Interpolyelectrolyte complexes formation in dependence on the nature of polyelectrolytes

Interpolyelectrolyte complexes (PECs) were obtained starting from polycations with (N,N-dimethyl-2-hydroxypropylenammonium chloride) units in the main chain and sodium salts of the poly(acrylic acid), on one hand, and poly (2-acrylamido-2-methylpropane sulfonic acid), on the other hand, as polyanions. The polycations were different as concerns both the content of the quaternary ammonium salt groups and the degree of branching. The polyanions were different both by their structure and molecular weight. The complex formation was followed through the variation of the reduced viscosity and of the conductivity of the reaction medium vs. the unit molar ratio polyanion/polycation in two ranges of concentration.     

Potentiometric response of graphite electrodes coated with modified polymer films

Graphite electrodes coated with chemically-modified polymer films are described. Several different polymers were used, including poly(acrylic acid), poly[triethyl(vinylbenzyl)ammonium chloride], poly[trihexyl(vinylbenzyl)ammonium chloride], and poly[trihexyl(vinylbenzyl)ammonium thiocyanate]. A cation-responsive electrode can be prepared from poly(acrylic acid)-coated graphite. Anion-responsive electrodes can be prepared from graphite coated with polymeric quaternary amines. In these electrodes, the ion-sensing species is irreversibly attached to the polymer (rather than physically entrapped within a polymer matrix); this factor eliminates leaching of the active component, and the addition of a plasticizer is unnecessary. A selective sensor for thiocyanate is described; it yields a Nernstian response over the concentration range 1 × 10^?1–1 × 10^?5 M sodium thiocyanate.     

Synthesis and evaluation of cationic and cationogenic polymeric sorbents for removing surfactants from aqueous solutions

Polymers based on 2‐dimethylaminoethyl methacrylate (DMAEMA) crossslinked with ethylene glycol dimethacrylate (EGDMA) or N,N′‐methylenebisacrylamide (MBAA) have been prepared by solution‐suspension polymerization. Polymers containing ammonium groups were synthesized by quaternization of aminofunctional polymers obtained with ethyl or dodecyl bromide or by the polymerization of respective quaternized monomers. Influence of the content of DMAEMA in the polymers, nominal degree of crosslinking, length of alkyl substituent in quaternary ammonium groups as well as particle size on the sorption of anionic and nonionic surfactants from aqueous solutions has been studied.     

Cyclopolymerization of diallylamine derivatives in dimethyl sulfoxide

Diallyl quaternary ammonium chlorides, bromides and N-alkyldiallylamine hydrochlorides were polymerized with ammonium persulfate (APS) in dimethyl sulfoxide (DMSO). The dependences of yield and molecular weight of polymers on polymerization conditions were examined and quaternary ammonium chlorides were found to have better polymerizability than bromides. The poly(diallyl quaternary ammonium chlorides) obtained with APS—DMSO system are expected to have quite high molecular weights, as determined from the measurement of limiting viscosity numbers of the polymers in NaCl aqueous solution.     

Molecular imprinting on amphiphilic folded polymers for selective molecular recognition in water

We report amphiphilic folded polymers with imprinted nanocavities for selective molecular recognition in water. For this, a molecular imprinting technique is applied to the polymer synthesis: amphiphilic polymer micelles interacting with template molecules are crosslinked in water to fix the folded architecture and memorize the template structure within the polymers; the removal of the templates provides imprint polymers bearing template-specific nanospaces. Here, a hydrophilic dye bearing two anionic groups, Orange G (OG), is used as a model template. For the imprinting, we design amphiphilic random copolymers bearing hydrophilic poly(ethylene glycol) (PEG) chains, hydrophobic olefin groups, and quaternary ammonium groups that can interact with the template. The copolymers were prepared by living radical polymerization and post functionalization. In the presence of OG and methyl blue (MB), the imprinted nanocavity polymers simultaneously capture both of the dyes in water. The total number of encapsulated dyes increased with increasing the number of polymer-bound quaternary ammonium groups. The selectivity of OG against MB increased with the crosslinking density, while imprint polymers encapsulated OG more efficiently than nonimprint polymers. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 215–224     

