Preparation of tetrafluoro-λ6-sulfanyl bridged-bonding perfluoroalkyl styrene and its emulsion copolymerization with acrylate monomers for cotton fabrics finishing

4-(Perfluorobutyl)styrene, 4-(Perfluorohexyl)styrene, 4-[Perfluorobutyl(tetrafluoro-λ⁶-sulfanyl)]styrene (C₄F₉ SF₄ styrene), and 4-[Perfluorohexyl(tetrafluoro-λ⁶-sulfanyl)]styrene (C₆F₁₃ SF₄ styrene) were prepared in two or three steps. The short-chain perfluoroalkyl groups are modified through the insertion of tetrafluoro-λ⁶-sulfanyl linked groups ( SF₄ ). The prepared perfluoroalkyl styrene acts as functional monomers to react with butyl acrylate, methyl methacrylate, and hydroxyethyl methacrylate for emulsion copolymerization to obtain side-chain fluoropolymers. The long-chain fluoropolymer formed in contrast to the tetrafluorosulfanyl ( SF₄ ) modified ones. The emulsions were applied on cotton fabrics to give hydrophobicity. The result showed that the fabrics treated with tetrafluorosulfanyl-modified fluoropolymers were more hydrophobic, indicating that the introduction of  SF₄ was beneficial to provide lower surface energy and obtain better water repellent performance. The water contact angles record the varying degrees of variation in polymer degradation under UV exposure. The result showed that, as the perfluoroalkyl is bonded by  SF₄ , when comparing with the carbon-chain perfluoroalkyl polymer, the tetrafluorosulfanyl-modified fluoropolymer is more degradable during UV irradiation.     

Electrochemical behaviour and electrochemical polymerization of fluoro‐substituted anilines

The electrochemical behaviour of three fluoro‐substituted aniline monomers, 2‐fluoroaniline (2FAN), 3‐fluoroaniline (3FAN) and 4‐fluoroaniline (4FAN), was investigated in aqueous acidic and organic media by means of cyclic voltammetry (CV) studies. Constant potential electrolysis (CPE) of the monomers in acetonitrile–water mixture (1:1 by volume) using NaClO₄ as supporting electrolyte yielded soluble polymers. The mechanism of electrochemical polymerization was investigated using in situ electron spin resonance (ESR) and in situ UV–VIS spectroscopic techniques for one of the monomers (4FAN). Both CV and in situ UV–VIS measurements indicated that the polymers obtained are in the emeraldine base form. In situ ESR studies indicated that electrochemical polymerization involves a radical‐cation as an intermediate. Characterization of polymer products have been carried out using FTIR and NMR spectroscopic techniques, and thermal behaviour was studied using differential scanning calorimetry (DSC). It was found that conductivity can be imparted to as‐synthesized polyfluoroanilines via iodine doping. © 2002 Society of Chemical Industry     

Synthesis,characterization, and thermotropic properties of side-chain liquid crystalline polysiloxane polymers with an oligo(ethylene oxide) unit in the side chain

A series of new alkene and octenyloxy monomers containing 4′-[oligo(ethylene oxide)] n monomethyl ether 4-biphenyl ether carboxyl benzoate [MS3BDBE_n] (n = to 3) and 1- (p-methoxydiphenyl)–(carboxyl benzoate) [oligo(ethylene oxide)]n [MS_m+2BEnDB] (m = 1, 6; n = 1 to 3) as end groups were synthesized. The molecular structure of the monomers was charaterized using nuclear magnetic resonance (NMR) spectroscopy. These monomers were grafted onto poly(methylhydrosiloxane)s (PMHS) by the platinun-catalyzed hydrosilylation process. The thermal transition temeratures and mesophase textures of the monomers and the polysiloxane polymers have been determined by diffential scanning calorimetry (DSC) and by polarized optical microscopy. The effect of changes in chemical structure on the mesophase properties, glass transition temperature, isotropic temperature, and mesophase texture of the monomers and the polysiloxane polymers is discussed. Polymers PS3BDBEn showed smectic and nematic phases which were not analogous to their precursor nematic monomers MS3BDBEn. Both monomers MS_m+2BE_nDB and their polymeric homologous PS_m+2BE_nDB did not exhibit mesophase properties. This demonstrated that the polymer effect could not stabilize the mesophase obtained from mesogenic core which contained a flexible oligo(ethylene oxide) unit interconnecting aromatic group. © 1995 John Wiley & Sons, Inc.     

