Cationic polyelectrolytes. II. Amination of chloromethylated polystyrene with hydroxyalkylic secondary amines

The reaction of chloromethylated polystyrene with methyl(2- hydroxyethyl)amine and butyle (2-hydroxyethyl)amine was studied kinetically. The reaction of benzyl chloride with these amines was also investigated for comparison. N,N-dimethylformamide and dioxane were used as solvents. The reactions of benzyl chloride with the two amines in these solvents took place according to normal kinetics of the second order. Reaction kinetics depend on the nature of the amine and solvent in Chloromethylated polystyrene reactions. In dioxane the self-accelerating effect of the reaction for β ? 0.5 is apparent. Steric hindrance of the reaction, beginning with a conversion degree of about 75%, wss observed for butyl(2-hydroxyethyl)amine in N,N-dimethylformamide. This self-accelerating effect is observed in dioxane at the same reaction degree. The activation energies and frequency factors were calculated for the amination of benzyl chloride and chloromethylated polystyrene with the two amines in N,N-dimethylformamide and dioxane.     

Benzimidazole polymers from aldehydes and tetraamines

A new method for the preparation of benzimidazole polymers is described. The solution polymerization of aromatic tetraamines with isophthalaldehyde bis bisulfite adduct in N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (MP), and dimethyl sulfoxide (DMSO) produced polybenzimidazoles with viscosities (ηinh) in the range of 0.3–0.5 measured in formic acid solution. Also a model compound study with benzaldehyde, benzaldehyde diethyl acetal, and benzaldehyde bisulfite adduct with o-phenylenediamine was carried out. The results showed that the reaction of benzaldehyde bisulfite adduct with o-phenylenediamine in DMAc as the solvent gave quantitative yields of 2-phenylbenzimidazole. Excellent yields of 2-phenylbenzthiazole, 2-phenylbenzoxazole, and 2-pyridylbenzimidazole were also obtained with the benzaldehyde bisulfite adduct and picoline-2-carboxaldehyde bisulfite adduct with o-aminothiophenol, o-aminophenol, and o-phenylenediamine. The reaction conditions for the preparation of the polymers and the model compounds are very mild and the reaction times range from 15 min to 1 hr for the model compounds and 3–5 hr for the polymers. Longer reaction times did not increase the viscosities of the polymers to any extent.     

Polymerization of asymmetric polyfunctional monomers. III. Ionic polymerization of acrylic and methacrylic esters of 2-allylphenol

The polymerization of acrylic and methacrylic esters of 2-allyphenol with different anionic, cationic and coordination catalysts was studied. The polymerization occurs exclusively or predominantly through (meth)acrylic C?C double bonds in all the studied cases. With anionic catalysts the allylic groups are not polymerizable and the polymers have linear structure. Polymerization with catalysts based on dialkylaluminum chloride (alone or associated with some metal salts) yields soluble or partially crosslinked polymers, depending on the reaction conditions. The crosslinking is due to the participation of allylic groups in the polymerization reactions. Copolymers of acrylic and methacrylic esters of 2-allylphenol with styrene, acrylonitrile, methyl methacrylate, N-vinylcarbazole and 1,3-pentadiene were synthesized by copolymerization in the presence of anionic catalysts and of systems based on dialkylaluminum chloride.     

Effect of the Medium on the (Co)polymerization Kinetics and Properties of N-Vinyl-3(5)-methylpyrazole (Co)polymers

The kinetics of homopolymerization of N-vinyl-3(5)-methylpyrazole, its copolymerization with vinyl acetate, 2-hydroxyethyl methacrylate, and acrylic acid, as influenced by the reaction medium, were studied. The properties of the resulting (co)polymers were determined.     