Substitution and elimination reactions of poly(epichlorohydrin) and poly(2-chloroethyl vinyl ether) using phase transfer catalysis

The reactions of poly(epichlorohydrin) (PECH) and poly(2-chloroethyl vinyl ether) (PCEVE) with various reagents were investigated using phase transfer catalyst (PTC) such as tetra-n-butylammonium bromide (TBAB), 18-crown-6 (CR6), and dicyclohexyl-18-crown-6 (DCHC) is a solid—liquid two-phase system. Although the reactions of these polymers hardly occurred without PTC in nonpolar solvents such as toluene and diglyme under mild conditions, the addition of PTC caused the reactions to proceed smoothly under the same conditions. In addition, the reactions of PECH and PCEVE with a strong base such as potassium hydroxide proceeded selectively through β-elimination reaction to produce the polymers with pendant vinyl groups. These results suggested this method is useful for the syntheses of functional polymers. On the other hand, it turned out that quaternary ammonium salts such as TBAB have higher catalytic activity than crown ethers such as CRG and DCHE in these reactions. Furthermore, the catalytic activity of quaternary ammonium salts was strongly influenced by their chain length and the structure of the polymers.     

两亲性全季铵盐超支化聚合物的设计与合成及主-客体超分子着色应用研究

采用高效的巯基-炔点击化学与Menschutkin季铵化反应,合成了一种带有1个叠氮基、2个炔基和2个季铵盐基团的AB2型季铵盐单体,通过核磁共振、红外光谱、质谱等方法对单体结构进行了确认.将所得单体进行点击聚合,得到全季铵盐超支化聚合物,并用端叠氮基的长链烷烃封端,得到核亲水-壳憎水的两亲性超支化聚季铵盐.研究所得两亲性超支化聚合物对染料的装载性能,结果表明所合成的带正电荷两亲性聚合物对多种带负电荷的水性染料装载效果好,平均相转移率高达95%.进一步将装载染料的主-客体超分子复合物用于聚合物制品着色,发现其对SBS及PMMA等聚合物有很好的着色效果,着色均匀且不掉色,着色的膜色泽鲜艳透明.     

Esterification of polymeric carboxylic acids

Polymers containing pendant carboxyl groups have been essentially completely esterified with little apparent change in molecular weight by the use of one of the following reagents: (1) trialkyl orthoesters, (2) dimethylformamide dialkyl acetals, (3) tertiary amines followed by alkyl halides, (4) quaternary ammonium hydroxide followed by alkyl halides. The use of some of these methods permits preparation of certain polymers that were previously not readily accessible.     

Amphiphilic poly(N,N-dimethylamino-2-ethyl methacrylate)-g-poly(ε-caprolactone) graft copolymers: synthesis and characterisation

Amphiphilic poly(N,N-dimethylamino-2-ethyl methacrylate)-g-poly(ε-caprolactone) graft copolymers (PDMAEMA-g-PCL) with various compositions and molecular weights were synthesised via a fully controlled three-step strategy. First, poly(ε-caprolactone) macromonomers (PCLMA) were prepared by ring-opening polymerization (ROP) of ε-caprolactone (CL) initiated by aluminum triisopropoxide (Al(OⁱPr)₃), followed in a second step by quantitative esterification of PCL hydroxy end-groups with a methacrylic acid derivative. Finally, the controlled copolymerization of PCLMA and N,N-dimethylamino-2-ethyl methacrylate (DMAEMA) was carried out by atom transfer radical polymerisation (ATRP) in THF at 60 °C using CuBr ligated with 1,1,4,7,10,10, hexamethyl triethylenetetramine and ethyl 2-bromoisobutyrate as catalyst and initiator, respectively. Furthermore, PDMAEMA-g-PCL graft copolymers were reacted with methyl iodide to convert the pendant tertiary amines into quaternary ammonium iodides increasing accordingly their water solubility. Some preliminary experiments was further carried out by tensiometry and dynamic light scattering in order to shed so light on the tensioactive behaviour of these amphiphilic graft copolymers (with protonated amines or quaternary ammonium cations).     

