Synthesis and characterization of optically active helical vinyl polymers via free radical polymerization

A facile synthetic route to prepare the dual‐functional molecule, 2,5‐bis(4′‐carboxyphenyl)styrene, was developed. The esterification of this compound with chiral alcohols, that is, (S)‐(+)‐sec‐butanol/(R)‐(?)‐sec‐butanol, (S)‐(+)‐sec‐octanol/(R)‐(?)‐sec‐octanol, and D ‐(+)‐menthol/L ‐(?)‐menthol, respectively, yielded three enantiomeric pairs of novel vinyl monomers, which underwent radical polymerization to obtain helical polymers with an excess screw sense. These polymers exhibited optical rotations as large as fourfold those of the corresponding monomers. Their helical conformations were quite stable as revealed by the almost unchanged chiroptical properties measured at different temperatures. The polymers with linear alkyl tails in the side‐groups formed irreversibly columnar nematic phases in melt although the corresponding monomers were not liquid crystalline. Whereas, the polymers with cyclic tails generated no mesophase. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2408–2421, 2009     

Synthesis and characterization of 2, 4-dihydroxy-benzaldehydeoxime-formaldehyde polymers and their application as ion-exchangers

Polymers were prepared by the condensation of 2, 4-dihydroxybenzaldehydeoxime (2, 4-DBO) and formaldehyde (F) in the presence of oxalic acid as catalyst with varying molar ratios of reacting monomers. Polymers were characterized by their IR spectra, elemental analyses, TGA and M_n as determined by vapour pressure osmometry as well as by non-aqueous conductometric titrations. Viscosity measurements of the solutions of polymer samples were carried out in dimethylformamide. Chelation ion-exchange properties have also been studied employing the batch equilibration method. This method involved the measurement of distribution of a given metal between the polymer sample and a solution containing metal ions. The study was carried out over a wide pH range and in media of various ionic strengths. The polymer showed a higher selectivity for UO ₂ ²⁺ and Fe³⁺ ions than for Cu²⁺, Ni²⁺, Co²⁺ and Mn²⁺ ions.     

Synthesis, characterization and pharmacologically active sulfamethoxazole polymers

Three anti-microbial pharmaceutical drugs were synthesized from two different synthetic routes. 4-acrylamido-N-(5-methyl-3-isoxazolyl)benzenesulfonamide (AMBS) and 4-methacrylamido-N-(5-methyl-3-isoxazolyl)benzenesulfonamide (MMBS) were prepared by reacting acryloyl chloride and methacryloyl chloride with 4-amino-N-(5-methyl-3-isoxazolyl)benzenesulfonamide in the presence of triethylamine. N-[4-sulfamido-N-(5-methyl-3-isoxazolyl)phenyl]maleimide (SMPM) was prepared by reacting maleic anhydride with 4-amino-N-(5-methyl-3-isoxazolyl)benzenesulfanamide. These monomers (AMBS, MMBS and SMPM) were polymerized using BPO as a free radical initiator. The pharmacological activity of SMPM compound depends on the functional group in the structure and small structural changes has resulted in higher pharmacological activity of sulfamethoxazole. Thus, maleimide polymer drug conjugate showed greater anti-microbial activity when compared with that of the native drug.     

Preparation, characterization, and X-ray crystal structures of helical and syndiotactic zinc-based coordination polymers

The reactions of (facac)2Zn.2H2O (facac = 1,1,1,5,5,5-hexafluoroacetylacetonate) with 2,5-bis(4-ethynylpyridyl)furan (1) and 1,2-bis(4-ethynylpyridyl)benzene (2) yield, upon crystallization, coordination polymers. The former polymer, ((facac)2Zn.1)n, has an isotactic, helical structure in the solid state [monoclinic space group P2(1)/n; a = 11.0374(3) A, b = 24.2179(10) A, c = 14.3970(4) A, beta = 92.880(2) degrees; Z = 4]. The latter polymer, ((facac)2Zn.2)n, adopts a syndiotactic structure in the solid state [monoclinic space group P2(1)/n; a = 9.1344(1) A, b = 21.7985(5) A, c = 16.0322(4) A, beta = 99.6680(11) degrees; Z = 4]. The solution structures of the corresponding oligomers have been studied by low-temperature 1H and 19F NMR spectroscopy. Chiral polymers were prepared using the fragment [(+)-tfc]2Zn ((+)-tfc = 3-((trifluoromethyl)hydroxymethylene)-(+)-camphorate). A linear, zigzag structure was found for ([(+)-tfc]2Zn.1)n [triclinic space group P1; a = 7.4833(2) A, b = 14.1563(5) A, c = 21.21230(5) A, alpha = 78.4440(15) degrees, beta = 81.5644(15) degrees, gamma = 76.4976(13) degrees; Z = 1]. Reaction with tris(4-pyridyl)methanol (3) yielded a homochiral, helical polymer, ([(+)-tfc]2Zn.3)n [monoclinic space group C2; a = 25.0633(12) A, b = 11.8768(7) A, c = 17.1205(9) A, alpha = 90 degrees, beta = 117.954(3) degrees, gamma = 90 degrees; Z = 4].     

