ß-Cyclodextrin-derived diallylamine salt: Synthesis and its copolymerizations.

A diallyl amine salt monomer bearing a ß-CD substituent was cyclopolymerized for the first time. The reaction of 6-O-toluenesulfonyl-ß-cyclodextrin [(C6H10O5)6-(C5H7)]-CH2OTs with diallylamine followed by protonation afforded the diallylamine salt monomer [(C6H10O5)6-(C5H7)]-CH2NH+(CH2CH=CH2)2 Cl-] (I). The cyclopolymerization of monomer I and its copolymerization with monomer [Me2N+(CH2CH=CH2)2 Cl-] (II), [-O2CCH2NH+(CH2CH=CH2)2] (III), [H2O3PCH2NH+(CH2CH=CH2)2 Cl-] (IV) or [HO2CCH2CH(CO2H)NH+(CH2CH=CH2)2 Cl-] (V) yielded a series of copolymers having residues of ß-CD and glycine or methyl phosphonate or aspartic acid. Terpolymerization in the presence of SO2 afforded polymers with alternating placements of the SO2 units. The solution properties of the pH-responsive polyzwitterions, including their viscosity, were examined. The water-insoluble terpolymer I/V/SO2 with 20 mol% ß-CD residues removed the organic micropollutant 2-naphthol from an aqueous system via host/guest complexation. This work paves the way for the possible synthesis of cross-linked polymers that can simultaneously remove organic micropollutants and toxic metal ions (by complexation with the chelating glycine, aspartic acid, and aminomethyl phosphonate ligands) from contaminated aqueous systems.

Polyacetylene-Based Asymmetric Bicyclic Polymer by Blocking-Cyclization Technique.

A rare asymmetric bicyclic polymer containing different length of conjugated polyacetylene segments is synthesized by metathesis cyclopolymerization-mediated blocking-cyclization technique. The size of each single ring differs from each other, and the unique cyclic polymer topology is controlled by adjusting the feed ratio of monofunctional monomer to catalyst. The topological difference between linear and bicyclic polymers is confirmed by several techniques, and the visualized morphology of asymmetric bicyclic polymer is directly observed without tedious post-modification process. The photoelectric and thermal properties of polymers are investigated. This work expands the pathway for the derivation of cyclic polymers, and such unique topological structure enriches the diversity of cyclic polymer classes.

Iodine and Nickel Ions Adsorption by Conjugated Copolymers Bearing Repeating Units of Dicyclopentapyrenyl and Various Thiophene Derivatives.

The synthesis of three conjugated copolymers TPP1-3 was carried out using a palladium-catalyzed [3+2] cycloaddition polymerization of 1,6-dibromopyrene with various dialkynyl thiophene derivatives 3a-c. The target copolymers were obtained in excellent yields and high purity, as confirmed by instrumental analyses. TPP1-3 were found to divulge a conspicuous iodine adsorption capacity up to 3900 mg g-1, whereas the adsorption mechanism studies revealed a pseudo-second-order kinetic model. Furthermore, recyclability tests of TPP3, the copolymer which revealed the maximum iodine uptake, disclosed its efficient regeneration even after numerous adsorption-desorption cycles. Interestingly, the target copolymers proved promising nickel ions capture efficiencies from water with a maximum equilibrium adsorption capacity (qe) of 48.5 mg g-1.

Stimuli-Responsive Macromolecular Architecture by Butler Cyclopolymerizations: Synthesis and Applications.

This article reviews the synthesis of polyzwitterions (PZs) (poly-carboxybetaines, -phosphonobetaines, and -sulfobetaines) having multiple pH-responsive centers. The synthesis follows the Butler cyclopolymerization protocol involving a multitude of diallylammonium salts and their copolymerization with SO2 and maleic acid. The PZs have been transformed into cationic-, anionic-polyelectrolytes, and polyampholytes under the influence of pH. Particular attention is given to the application of these polymers as antiscalants, mild steel corrosion inhibitors, components in constructing Aqueous Two-Phase Systems (ATPSs), and membrane modifiers. The ATPSs could be used to separate various biomolecules, including proteins. Many amphiphilic polymers incorporating a few mol % hydrophobic monomers have shown enhanced viscosities and could be suitable for applications in oil fields. The progress of applying Butler cyclopolymerization in reversible addition-fragmentation chain transfer (RAFT) chemistry has been discussed. Future works are expected to focus on RAFT cyclopolymerization to construct block copolymers.