Microencapsulation of dichromate and paracetamol with Eudragit Retard polymers using phase separation by nonsolvent addition

A coacervation technique for microencapsulation using Eudragit Retard polymers [poly(methyl methacrylates) substituted by quaternary ammonium groups] as wall material is described, based upon phase separation using a cold chloroform-cyclohexane mixture together with polyisobutylene as a stabilizer. The effect of various parameters on the nature and properties of the microcapsules of potassium dichromate and paracetamol has been studied, in particular the alteration in wall content and structure and release rate of contents. The microcapsules are discrete, their properties are reproducible, and various degrees of sustained release are obtained.     

Solution behavior and solid phase transitions of quaternary ammonium surfactants with head groups decorated by hydroxyl groups

Hydrogen bonds are strong intermolecular interactions, which are very important in molecular aggregation and new phase formation. Three long-chain quaternary ammonium surfactants, N,N-diethyl-N-(2-hydroxyethyl)-N-octadecylammonium bromide with one hydroxyl group, N-ethyl-N,N-bis (2-hydroxyethyl)-N-octadecylammonium bromide with two hydroxyl groups and N,N,N-tris (2-hydroxyethyl)-N-octadecylammonium bromide with three hydroxyl groups, abbreviated as SHQ, DHQ, and THQ, respectively, were synthesized in this work. Their solution behavior and solid phase transitions were investigated by surface tension, differential scanning calorimetry (DSC), X-ray diffraction (XRD), polarizing optical microscopy (POM), and Infrared (IR) spectroscopy. The hydrogen bonds introduced by the substituted hydroxyl groups promoted surfactant adsorption at the air/water interface and aggregation in solution. In the crystal state, an increased number of hydroxyl groups caused a larger tilt angle of the long axis of surfactant molecules with the layer normal. Above certain temperatures, SHQ and DHQ formed highly ordered smectic T and smectic A phases while THQ only formed less ordered smectic A phase. The weakened electrostatic attractions between opposite ions and the thicker polar sublayers of mesophases caused by the enhanced number of hydrogen bonds are responsible for the mesophase formation and transition of these surfactants.     

Synthesis of anion conducting polymer electrolyte membranes by Pd-Catalyzed Buchwald-Hartwig Amination coupling reaction

A novel aryl bromine bearing polymer was synthesized by Friedel-Crafts polycondensation. This precursor polymer substrate was used for C–N coupling via Buchwald-Hartwig amination to incorporate 9 examples of aryl amines into the polymer chains with high conversions (80–100%). Two aminated polymers were subsequently quaternized to give anion conducting polymers. These quaternary ammonium polymers show promising electrochemical membrane property because of their ability to transport mobile anions through the material while being electrically insulating. Membrane characteristics crucial to high electrochemical performance including ion exchange capacity, anion conductivity, water uptake, swelling ratio, and alkaline stability were evaluated.     

Simultaneous two- and three-component determinations in multicomponent mixtures by extraction-spectrophotometry and thermochromism of ion-association complexes

A selective method of determination of amines and quaternary ammonium salts by solvent extraction and thermochromism of ion-association complexes has been established. The method is based on the formation of ion-association species with tetrabromophenolphthalein ethyl ester and the thermochromism effect in the organic phase at low temperature. The absorbance of the red amine charge-transfer complexes decreases quantitatively (DeltaA) with increase in temperature (DeltaT), and Delta A Delta T is characteristic of a particular species. This characteristic has been applied for the sensitive and selective determination of amines. The absorbance of the blue quaternary ammonium ion-association complexes does not vary with temperature, however, and the quaternary ammonium compounds can be determined without interference by amines because of the disappearance of the red species at 60 degrees . Methylephedrine, diphenhydramine, ephedrine (amines), benzethonium and/or berberine (quaternary ammonium compounds) in two- and three-component mixtures can be determined by using the thermochromism effect. The method is highly selective, sensitive and reproducible.     