The effect of composition and the introduction of positive charge group (?N(CH3)2) on the multiphase morphology of polyurethane/polyacrylates interpenetrating polymer networks

A series of interpenetrating polymer networks (IPNs) of polyurethane/polyacrylates were synthesized. Their morphology was investigated by means of small‐angle X‐ray scattering (SAXS) and transmission electron microscope (TEM). The influence of an active positive charge group ( N(CH₃)₂) on the phase structure of the aforementioned IPNs was studied. The results show not only that the size of phase segregation zones varies with composition but also that the specific interfacial surface areas have a maximum when the weight ratio of polyurethane and polyacrylates is 1 : 2. Moreover, the introduction of an active positive charge group ( N(CH₃)₂) is an important way of increasing the miscibility between two component polymers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1898–1904, 1999     

Iodination of stable aromatic diazonium salt using crosslinked poly (4‐vinylpyridine)‐supported iodide

In this article, a series of carboxylated acrylate copolymer latices were prepared based on the semicontinuous emulsion polymerization via the pure monomer dropwise manner with three different kinds of carboxylic monomers in presence of reactive emulsifier. The effects of the carboxylic monomers [acrylic acid, methacrylic acid, and monobutyl itaconate (MBI)] on the conversion and the properties of acrylate latices and films have been investigated. The carboxylic groups ( COOH) distribution of these three kinds of latices were investigated as well. The results show that the concentration of surface  COOH (C_S) and embedded  COOH (C_b) both increase with the increase of the amount of carboxylic monomers. It shows that MBI, the most hydrophobic of the three carboxylic monomers used, tends to be concentrated inside the particle core, and the latex particles have a narrow size distribution. The results of common stability test have demonstrated that the stability of the latex is satisfactory. Moreover, the water absorption and the acid and alkaline resistance of the latex depend on the kind of carboxylic monomer. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High shape-memory effect of hindered phenol/nitrile–butadiene rubber composites by forming hydrogen bonding

To widen the type and scope of use of shape memory polymers (SMPs), we added hindered phenol (AO-80) to nitrile–butadiene rubber (NBR) to gain a group of AO-80/NBR rubber composites. The glass transition temperature (T_g), structure, mechanical properties, and shape memory properties of the AO-80/NBR rubber composites were characterized. It was concluded that the dispersion of AO-80 in the NBR matrix was homogeneous and intra-molecular hydrogen bonds were formed between the hydroxyl groups ( OH) of AO-80 and the cyano groups ( CN) of NBR molecular chain. The dosage of AO-80 added could be changed to tune the T_g. AO-80/NBR rubber composites revealed outstanding shape fixity and shape recovery. The method for tuning the T_g of AO-80/NBR rubber composites will provide an idea for the fabrication and design of new SMPs. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48911.     

Synthesis,chemical, and thermoelectric properties of n‐type π‐conjugated polymer composed of 1,2,4‐triazole and pyridine rings and its metal complexes

A soluble n‐type π‐conjugated polymer ( polymer 1 ) composed of a 1,2,4‐triazole ring substituted by a 4‐n‐octylphenyl subunit at the 4‐position of the 1,2,4‐triazole ring and pyridine‐2,5‐diyl rings was synthesized by Ni(cod)₂ (cod = 1,5‐cyclooctadiene) promoted dehalogenation polycondensation of 3,5‐bis(2‐bromopyridyl)‐4‐n‐octylphenyl‐1,2,4‐triazole ( monomer 1 ). A polymer complex ( polymer‐BiCl₃ ) was synthesized by the reaction of polymer 1 with BiCl₃. The UV–vis spectrum of polymer 1 exhibited an absorption maximum (λ_max value) at a longer wavelength than that exhibited by monomer 1 revealing that its π‐conjugation system was expanded along the polymer chain. Polymer 1 was electrochemically active in film, and the electrochemical reaction was accompanied with electrochromism. Thermoelectoric properties of polymer 1 and polymer‐BiCl₃ were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39928.     

Comparison of thermal,thermomechanical, and rheological properties of blends of divinylbenzene-based hyperbranched and linear functionalized polymers

A range of polymer blends were prepared via a solvent-based film casting process using highly/hyperbranched (HB) polydivinylbenzenes (PDVB) polymers of two different molecular weights, linear functionalized (LF), hydrogenated hyperbranched (H-HB2) PDVB, and linear polystyrene (LP). The thermal, thermomechanical, and rheological properties of the pure polymers and blends were then investigated and the results related to the concentration of “branched” polymer in the blend and the level of branching/polymer end groups present in the “branched” polymers used. Differential scanning calorimetry (DSC) analysis revealed an increase of the glass transition temperature (T_g) for the blends containing the nonhydrogenated HBs (~108 °C compared to ~102 °C for LP), which was attributed to crosslinking via the unsaturated reactive chain end/pendant groups in the HB ( CHCH₂). In contrast at the blends, containing the hydrogenated polymers H-HB2, exhibited the same T_g as LP (~102°C) due to absence of crosslinking from the (H-HB2) polymer. As the unsaturated HBs were found to be thermally curable, curing temperature rheology measurements were carried out employing a temperature ramp. No specific T_gel (the temperature at which HB gets crosslinked) was identified for LP-HB1 and LP-HB2 blends, which might be suggested to be due to the fact that both chain entanglement from linear polystyrene. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48547.     