Synthesis and Properties of Polyol Copolymer with Alternating Methacrylate-Vinyl Ether Backbone.

Radical polymerization of a tailored diphenylsilane-bridged bi-functional monomer consisting of methacrylate and vinyl ether moieties is conducted in diluted monomer concentration, in which both two moieties are consumed at almost the same rate despite their huge difference in monomer reactivity ratio. The vinyl ether content in the backbone is quantified as 45% by 1 H NMR after removal of the silane bridge. Since vinyl ether alone cannot be polymerized in such radical polymerization, it should be incorporated in an alternating fashion with methacrylate into the copolymer main chain. The cleavage of silane bridge also yields a series of polyol materials composed of ethylene glycol monovinyl ether (EGVE) and hydroxyethyl methacrylate (HEMA), and the EGVE content in the backbone can be regulated from 45% to 18% by increasing the bi-functional monomer concentration. Interestingly, although containing more than 50% HEMA units, the alternating copolymer exhibits new properties totally different from poly(HEMA), but more similar to poly(EGVE), e.g., good water solubility and a markedly low glass transition temperature (Tg ) of -31 °C, which is attributed to the major HEMA-EGVE repeating unit that replaced HEMA-HEMA consecutive segments so that the properties of poly(HEMA) such as 95 °C Tg are completely altered.

Cascade Cyclopolymerization of 5-Ethynyl-1,8-Nonadiyne Derivatives to Synthesize Low Band Gap Conjugated Polyacetylenes Containing a Fused Bicyclic Structure.

Cyclopolymerization is a powerful method for synthesizing polyacetylenes containing four- to seven-membered rings. However, the structure of the repeat unit only consists of mono-cycloalkene due to the single cyclization of diyne monomers. Herein, we demonstrate a novel cascade cyclopolymerization to synthesize polyacetylenes containing fused bicyclic rings from triyne monomers containing bulky dendrons via sequential cascade ring-closing metathesis. These dendrons provided solubility and stability to the rigid bicyclic polyacetylene backbone. In addition, we controlled the regioselectivity of the catalyst approach by altering its structure and synthesized polymers containing fused bicyclo[4,3,0] or [4,4,0] rings with high molecular weights of up to 120 kg mol-1 . Interestingly, the resulting polymers showed narrower band gaps (down to 1.6 eV) than polymers with mono-cycloalkene repeat units due to the planarization of the conjugated segment resulting from the fused bicyclic structure.

A resin containing motifs of maleic acid and glycine: a super-adsorbent for adsorptive removal of basic dye pararosaniline hydrochloride and Cd(II) from water.

The cyclocopolymerization of N,N-diallylglycine hydrochloride, maleic acid and 1,1,4,4-tetraallylpiperazinium dichloride afforded a cross-linked polyzwitterionic acid, which, upon treatment with NaOH, gave the corresponding cross-linked anionic polyelectrolyte (CAPE) in quantitative yield. The pH-responsive resins contained a high density of CO2 - motifs as well as the chelating motifs of glycine residues. The resin CAPE was found to be a super-adsorbent for the removal of pararosaniline hydrochloride (PRH); having a q max of 1534 mg/g. The adsorption process followed pseudo-second-order kinetics and was found to be a nearly irreversible process as suggested by the parameters obtained from Elovich kinetic model. The resin demonstrated excellent adsorption/desorption efficiencies, thereby ensuring its recycling and reuse in potent applications like remediation of industrial dye-waste water. The resin's chelating motifs were also efficient in the adsorptive removal of Cd(II) ions with a q max of 248 mg/g. It was also employed for the simultaneous and effective trapping of Cd(II) and the dye from industrial wastewater. The resin's impressive performance accords it a prestigious place among many sorbents in recent works.

1,6-heptadiynes based cyclopolymerization functionalized with mannose by post polymer modification for protein interaction.

