Complex-induced coupling effect: adhesion of some polymers to copper metal promoted by benzimidazole

Improved adhesion of a polymer with polar functional groups to copper has been achieved by pretreating the copper surface with benzimidazole solution. The adhesion strength was found to increase by two to three times. The coupling mechanism and interfacial structure of the copper-polymer composite have been investigated by X-ray photoelectron and Fourier transform infrared relection-absorption spectroscopies. We found that benzimidazole reacted with copper metal in the presence of oxygen to form benzimidazolato copper(+1), which covered the surface in the form of a thin polymeric layer. As the surface was exposed to air, some of the cuprous cations were oxidized to cupric ions. When poly(vinylpyridine) was coated onto the pretreated surface, the nitrogen atoms of the side groups of the polymer chains co-ordinated to the cupric cation to form interfacial bonding connecting the polymer to the copper metal.     

Conjugation of a zwitterionic polymer with dimethyl chains to lipase significantly increases the enzyme activity and stability

Enzyme-polymer conjugates are complex molecules with great practical significance. This work was designed to develop a novel enzyme-polymer conjugate by covalently coupling a zwitterionic polymer with side dimethyl chains (pID) to Candida rugosa lipase (CRL) via the reaction between the anhydrides of polymer chains with the amino groups of the enzyme. The resulting two CRL-pID conjugates with different pID grafting densities were investigated in term of the catalytic activity, stability and structural changes. In comparison with native CRL, both the CRL conjugates displayed 2.2 times higher activity than the native enzyme, and showed an increase in the maximum reaction rate (V_max) and a decrease in the Michaelis constant (K_m), thus resulting in about three-fold increases in the catalytic efficiency (k_cat/K_m). These are mainly attributed to the activation of lipase by the hydrophobic alky side chains. Moreover, the thermostability and pH tolerance of the lipase conjugates were significantly enhanced due to the stabilizing effect of the zwitterion moieties. For instance, a five-fold increase of the enzyme half-life at 50℃ for the high-pID conjugated CRL was observed. Spectroscopic studies reveal that the pID conjugation protected the enzyme in the changes in its microenvironment and conformation, well correlating with enhanced activity and stability of lipase conjugates. The findings indicate that enzyme conjugation to the zwitterionic polymer is promising for improving enzyme performance and deserves further development.     

Radical crossover reactions of a dynamic covalent polymer brush for reversible hydrophilicity control

Reversible hydrophilicity control of a radically exchangeable polymer brush with dynamic covalent linkages was successfully demonstrated. A polymer brush with alkoxyamine units was prepared via surface-initiated atom transfer radical polymerization, and reversible surface hydrophilicity control was achieved via dynamic covalent exchange reactions of alkoxyamines. Exchange reactions between alkoxyamine units in the side chains of the polymer brush and the terminal of poly(4-vinylpyridine) (P4VP) were carried out in order to prepare a side-chain functionalized polymer brush. Subsequent quaternization of P4VP chains with iodomethane was carried out to prepare a more hydrophilic surface. In addition, a de-grafting reaction of the quaternized P4VP side chains was performed to confirm reversibility of the alkoxyamine via radical exchange reactions on the surface. All the composition and wettability changes were investigated via X-ray photoelectron spectroscopy and contact angle measurements.     

Synthesis of a novel fluorene-based conjugated polymer with pendent bulky caged adamantane moieties and its application in the detection of trace DNT explosives

A novel fluorene-based conjugated polymer with phenylene spacers and steric bulky adamantane moieties in side chains has been synthesized by palladium-catalyzed Suzuki coupling reactions. This design strategy offers several advantages for the detection of trace 2,4-dinitrotoluene (DNT) vapor. The incorporation of the two groups into polymer side chains could retain an effective conjugation length and prevent the π-stacking of polymer chains. The detection of DNT vapor indicated that the polymer displayed higher fluorescence quenching sensitivity toward the explosives in films compared to reference polymers. The fluorescence quenching efficiency of the fluorescent polymer achieved 33.3% in 10 s and 71.1% in 60 s. The pathways or cavities generated by the two spacers are beneficial for the rapid diffusion of explosive vapor into the film interiors and increase the fluorescence quenching efficiency of the film.     

