Synthesis and properties of poly(ferrocenylsilane) high polymers

Ring-opening polymerization of strained, ring-tilted cyclic ferrocenylsilanes has recently provided access to the first examples of high molecular weight poly(ferrocenylsilanes) [1], which possess backbones of alternating ferrocenyl groups and silicon atoms. In this paper we provide an overview of the progress to date on the synthesis and properties of these unusual polymers.Presented at the XXVIth Silicon Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

Synthesis and characterization of thermally stable polymers (polybenzimidazoles)

In this study, an alternative synthesis of polybenzimidazoles was performed with aromatic hydroxamoyl chloride. In contrast to the literature, polybenzimidazoles were obtained through the reaction of hydroxamoyl chlorides with 3,3′‐diaminobenzidine or 1,2,4,5‐tetraaminobenzene. The characterization of the polymers was performed with Fourier transform infrared, ¹H‐NMR, elemental analysis, LC mass spectrometry, and differential thermogravimetry/thermogravimetric analysis. Finally, the adhesion, corrosion resistance, and conducting properties of the synthesized polymers were examined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(pyridylurea) and poly(pyridylthiourea), potentially semiconducting polymers

Poly(pyridylureas) and poly(pyridylthioureas) were synthesized by reacting 2,6‐diaminopyridine with phosgene and thiophosgene, respectively, using THF and pyridine as solvent. The synthesized polymers were characterized by IR‐spectroscopy, elemental analysis, and X‐ray photoelectron spectroscopy. Thermal stability of the polymers was determined by thermal degradation between 35°C and 700°C. The 50% weight loss of polypyridylureas was above 400°C while for the polypyridylthioureas it was above 450°C. Undoped poly(pyridylureas) and poly(pyridylthioureas) behave as semiconductors, σ = 10^?9 (Ω cm)^?1. After doping with I₂ and SbF₅, the electrical conductivity increases several orders of magnitude, σ = 10^?7(Ω cm)^?1. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of novel polythiophenes containing poly(ethylene oxide) side chains

Thiophene copolymers and their derivatives with poly(ethylene oxide) side chains were synthesized. The starting monomers were 3‐hexylthiophene and 2‐(3‐thienyl) ethanol with poly(ethylene oxide) grafted to the side chains. New functionalized polythiophenes were prepared by both chemical oxidation with FeCl₃ and electropolymerization. The conjugating polymers were characterized. The structures of the polythiophene derivatives agreed with the design. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1803–1808, 2006     

Synthesis,characterization and antimicrobial properties of new poly(ether-ketone)s and copoly(ether-ketone)s containing diarylidenecycloalkanone moieties in the main chain

A new category of linear poly(ether-ketone)s IV_a–d and copoly(ether-ketone)s V_a–f containing diarylidenecycloalkanone moieties in the main chain has been synthesized by solution polycondensation of 4,4′-bis (chloroacetyl)diphenylether I , with different phenoxides of diarylidenecycloalkanones II_a–d . The model compound III was synthesized from the monomer I with sodium phenoxide in DMF and K₂CO₃, and its structure was confirmed by elemental and spectral analyses. The resulting polyketones and copolyketones were characterized by elemental and spectral analyses, beside solubility and viscometry measurements. The thermal properties of those polymers were evaluated by TGA and DTA measurements and correlated to their structural units. X-ray analysis showed that polymers having some degree of crystallinity in the region 2θ = 5–60°. In addition, the biological screening and morphological properties of selected examples of the polymers were tested. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization, and redox and electrochromic behaviors of poly(3-n-octyloxythiophene)

Poly(3-n-octyloxythiophene), a conjugated polymer, which possessed solubility in common organic solvents, was synthesized by electrochemical polymerization in the presence of lithium perchlorate as the supporting electrolyte and sodium dodecyl sulfate as the surfactant in an aqueous medium. Characterizations of the intermediate, monomer, and polymer were performed by NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, and gel permeation chromatography. The process of electrochemical polymerization and the electrochemical redox behaviors were investigated by cyclic voltammetry and the potentiostatic method. A poly(3-n-octyloxythiophene) film that was deposited on a platinum electrode was found to exhibit electrochromic behaviors, and it switched electrochemically between blue–green oxidized and dark red reduced states. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Variable-color poly(3,4-propylenedioxythiophene) electrochromics from precursor polymers