Synthesis and properties of novel poly(N-oxyimide)s

Novel poly(N-oxyimide)s (PNOI) were synthesized by the room temperature polycondensation of N,N′-dihydroxypyromellitimide (I) with dichloro compounds in N,N-dimethylformamide (DMF) in the presence of triethylamine both as base as well as catalyst. The dichloro compounds used were 1,4-bis(chloromethyl)-2,5-dimethylbenzene (II), 1,5-bis(chloromethyl)-2,4-dimethylbenzene (III), 1,4-bis(chloromethyl)-2,5-dimethoxybenzene (IV) and 1,4-dichlorobut-2-yne (V). Polymer synthesis, characterization, and properties such as density, viscosity, solubility, crystallinity, and thermal stability were described. Two model compounds, viz. (i) MNOI-1 from N-hydroxyphthalimide and a dichloro compound (III), (ii) MNOI-2 from I and benzyl chloride were also synthesized to confirm the formation of polymers. The polymers thus obtained had high intrinsic viscosities in the range 1.09–1.18 dl/g. The thermal decomposition of the polymers started around 260°C with 20–25% decomposition and about 50% weight loss was observed at 400°C.     

Prodendronic polyamines from stable or labile methacrylates obtained by selective Michael addition onto asymmetric diacrylic compounds

A new synthetic strategy for the preparation of methacrylic monomers and polymers carrying acyl β‐amino groups is presented. The approach is based on the Michael addition of aliphatic amines onto asymmetric acrylic/methacrylic compounds, reacting the amine highly selectively with the acrylic unit while leaving the methacrylic moiety unreacted. The corresponding polymers are then obtained by conventional radical polymerization. The use of N,N,N′,N′‐tetraethyldiethylenetriamine (TEDETA) as the secondary amine leads to TEDETA moieties supported on polymeric chains. The new aminopolymers are sensitive to pH and to temperature exhibiting a lower critical solution temperature of between 50 and 90 °C. A further interesting feature of the new approach is that the stability toward hydrolysis of the side β‐amino acyl compounds was found to be dependent on whether an acrylamide or an acrylate is employed as the acrylic group of the asymmetric starting material. The esters exhibit an enhanced sensitivity to hydrolysis, compared to standard aliphatic esters, and decompose releasing a derivative of the amine precursor, within hours or weeks, depending on the pH and temperature conditions. The use of the amides leads to stable polymers when the same experimental conditions are applied. The novel dendronic polyamines have been proven to interact with DNA and to transfect cells with efficiency close to that obtained with polyethyleneimine vectors used as positive controls. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2297–2305     

Uncatalyzed polymerization of bistriazolinediones with electron-rich aromatic compounds via electrophilic aromatic substitution

The reaction of 4-substituted-1,2,4-triazoline-3,5-diones(4R-TD's), i.e., MeTD(4-methyl substituted) and PhTD(4-Phenyl substituted) with electron rich aromatic compounds were investigated. N,N-Dimethylaniline undergoes reaction instantaneously with MeTD and PhTD. Electrophilic aromatic substitution occurred at room temperature at the para position without use of any catalyst. N,N,N′,N′-tetramethyl-m-phenylenediamine (TMPDA) undergoes reaction with 2 mol of PhTD and MeTD which lead to the formation of 2:1 adducts in high yields. These compounds were fully characterized by IR, ¹³C-NMR, ¹H-NMR and elemental analysis and were used as model compounds. The reaction of bistriazolinediones with TMPDA was performed in dimethylformamid at room temperature. The reactions are exothermic, fast, and gave novel polymer structures via electrophilic aromatic substitution. Some physical properties and structural characterization of these new polymers have been studied, and will be reported.     

Copolymerization of cationic monomers with acrylamide in an aqueous solution

The radical copolymerizations of commercially available cationic monomers (M₁) with acrylamide (M₂) have been investigated at pH 6.1 in aqueous solutions. The cationic groups in copolymers were analyzed by a colloid titration method and the reactivity ratios were determined by the Fineman–Ross method. The values of r₁ and r₂ were 1.71 and 0.25 for methacryloyloxyethyltrimethylammonium chloride? M₂, 1.68 and 1.26 for N,N-dimethylaminoethylmethacrylate? M₂, 1.13 and 0.57 for methacrylamidopropyltrimethylammonium chloride? M₂, 1.10 and 0.47 for N,N-dimethylaminopropylmethacrylate? M₂, 0.47 and 0.95 for N,N-dimethylaminopropylacrylamide? M₂, 0.48 and 0.64 for acryloyloxyethyltrimethylammonium chloride-M₂, and 0.58 and 6.7 for dimethyldiallylammonium chloride-M₂ systems. The Alfrey-Price Q and e values were calculated and the linear relationship between log Q and ultraviolet absorption maxima of cationic monomers was found.     