Jamming rheology of model cementitious suspensions composed of comb‐polymer stabilized magnesium oxide particles

The colloidal microstructure of concentrated suspensions containing anionic comb‐polymer‐stabilized magnesium oxide (MgO) particles in water was analyzed by shear rheometry for indications of changes in particle microstructure based on particle size and comb‐polymer usage. As the suspensions were sheared at different rates, jamming in the sheared MgO suspensions was observed as shear stress overshoots. The shear‐induced evolution of the suspension's microstructure was strongly related to the perceived interactions between neighboring MgO particles in the suspension. In the jammed state, interactions are believed to be enhanced by the formation of entanglements between opposing comb‐polymer side‐chains. Steric repulsion between side‐chains was lessened for large particles on account of their diameters, which further enabled side‐chain entanglement during close particle contact under shear. Suspensions with relatively wide particle size distributions (0.5–400 μm) were theorized to form hydrocluster aggregates, while suspensions with narrower particle size distributions (0.5–40 μm) most likely resulted in networked microstructures under the influence of the chain entanglements from the adsorbed comb‐polymer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40429.     

Simultaneous construction of polymer backbone and side chains by terpolymerization. Synthesis of polyethers with the allyl side chains from dialdehydes, alkylene bis(trimethylsilyl) ethers, and allyltrimethylsilane

Polyethers with allyl side chains were synthesized by the simultaneous acid-catalyzed reaction of dialdehydes (1), alkylene bis(trimethylsilyl) ethers (2), and allyltrimethylsilane (3). The reactions of 1, 2 and 3 were carried out in the presence of 10 mol% of triphenylmethyl (trityl) perchlorate at −55°C to yield polyethers having allyl groups in the side chains. When the dialdehyde having the ester moieties as 1, ethylene bis(trimethylsilyl) ether and 1,4-bis(trimethylsiloxy)cyclohexane as 2 were used, high molecular weight polymers were obtained. In the polymerizations at ambient temperature, the polymer was precipitated during the reaction because of crosslinking between the aromatic rings via a trityl perchlorate assisted Friedel-Crafts reaction. The soluble polyether with the allyl side chains reacted with 1,2-ethanedithiol in the presence of a radical initiator in benzene at 60°C to yield a crosslinked polymer quantitatively within 1 h. This polymer synthesis is unusual in that it concurrently constructs both the polymer backbone and the functional side chains from three monomers.     

Highly efficient synthesis of cylindrical polymer brushes with various side chains via click grafting-onto approach

Though much attention has been paid to synthesis of cylindrical polymer brushes, it is still not easy to prepare well-defined brushes by a general approach. Herein, well-defined cylindrical polymer brushes with various side chains were synthesized via grafting-onto approach by CuAAC click chemistry. Narrowly dispersed polymer backbones functionalized with azide groups were obtained by post-modification of poly(glycidyl methacrylate) (PGMA) which was prepared by reversible addition-fragmentation chain transfer (RAFT) mediated radical polymerization. The alkyne-terminated side chains, polystyrene, polyacrylates, polymethacrylates and poly(N-alkyl acrylamide)s, were synthesized by RAFT mediated radical polymerization with alkyne-containing chain transfer agents (CTAs). The CuAAC reactions between the backbone and side chain polymers were conducted with an equivalent feed of alkyne-terminated side chains and azide groups under mild conditions. Influences of reaction conditions and chemical composition of polymer side chains on grafting efficiency and molecular weight distribution of the polymer brushes were investigated. It is demonstrated that the side chains of polystyrene, polyacrylates and poly(N-alkyl acylamide)s were grafted at a density above 85% while that of polymethacrylates decreased to ca. 50%. The polymer brushes synthesized under the optimized reaction conditions had well-defined chemical composition and narrow distribution of molecular weight, and their wormlike morphology was visualized by atomic force microscopy (AFM).     

