2005 Volume 23 Issue 1

SYNTHESIS OF HYPERBRANCHED CONJUGATIVE POLY(ARYLENEETHYNYLENE)S BY ALKYNE POLYCYCLOTRIMERIZATION
Han Peng , Rong-hua Zheng , Hong-chen Dong , De-min Jia , Ben-zhong Tang
2005, 23(1): 1-3
[Abstract](526) [FullText HTML] [PDF 0KB](0)
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A series of new hyperbranched poly(aryleneethynylene)s are synthesized by the copolycyclotrimerizations of tetraynes (I and II) with aliphatic monoynes (A–C) catalyzed by tantalum-, niobium-, and cobalt-based catalysts. All the reactions proceed smoothly and soluble polymers of high molecular weights (Mw up to 3.8  104) are obtained in high yields (up to 97%).
SYNTHESIS AND CHARACTERIZATION OF POLYMERS BEARING AZOBENZENE AND CARBAZOLE GROUPS VIA POST-AZO-COUPLING REACTION
Jun Shi , Zhi-wei Jiang , Li Zhang , Shao-kui Cao
2005, 23(1): 5-9
[Abstract](536) [FullText HTML] [PDF 0KB](0)
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A series of polymers bearing azobenzene and carbazole groups for photorefractive purpose were prepared via post-azo-coupling reaction. The successful reaction was identified by spectroscopic analysis and gel permeation chromatography. This approach is more facile compared with the direct polymerization of corresponding functional monomer. The polymers prepared have weight average molecular weight of higher than 1.5  104 and are easily soluble in common organic solvents like chloroform and tetrahydrofuran, polymer films with high optical quality could be easily fabricated through solution casting. Glass transition temperature (Tg) of the polymers ranges from 60℃ to 182℃, depending on the alkylene spacer length between the functional side group and the polymer backbone, and the polymers are relatively stable under 300℃.
LONG-RANGE CORRELATIONS IN DNA SEQUENCES USING TWO-DIMENSIONAL DNA WALKS
Jin Chen , Lin-xi Zhang , De-lu Zhao
2005, 23(1): 11-16
[Abstract](585) [FullText HTML] [PDF 0KB](0)
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The characterization of long-range correlations and fractal properties of DNA sequences has proved to be a difficult though rewarding task mainly due to the mosaic character of DNA consisting of many patches of various lengths with different nucleotide constitutions. In this paper we investigate statistical correlations among different positions in DNA sequences using the two-dimensional DNA walk. The root-mean-square fluctuation F(l) is described by a power law. The autocorrelation function C(l), which is used to measure the linear dependence and periodicity, exists a power law of C(l)  l. We also calculate the mean-square distance along the DNA chain, and it may be expressed as l r with 2 > > 1. Our investigations can provide some insights into long-range correlations in DNA sequences.
MECHANICAL PROPERTIES OF OZONIZED HDPE FILLED WITH SERICITE-TRIDYMITE-CRISTOBALITE
Mian Zhou , Yi Fu , Wen Xu , Xi Xu
2005, 23(1): 17-21
[Abstract](533) [FullText HTML] [PDF 0KB](0)
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The mechanical properties of ozonized high density polyethylene (HDPE) blended with sericite-tridymite-cristobalite (STC) were studied in this paper. The experimental results show that some oxygen containing polar groups are introduced on the molecular chain of HDPE through ozonization, the compatibility between HDPE and STC is thus improved, the mechanical properties of the blend are markedly enhanced. Compared with untreated HDPE/STC (60/40) blend, the yield strength and notched impact strength of ozonized HDPE/STC (60/40) blend are increased from 27.0 MPa to 29.5 MPa and from 2.8 kJ/m2 to 13.3 kJ/m2, respectively, the notched impact strength is close to that of HDPE (13.6 kJ/m2), the yield strength is in excess of 3.9 MPa of that of HDPE. The yield strength and notched impact strength will be further increased to 30.7 MPa and 32.4 kJ/m2 in case the ozonized HDPE is blended with STC pretreated with silane coupling agent.