Novel synthesis of polymeric phase transfer catalyst containing polar unit

Soluble polymeric phase transfer catalysts (PTCs) containing benzyltributylphosphonium chloride moieties and p-nitrophenoxy group or N,N-dimethylacrylamide as a polar unit were prepared via two-step reactions from polymers with chloromethyl group and polar units. These polymers were synthesized by copolymerization of p-chloromethylstyrene and the corresponding monomer or substitution of some parts of chloromethyl group with potassium p-nitrophenoxide. When the obtained polymers were added, the phase transfer catalyzed reaction of benzylchloride with solid potassium acetate to proceed smoothly. The catalytic activity was strongly affected by the content of phosphonium chloride and the varieties of comonomer unit in the polymeric PTC. The polymeric PTC containing N,N-dimethylacrylamide unit showed much higher catalytic activity than the corresponding low molecular weight PTC when the phase transfer catalyzed reaction was carried out in low polar solvent. © 1994 John Wiley & Sons, Inc.     

Cationic polyelectrolytes. I. Soluble polymers prepared from reaction of chloromethylated polystyrene with tris(2-hydroxythyl)amine

The reaction of chloromethylated polystyrene with tris(2-hydroxyethyl)amine in N,N-dimethylformamide is described for the conditions to prepare soluble reaction products. The groups of the quaternary ammonium salt, which appear in the first stage of the reaction, transpose to the amino-ether groups. The reaction was followed by elementary analysis, IR and ¹H-NMR spectra, and viscosimetric measurements for nondialyzed and dialyzed samples. The presence of the tertiary amine groups on obtained polymers was also shown by titration. The polymers from the reaction of chloromethylated polystyrene with tris(2-hydroxyethyl)amine reacted easily with benzyl chloride.     

Polyimides derived from bismethylolimides. II. Polyamine-imides from bismethylolimides and diamines

Compounds in the N-methylolimide group reacted smoothly with amines in the presence of water to yield the corresponding condensation products. Polycondensations of bismethylolimides, N,N′-bismethylolpyromellitic diimide, and N,N′-bismethylolbenzophenonetetracarboxylic diimide, with amines such as aromatic diamines, piperazine, and n-butylamine, were carried out in DMAc that contained 1% water to produce linear polyamine-imides. The polyamine-imides assumed various colors, from very pale yellow to deep purple, and had inherent viscosities in the 0.07–0.37-dl/g range. Most of these polymers were soluble in polar solvents such as DMAc and DMSO. The thermal stability of the polymers was examined by thermogravimetric analysis; decomposition started at 210–350°C and weight residue at 500°C was 22–85% in air.     

Zerovalent metal polymer composites. II. Metal–polymer microdispersions

Metallization of water-soluble polymers incorporating metal-binding ligand is achieved by binding palladium ions at substoichiometric quantities, followed by reduction to polymer–zero-valent palladium complex and deposition of transition metal ions by electroless plating solutions. The polymers studied include poly[N,N,N-trimethyl-N-(m- and p-vinylbenzyl)ammonium chloride], poly-L -glutamic acid, poly-L -lysine, and a copolymer of 2-phenylhydroquinone-2-amino-phthalic acid. Noble metal polyelectrolyte solutions were directly reduced with dimethylamineborane to stable microdispersions. The reactive nickel, cobalt and copper microdispersions were coated on KODAK ESTAR filmbase. Scanning electron microscopy (SEM), ESCA, and IR were used for material characterization. Conductivity and magnetic properties were also measured. Hydrophobic materials such as graphite and fluorinated graphite were metallized in organic solvents using hydrophobic trioctylammonium–tetrachloropalladate as the activating noble metal complex. The metallized conductive graphites were evaluated for their electrochemical properties.     

Preparation and properties of N-phenylated aromatic polyamides from N,N′-diphenyl-p-phenylenediamine and aromatic diacid chlorides

N-Phenylated aromatic polyamides and copolyamides derived from N,N′-diphenyl-p-phenylenediamine, isophthaloyl, and terephthaloyl chloride were prepared by high-temperature solution polycondensation in anisole at 155°C. Factors that influenced the reaction, such as monomer concentration, solvent, temperature, and time, were studied to determine the optimum conditions for the preparation of high molecular weight polymers. Compared with analogous unsubstituted aromatic polyamides, the N-phenylated polymers exhibited better solubility in chlorinated and amide solvents, reduced crystallinity, and lower glass transition temperatures (above 200°C). All polymers except the polyterephthalamide could be solvent-cast, as well as hot-pressed, into transparent flexible films.     