Synthesis and characterization of soluble polymer ligands possessing sulfide side chains

Soluble polymer ligands possessing aryl monosulfide side chains [poly(4-vinylphenylmethyl sulfide) (PVPMS)], alkyl monosulfide side chains [poly(4-vinylbenzylmethyl sulfide) (PVBMS)] and branched tetrasulfide side chains [poly(7-(4′-vinylbenzyloxy)-2,5,9,12-tetrathiatridecane) (PTeSSD)] were prepared by radical polymerization of the corresponding monomers. These polymer ligands had specific binding abilities for soft acids only, such as Ag(I) and Hg(II) ions. The tetrasulfide-type polymer ligand, PTeSSD, bound the metal ion only by the tetrasulfide side chain itself. The monosulfide-type polymer ligands, PVPMS and PVBMS, bound the metal ion by co-operative interaction between their monosulfide side chains. The resulting polymer-Ag(I) complexes were soluble in organic solvents. Interestingly, a polyester cloth coated with the polymer-Ag(I) complex exhibited significant antibacterial activity against Staphylococcus aureus.     

Interaction of cyclodextrins with side chains of water soluble polymers: A simple model for biological molecular recognition and its utilization for stimuli-responsive systems

This article demonstrates that the interaction of cyclodextrins (CDs) with side chains of water soluble polymers is useful not only as simple models for biological molecular recognition but also as building blocks in nanotechnological applications. In the interaction of CDs with polymer side chains, the selectivity of CDs was enhanced by the steric effect of the polymer main chain and by interaction at multi-sites (i.e., collectivity). Utilizing the interaction of CDs with polymer side chains, stimuli-responsive systems were constructed from simple components.     

Properties of branched polymer chains adsorbed on a patterned surface

The aim of this study was to investigate the properties of polymer chains strongly adsorbed on a planar surface. Model macromolecules were constructed of identical segments, the positions of which were restricted to nodes of a simple cubic lattice. The chains were in good solvent conditions, thus, the excluded volume was the only interaction between the polymer segments. The polymer model chain interacted via a simple contact potential with an impenetrable flat surface with two kinds of points: attractive and repulsive (the latter being arranged into narrow strips). The properties of the macromolecular system were determined by means of Monte Carlo simulations with a sampling algorithm based on the local conformational changes of the chain. The structure of adsorbed chains was found to be strongly dependent on the distance between the repulsive strips, whenever this distance was very short. The mobility of the chains was also studied and it was found that diffusion across repulsive strips was suppressed for large distances between the strips.     

Untersuchungen zur Synthese und den Eigenschaften von amphiphilen Polymeren

Investigations of the Synthesis and Properties of Amphiphilic Polymers By reaction of propylene/maleic anhydride copolymers with the sodium salt of α-dodecyl-ω-hydroxy-trioxyethylene ionic polymers with different shares of long aliphatic side chains were prepared. The properties of these amphiphilic polymers were studied. Like micelles they are able to solubilize nonpolar probe molecules (N,N-dimethyl-aminoazobenzene). Viscosity measurements show the dependence of the conformation of the polymeric chain in solution on the share of aliphatic side chain and the degree of protonation. The polymers from micelle-like aggregates. It is supposed that the polymer with a high share of aliphatic side chains froms several local aggregates per polymer chain, while the polymer containing only few side chains seems to form intermolecular aggregates between different polymer chains. These investigations were performed with pyrene as probe molecule. Pyrene was also used to examine the micropolarity of the aggregates. Like polyelectrolytes the amiphilic polymers are able to cause the aggregation of opposite charged dyes (thionine).     

侧链含有环糊精的聚合物的研究进展

聚合物侧链可通过化学键及分子间力与环糊精相互作用。当聚合物侧链通过化学键与环糊精作用时,环糊精空腔一般为空,可与小分子包合,对不同立体结构的分子具有选择性,在分析化学方面具有潜在的应用。当聚合物侧链与环糊精包合时,环糊精空腔与一定结构的侧链包合,形成侧链型多聚(准)轮烷。侧链型环糊精基多聚(准)轮烷的结构、性能独特,在许多领域具有潜在的应用。本文介绍了国内外文献中关于侧链含有环糊精的聚合物的研究进展,包括合成方法以及在各领域的应用等。     

Refractive index changes in polyacrylates bearing alkyl sulfur groups through the sulfur oxidation reaction