6AZO-CONTAINING SELF-ASSEMBLY ULTRA-THIN FILMS AND THEIR PHOTOVOLTAIC PROPERTIES
Mao-feng Zhang , Qiao-hong Yao , Chun-hui Huang , Wei-xiao Cao
2005, 23(1): 27-27
[Abstract](529) [FullText HTML] [PDF 0KB](0)
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A kind of azo-containing resin (Azo-R) was synthesized by a simple way through the coupling reaction of 2-nitro-N-methyldiphenylamine-4-diazoresin (NDR) with phenol, and a new covalentely attached multilayer film from Azo-R as H-donor and photosensitive diazoresin, diphenylamine-4-diazoresin (DR) as H-acceptor via H-bonding attraction by self-assembly technique has been fabricated. Following the decomposition of diazonium group of DR under exposure to UV light, the H-bonds between the layers of the film convert to covalent bonds and the film becomes very stable toward polar solvents or electrolyte aqueous solutions. Thus the UV-irradiated azo-containing films can be used to measure photocurrent in a conventional three-electrode photoelectrochemical cell using KCl as supporting electrolyte. It was confirmed that the azo-containing multilayer film is responsible for the photocurrent generation.
MICELLIZATION STUDIES OF DODECYL BENZENESULFONIC ACID AND ITS INTERACTION WITH POLYVINYLPYRROLIDONE
Mohammad Saleem Khan , Zarshad Ali
2005, 23(1): 29-35
[Abstract](581) [FullText HTML] [PDF 0KB](0)
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Dodecyl benzenesulfonic acid (DBSA) surfactant was used in the present study to find the effect of concentration on its electrical conductance in solution from 293323 K above and below the critical micelle concentration (CMC). The micellization parameters i.e. degree of counter ion binding (b), aggregation number (n) and number of counter ion micelle (m) were measured. The interaction of DBSA with polyvinylpyrrolidone (PVP) was also studied at 293 K through conductance and surface tension measure ments. A number of important parameters i.e. critical aggregation concentration (CAC), Gibb’s free energy (DG) and binding ratio (R) were determined and the effect of NaCl on the CAC and polymer saturation point (PSP) was also investigated.
PREPARATION, CHARACTERIZATION AND ELECTROCHEMICAL PROPERTIES OF POLYPYRROLE-POLYSTYRENE SULFONIC ACID COMPOSITE FILM
Liang-ti Qu , Gao-quan Shi , Chen Liu , Jin-ying Yuan , Wen-bin Qian
2005, 23(1): 37-46
[Abstract](516) [FullText HTML] [PDF 0KB](0)
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Polypyrrole-polystyrene sulfonic acid (PPy-PSSA) composite films have been electrosynthesized in an aqueous solution of PSSA. The electro-active films exhibit cation exchange during the redox process. Infrared, Raman and energy-dispersive spectroscopic results demonstrated that the polyanion of PSS is co-deposited into the PPy matrix and couldn’t be stripped from the film extensively by dedoping. The doping level together with dipolaron content of the PPy-PSSA composite film increases during electrochemical polymerization process. SEM images revealed that the composite film has smooth and compact morphology and AFM pictures suggested that PPy chains are possibly grown perpendicular to the electrode surface. TGA tests indicated that the composite films has much better thermal stability than that of pure PPy. Furthermore, electrochemical studies showed that the relaxation process at certain holding potential has great effect on the shape of the cyclic voltammetric curves of PPy-PSSA composite film. The composite film exhibits cation and anion exchange during the redox process after undergoing the relaxation step. It is more difficult for divalent anion to enter the polymer matrix than a univalent ion, and a large cation such as (CH3CH2CH2CH2)4N+ cannot be involved in the ion exchange process.