Carbohydrate functionalized polymers or Glycopolymers have earned a great deal of interest in recent times for their potential biomedical applications. In the present study, a mannose containing glycopolymer was synthesized by cyclopolymerization of malonic acid derivative using second generation Hoveyda Grubbs' catalyst. Post-polymerization modification was done to install a propargyl moiety. Finally, functionalization of the propargylated polymer with 2-azidoethyl mannoside using azide-alkyne "click chemistry" furnished the target glycopolymer which was successfully characterized using NMR, FT-IR, mass spectroscopy and advanced polymer chromatography. The glycopolymer was found to self-assemble into capsule and spherical shape in water and DMSO respectively and these morphologies were observed through SEM and TEM. Upon interaction with Con A, the mannose containing glycopolymer showed an increment in aggregation induced fluorescence with increasing concentration of the lectin. In vitro cytotoxicity studies on MCF 7 cell line showed 90% cell viability up to glycopolymer concentration of 500 µg/mL.

Cation Template-Assisted RAFT Cyclopolymerization of Hexa(Ethylene Glycol) Di(meth)acrylates to Thermoresponsive Pseudo-Crown Ether Polymers.

Cation template-assisted reversible addition fragmentation/chain transfer (RAFT) cyclopolymerization of hexa(ethylene glycol) diacrylate (PEG6DA) or hexa(ethylene glycol) dimethacrylate (PEG6DMA) is developed as a versatile system to produce large in-chain ring cyclopolymers, thermoresponsive pseudo-crown ether polymers. For an efficient synthesis, potassium hexafluorophosphate (KPF6 ) is employed as a cation template; PEG6DA as well as PEG6DMA recognizes the potassium cation with the hexa(ethylene glycol) spacer to dynamically form a pseudo-cyclic divinyl monomer. Those monomers interacting with the potassium cations are efficiently polymerized with RAFT agents and radical initiators into cyclopolymers comprising 24-membered hexa(ethylene glycol) rings. The cation template-assisted RAFT cyclopolymerization is also effective for the synthesis of amphiphilic random cyclocopolymers bearing hydrophilic hexa(ethylene glycol) rings and hydrophobic butyl groups. Cyclopolymers of PEG6DA and PEG6DMA further show thermoresponsive solubility in water. The cloud point temperature of cyclopoly(PEG6DA)s is higher than that of a cyclopoly(PEG6DMA).

Ring-Forming Polymerization toward Perfluorocyclobutyl and Ortho-Diynylarene-Derived Materials: From Synthesis to Practical Applications.

Many desirable characteristics of polymers arise from the method of polymerization and structural features of their repeat units, which typically are responsible for the polymer's performance at the cost of processability. While linear alternatives are popular, polymers composed of cyclic repeat units across their backbones have generally been shown to exhibit higher optical transparency, lower water absorption, and higher glass transition temperatures. These specifically include polymers built with either substituted alicyclic structures or aromatic rings, or both. In this review article, we highlight two useful ring-forming polymer groups, perfluorocyclobutyl (PFCB) aryl ether polymers and ortho-diynylarene- (ODA) based thermosets, both demonstrating outstanding thermal stability, chemical resistance, mechanical integrity, and improved processability. Different synthetic routes (with emphasis on ring-forming polymerization) and properties for these polymers are discussed, followed by their relevant applications in a wide range of aspects.

Catalyst-Free Multicomponent Cyclopolymerizations of Diisocyanides, Activated Alkynes, and 1,4-Dibromo-2,3-Butanedione: a Facile Strategy toward Functional Polyiminofurans Containing Bromomethyl Groups.

Polymers containing iminofuran (PIFs) are rarely reported due to the lack of simple and effective synthesis methods. In this work, a novel multicomponent cyclopolymerization (MCCP) of diisocyanides, activated alkynes, and 1,4-dibromo-2,3-butanedione using catalyst-free one-pot reactions under mild conditions to prepare PIFs containing bromomethyl groups is reported. PIFs with good solubility and thermal stability are obtained with high Mw s (up to 19 600) and good yields (up to 89.5%) under optimized polymerization conditions. The structure of the PIFs is characterized by nuclear magnetic resonance, Fourier transform infrared spectroscopy, and gel permeation chromatography. The photophysical properties indicate that polymers P1a2b3 and P1c2b3 have cluster-triggered emission characteristics. Thin films made from PIFs quickly degrade under UV irradiation. Moreover, the obtained polymers are decorated with bromomethyl and carboxylate groups in the side chain, which can be postfunctionalized to prepare multifunctional materials, such as star branched polymers and biomedical carrier materials. Thus, this work not only enriches the field of polymerization based on isocyanates and activated alkynes but also provides a facile strategy toward functional iminofuran polymers.