We have developed two approaches to processable precursors to conjugated polymers: main-chain and side-chain. Upon oxidative conversion to the conjugated polymer, a main-chain precursor yielded a nearly perfect spectral match, an identical λ_max, and an equivalent band gap to that of electrodeposited chromophore, resulting in a color match. This precursor method has the potential to incorporate any chromophore and achieve spectral and color matching with relative ease, as opposed to extensive synthetic monomer design. We describe the synthesis and characterization of a new side-chain and two new main-chain precursor polymers, each of which contains a derivative of 3,4-propylenedioxythiophene, ProDOT-Me₂. The side-chain precursor tethers one ProDOT-Me₂ molecule to a poly(norbornene) backbone; the main-chain systems are perfectly alternating copolymers of ProDOT-Me₂, one with dimethylsilane and one with tetramethyldisiloxane. Electronic and optical properties for these converted precursors were described and compared to electrodeposited PProDOT-Me₂.     

Regioregular poly(3‐alkylthiophenes): Synthesis,characterization, and application in conductive fabrics

Poly(3‐dodecylthiophene) (P3DDT) and poly(3‐decylthiophene) (P3DT) with high contents of head‐to‐tail linkages (86 and 85%, respectively) were synthesized in high yields by a facile oxidative polymerization with ferric chloride in chloroform at room temperature. We believe that the low concentration and ultraslow addition of monomers to ferric chloride contributed to the high regioregularity. Differential scanning calorimetry thermograms indicated that the formed polymers consisted of crystalline, quasiordered, and disordered phases, which is a common feature of highly regioregular polymers. We prepared conductive fabrics with specific resistance of 30 and 100 Ω/sq by impregnating polyamide fabrics in a chloroform solution of P3DDT and P3DT, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2131–2135, 2004     

Synthesis and properties of readily recyclable polymers from bisfuranic terminated poly(ethylene adipate) and multi-maleimide linkers

Polymers that can repeatedly polymerize and depolymerize at moderate conditions was designed and synthesized. Furyl-telechelic poly(ethylene adipate) [PEA2F] was prepared and copolymerized with bis- and tris-maleimides by Diels-Alder [DA] reaction at 60 °C. Though the reaction with bismaleimide proceeded partially to give a polymer whose molecular weight was only twice as large as PEA2F, the reaction with trismaleimide gave a product with a 3D-network structure. The latter product shows elasticity at room temperature. By keeping at 145 °C, these DA products were easily disconnected by retro-Diels-Alder [rDA] reaction to reproduce the starting macromonomer, PEA2F. The repetition of the cycle of the DA and rDA reactions induce the reduction of neither the mechanical properties of the DA products nor the molecular weight of the rDA products. Therefore, we have successfully obtained readily recyclable polymers.     

Synthesis and properties of novel poly(coumarin‐amide)s

A novel monomer diacid, 6,6′‐methylenebis(2‐oxo‐2H‐chromene‐3‐carboxylic acid), was synthesized and used in a direct polycondensation reaction with various aromatic diamines in N‐methyl‐2‐pyrrolidone solution containing dissolved LiCl and CaCl₂, using triphenyl phosphite and pyridine as condensing agents to give a series of novel heteroaromatic polyamides containing photosensitive coumarin groups in the main chain. Polyamide properties were investigated by DSC, TGA, GPC, wide‐angle X‐ray scattering, viscosity, and solubility measurements. The copolymers were soluble in aprotic polar solvents, and their inherent viscosities varied between 0.49 and 0.78 dL g^?1. The weight‐average and number‐average molecular weights, measured by gel permeation chromatography, were 27,500–43,900 g mol^?1 and 46,500–66,300 g mol^?1, respectively, and polydispersities in the range of 1.48–1.69. The aromatic polyamides showed glass‐transition temperatures (T_g) ranging from 283 to 329°C and good thermal properties evidenced by no significant weight loss up to 380°C and 10% weight loss recorded above 425°C in air. All the polyamides exhibited an amorphous nature as evidenced by wide‐angle X‐ray diffraction and demonstrated a film forming capability. Water uptake values up to 3.35% were observed at 65% relative humidity. These polymers exhibited strong UV‐vis absorption maxima at 357–369 nm in DMSO solution, and no discernible photoluminescence maxima were detected by exciting with 365 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Water‐soluble poly(ethylene glycol) prodrug of pemetrexed: Synthesis,characterization, and preliminary cytotoxicity

