Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and I afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in in-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 degrees C and 526 to 565 degrees C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 degrees C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.

Synthesis, structure and ring-opening polymerization of phenolphthalein macrocyclic polyarylates

Phenolphthalein based polyarylate macrocyclic oligomers were selectively synthesized by an interfacial polycondensation reaction of o-phthaloyl dichloride with phenolphthalein. The high selectivity benefits from the role of phenolphthalein as a color indicator, an efficient phase transfer catalyst, acid a preferred conformation of the starting materials as indicated by analyzing a single-crystal X-ray structure of an analogous macrocycle. The melt ROP of phenolphthalein polyarylate cyclic dimer was studied using nucleophilic initiators, The molecular weight of the resulting polymers builds up very rapidly at the very early stage of polymerization but decreases with time. During the ROP of cyclic dimer, analogous macrocycles with higher degree of polymerization (n greater than or equal to 3) and linear oligomers were produced by backbiting reaction especially at later stage of polymerization. Conversion of cyclic dimer is very fast at the earlier stage of polymerization and then increases slowly with time as analyzed by gel permeation chromatography. However, the total amount of cyclic oligomers in the ROP system increases with time at the later stage of polymerization because of the formation of larger macrocycles. The resulting polymers are amorphous. Glass transition temperatures (T(g)s) of these polymers are influenced by the polymerization time, type of initiator, and initiator concentration.

Gas and water vapor transport through a series of novel poly(aryl ether sulfone) membranes

The permeation behavior of water vapor, H-2, CO2, O-2, N-2, and CH4 gases in a series of novel poly(aryl ether sulfone)s has been examined over a temperature range of 30-100 degreesC. These polymers include four alkyl-substituted cardo poly(aryl ether sulfone)s and four intermolecular interaction enhanced poly(aryl ether sulfone)s. Their water vapor and gas transport properties were compared to the unmodified cardo poly(aryl ether sulfone) (PES-C). It was found that the bulky alkyl substituents on the phenylene rings were advantageous for gas permeability, while the intermolecular hydrogen bonds and ionic bonds resulted in a considerable increase in gas permselectivity. The causes of the trend were interpreted according to free volume, interchain distance, and glass transition temperature, together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest was the observation that IMPES-L, which simultaneously bears bulky isopropyl substituent and pendant carboxylic groups, displayed 377% higher O-2 permeability and 5.3% higher O-2/N-2 permselectivity than PES-C. Furthermore, sodium salt form PES-Na+ and potassium salt form PES-K+ exhibited water vapor permeability twice as high as PES-C and H2O/N-2 selectivity in 10(5) order of magnitude.

NMR investigation of phenolphthalein polyether ether ketone .1. The chain structure and assignments of H-1, C-13 NMR lines of PEK-C

Amorphous samples of polyether ketone with cardo(PEK-C) have been studied in the solution state by C-13, H-1 high-resolution NMR, The H-1 and C-13 1D NMR spectra were assigned using two dimensional chemical shift correlated spectroscopy, 2D homonuclear correlated(COSY) and heteronuclear correlated (HETCOR) spectroscopy present important information. In this work, the structural units of PEK-C was determined by NMR. For some peaks, these assignments are confirmed by two dimensional long-range heteronuclear correlation experiments, A little modification is made on the original C-13 peak assignments for the main chain, The symmetry and the isotacticity of the chain structure for PEK-C are obvious on NMR data.

Local chain motions in a dilute solution of phenolphthalein poly(ether sulfone)

C-13 and H-1 relaxation times were measured as a function of temperature in two magnetic fields for dilute solutions of phenolphthalein poly(ether sulfone) (PES-C) in deuterated chloroform. The spin-lattice relaxation times were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (J. S. model). The phenyl group rotation is treated as a stochastic diffusion by the J. S. model. The restricted butterfly motion of the phenyl group attached to the cardo ring in PES-C is mentioned but is not discussed in detail in this work. Correlation times for the segmental motion are in the picosecond range which indicates the high flexibility of PES-C chains. The correlation time for the phenyl group internal rotation is similar to that of the segmental motion. The temperature dependence of these motions is weak. The apparent activation energy of the motions considered is less than 10 kJ/mol. The simulating results for PES are also reasonable considering the differences in structure compared with PES-C. The correlation times and the apparent activation energy obtained using the J. S. model for the main chain motion of PES-C are the same as those obtained using the damped orientational diffusion model and the conformational jump model.