Metathesis Cyclopolymerization Triggered Self-Assembly of Azobenzene-Containing Nanostructure.

Azobenzene (AB) units were successfully introduced into poly(1,6-heptadiyne)s in order to ensure smooth synthesis of double- and single-stranded poly(1,6-heptadiyne)s (P1 and P2) and simultaneously realize the self-assembly by Grubbs-III catalyst-mediated metathesis cyclopolymerization (CP) of AB-functionalized bis(1,6-heptadiyne) and 1,6-heptadiyne monomers (M1 and M2). Monomers and polymers were characterized by 1H NMR, mass spectroscopy, and GPC techniques. The double-stranded poly(1,6-heptadiyne)s exhibited a large scale of ordered ladder nanostructure. This result was attributed to the π-π attractions between end groups along the longitudinal axis of the polymers and van der Waals interactions between the neighboring polymeric backbones. While the Azo chromophore connected in the side chain of P2 induced conformation of micelles nanostructure during the CP process without any post-treatment. Furthermore, the photoisomerization of Azo units had an obviously different regulatory effect on the conjugated degree of the polymer backbone, especially for the single-stranded P2, which was attributed to the structural differences and the interaction between AB chromophores in the polymers.

Unprecedented Sequence Control and Sequence-Driven Properties in a Series of AB-Alternating Copolymers Consisting Solely of Acrylamide Units.

Herein, we report a method to synthesize a series of alternating copolymers that consist exclusively of acrylamide units. Crucial to realizing this polymer synthesis is the design of a divinyl monomer that contains acrylate and acrylamide moieties connected by two activated ester bonds. This design, which is based on the reactivity ratio of the embedded vinyl groups, allows a "selective" cyclopolymerization, wherein the intramolecular and intermolecular propagation are repeated alternately under dilute conditions. The addition of an amine to the resulting cyclopolymers afforded two different acryl amide units, i.e., an amine-substituted acryl amide and a 2-hydroxy-ethyl-substituted acryl amide in alternating sequence. Using this method, we could furnish ten types of alternating copolymers; some of these exhibit unique properties in solution and in the bulk, which are different from those of the corresponding random copolymers, and we attributed the differences to the alternating sequence.

Regio- and Stereospecific Cyclopolymerization of α,ω-Diynes by Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes.

Both solvent-free and acetonitrile-containing cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes of the general formula [Mo(NR')(CHCMe2 R)(NHC)(X)+ A- ] (R' = 2,6-Cl2 -C6 H3 , tBu, 2-CF3 -C6 H4 , 2-tBu-C6 H4 , 2,6-iPr2 -C6 H3 , 2,6-Me2 -C6 H3 ; R = Me, Ph; NHC = 1,3-dimesitylimidazol-2-ylidene (IMes), 1,3-di-iPr-imidazol-2-ylidene (IPr), 1,3,5-triphenyl-1,3,4-triazol-2-ylidene); X = CF3 SO3 , C6 F5 O, OCH(CF3 )2 , OC(CF3 )3 , pyrrolide, C6 F5 COO, 2,6-(CF3 )2 -C6 H3 COO; A- = B(ArF )4 - , Al(OC(CF3 )3 )4 - ), have been investigated for their propensity to cyclopolymerize 4,4-disubstituted 1,6-heptadiynes. All metal complexes contain a stereogenic (chiral) metal center, which accounts for the high reactivity and high regioselectivity of insertion (>99%) that are observed for all metal complexes, leading to highly conjugated, α-insertion-derived polyenes that are based on a highly regular polymer backbone and that show absorption maxima close to 600 nm. With the chiral monomer 4-(ethoxycarbonyl)-4-(1S,2R,5S)-(-)-menthoxycarbonyl-1,6-heptadiyne, high syndiospecifity (>99% syndiotactic) is observed. A mechanism explaining the high regio- and stereoselectivity is presented. Thus, α-addition of the monomers proceeds chain-end-controlled trans to the NHC and is preferred over ß-addition through intramolecular Mo-O chelation. Insertion of the monomers entails double inversion at the stereogenic metal center in the course of one complete monomer insertion.