Synthesis, characterization and thermal properties of metaloquinolate-containing polymers

The monomer, 5-methyl(2-methacryloylethyloxy)-8-quinolinol(HEMA-CH₂-Hq), which possesses both double bond and 8-hydroxyquinoline groups, was synthesized from 2-hydroxyethyl methacrylate (HEMA) and 5-chloromethyl-8-quinolinol hydrochloride. The model polymer with 8-hydroxyquinoline ligands was obtained by free-radical copolymerization with styrene. So metaloquinolate (AlQ₃, ZnQ₂)-containing polymers are prepared by coordinating reaction with di(8-hydroxyquinoline) aluminum(AlQ₂) chelates or mono(8-hydroxyquinoline) zinc(ZnQ) chelates without cross-linking. Both polymer and polymer complexes were analyzed by FT-IR, UV-vis, DSC, TGA and photoluminescence spectroscopies. They are soluble in common solvents and easy to form films. The use of AlQ₂ and ZnQ avoided the cross-linking caused by the AlQ₃, ZnQ₂ formation between different polymer chains. High glass transition temperature, good thermal stability, and strong yellow-green fluorescence were observed for the prepared polymers. These polymers were expected to have the potential application in yellow-green OLEDs.     

Synthesis,crystal structures,and magnetic properties of three isomorphous helical coordination polymers

Three isomorphous coordination polymers of general formula {[M(H₂bna)·(DMF)₂·(H₂O)₂]·DMF}_n (M = Co for 1, Mn for 2, Ni for 3, respectively, where H₄bna = 2,2′-dihydroxy-[1,1′]-binaphthalene-3,3′-dicarboxylate) were synthesized under solvothermal conditions and characterized by FTIR, single crystal X-ray diffraction, thermogravimetric analysis, and X-ray power diffraction analysis. All three polymers crystallize in the same monoclinic space group P2₁/n. The complexes are assembled into 1D helical chains, and each adjacent helical chain of the same chirality is further connected to form a chiral layer by hydrogen bond interactions. The layers are packed in alternating left-(M) and right-handed (P) chirality arrays. Magnetic studies reveal the presence of antiferromagnetic coupling interactions in complexes 1 and 2.     

Synthesis and characterization of silicate polymers

In this work an inorganic polymer is developed based on Elkem microsilica and potassium hydroxide. Using experimental data and the partial charge model a model for the gelation is suggested based on the hydrolysis and condensation reactions occurring during synthesis. In addition the optimal composition of the binder system was determined using compressive strength test and solubility experiments. Based on partial charge calculations and experimental data for the hydroxide concentration and the viscosity obtained in this study it is suggested that the polymerization of the inorganic polymer is determined by the concentration of silica species. It was found that the alkalinity has a crucial effect on the condensation process. The optimal potassium hydroxide concentration used in the synthesis of the inorganic polymer was found to be around 3.5 M, which resulted in a compressive strength of the product in the region of 50 MPa.     

Synthesis and characterization of furfural-acetone polymers

The polymeric products obtained from 2-furfurylidene methyl ketone and from furfural and acetone in the presence of base have been characterized by u.v. and i.r. spectral study, molecular weight estimation by vapour pressure osmometry and viscometric study of solutions in dioxane. Gel Permeation Chromatography of selected polymer samples was carried out to estimate polydispersity index; thermal behaviour was studied by thermogravimetric analysis. A likely course of the polymerization and the structure of polymers prepared from 2-furfurylidene methyl ketone (PFMK) are proposed.     