Bamboo is a suitable template for polymerizations

In situ hydrosilation reactions and ring‐opening metathesis polymerizations were demonstrated to occur in bulk samples of bamboo. Bamboo was infused with silicone precursors or cyclodiene monomers with the assistance of supercritical CO₂ and subsequently crosslinked or polymerized, respectively. Bending stiffness, energy release rate, and specific fire resistance properties of the bamboo‐polymer composites were measured and compared with unmodified bamboo. Bamboo‐silicone composites showed an increase in fire resistance and a slight increase in mechanical properties. The bamboo‐poly(alkenamer) composites showed significant increases in mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ferrocenyl Monomers and Polymers of <Emphasis Type="Italic">N</Emphasis>-Allyl and <Emphasis Type="Italic">N</Emphasis>-Acrylatenaphthalimides

A series of N-allyl, N-ethylmethacrylate and N-phenylmethacrylatenaphthalimide monomers have been prepared with –C=CFc, –C≡CFc and –C≡CSiMe₃ substituents at the 4-position of the naphthalimide ring. All have been characterised by elemental analysis and spectroscopy; the X-ray structure of N-allyl-4-ethenylferrocenylnapththalimide is also reported. Free-radical polymerisation of these monomers gave homopolymers, random co- and terpolymers with polydispersities ranging from 1.7 to 3.2. Incorporation into a polymer matrix has no effect on the spectroscopic and electrochemical properties of the naphthalimide or ferrocenyl components. The ferrocenyl polymers are electrochromic and when oxidised give naphthalimide charge-transfer bands in the NIR; this electrochromism was examined by OTTLE techniques.     

Synthesis and photoluminescence property of polyacetylenes containing liquid crystalline side groups

A series of new side-chain liquid crystalline (LC) polyacetylenes containing 4-(trans-n-alkylcyclohexanylcarbonyloxy)phenyl 4-alkynyloxybenzoate side groups were synthesized by using [Rh(nbd)Cl]₂, WCl₆ and MoCl₅ as polymerization catalysts. The synthesized polymers were characterized by differential scanning calorimetry, optical microscopy and X-ray diffraction measurements. The monomers showed a nematic phase while all polymers revealed the nematic, smectic A and smectic C phases. X-ray diffraction measurements proved that all the polymers show an interdigitated bilayer structure. The optical properties of the polymers were investigated by UV-vis and photoluminescent spectroscopies. The polymer films emitted green-blue photoluminescence at about 500 nm.     

Synthesis and properties of polymer from bis‐3,4‐ethylenedioxythiophene substituted acenaphthenequinoxaline

A new electrochoromic polymer poly(8,11‐bis(3,4‐ethylenedioxy thiophen‐2‐yl)acenaphtho[1,2‐b]‐quinoxaline) (PBEAQ) was synthesized by electrochemical polymerization of the corresponding monomer (BEAQ) in a 0.1 M tetraethylammonium tetrafluoroborate (TEABF₄) dichloromethane–acetonitrile (2 : 1, v : v) solution. The monomer and polymer were characterized by elemental analysis, ¹H‐NMR, IR, and UV‐vis spectroscopy. The electrochemical and optical properties of polymer were investigated by cyclic voltammetry and UV‐vis spectroscopy. Cyclic voltammetry and spectroelectrochemistry studies demonstrated that the polymer can be reversibly reduced and oxidized (both n‐ and p‐doped) between ?2 V and +1.5 V vs. Ag/Ag⁺. The polymer had a transmissive light blue color in the oxidized state and reddish color in the reduced state. Undoped polymer shows UV‐vis absorption peaks at 615 nm in solution, 650 nm in solid state, and has an optical band gap of 1.5 eV. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Photochemical reactions of polymers bearing chalcone residues

Photosensitive polymers based on pendent chalcone moieties were prepared directly by radical polymerization of vinyl-chalcone monomers. The monomers were synthesized by the esterification reactions of the hydroxyl groups of 4- and 4′-hydroxychalcones with methacryloyl chloride. The monomers (4- and 4′-(methacryloyloxy)chalcones) were polymerized to give the corresponding homo-and co-polymers containing different ratios of p-nitrophenyl methacrylate as photosensitizer group. Investigation of the photosensitivities of the chalcone polymers was carried out through study of the photochemical reactions on exposure to UV light and measuring the changes in UV spectra before and after irradiation. The results obtained from the disappearance rates of the C=C bonds indicate that the photoreactivities of the polymers are largely affected by the position of the attachment of the chalcone to the polymer backbone and by the concentration of the photosensitizer group.     