Functional Block Copolymers Carrying One Double-Stranded Ladderphane and One Single-Stranded Block in a Facile Metathesis Cyclopolymerization Procedure.

In order to improve the poor film-forming ability of polymeric ladderphane, di-block copolymers containing perylene diimide (PDI)-linked double-stranded poly(1,6-heptadiyne) ladderphane and branched alkyl side chains modified single-stranded poly(1,6-heptadiyne) were synthesized by metathesis cyclopolymerization (MCP) using Grubbs third-generation catalyst (Ru-III) in tetrahydrofuran solvent. The first block containing the ladderphane structure leads to higher thermal-stability, wider UV-vis absorption, lower LUMO level and ladderphane-induced rigidity and poor film-forming ability. The second block containing long alkyl chains is crucial for the guarantee of excellent film-forming ability. By comparing the effect of ladderphane structure on the resulted copolymers, single-stranded poly(1,6-heptadiyne) derivatives with PDI pedant were also processed. The structures of copolymers were proved by 1H NMR and gel permeation chromatography, electrochemical, photophysical, and thermal-stability performance were achieved by cyclic voltammetry (CV), UV-visible spectroscopy and thermogravimetric analysis (TGA) measurements. According to the experiment results, both copolymers possessed outstanding film-forming ability, which cannot be realized by small PDI molecules and oligomers. And they can serve as a superior candidate as for n-type materials, especially for their relatively wide range of light absorption (λ = 200~800 nm), and lower LUMO level (-4.3 and -4.0 eV).

Fast removal of methylene blue and Hg(II) from aqueous solution using a novel super-adsorbent containing residues of glycine and maleic acid.

The alternate cyclo-copolymerization of diallylammonioethanoate [(CH2=CHCH2)2NCH2CO2-] and maleic acid in the presence of a cross-linker afforded a novel pH-responsive resin (90% yield). The resin has turned out to be a super-adsorbent for methylene blue (MB) removal with a qMax of 2101 mg g-1. The adsorption of the dye followed pseudo second-order kinetics with an energy of activation (Ea) of 31.5 kJ mol-1. The process showed an extraordinarily fast adsorption rate owing to faster film diffusion; the resin (250 mg) was able to trap 78 and 99.4% MB from its 3000 mg L-1 solution (100 mL) within 3 and 30 min, respectively. Equilibrium constants from Langmuir nonlinear isotherm model in the range 288-328 K gave ΔGo ΔHo, and ΔSo values of ≈ -25 kJ, -13 kJ and 39.5 J mol-1 K-1, respectively. Immobilization mechanism was discussed using FTIR, SEM, and Elovich kinetic model. The presence of the chelating glycine residues was exploited for the removal of Hg(II) ions; the qHg was determined to be 263 mg g-1. The resin also removed MB and Hg(II) simultaneously from industrial wastewater with remarkable efficacy. The very impressive performance along with efficient recycling conferred the resin a top position among many sorbents.

Conjugated Nitroxide Radical Polymers: Synthesis and Application in Flexible Energy Storage Devices.