ORGANO-SOLUBLE FLUORINATED POLYIMIDES DERIVED FROM a,a-BIS(4-AMINO-3,5- DIMETHYLPHENYL)-4′-FLUOROPHENYL METHANE AND VARIOUS AROMATIC DIANHYDRIDES
Jin-gang Liu , Yang-xi Peng , Hong-shen Li , Lin Fan , Shi-yong Yang
2005, 23(1): 47-53
[Abstract](535) [FullText HTML] [PDF 0KB](0)
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Organo-soluble fluorinated polyimides were synthesized by the polycondensation of a new aromatic diamine -bis(4-amino-3,5-dimethylphenyl)-4′-fluorophenyl methane with several aromatic dianhydrides. The one-step polymerization procedure was conducted at 180℃ in m-cresol, producing the polyimides with inherent viscosities of 0.680.76 dL•g1. The polyimides could be soluble not only in polar aprotic solvents, such as N-methyl-2-pyrrolidinone, and N,N-dimethylacetamide, but also in common organic solvents, such as chloroform, cyclopentanone, m-cresol and so on. The polyimide films show excellent transparency with the UV-Vis cut-off lengths of 310360 nm and light transmittances of higher than 80% in the visible region. In addition, the polyimides exhibit good thermal stability with an initial decomposition temperature (Td) higher than 530℃ and have more than 60% of residual weight retentions at 700℃.
SYNTHESIS AND CHARACTERIZATION OF ORGANO-SOLUBLE FLUORINATED POLYIMIDES FROM 4,4′-BIS(3-AMINO-5-TRIFLUOROMETHYLPHENOXY)-BIPHENYL AND VARIOUS AROMATIC DIANHYDRIDES
Gui-long Wu , Jin-gang Liu , Zuo-bang Li , Zi-yi Ge , Lin Fan , Shi-yong Yang
2005, 23(1): 55-61
[Abstract](548) [FullText HTML] [PDF 0KB](0)
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An aromatic diamine monomer, 4,4′-bis(3-amino-5-trifluoromethyl phenoxy)-biphenyl (TFBPDA), was synthesized via the nucleophilic displacement reaction of 3,5-dinitrobenzotrifluoride and 4,4′-biphenol. The monomer was reacted with various aromatic dianhydrides via the high temperature polycondensation procedure to provide a series of polyimides. The polyimides, PI-1 to PI-4, show good solubility not only in aprotic solvents, such as N-methyl-2-pyrrolidinone and N,N-dimethylacetamide, but also in many common solvents, such as m-cresol, chloroform and cyclopentanone. PI-4, derived from 4,4′-(hexafluoroisopropylidene)diphthalic anhydride and TFBPDA, was even soluble in toluene. Moreover, PI films exhibit good thermal stability, outstanding transparency in the visible light region and acceptable mechanical and electrical properties. The excellent combined properties of the polyimides make them as a good candidate for fabricating microelectronics.
RAPID SYNTHESIS OF NOVEL OPTICALLY ACTIVE POLY(AMIDE-IMIDE)S DERIVED FROM N,N΄-(PYROMELLITOYL)-BIS-L-ALANINE DIACID CHLORIDE AND HYDANTOIN DERIVATIVES UNDER MICROWAVE IRRADIATION
Khalil Faghihi , Azizollah Mirsamie
2005, 23(1): 63-69
[Abstract](541) [FullText HTML] [PDF 0KB](0)
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Eight novel poly(amide-imide)s were synthesized under microwave irradiation by using a domestic microwave oven from the polycondensation reactions of N,N΄-(pyromellitoyl)-bis-L-alanine diacid chloride (1) with eight different derivatives of hydantoin compounds (2a-h) in the presence of a small amount of a polar organic medium such as o-cresol. The polycondensation proceeded rapidly, compared with the conventional solution polycondensation and was completed within 810 min, producing a series of new poly(amide-imide)s (3a-h) with inherent viscosities about 0.350.68 dL/g in high yields. The obtained PAIs (3a-h) were fully characterized by means of FT-IR spectroscopy, elemental analyses, inherent viscosity (inh), solubility and specific rotation measurements. All of the resulting polymers show optical rotation and are optically active. Thermal properties of the poly(amide-imide)s were investigated by using thermal gravimetric analysis (TGA).