Novel synthesis of polymeric phase transfer catalysts containing N,N-dialkylacrylamide unit and their catalytic activity

Soluble polymeric phase transfer catalysts (PTCs) containing benzyltributylphosphonium chloride moieties and polar N,N-dialkyl-acrylamide with long alkyl groups such as N,N-dipropylacrylamide, N,N-dibutylacrylamide, N,N-dihexylacrylamide, and N,N-dioctylacrylamide were prepared via two-step reactions from p-chloromethylstyrene and the corresponding N,N-dialkylacrylamide. When the obtained polymers were added, the phase transfer catalyzed reaction of benzylchloride with solid potassium acetate to proceed smoothly. The catalytic activity was strongly affected by the content of phosphonium chloride and the varieties of comonomer unit in the polymeric PTC. The polymeric PTC containing the N,N-dihexylacrylamide unit showed excellent high catalytic activity in a low polar solvent such as the mixed solvent of toluene with 70 vol % n-tridecane. Therefore, the polymer containing lipophilic long chains such as the hexyl group is desirable for polymeric PTC. © 1996 John Wiley & Sons, Inc.     

Polyimides derived from bis-N-hydroxyimides. II. Synthesis and properties of polyimide-esters

Polycondensation of bis-N-hydroxyimides, N,N′ dihydroxypyromellitic diimide, and N,N′ -dihydroxybenzophenonetetracarboxylic diimide with dicarboxylic acid chlorides was carried out in dimethylacetamide in the presence of triethylamine to produce novel polyimide-esters. The resulting polymers had inherent viscosities up to 0.27 dl/g. These polyimide-esters and model compounds exhibited high reactivity toward nucleophiles such as aniline and n-butylamine, which brought about rapid reductions in the viscosity of the polymers. These polymers were fairly resistant to organic solvents but soluble in m-cresol. Thermal stability oft he polyimide-esters was evaluated by thermogravimetry and their good heat-resistant properties were confirmed.     

Studies of some new bioactive acrylic esters

Four typical bioactive esters of acrylic monomers, N-p-acryloxybenzoyloxysuccinimides, 3-ac-ryloxy-4-oxo-3,4-dihydro-1,2,3-benzotriazines, N-acryloxy-5-norbornene-2,3-dicarboximides, and I-p-acryloxybenzoyloxybenzotriazoles, were Synthesized and polymerized as reactive polymers. Twelve new monomers were prepared by coupling acrylic acid, methacrylic acid, p-acryloxybenzoic acid, or p-methacryloxybenzoic acid with four N-hydroxy compounds such as N-hydroxysuccinimide (HOSu), 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOObt), N-hydroxy-5-norbornene-2,3-dicarboximide (HONB), and I -hydroxybenzotriazole (HOBT) in the presence of dicyclohexylcarbodimide. All monomers polymerized readily in solution with azobisisobutyronitrile (AIBN) as free radical initiator. The resulting reactive polymers with reactive ? OSu, ? OObt, ? ONB, or ? OBT group on the side chain are equally reactive toward n-butylamine at room temperature in the formation of corresponding polyacrylamides. Reactive polymers were used to immobilizetrypsin. It has been found that poly(N-p-methacryloxybenzoyloxy-5-norbornene-2,3-dicarboximide)-trypsin matrix had high activity around three times that of the poly(N-methacryloxy-5-norbornene-dicarboximide)-trypsin matrix. It is proposed that this activity may be due to the presence of a long spacer arm with a hydrophobic and rigid benzene ring between the ligand and matrix. The reactive poly(N-p-methacryloxybenzoyloxysuccinimide-p-methacryloxybenzoic acid) copolymer was used to immobilize the serum protein. This immobilized protein was a hopeful bioactive solid immunoadsorbent.     