Recent advances in acetylene-based helical oligomers and polymers: Synthesis,structures, and properties

In this review, we describe the recent advances in the chemistry of helical polymers and oligomers containing acetylene units in the main chain. Owing to their great benefits such as high availability and handleability, good reactivity, rigidity, linearity, and low bulkiness, acetylene units have been utilized and incorporated in helical folding oligomers and polymers such as oligo- and poly(m-phenylene ethynylene)s. General synthetic methods as well as the structures, functions, and properties of acetylene-based helical oligomers and polymers are discussed by focusing on recent examples from 2009 to 2017.     

Synthesis, characterization, and thermal properties of new silarylene-siloxane-acetylene polymers

New silarylene-siloxane-acetylene polymers have been synthesized by coupling reactions employing 1,3-bis(p-ethynylphenyl)-1,1,3,3-tetraphenyldisiloxane (3) as the key monomer. Their thermal properties have been evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). All of the new polymers showed good thermal stability, with their temperatures at 5% weight loss (T_d5) being higher than 540 °C under nitrogen and higher than 460 °C in air. Their char yields at 1000 °C under N₂ were above 80%. Broad exothermic peaks, attributable to reaction of the acetylenic units, were observed by DSC analysis in the temperature range 270-450 °C.     

Synthesis,characterization and recent developments of liquid crystalline polymers

Recent developments of polymer liquid crystals (PLCs) are reviewed. The virial expansion method of Onsager and the lattice model used by Flory to appreciate the most relevant parameters in establishing mesomorphic behavior in polymeric systems are presented. These and other theoretical predictions are confirmed by numerous experiments. Both lyotropic (polymer solutions) and thermotropic (polymer melts) types of PLCs are considered with emphasis placed on the latter. The general properties of mesophases formed by such polymers are surveyed and some chemical structures capable of producing mesophases are classified in relation to their ability to form lyotropic and thermotropic systems. The synthetic routes, the effects of polymer structure on physical properties, and applications of two major classes of lyotropic systems (polypeptides, polyamides) and of a range of potentially important thermotropic polymers are discussed.     

Synthesis and characterization of new calixarene-chitosan polymers

Triflate Ester of Calix[n]arene (n = 4, 6, 8) (TEC[n] (n = 4, 6, 8)) were synthesized based on a new synthetic route, then TEC[n] (n = 4, 6, 8) were further modified by reacting with low molecular weight Chitosan (CS) to get three kinds of new Calix[n]arene-Chitosan polymers (n = 4, 6, 8) (C[n]CSP (n = 4, 6, 8)) through Buchwald-Hartwig cross coupling reaction. The structures of the polymers were characterized by FT-IR, SEM, Elemental analyzer and ¹³C SSNMR. And the results found that Chitosan was successfully introduced to Calix[n]arene (n = 4, 6, 8) (C[n] (n = 4, 6, 8)) without any long-chain alkyl between Chitosan and Calixarene. These new polymers are partially substituted calixarene. The substitute degree of C[4]CSP, C[6]CSP and C[8]CSP is 17.75%, 21.08% and 54.53% respectively. And the optimal preparation conditions were discussed and the results were listed as following, molar ratio (1:2), catalyst (0.05 mmol), solvent ratio (1:1.5 (10 mL?1.0 mmol^?1)) and reaction time (5h).     

Synthesis and characterization of glass-containing superabsorbent polymers

By embedding hollow glass spheres of different sizes and densities into a matrix of crosslinked sodium polyacrylate, superabsorbent polymers were synthesized using a water-in-oil suspension polymerization. These glass-containing superabsorbents were capable of taking up water not only in form of a swollen polyacrylate gel, but also in form of additional free water between the glass spheres and the surrounding polyacrylate matrix. According to swelling measurements the maximum volume swelling degree of the glass-containing superabsorbents is in certain cases nearly double as large as the value of a superabsorbent without embedded glass spheres.     