FLUORINATED PHTHALAZINONE-CONTAINING COPOLYIMIDES FOR PASSIVE OPTICAL WAVEGUIDES
Jin-yan Wang , Gong-xiong Liao , Yuan Song , Shu-de Xiao , Xi-gao Jian
2005, 23(1): 71-74
[Abstract](510) [FullText HTML] [PDF 0KB](0)
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A series of fluorinated copolyimides containing phthalazinone moieties were prepared from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), 3,3'4,4'-benzophenone-tetracarboxylic dianhydride (BPDA) and 2-(4-aminophenyl)-4-[4-(4-aminophenoxyl)phenyl]-2,3-phthalazin-1-one (DHPZ-2NH2) for making polymeric optical waveguides. The resulting copolymers containing 050 mol% BPDA/ DHPZ-2NH2 show good solubility and are soluble in some organic polar aprotic solvents. The copolyimides also present excellent thermal stability. These polymers possess high glass transition temperature higher than 603 K and high decomposition temperature above 742 K determined by differential scanning calorimetry and thermogravimetric analysis, respectively, under a nitrogen atmosphere. Their refractive indices could be controlled by varying the ratio of 6FDA and BPDA in the copolymer from 0.5 to 1.0, and the in-plane refractive indices (nTE) range from 1.6366 to 1.6668 and the out-of-plane refractive indices (nTM) from 1.6024 to 1.6280 at 632.8 nm. The polymers birefringence (0.03420.0388) is almost independent of the 6FDA content of copolymer, which indicated that the phthalazinone-containing copolyimides could be suitable to fabricate optical waveguides possessing a low polarization dependent loss (PDL).
PREPARATION OF POLYVINYLIDENE FLUORIDE/POLYVINYL DIMETHYLSILOXANE COMPOSITE HOLLOW FIBER MEMBRANES AND THEIR SEPARATION PROPERTIES
Bo Meng , Nai-tao Yang , Xiao-yao Tan , Bao-yan Zhang
2005, 23(1): 75-82
[Abstract](550) [FullText HTML] [PDF 0KB](0)
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Microporous polyvinylidene fluoride (PVDF) hollow fibre membranes were spun using the dry-wet phase inversion method. By means of dip-coating technique, a uniform coating with thickness of around 5–12 m of polyvinyl dimethylsiloxane (PVDMS) was formed on the surface of porous PVDF hollow fibers. The structural parameters of PVDF substrate membrane were estimated by gas permeation test. Using N2/O2 as the medium, the separation properties of PVDMS-PVDF composite hollow fiber membranes were also evaluated experimentally. The experimental data of both permeability and selectivity are in good agreement with the theoretical results predicted by the presented pore-distribution model. In order to obtain the compact composite membrane free of defects by the dip-coating technique, the thickness of PVDMS skin must be higher than 5 m.
INTROMISSION OF WATER-REPELLENT AND HYDROSCOPIC PROPERTIES SIMULTANEOUSLY TO PP BY PLASMA DISCHARGE METHOD
Jie Liang , Bi-qian Liu
2005, 23(1): 83-92
[Abstract](569) [FullText HTML] [PDF 0KB](0)
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Plasma-induced surface graft copolymerization of acrylic acid on polypropylene non-woven fabric (PP-g-AA) and polypropylene membrane were reported. The extents of grafting were controlled by the plasma and polymerization condition. Hexadecyltrimethyl ammonium bromide was then coupled with the carboxyl group of PP-g-AA to obtain a polyion complex (PIC). At last, CF4 plasma was used to give PICs hydrophobic property. The moisture regain and water-repellency of the processed PICs was investigated. The surfaces were characterized using ATR FT-IR and XPS. The result indicates that the products have very high ability to adsorb moisture, even better than cotton fiber. At the same time, the products show excellent hydrophobic property, which can’t be wetted by those reagents whose surface tensions were higher than 327 mN/m.
MOLECULAR ENGINEERING STUDIES ON NONTHROMBOGENIC BIOMATERIALS−−A NOVEL CLASS OF NONTHROMBOGENIC BIOMATERIALS WITH ZWITTERIONIC STRUCTURE OF CARBOXYBETAINES
Jun Zhou , Yong-zhi Qiu , Xiao-peng Zang , Chang-wang Pan , Qiang Chen , Jian Shen , Si-cong Lin
2005, 23(1): 93-102
[Abstract](541) [FullText HTML] [PDF 0KB](0)
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N,N-dimethyl-N-methacryloyloxyethyl-N-carboxyethyl ammonium (DMMCA) was graft-copolymerized onto the surface of segmented poly(ether urethane)(SPEU)and PE film. The carboxybetaine structure on SPEU and PE film surfaces was confirmed by ATR-FTIR, XPS and water contact angle measurements. Through the experiments with platelet adhesion and protein adhesion assay in vitro, the two materials studied, including poly-DMMCA gel, all show excellent nonthrombogenicity. This confirms once again that the zwitterionic molecular structure on the surfaces of materials is essential for improving their nonthrombogenicity and biocompatibility.