Active nickel-based reduction of organic compounds

The reducing system NiCl₂·2H₂O—Li—arene_cat (cat is catalyst) was proposed for use to reduce a wide range of organic compounds, including alkenes, alkynes, carbonyl compounds, imines, halogenated derivatives, sulfonates, aromatic compounds, hydrazines, azo and azoxy compounds, N-oxides, and nitrones. The degree of reduction can be controlled for some substrates. Deuterium can be incorporated in the reaction products using nickel chloride deuteriohydrate. Nitrones, N-alkoxyamides, and acyl azides are also reduced with the Li—arene_cat system containing no nickel salt.     

Synthesis and insecticidal evaluation of novel N‐oxalyl derivatives of diacylhydrazines containing methylcarbamate moieties

A series of new N‐oxalyl derivatives of diacylhydrazines containing methylcarbamate moieties were synthesized by the reaction of N‐oxalyl chloride of N‐methylcarbmates with N‐tert‐butyl‐N,N′‐diacylhydrazines in the presence of sodium hydride. The reaction of oxalyl chloride with N‐tert‐butyl‐N, N′‐diacylhydrazines to yield 1,3,4‐oxadiazole and 4‐tert‐butyl‐2‐substituted‐phenyl‐4H‐1,3,4‐oxadiazine‐5,6‐dione was found, and the reaction was studied in some detail. The title compounds were evaluated for molting hormone mimicking activity. The results of bioassay showed that the title compounds exhibit moderate larvicidal activities, and toxicity assays indicated that these compounds can induce a premature, abnormal, and lethal larval molt. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:472–475, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20135     

Pseudo-poly(amino acid)s: study on construction and characterization of novel chiral and thermally stable nanostructured poly(ester-imide)s containing different trimellitylimido-amino acid-based diacids and pyromellitoyl-tyrosine-based diol

A new class of chiral and potentially biodegradable poly(ester-imide)s (PEI)s as pseudo-poly(amino acid)s (PAA)s bearing natural amino acids in the main chain was synthesized. In this investigation, N,N′-(pyromellitoyl)-bis-(L-tyrosine dimethyl ester) as a biodegradable optically active diphenol and synthesized trimellitic anhydride-derived dicarboxylic acids containing different natural amino acids such as S-valine, L-methionine, L-leucine, L-isoleucine, and L-phenylalanine were used for direct polyesterification. With the aim of tosyl chloride/pyridine/N,N′-dimethylformamide system as a condensing agent, the new optically active PEIs were obtained in good yields and moderate inherent viscosity up to 0.42 dL/g. The obtained polymers were characterized with FT-IR, ¹H-NMR, X-ray diffraction (XRD), field emission scanning electron microscopy, elemental, and thermogravimetric analysis techniques. These polymers show high solubility in organic solvents, such as N,N′-dimethyl acetamide, N-methyl-2-pyrrolidone, and sulfuric acid at room temperature, and are insoluble in solvents, such as methylene chloride, cyclohexane, and water. Morphology probes showed these pseudo-poly(amino acid)s were noncrystalline and nanostructured polymers. On the basis of thermogravimetric analysis data, such PAAs are thermally stable and can be classified as self-extinguishing polymers. In addition due to the existence of amino acids in the polymer backbones these pseudo-PAAs not only are optically active but also are expected to be biodegradable and therefore could be classified under eco-friendly polymers.     

Microphase separated structures based on N-substituted polydiallylamines

The ionogenic polymers namely poly(N,N-diallyl-N-cetylammonium hydronitrate) (PDACA · HNO₃) and poly(N,N-diallyl-N,N-dimethylammonium chloride)-block-poly(cetyl acrylate) (PDADMACl-block-PA-16) were synthesized via activation of the terminal double bond of the PDADMACl precursor and initiation of the polymerization of the acrylic monomer in alcohol solution. The microphase separated structure of a blend of both homopolymers and of the block copolymer was proved by differential scanning calorimetry (DSC) and X-ray diffraction measurements. Side chain crystallization in PDA-CA · HNO₃ completely restricts the crystallization of the ionogenic backbones which, however, control the layered structure and the crystallization of the aliphatic chains. In PDADMACl-block-PA-16 crystalline polyacrylate blocks coexist with crystalline ionogenic blocks. The length of the polyacrylate block influences the ability of the ionogenic block to form the crystalline structure.