Synthesis and characterization of phenylated pyrazino-benzimidazophenanthroline polymers

Novel phenylated quinoxaline tetraamines have been prepared and polymerized with 1,4,5,8-naphthalenetetracarboxylic acid in polyphosphoric acid solution. The resulting BBB-type polymers with pendant phenyl groups along the polymer backbone are soluble in m-cresol. The polymers, with inherent viscosities ranging from 0.3 to 0.6 dl/g in sulfuric acid, exhibited thermal stabilities near 500°C under nitrogen and near 400°C in air.     

Synthesis and characterization of perfluorinated arylenevinylene polymers

Fully fluorinated arylenevinylene polymers have been synthesized via a methodology based on the Stille cross‐coupling reaction and characterized by FTIR spectroscopy and MALDI‐TOF mass spectrometry. Investigation of thin film properties by cyclic voltammetry and ellipsometry shows that complete substitution of hydrogen atoms with fluorine atoms on the conjugated backbone of the poly(arylenevinylene)s results in a strong increase of the band gap. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 285–291, 2010     

非诺贝特印迹聚合物的制备与性能研究

以非诺贝特(FNB)为模板分子,α-甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,采用本体聚合方法合成了FNB分子印迹聚合物(MIP)。IR和SEM表征的结果显示:FNB分子印迹聚合物中存在与模板分子相互作用的特征基团,与空白聚合物(NIP)的表面形态显著不同,说明MIP存在与模板分子相互识别的结合位点。采用静态平衡结合方法和Scatchard模型评价了FNB分子印迹聚合物的结合特性和识别机理,并考察了其选择性吸附能力。结果表明,FNB分子印迹聚合物存在能量相异的两类特异性结合位点,对FNB具有高选择吸附特性,饱和吸附量为6.363mg/g。     

Synthesis,spectroscopic and thermal characterization of new metal-containing isocyanate-based polymers

Journal of Thermal Analysis and Calorimetry - To overcome the polyurethanes low heat resistance and obtain new PU-based materials, in continuation of our research in the synthesis of hybrid...     

Synthesis and characterization of biocompatible and biodegradable polymers

New polyesters were synthesized using Krebs cycle acids. Poly(1, 4-butanediol dilactate succinate)(PBDS) and poly(1, 4-butanediol dilactate 2-acetoxy succinate)(PBDAS) were prepared by the polycondensation of 1, 4-butanediol dilactate with succinic anhydride and 2-acetoxy succinic acid, respectively. Poly(1, 4-butanediol succinate)(PBS) was also synthesized from 1, 4-butanediol and succinic anhydride. PBS/PBDS and PBS/PBDAS blends were prepared by the method of solvent casting. The effects of crystallization time and temperature onto melting behavior of PBS/PBDS and PBS/PBDAS blends were investigated by differential scanning calorimetry. The compatibility of each blend system was discussed using equilibrium melting point depressions. The biodegradation behavior was studied using PBS, PBDS, and PBDAS as the sole carbon source by Aspergillus niger. The molecular weights of the polymers which were obtained from GPC analysis decreased after degradation in five weeks.     

Synthesis and characterization of polymers of 1,4-hexadienes

The homopolymerization of trans-1,4-hexadiene, cis-1,4-hexadiene, and 5-methyl-1,4-hexadiene was investigated with a variety of catalysts. During polymerization, 1,4-hexadienes undergo concurrent isomerization reactions. The nature and extent of isomerization products are influenced by the monomer structure and polymerization conditions. Nuclear magnetic resonance (NMR) and infrared (IR) data show that poly(trans-1,4-hexadiene) and poly(cis-1,4-hexadiene) prepared with a Et₃Al/α-TiCl₃/hexamethylphosphoric triamide catalyst system consist mainly of 1,2-polymerization units arranged in a regular head-to-tail sequence. A 300-MHz proton NMR spectrum shows that the trans-hexadiene polymer is isotactic; it also may be the case for the cis-hexadiene polymer. These polymers are the first examples of uncrosslinked ozone-resistant rubbers containing pendant unsaturation on alternating carbon atoms of the saturated carbon-carbon backbone. Polymerization of the 1,4-hexadienes was also studied with VOCl₃- and β-TiCl₃-based catalysts. Microstructures of the resulting polymers are quite complicated due to significant loss of unsaturation, in contrast to those obtained with the α-TiCl₃-based catalyst. In agreement with the literature, there was no discernible monomer isomerization with the VOCl₃ catalyst system.