Four polyacrylates with sulfur-containing side chains were prepared to examine the changes in refractive index (RI) induced by sulfur oxidation. Linear alkyl sulfides and alicyclic sulfides, such as 1,3-dithiolane and 1,4-dithiane, were introduced to impart large RIs to polyacrylates. Oxidation of the sulfur polymers by O₃ and m-chloroperoxybenzoic acid led to the formation of the corresponding sulfoxide and sulfone polymers, respectively. Sulfur oxidation occurred completely, which was highlighted by the oxidized polymer exhibiting a refractive index comparable to a polymer that was synthesized using a sulfone monomer. The RI of the linear sulfur polymer increased and decreased due to the formation of sulfoxide and sulfone polymers, respectively. The Abbe number of the polymer with a linear sulfide side chain was 33.4, which increased to 48.7 after oxidation.     

Polymer-metal complexes,based on poly(itaconic acid ester) derivatives,as catalysts for the decomposition of hydrogen peroxide

Poly(methyl itaconates) and poly(heptyl itaconates), modified with ethylene diamine (EN) and tetraethylene pentamine (TETRAEN) side chains, were complexed with cobalt and copper ions, and their efficiencies as catalysts for the decomposition of hydrogen peroxide were assessed. All the polymer complexes studied were found to be active catalysts, but it was observed that the polymers with TETRAEN side chain, when complexed with CoCl₂ and CuCl₂ were less efficient than polymers with EN side chains which were complexed with trans-dichlorobis(ethylenediamine) cobalt(III) chloride, trans-[Co(EN)₂Cl₂]Cl. One feature of interest was that when the alkyl side chain of the poly itaconate was heptyl the rate of decomposition of hydrogen peroxide was faster than when the alkyl group was methyl.     

Phase changes of poly(alkoxyphosphazenes), and their behavior in the presence of oligoisobutylene

A series of closely related polyphosphazenes with propoxy, pentoxy, hexoxy, octoxy, isostearyloxy, and 2‐(2‐methoxyethoxy)ethoxy (MEE) side groups, together with cosubstituent species with both the alkoxy and MEE side chains, were studied for their morphology and miscibility with oligoisobutylene (OIB). All the pure polymers except one had a single glass transition temperature. The exception was the species with both isostearyloxy and MEE side groups, which underwent two low‐temperature second‐order transitions, even though 31P NMR spectra indicated the absence of a block‐type structure. For the single‐substituent macromolecules, the solubility at 80°C in OIB increased as the length of the unbranched alkoxy side groups rose from propoxy to octoxy (from 1 to 11 wt/wt%). However, the polymer with two isostearyloxy side chains per repeat unit had a low solubility in OIB (3 wt/wt%), and the species with the two MEE side groups on every repeat unit was totally insoluble. When both alkoxy and MEE side groups were present, the solubility in OIB was also low (0–3%), except for the species with both isostearyloxy and MEE side groups, which was soluble in OIB at a level of 21 wt/wt% at 80°C, and showed T_g evidence of polymer/oligomer miscibility even at ?80°C. Explanations are suggested for the unusual behavior of this polymer. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthesis and catalytic activity of the thermoresponsive polymers having pyrrolidine side chains as base functionalities

Optically active polymers having chiral 2‐aminomethylpyrrolidine side chains have been newly synthesized by a radical homopolymerization of the corresponding protected acrylamide monomer and copolymerization with N‐isopropylacrylamide followed by deprotection. The resulting polymers were found to be thermoresponsive showing lower critical solution temperatures (LCSTs) at 27–65°C in their aqueous solutions. The pyrrolidine side chains of the resulting thermoresponsive polymer promoted aldol reaction between cyclohexanone and p‐nitrobenzaldehyde in water, and the reaction proceeded most smoothly at its LCST. Moreover, the diastereomeric ratio (syn : anti) of the aldol adducts obtained at the reaction at 40°C was 22 : 78, whereas the diastereomeric ratio (syn : anti) was 55 : 45 at 20°C. These results indicate that the pyrrolidine side chains catalyze the aldol reactions in the relatively hydrophobic field generated by the thermoresponsive polymer at its LCST. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of partially biobased polymer-bearing reactive epoxy groups in the side chains by radical copolymerization of limonene oxide with methyl acrylate