Nonleaching antibacterial glass surfaces via "Grafting Onto": the effect of the number of quaternary ammonium groups on biocidal activity

Antimicrobial surfaces were prepared using the "grafting onto" technique. Well-defined block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) and poly(3-(trimethoxysilyl)propyl methacrylate) segments (PDMAEMA/PTMSPMA) and corresponding random copolymers were prepared via atom transfer radical polymerization (ATRP), followed by covalent attachment to a glass surface through reaction of the trimethoxysilyl groups with surface silanol groups. The density of quaternary ammonium (QA) groups available to bind small molecules in solution increased with polymer solution concentration and immobilization time. For the PDMAEMA 97- b-PTMSPMA xdiblock copolymers with a fixed length of PDMAEMA segment (degree of polymerization (DP) = 97) and varied lengths of PTMSPMA segments, maximal available surface charge was observed when the ratio of DP PDMAEMA to DP PTMSPMA was 5:1. The tertiary amino groups in immobilized PDMAEMA segments were reacted with ethyl bromide to form QA groups. Alternatively, block copolymers with prequaternized PDMAEMA segments were attached to surfaces. Biocidal activity of the surfaces with grafted polymers versus Escherichia coli ( E. coli) increased with the density of available QA units on the surface. The number of bacteria killed by the surface increased from 0.06 x 10(5) units/cm2 to 0.6 x 10(5) units/cm2, when the density of surface QA increased from 1.0 x 10(14) unit/cm2 to 6.0 x 10(14) unit/cm2. The killing efficiency of QA on all surfaces was similar with approximately 1 x 10(10) units of QA needed to kill one bacterium. The AFM analysis indicated that grafting onto the surface resulted in small patches of highly concentrated polymer. These patches appear to increase the killing efficiency as compared to surfaces prepared by grafting onto with the same average polymer density but with a uniform distribution.     

Capillary electrochromatography of hydrophobic amines on continuous beds

The capillary electrochromatographic separation performance of hydrophobic amines and a related quaternary ammonium compound on continuous beds based on polymers of acrylamide has been studied. The chromatographic bed is polymerized in situ and the character of the polymers with regard to hydrophobicity and charge has been systematically changed by regulating its content of isopropyl and sulfonate ligands, respectively. The best performance was obtained for columns with a molar ratio of 1:80 for the sulfonate and isopropyl groups, and resulted in efficiencies up to 200000 plates per meter. The effects on retention, resolution and elution order by ionic strength, pH, and content of acetonitrile in the mobile phase have been investigated. The quaternary ammonium compound was always the least retained irrespective of pH. By increasing the pH, a reversal of the migration order between the tertiary and secondary amine was obtained. The results indicate a complex migration/retention mechanism where ion-exchange, adsorption and electrophoretic mobilities play a role. The concentration limit of detection could be lowered from 1.3 microg/mL to 50 pg/mL by using a high content of 2-propanol (96%) in the sample compared to dissolving the analytes in the mobile phase.     

Polymers with Tethered Anionic and Cationic Groups as Membranes for Fuel Cells

Ionic clustering, water binding, and ion conductivity were studied in polymers functionalized with sulfonic acid and quaternary ammonium hydroxide groups. Small-angle x-ray scattering showed that no clustering occurred in the quaternary ammonium containing anion exchange membranes, while evidence of ionic clusters was present in both sulfonated poly(phenylene) and in Nafion, a poly(perfluorosulfonic acid). Interestingly, the water self-diffusion coefficients of the anion exchange membranes were generally greater than those observed for the sulfonated poly- (phenylene)s, and moreover, the water self diffusion coefficients in anion exchange membranes were not a strong function of diffusion time. The water binding behavior lead to increased normalized conductivity in anion exchange membranes as compared to proton exchange membranes at the highest ion exchange capacities.     