SEQUENCE-ANALYSIS OF FLUORINE-CONTAINING POLYARYLETHERSULFONE COPOLYMERS BY C-13-NMR

HexafluorobisA polyethersulfone-cardo polyethersulfone, random and block copolymers with different segment lengths were synthesized by a reaction of 4,4'-(hexafluoroisopropylidene)diphenol and 3,3'-bis(4-hydroxyphenyl)-1-isobenzopyrrolidone with bis(4-chl

新型聚芳醚砜(PES—C)树脂及其漆包线的初试

新型聚芳醚砜是在一般聚芳醚砜主链上附上圈型(Cardo)侧基的聚合物,从而可使该聚合物在一般溶剂中的溶解性及耐热稳定性均相应提高。关于本工作所用主链上附上酞侧基的新型聚芳醚砜(PES—C),苏联于70年代已开始研究,但因采用传统的二步法而未得到高分子量的聚合物,刘克静等采用一步法合成路线,成功地得到了高分子量的

Molecular determination of oxytetracycline-resistant bacteria and their resistance genes from mariculture environments of China

Aims: To assess the diversity of antibiotic-resistant bacteria and their resistance genes in typical maricultural environments. Methods nand Results: Multidrug-resistant bacteria and resistance genes from a mariculture farm of China were analysed via cultivation and polymerase chain reaction (PCR) methods. Oxytetracycline (OTC)-resistant bacteria were abundant in both abalone and turbot rearing waters, accounting for 3.7% and 9.9% of the culturable microbes. Multidrug resistance was common, with simultaneous resistance to OTC, chloramphenicol and ampicillin the most common resistance phenotype. 16S rDNA sequence analyses indicate that the typical resistant isolates belonged to marine Vibrio, Pseudoalteromonas or Alteromonas species, with resistance most common in Vibrio splendidus isolates. For OTC resistance, tet(A), tet(B) and tet(M) genes were detected in some multidrug-resistant isolates, with tet(D) being the most common molecular determinant. For chloramphenicol resistance, cat II was common, and floR was also detected, especially in marine Pseudoalteromonas strains. Conclusions: There is the risk of multidrug-resistant bacteria contamination in mariculture environments and marine Vibrio and Pseudoalteromonas species serve as reservoirs of specific antibiotic resistance determinants. Significance and Impact of the Study: This paper and similar findings from Korea and Japan indicate the potential for widespread distribution of antibiotic resistance genes in mariculture environments from the East Asian region of the world.

Molecular characterizations of chloramphenicol- and oxytetracycline-resistant bacteria and resistance genes in mariculture waters of China

In order to gain an understanding of the diversity and distribution of antimicrobial-resistant bacteria and their resistance genes in maricultural environments, multidrug-resistant bacteria were screened for the rearing waters from a mariculture farm of China. Both abalone Haliotis discus hannai and turbot Scophthalmus maximus rearing waters were populated with abundant chloramphenicol-resistant bacteria. These bacteria were also multidrug resistant, with Vibrio splendidus and Vibrio tasmaniensis being the most predominant species. The chloramphenicol-resistance gene cat II, cat IV or floR could be detected in most of the multidrug-resistant isolates, and the oxytetracycline-resistance gene tet(B), tet(D), tet(E) or tet(M) could also be detected for most of the isolates. Coexistence of chloramphenicol- and oxytetracycline-resistance genes partially explains the molecular mechanism of multidrug resistance in the studied maricultural environments. Comparative studies with different antimicrobial agents as the starting isolation reagents may help detect a wider diversity of the antimicrobial-resistant bacteria and their resistance genes. (C) 2009 Elsevier Ltd. All rights reserved.