A radical copolymerization behavior of limonene oxide and methylacrylate was investigated, by which a partially biobased polymer-bearing reactive epoxy groups in the side chains was obtained in 43 % yield in the maximum. Degree of LO incorporation into the copolymer was determined to be 34–37 % when 5.0 mol % of 2,2′-azobis(isobutyronitrile) was employed, despite initial feed ratios. Reactivity of the epoxy groups in the side chains was investigated by two different methods. One is ring-opening of the epoxy groups with benzyl thiol, giving the corresponding polymer with β-hydroxyl sulfide moieties in 95 % yield. Another one is hydrolyzation of the epoxy groups in HCl aqueous solution at room temperature, providing a quantitative formation of the dihydroxyl groups in the side chains.     

A rapid photomechanical switching polymer blend system composed of azobenzene-carrying poly(vinylether) and poly(carbonate)

A new material with photomechanical switching ability was developed. The material is a binary polymer blend composed of a poly(vinylether) having azobenzene moiety in the side chain and a polycarbonate as a matrix. Upon switching UV-irradiation on and off, the developed polymer blend showed deformation that was both rapid and reversible. This observed photomechanical effect is attributed to a reversible modulus change in the polymer blend, arising from an UV-controlled isomerization of the azobenzene moiety, causing a switching behavior between its highly aggregated and dissociated states. These two states are the physical crosslinking and decrosslinking of the polymer chains.     

Influence of Macromolecular Brushes with Polyimide Backbones and Poly(methyl methacrylate) Side Chains on Structure,Physical, and Transport Properties of Polyphthalamide

Composite films based on polyamide (poly(m-phenylene-iso-phthalamide)) (PA) and a brush-like polymer with polyimide (PI) backbone and side poly(methyl methacrylate) chains (PI-PMMA) were prepared by mixing individual solutions of PA and PI-PMMA and subsequent film casting. Macromolecular brushes with the same backbone length and density of side chains but with various lengths of side PMMA chains were synthesized via activator generated by electron transfer atom transfer radical polymerization. Interactions between PA and PI-PMMA, as well as distribution of PI-PMMA filler inside the PA matrix, were studied by viscometry, dynamic light scattering, differential scanning calorimetry, scanning electron microscopy, and IR spectroscopy. The mechanical properties of polymer samples were also investigated. Microphase separation was revealed in PA/PI-PMMA films. The length of side chains influences interactions between PA and PI-PMMA. At the same time, the degree of reduction in the rigidity parameters and in the elasticity parameter depends on the side chain length. Diffusion membranes were prepared on the basis of compositions with the best mechanical properties; these membranes proved to be highly efficient in pervaporation of methanol–hexane mixture. It was established that the fluxes and separation factors of the studied membranes are several times higher as compared to the corresponding characteristics of known commercial membranes. POLYM. ENG. SCI., 60:481–490, 2020. © 2019 Society of Plastics Engineers     

Die polymerisation der lactame VI. Die copolymerisation von 6-caprolactam und 8-capryllactam

The process of incorporating 6-caprolactam and 8-capryllactam into polymer chains was studied during the hydrolytic, cationic, and anionic copolymerization in the case of equimolar ratio of the above mentioned monomers. At the beginning of the hydrolytic copolymerization at temperatures between 200 and 260°C, 6-caprolactam was more rapidly incorporated into the chains. Decreasing temperature led to a decrease in the total rate of polymerization with increasing difference between rates of incorporating the two components. Contrary to this, at the initial stage of the cationic copolymerization, the incorporation of 8-capryllactam was faster by orders of magnitude than that of 6-caprolactam, the changes of the copolymer composition being independent of temperature. Under the conditions of interest, in the course of the anionic copolymerization the two monomers were characterized with the same rates of incorporation into the polymer chains. Different melting points of products separated at various stages of the copolymerization process corresponded to the above mentioned differences in rates of incorporating individual monomers into polymer chains when different reaction mechanisms were employed.