Chain‐growth limiting reactions in the cationic polymerization of 3‐ethyl‐3‐hydroxymethyloxetane

3‐Ethyl‐3‐hydroxymethyloxetane (EOX) polymerizes readily to branched multihydroxyl polyethers. Molecular weights of the polymers are, however, limited, and macromolecules are predominantly cyclic. This indicates that intramolecular chain transfer to polymer (back‐biting) proceeds in the system. Repeating units in poly‐EOX contain two nucleophilic sites that may participate in back‐biting, namely ether groups and hydroxyl groups. Analysis of matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectra of poly‐EOX prepared in the presence of analogous polyether that does not contain HO? groups (poly(3,3‐dimethyloxetane)‐poly‐DMOX) shows that the ether group in the repeating unit of poly‐DMOX does not participate in chain transfer to the polymer. However, when DMOX was polymerized in the presence of poly‐EOX, clear evidence of participation of HO? groups in intramolecular chain transfer was obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 245–252, 2004     

Polyimides having pendant hydroxy and acetoxy groups. I. Synthesis of polyimides from pyromellitimide and bisepoxides

Polyimides having pendant hydroxy groups were prepared by addition of pyromellitimide with bisepoxides. Tertiary amines and quaternary ammonium halides were effective as a catalyst. The polyimides were soluble in dichloroacetic acid and had inherent viscosities in the range 0.16–0.19 dl/g. Thermogravimetric analysis showed that a rapid weight loss of the polymers occurred at about 400°C. The pendant hydroxy groups were easily acetylated by treating the polymers with a mixture of acetic anhydride and pyridine. The acetylated polyimides were soluble in dimethylformamide, dimethylacetamide, and dioxane and melted at 120–150°C.     

FUNCTIONALIZED β-CYCLODEXTRIN POLYMERS FOR THE SORPTION OF BILE SALTS

Poly(β-cyclodextrin) (PCD) resins were prepared by a crosslinking reaction of β-cyclodextrin with different amounts of epichlorhydrin. Some hydroxyl groups of these polymers were functionalized with alkyl quaternary ammonium groups. The polymers were tested for their ability to bind several bile salts (including the sodium salts of cholic acid, glycocholic acid, and chenodeoxycholic acid), individually and competitively, from phosphate buffer solutions. In all cases, the aminated PCD resin had a higher binding capacity for bile salts. The binding of chenodeoxycholate by the resins was much more effective than that of cholate and its conjugate, which indicates the importance of the host cavity size relative to that of the guest molecules. The degree of hydrophobicity of bile acids also plays a role in their binding by PCD resins. The variable temperature studies indicate that the electrostatic interactions become weaker at higher temperatures while the hydrophobic interactions are not as much affected.     

Novel copolymer networks via the combination of polyaddition and anionic polymerization

A two‐step synthetic route to novel copolymer networks, consisting of polymethacrylate and polyacetal components, was developed by combining the polyaddition and anionic polymerization techniques. The functional polymethacrylates containing hydroxyl or vinyloxyl side groups were used as crosslinkers. They were anionically synthesized as follows: the copolymer of 2‐hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) was prepared by the anionic copolymerization of 2‐(trimethylsiloxy)ethyl methacrylate and MMA, followed by hydrolysis. The copolymer poly(HEMA‐co‐MMA) thus obtained possessed a hydroxyl group in each of its HEMA units. Another kind of vinyloxyl‐containing (co)polymer was prepared by the anionic homopolymerization of 2‐(vinyloxy)ethyl methacrylate (VEMA) or its copolymerization with MMA. The resulting (co)polymer possessed reactive vinyloxyl side groups. The copolymer networks were obtained by reacting each of the above‐mentioned (co)polymers with a polyacetal prepared via the polyaddition between a divinyl ether and a diol. Three divinyl ethers (ethylene glycol divinyl ether, 1,4‐butanediol divinyl ether, and 1,6‐hexanediol divinyl ether) and three diols (ethylene glycol, 1,4‐butanediol, and 1,6‐hexanediol) were employed as monomers in the polyaddition step, and their combinations generated nine kinds of polyacetals. When a polyaddition reaction was terminated with a divinyl ether monomer, a polyacetal with two vinyloxyl end groups was obtained, which could further react with the hydroxyl groups of poly(HEMA‐co‐MMA) to generate a copolymer network. On the other hand, when a diol was used as terminator in the polyaddition, the resulting polyacetal possessed two hydroxyl end groups, which could react with the vinyloxyl groups of poly(VEMA) or poly(VEMA‐co‐MMA), to generate a copolymer network. All the copolymer networks exhibited degradation in the presence of acids. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 117–126, 2001