Synthesis of chiral side-chain liquid crystalline polyacetylenes bearing succinic acid spacer

A chiral acetylene monomer having a cholesteryl group (PSCh) and novel three types of chiral acetylene monomers having a o-substituted tyrosine methyl ester (PSMY-Rs: –COC₆H₅=PSMY-Bz; –COC₆H₄CN=PSMY-BzCN; –COC₁₂H₉=PSMY-PhBz) as a pendant group were synthesized from 4-oxo-4-(prop-2-ynyloxy)butanoic acid (PS), and polymerized with the rhodium-catalyzed system. Structures and properties of the monomers and the resulting polymers were characterized and evaluated by NMR, IR, GPC, and DSC. In addition, these optical properties were investigated by polarimetric detector and circular dichroism (CD) analyses.     

Synthesis and electrochromic performance of a novel polymer based on an oxidative polymer derived from carbazole and thiophene

A polymer derived from poly-9-bis[4-(thiophen-3,4-yloxy)biphenyl)]-9H-carbazole containing a carbazole and thiophene group, abbreviated as B2, was synthesized via the oxidation method by using FeCl₃ as an oxidant. Additionally, the electrochemical polymer of B2 was synthesized and coated onto an ITO–glass surface via electrochemical oxidative polymerization. The electrochemical synthesis of the polymer was performed in 0.05 M AN/LiClO₄ solvent/electrolyte solution containing 0.1 M concentration of B2 between +0.3 and +1.4 V potentials. The compounds were characterized by FT-IR, NMR, and elemental analysis techniques. The spectroelectrochemical and electrochromic properties of this polymer were also investigated in 0.05 M AN/LiClO₄ solvent/electrolyte solution for 200 s and at a constant potential of +1.4 V. Switching ability of this polymer was measured as the percent transmittance (?T%) at its changing point of maximum contrast. Additionally, the scan rate study was performed at different scan rates: 400, 300, 200, 100, 50, 20 mV/s. According to the electrochromic measurements, the synthesized polymer had a light blue color when it was oxidized, and when it was reduced, it had a transparent color. As a result, the synthesized polymer P(B2) can be used to produce new polymeric electrochromic devices, and it can be considered a good candidate for applications of electrochromic devices (ECDs) because of its short response time of 3.5 s.     

Corrosion protection of carbon steel and copper by polyaniline and poly(ortho-methoxyaniline) films in sodium chloride medium. Electrochemical and morphological study

The aim of this work was to obtain polyaniline (Pani) and poly(ortho-methoxyaniline) (Poma) by chemical synthesis and to evaluate their corrosion protection properties on carbon steel (CS) and copper (Cu) in an aggressive media such as sodium chloride. The syntheses of the polymers were carried out by chemical oxidation of the monomers by (NH₄)₂S₂O₈ in nitric acid solutions. Under these conditions, the polymers were obtained in the oxidized form, dissolved in 1-methyl-2-pyrrolidone and casted by solvent evaporation onto the metallic substrates (carbon steel and copper) for corrosion evaluation. The morphology of the polymers was evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The electrochemical behavior was determined by open circuit potential (OCP) measurements and polarization curves (PC). The best results were obtained with Pani because this polymer film participates in the formation of an oxide film at the polymer–metal interface, a phenomenon which is not observed with Poma. This oxide film increases the barrier effect that the polymeric film has by itself.     

Anchoring hydroxyl intermediate on NiCo(OOH)x nanosheets to enable highly efficient electrooxidation of benzyl alcohols