Pemetrexed is a novel antifolate of antimetabolite with multiple enzyme targets involved in both pyrimidine and purine synthesis. It has entered the clinical usage due to favorable profiles especially in the cancer treatment of mesothelioma and non–small‐cell lung carcinoma. But it presents numerous challenges associated with poor water solubility and unstability in its original form of glutamic acid. The aim of this study is to solubilize pemetrexed by designing and synthesizing its aqueous‐soluble prodrug using high aqueous‐soluble polymeric carrier poly(ethylene glycol) (PEG). A new type of soluble pemetrexed prodrug was synthesized with dihydroxyl PEG and a single amino acid linkage, and was extensively characterized using ¹H‐NMR, ¹³C‐NMR, Fourier‐transform infrared, and matrix‐assisted laser desorption time of flight mass spectrometry. In addition, the prodrugs were evaluated for the drug loading capability, the aqueous solubility, and the preliminary in vitro cytotoxicity. The results indicate that the new PEGylated pemetrexed conjugates possess enhanced water solubility and stability, and provide another feasible choice of the pharmaceutical form of pemetrexed in the clinical application. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(dimethylsiloxane)–polythiophene composites

The synthesis was performed by the electropolymerization of thiophene on a poly(dimethylsiloxane) (PDMS)‐coated platinum electrode at 2.2 V with tetrabutylammoniumtetrafloroborate (TBAFB) as a supporting electrolyte and with acetonitrile as a solvent. The characterization of the PDMS–polythiophene (Pth) composites was carried out with cyclic voltammetry, Fourier transform infrared (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis, and conductivity measurements. The observed conductivities of the PDMS composites were 2.2–5.2 S/cm. The conductivity of Pth did not change appreciably with the addition of up to 30% insulating PDMS, but its processability improved. FTIR, SEM, and DSC studies showed the existence of a strong interaction, rather than physical adhesion, between PDMS and Pth. Highly flexible and foldable PDMS–Pth composites were obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2113–2119, 2003     

Synthesis,exchange reactions,and biological activity of poly(8‐methacryloxyquinoline)

8‐Methacryloxyquinoline (MAQ) was prepared through the reaction of 8‐hydroxyquinoline with either methacryloyl chloride or methacrylic acid in the presence of triethylamine or N,N‐dicyclohexylcarbodiimide, respectively. MAQ was polymerized in dimethylformamide with 2,2‐azobisisobutyronitrile as the initiator. The reactions of the resulting polymers with hydroxyl and amino compounds were studied. The polymers were characterized with IR, ¹H‐NMR, and mass spectroscopy. Some of the synthesized polymers were tested for their antimicrobial activity against bacteria and fungi. Generally, all the polymers were effective against the tested microorganisms, but their growth‐inhibition effects varied. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and chemical modification of new luminescent substituted poly(p-phenylene) polymers

A new acyl-functionalized poly(p-phenylene) (Ac-PPP) was synthesized by Yamamoto cross-coupling and chemically modified to obtain an anthracene-containing derivative (An-PPP). The chemical structures of the polymers were confirmed by ¹H-NMR, ¹³C-NMR, and FTIR spectroscopic analysis. They are fully soluble in common organic solvents and have number-average molecular weight of 2.70 × 10³ and 5.26 × 10³ g mol⁻¹ for Ac-PPP and An-PPP, respectively. The optical properties of the polymers were investigated by UV–visible absorption and photoluminescence spectroscopies. A green emission was observed in Ac-PPP solid thin film and a yellow one in the anthracene-containing polymer An-PPP. The optical bandgap values were 3.21 and 3.08 eV for Ac-PPP and An-PPP, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of novel anti-inflammatory poly(spiro thiazolidinone)s

