerted by the type of solvent. The kinetics of the copolymerization is studied; the structuring of the copolymers is determined.     

Complexation of sodium 2-acrylamido-2-methylpropanesulfonate-monoethanolamine vinyl ether copolymer with polyelectrolytes in aqueous medium

A new water-soluble polyelectrolyte—the copolymer of sodium 2-acrylamido-2-methylpropanesulfonate and monoethanolamine vinyl ether—has been synthesized by free-radical copolymerization. The concentration behavior of the reduced viscosity of copolymer solutions that is typical for polyelectrolytes has been revealed. The reactivity ratios of the monomers have been measured. These values indicate a lower reactivity of monoethanolamine vinyl ether than that of sodium 2-acrylamido-2-methylpropanesulfonate. The complexation of this copolymer with poly(acrylic acid) and poly(N,N-dimethyl-N,N-diallylammonium chloride) has been studied. It has been found that the copolymer demonstrates the polyampholytic behavior and is able to form interpolymer complexes both with polycations and polyanions. It has been established that the polycomplex of the copolymer with polyacrylic acid has the unfolded structure due to the presence of sulfonate groups uninvolved in complexation, while the complex of the copolymer with poly(N,N-dimethyl-N,N-diallylammonium chloride) is compact owing to enhancement of hydrophobic interactions, and the sizes of its species are of the order of 80 nm.     

Homo-and copolymerization of propylene and ethylene in the presence of titanium dichloride complexes with dioxolane dicarboxylate and bis(difurylmethanephenoxyimine) ligands

The polymerization of propylene and ethylene and the copolymerization of these olefins with postmetallocene catalysts [(4R,5R)-2,2-dimethyl-α,α,α′,α′-tetra(perfluorophenyl)-1,3-dioxolane-4,5-dimethanol] titanium(IV) dichloride and bis{N-(3,5-ditert-butylsalicylidene)-4-[bis(5-methyl-2-furyl)methyl]aniline}titanium( IV) dichloride have been studied. The polymerization of propylene and its copolymerization with ethylene have been carried out in a liquid monomer, while the polymerization of ethylene has been performed in toluene at the constant concentration of the monomer. Polymethylaluminoxane has been used as a cocatalyst. The activity of the catalysts in the polymerization of propylene and ethylene at 50°C is ～ 10 and ～45 kg PP/mol Ti h mol C₃H₆/l and 178.5 and 2700 kg PE/mol Ti h mol C₂H₄/l, respectively. It has been established that, in the copolymerization of propylene with ethylene, the active sites of both catalysts selectively polymerize ethylene. The resulting copolymers have a block structure (r ₁ r ₂= 4.6); as a result, the crystalline phase of polyethylene is formed in them. Polypropylene and propylene-ethylene copolymers are elastomeric materials. Polypropylene samples synthesized with [(4R,5R)-2,2-dimethyl-α,α,α′,α′-tetra(perfluorophenyl)-1,3-dioxolane-4,5-dimethanol]titanium(IV) dichloride demonstrate a high melting point (150–157°C) in combination with good elastic properties. Polyethylene is a linear polymer with the degree of crystallinity varying from 37 to 45% and a melting point of 133–134°C. The mechanical properties of the polymers and copolymers have been investigated.     

Copper(II) complexes derived from substituted 2,2′-bis-(4-isopropyl-4-methyl-4,5-dihydro-1H-imidazol-5-one) ligands: Synthesis,structure and catalytic activity

New chiral N,N-bidentate 2,2′-bis-(4-isopropyl-4-methyl-4,5-dihydro-1H-imidazol-5-one) ligands have been prepared and characterised by their ¹H and ¹³C NMR spectra and/or optical rotation. The ligands prepared were then tested for their ability to form complexes with copper(II) salts. It was found that the most stable complex is formed from the 2,2′-bis-(4-isopropyl-1,4-dimethyl-4,5-dihydro-1H-imidazol-5-one) ligand and copper(II) chloride. The structure of this complex was determined by means of quantum-chemical computations at the B3LYP or UB3LYP/6-31G(d,p) level. According to the computations, the geometry of the copper atom most resembles a tetrahedral arrangement, which was also confirmed by means of X-ray structural analysis. It was found that the structure of this copper(II) complex does not allow the copper atom to coordinate to additional ligands; therefore, it is catalytically inactive in the asymmetric Henry reaction.     

Copolymerization of N,N-diallyl-N,N-dimethylammonium chloride and vinyl acetate

The free-radical copolymerization of N,N-diallyl-N,N-dimethylammonium chloride with vinyl acetate in DMSO, methanol, and a methanol-water (70: 30, mol %) mixture proceeds to yield statistical copolymers. The nature of solvents significantly affects the reactivity ratios of the comonomers. N,N-Diallyl-N,N-dimethylammonium chloride shows a higher reactivity than vinyl acetate. The kinetic features of the processes have been investigated, and the structure and properties of the copolymers have been studied.     

The preparation and some chemistry of 2,2-dimethyl-1,2-dihydroquinolines

The cyclisation of N-(1,1-dimethylpropargyl) anilines, using cuprous chloride in refluxing toluene, yields 6-substituted-2,2-dimethyl-1,2-dihydroquinolines. The reactivity of the double bond in the heterocyclic ring of these products is exemplified by chlorination, to yield 6-substituted-3,4-cis-dichloro-2,2-dimethyl-1,2,3,4-tetrahydroquinolines which can be selectively dechlorinated to provide 6-substituted-3-chloro-2,2-dimethyl-1,2,3,4-tetrahydroquinolines; epoxidation to yield an epoxide, which can be hydrogenolysed to the corresponding 3-hydroxy product and in turn oxidised to the 3-keto derivative; and oxymercuration to provide a 4-hydroxy product and hence a 4-keto derivative. Dehydrochlorination of a 3,4-dichloro product provides a 3-chloro-1,2-dihydroquinoline which can be hydrolysed to a 3-keto system. The formation of cis 3,4-dichloro products from the chlorination, as well as the formation of a cis chlorohydrin from the chlorination of N-acetyl-2,2,6-trimethyl-1,2-dihydroquinoline in partially aqueous solution, suggests that N-acetyl, or N-trifluoroacetyl groups, participate in the addition process.