THE EFFECT OF EC ON ORIENTATION AND RELAXATION OF PP OBTAINED VIA DYNAMIC PACKING INJECTION MOLDING
Yong Wang , Bing Na , Qiang Fu
2005, 23(1): 103-111
[Abstract](552) [FullText HTML] [PDF 0KB](0)
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As a long term project aiming at engineering plastics based on polypropylene (PP), in this work, we report the effect of ethylene-cellulose (EC) on the orientation and relaxation of PP obtained via dynamic packing injection molding (DPIM). 2d-WAXD results showed that PP with a highly oriented structure and a shish-kebab structure were achieved by DIPM, leading to an increase of tensile strength from 35.0 MPa to 48.6 MPa. The degree of orientation of PP was increased by adding only 1% of EC, resulting in a further increase of tensile strength from 48.6 MPa to 53.8 MPa. Shish-kebab was found to exist not only in the oriented layer but also in the core of the sample after adding EC, as evidenced by DSC result. This was understood as due to the overall decrease of viscosity by the addition of EC, thus an increasing of shear rate. Higher shear rate can favor the orientation of molecules and continuous growth of shish-kebab structure, resulting in a change of shish-kebab distribution along the sample thickness. On the other hand, the relaxation mode of shish-kebab in the melt re-crystallization of PP is also greatly affected by the presence of EC. A retarded relaxation of PP macromolecules was seen. Even more, SEM results showed that EC could form the short fibers in PP matrix along the shear flow direction. Compared with the morphology obtained by conventional injection molding, a much better dispersion and easy break-up of EC in PP matrix were observed for samples obtained by dynamic packing injection molding.
PLANTAGO PSYLLIUM-GRAFTED-POLYACRYLONITRILE: SYNTHESIS, CHARACTERIZATION AND ITS USE FOR SOLID REMOVAL FROM SEWAGE WASTEWATER
Anuradha Mishra , Alpa Yadav , Monika Agarwal , Rajani Srinivasan
2005, 23(1): 113-118
[Abstract](554) [FullText HTML] [PDF 0KB](0)
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Plantago psyllium mucilage (PSY), an anionic natural polysaccharide consisting of pentosan and uronic acid obtained from the seeds of Plantago psyllium (Plantago family), was grafted with acrylonitrile (AN). Graft copolymers were prepared by ceric ion initiated solution polymerization technique and were characterized by FT-IR spectroscopy, scanning electron microscopy and differential scanning calorimetry. These copolymers are good flocculating agents for removal of suspended (SS) and total dissolved solid (TDS) in sewage wastewater treatment. The effects of copolymer dose, pH and contact time on flocculation capacity of one selected copolymer sample were studied by jar test method. The suitable pH range for maximum solid removal was 7.0 to 9.2 and the optimum copolymer dose was 1.2 mg/L. The overall process for solid removal took 4 h. X-ray diffraction (XRD) patterns of grafted copolymer, PSY grafted polyacrylonitrile (PSY-g-PAN) and solid waste, before and after treatment are used to suggest the interaction of the solid waste with PSY-g-PAN copolymer.
EFFECT OF CRYOGENIC AND HEATING TREATMENT ON THE SOLUTION PROPERTIES OF NITROCELLULOSE
Li Li , Hu Yang , Rong-shi Cheng , Zhi-liu Wang
2005, 23(1): 119-122
[Abstract](564) [FullText HTML] [PDF 0KB](0)
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The effect of cryogenic and heating treatment on the solution properties of rigid polymer nitrocellulose (NC) in dilute tetrahydrofuran solution were studied with a sealed viscometer and a size exclusion chromatograph (SEC), respectively. The experimental results show that the relative viscosity of NC solution decreases after repeated freezing-thawing treatment. The decreased viscosity value of NC could not be restored but decreased further after the solution being re-heated. The experimental results of SEC are fully consistent with that of viscosity measurements. It is believed that the effect of two treatments on NC solution both causes the apparent hydrodynamic volume to decrease. But they are assumed to be ascribed to different mechanisms.
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