The synthesis and electrochemical behavior of nitroxide radical conjugated polymers (NCPs) have long been an intriguing topic in redox polymer-based energy storage. However, common (electro)chemical oxidation polymerization methods have proved difficult in the synthesis of well-defined NCPs, and many of these polymers have been difficult to process into thin films. In addition to these drawbacks and coupled with the complex charge-transfer and storage mechanisms, the use of NCPs as electrodes has been significantly limited. The aim of this work is to provide mechanistic insights into this complex charge-transfer and storage process using a new and well-defined NCP synthesized using an ultrafast cyclopolymerization with the Grubbs 3rd generation catalyst. The monomer, consisting of a 1,6-heptadiyne group and a TEMPO (i.e. 2,2,6,6-tetramethylpiperidine-1-oxy) radical, through the cyclopolymerization produced a well-defined NCP with a five-membered ring-containing polyene backbone. This polymer demonstrated excellent film formation properties, allowing the study of their thin-film electrochemical behavior. We found that the electrochemical oxidation of the conjugated backbone and its internal charge transfer to the nitroxide radicals were strongly affected by the applied potential window, current densities, and cycle numbers. Using these new insights, we successfully utilized our NCPs in a flexible energy storage device by fabricating high-performance NCP-coated carbon cloth-based flexible electrodes.

Control of the Alternating Sequence for N-Isopropylacrylamide (NIPAM) and Methacrylic Acid Units in a Copolymer by Cyclopolymerization and Transformation of the Cyclopendant Group.

An alternating copolymer of methacrylic acid and N-isopropyl acrylamide (NIPAM) was synthesized by selective cyclopolymerization of a special divinyl monomer and transformation of repeating cyclo-units in the resultant cyclopolymer. Crucial to the breakthrough is the monomer design in view of two types of cleavable bonds (3° ester and activated ester) in the pendant group of the monomer and the lower reactivity ratio of the two double bonds (methacrylate and electron-poor acrylate) for the polymerizable groups. The thus-obtained cyclopolymer was transformed into the alternating copolymer by transformation of the activated ester into amide by isopropyl amine and cleavage of the 3° ester by trifluoroacetic acid. The resultant copolymer showed thermal and pH response in aqueous solution that was different from the 1:1 random copolymer as well as the homopolymers.

Synthesis and polymerization of 1-(2-diallylaminoethyl)pyrimidines.

We report the preparation and characterization of three pyrimidine-based monomers, specifically: 1-(2-diallylaminoethyl)uracil, 1-(2-diallylaminoethyl)thymine and 1-(2-diallylaminoethyl)cytosine. Monomer synthesis was initiated by reaction of the pyrimidine with ethylene carbonate to form the hydroxyethyl adduct which was subsequently chlorinated to afford the chloroethyl intermediate. Reaction of the chloroethyl derivatives with diallylamine resulted in the desired monomers. We demonstrated a two-fold increase in the overall yield of the three monomers in comparison to reported procedures. The cyclopolymerization and cyclo-copolymerization of 1-(2-diallylaminoethyl)pyrimidine trifluoroacetate salts in water resulted in low-yield homopolymers. In contrast, the neutral 1-(2-diallylaminoethyl)pyrimidines cyclo-copolymerized with sulfur dioxide and V-50 initiator to yield the corresponding copolymers in higher yields ranging from 30 to 60%.

A new resin embedded with chelating motifs of biogenic methionine for the removal of Hg(II) at ppb levels.

Cyclopolymerization of N,N-diallylmethionine hydrochloride, derived from the biogenic amino acid methionine, (90 mol%) and cross-linker tetraallylpiperazinium dichloride (10 mol%) in presence of an azo-initiator afforded pH-responsive cross-linked polyzwitterion (CPZ). The structural morphology of the resin (i.e. CPZ) was examined by the BET and FESEM-EDX analyses. The methionine embedded resin demonstrated remarkable efficacies for the removal of Hg(II) ions at ppb levels. A 50 mg-dose of the resin immersed in aqueous medium (18 mL) could reduce the concentration of Hg(II) from 200 and 400 ppb to 1.8 and 4.4 ppb, respectively, within 15 min. The resin has also proven to be remarkably effective in the removal of several toxic and priority metal pollutants from industrial wastewater. The Hg(II) adsorption followed pseudo second-order process with Ea of 48.1 kJ mol-1. The initial rapid adsorption of metal ions and subsequent slower adsorption was attributed to film and intraparticle diffusion, respectively. The SEM-EDX analyses revealed the attachment of Hg(II) ions onto the resin. The favorability of the endothermic adsorption was ensured by the negative ΔGº values. The efficient adsorption/desorption process confirmed the recyclability of the resin. The current resin demonstrated superior metal removal capacities as compared to several other adsorbents in recent works.