Selective oxidation of alcohols to the carboxylic acid plays an important role in the production of valuable chemicals. Herein, NiCo hydroxide (NiCo(OOH)_x) nanosheets with a thickness of ~4 nm were controllably fabricated in a facile way efficient for the electrooxidation of benzyl alcohol (BAL) to benzoic acid (BAD). Mechanistic studies confirmed the hydroxyl active intermediate ( OH*) generated on the surface of NiCo(OOH)_x nanosheets through operando electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy analysis during the electrooxidation process. Importantly, we discovered that the  OH* was crucial to boost the selective oxidation of BAL by attacking the hydroxyl end group to achieve carboxylic acid. The early onset potential of 1.16 V_RHE in the presence of BAL was below 1.23 V_RHE for oxygen evolution reaction. The rotating ring-disk electrode further revealed that the electrocatalytic BAL oxidation reaction occurred earlier in the oxygen evolution reaction. In 150 mM BAL, NiCo(OOH)_x nanosheets generated a high BAD selectivity of >99% and full conversion of BAL in 3 h. The experimental and theoretical calculation revealed that the dominant pathway of BAL oxidation was the interaction between nucleophilic BAL with  OH* to form BAL-OH* directly by dehydrogenates, thereby producing BAD with high efficiency. This research sheds mechanism insights on the electrocatalytic alcohols oxidation reaction.     

Graft polymerization of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid onto starch

Mixtures of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid (AASO₃H) were graft polymerized onto starch by cobalt-60 irradiation, and the water absorbency and water solubility of the resulting products were determined. The conversion of monomers to polymer was nearly quantitative when pregelatinized wheat starch and a water solution of the two monomers were simultaneously irradiated (simultaneous irradiation conditions). Products with high water absorbency were obtained with equal weights of starch and total monomers when acrylamide:AASO₃H ratios ranged from 9:1 to 1:3. Water solubility of these polymers was over 50%. Neither of the two monomers gave absorbent polymers when graft polymerized individually onto starch. Although highly absorbent products were also obtained at a total monomer:starch ratio of 2:5, ratios of 1:5 and lower gave products with poor absorbency. Neutralization of AASO₃H with sodium hydroxide before graft polymerization drastically reduced both the water solubility and absorbency of the final products. A reaction with granular starch was also carried out under simultaneous irradiation with a total monomer:starch ratio of 2:5 and with equal weights of the two monomers. Conversion of monomers to polymer was once again nearly quantitative. To obtain good water absorbency from this granular product, it was necessary to first neutralize the AASO₃H portion with alkali, then disperse the polymer in hot water, and finally dry the resulting water dispersion. Graft copolymers with good water absorbency were also obtained by adding preirradiated starch to a water solution of acrylamide and AASO₃H, although only partial conversions of monomers to polymer were realized. Selected products from the various graft polymerizations were fractionated by extraction with either water or a 1% solution of sodium chloride. The synthetic polymer content of the resulting fractions and the percentage of AASO₃H in the synthetic portion of each polymer were determined. The M _n of some of the synthetic polymers was also determined after removal of carbohydrate by enzymatic hydrolysis.     

Radical polymerization of itaconic anhydride and reactions of the resulting polymers with amines and alcohols

Itaconic anhydride was polymerized in the presence of a radical initiator under various conditions. The bulk polymerization at 75°C yielded polymer with molecular weight of more than 20000. The reactions of the resulting polymer with water and alcohols gave poly(itaconic acid) and its esters, respectively. The polymers prepared by such reactions were found to have similar thermal properties to those prepared by homopolymerizations of the respective itaconic acid derivatives. Poly(N-substituted itaconomic acid)s, which are difficult to obtain by direct polymerization of their monomers, were prepared by the reactions of poly(itacononic anhydride) with amines. Copolymerizations of itaconic anhydride with electron-donating monomers, styrene and isobutyl vinyl ether, gave alternating copolymers which were then converted by esterification to the respective copolymers of dialkyl itaconates with such electron-donating monomers.     

Solid‐state single‐ion conducting comb‐like siloxane copolymer electrolyte with improved conductivity and electrochemical window for lithium batteries

Achievement of high conductivity and electrochemical window at ambient temperature for an all‐solid polymer electrolyte used in lithium ion batteries is a challenge. Here, we report the synthesis and characterization of a novel solid‐state single‐ion electrolytes based on comb‐like siloxane copolymer with pendant lithium 4‐styrenesulfonyl (perfluorobutylsulfonyl) imide and poly(ethylene glycol). The highly delocalized anionic charges of ? SO₂? N^(–)? C₄F₉ have a weak association with lithium ions, resulting in the increase of mobile lithium ions number. The designed polymer electrolytes possess ultra‐low glass transition temperature in the range from ?73 to ?54 °C due to the special flexible polysiloxane. Promising electrochemical properties have been obtained, including a remarkably high conductivity of 3.7 × 10^?5 S/cm and electrochemical window of 5.2 V (vs. Li⁺/Li) at room temperature. A high lithium ion transference number of 0.80, and good compatibility with anode were also observed. These prominent characteristics endow the polymer electrolyte a potential for the application in high safety lithium ion batteries. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45848.