A new series of spirothiazolidinone polymers has been accomplished by solution polycondensation of 4,12-dioxa-1,9-dithiadispiro[4.2.4.2]tetradecane-3,11-dione (3) with different aliphatic and aromatic diamines. A model compound 4 was prepared by the reaction of spiro-monomer 3 with benzyl amine and was characterized by elemental and spectral analyses. These polymers were characterized by elemental and spectral analyses. The thermal properties of these polymers were investigated by thermogravimetric analysis and differential thermal analysis measurements. The morphological properties of selected polymers 5c and 5e were tested using scanning electron microscope to study their surface morphology. The molar masses of polymers 5a, 5b, and 5d were determined by gel permeation chromatography. In addition, the anti-inflammatory activities were studied for these spiro-polymers in comparison with the model compound by determination in vivo using acute carrageenan-induced paw edema in rats.     

Synthesis and characterization of coordination polymers of Hg(II) with poly(thiooxamides)

Coordination polymers of Hg(II) with dithiooxamide, poly(ethylene thiooxamide), poly(butane thiooxamide), and poly(hexane thiooxamide) have been synthesized. All coordination polymers are solid compounds insoluble in common organic solvents. Coordination polymers have been characterized by elemental analysis, IR spectra, and thermogravimetric analysis and structures have been proposed leading to coordination of metal through S alone as well as N and S both. Thermal stability of the polymers has also been discussed.     

Monodisperse poly(p-chloromethylstyrene) microbeads by dispersion polymerization

In this study, an alternative dispersion polymerization method for the para isomer of chloromethylstyrene was proposed. Highly monodisperse poly(p-chloro-methylstyrene) (PCMS) particles in the size range of 1.67–3.75 μm were obtained. The monodispersity and the isolation yield of PCMS particles were significantly improved relative to the methods available in the literature. Azobisisobutyronitrile and polyacrylic acid were selected as the initiator and the steric stabilizer, respectively, in the dispersion medium composed of ethanol and methoxyethanol. The results indicated that the particle size increased with increasing initiator concentration. An increase in the stabilizer concentration led to a decrease in the particle size. The methoxyethanol/ethanol ratio was found as one of the most important parameters controlling the average size and the size distribution. Contrary to the tendencies noted in the literature, the particle size decreased with increasing polymerization temperature.     

环糊精聚合物的合成及应用研究

环糊精聚合物(CDPs)兼具了环糊精"内疏水?外亲水"的空腔结构特征和聚合物高分子稳定性的特点,是一类有巨大发展潜力的功能高分子材料。该文根据环糊精聚合物的结构特点对其进行分类并详细介绍了其合成方法,阐述了环糊精聚合物在食品、催化剂、化妆品、环境、医学、分离分析技术等多方面的应用研究。对环糊精聚合物的发展作了展望,为今后新型环糊精聚合物的制备及应用提供了参考依据。     

Thermotropic liquid‐crystalline polymers: Synthesis,characterization, and properties of poly(azomethine esters)

A series of poly(azomethine ester) copolymers were synthesized by the solution polycondensation method with different diamines. The synthesized polymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), hot‐stage polarized microscopy, wide‐angle X‐ray diffraction, and solution viscosity. All polymers showed good thermal stability. The thermotropic liquid‐crystalline properties were examined by DSC and by microscopic observations. Except for one, all of the polymers showed nematic liquid‐crystalline behavior. The effects of temperature on crystallinity and the substituent on solubility, thermal stability, melting temperature, and viscosity were also studied. The voluminosity and shape factor were also computed from the viscosity data. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 153–160, 2003     

Novel biocidal polymers based on branched and linear poly(hydroxystyrene)

New biocidal polymers based on branched as well as linear poly(p-hydroxystyrene) were synthesized. Biocidal polymers were synthesized in two steps by creation of active centers via chloroacetylation of linear and branched poly(p-hydroxystyrene) using chloroacetyl chloride. The second step involves the immobilization of onium salts onto the chloroacetylated polymers. All the prepared polymers were characterized using elemental microanalysis, FT-IR, ¹H NMR spectra, and TGA. Antimicrobial activity of the prepared polymers was tested against various pathogenic microorganisms. The antimicrobial activity was found to be affected by the active group and the tested microorganism. The phosphonium salts showed higher activity than ammonium salts.