2004 Volume 22 Issue 6

SYNTHESES AND CHARACTERIZATIONS OF HYPERBRANCHED POLYPHENYLENES
Han Penga-b , Hong-chen Dongb , Yu-ping Dongb , De-min Jiaa , Ben-zhong Tanga**
2004, 22(6): 501-503
[Abstract](598) [FullText HTML] [PDF 0KB](0)
Abstract:
New hyperbranched polyphenylenes with high molecular weights are synthesized by the copolycyclotrimerizations of 1,4-diethynylbenzene (I) with phenylacetylene (A), 1-octyne (B), and 1-dodecyne (C) catalyzed by TaCl5?Ph4Sn. The polymers are completely soluble in common solvents such as toluene, THF, chloroform, and dichloromethane. The polymers are characterized by spectroscopic methods and all of the polymers give satisfactory analysis data corresponding to their expected molecular structures.
CHARACTERIZATION OF ION EXCHANGE MEMBRANES BASED ON POLYVINYLIDENE FLUORIDE
Bo Tian , Chuan-wei Yan* , Fu-hui Wang
2004, 22(6): 505-510
[Abstract](640) [FullText HTML] [PDF 0KB](0)
Abstract:
A new ion exchange membrane based on polyvinylidene fluoride (PVDF) and sulfonated poly(styrene-divinylbenzene) was prepared by in-situ polymerization. The incorporation of sulfonic groups into the polyvinylidene fluoride composite membrane was confirmed by infrared spectroscopy (IR), ion exchange capacity (IEC) and energy dispersive X-ray analysis (EDAX). Area resistance, IEC and water uptake of the treated membrane were evaluated. When 20% of the crosslinked membrane was sulfonated at 80℃ for 22 h, the PVDF ion exchange membrane can attain 0.8 cm2 area resistance in NaCl aqueous solution at 25℃, IEC is as high as 2.43 millimoles per gram of the wet membrane. The hydrophilicity of PVDF membrane is also significantly improved after treatment. When 60% of crosslinked membrane was sulfonated at 80℃ for 6 h, water uptake of the treated membrane can attain 64.7%.
SYNTHESIS AND CHARACTERIZATION OF HIGHLY ORGANO-SOLUBLE POLYIMIDES BASED ON ALICYCLIC 1,8-DIMETHYL-BICYCLO[2.2.2]OCT-7-ENE-2,3,5,6-TETRACARBOXYLIC DIANHYDRIDE AND AROMATIC DIAMINES
Jin-gang Liu , Gui-long Wu , Zuo-bang Li , Hong-shen Li , Lin Fan , Shi-yong Yang
2004, 22(6): 511-519
[Abstract](614) [FullText HTML] [PDF 0KB](0)
Abstract:
Organo-soluble alicyclic polyimides (ALPIs) were synthesized from an alicyclic dianhydride, 1,8-dimethyl- bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMEA) and several multialkyl-substituted 4,4?-diaminodiphenylmethane compounds, including 3,3?-dimethyl-4,4?-diaminodiphenyl methane (DMDA), 3,3?,5,5?-tetra-methyl-4,4?-diaminodiphenyl methane (TMDA) and 3,3?,5,5?-tetraethyl-4,4?-diaminodiphenylmethane (TEDA). For comparison, the aromatic polyimides (ARPIs) were synthesized from the aromatic dianhydride, 3,3?,4,4?-benzo-phenonetetracarboxylic dianhydride (BTDA) and the same diamines. The ALPIs exhibited better solubility and transparency, but worse thermal stabilities and mechanical properties than those of the ARPIs. And the ALPIs could be dissolved in common organic solvents, such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), chloroform, tetrahydrofuran, m-cresol and so on. The ALPI films had an UV-Vis cut-off at 320 nm and a transmittance of higher than 80% in the visible region. In addition, the ALPIs showed thermal decomposition temperatures (Td) of about 450℃, which was nearly 100℃ lower than that of the ARPIs.
LOW MOLECULAR WEIGHT O-CARBOXYMETHYLATED CHITOSANS DERIVED FROM IRRADIATED CHITOSAN AND THEIR ANTIBACTERIAL ACTIVITY
Xu-pin Zhuang , Xiao-fei Liu , Zhi Li , Yun-lin Guan , Kang-de Yao
2004, 22(6): 521-527
[Abstract](642) [FullText HTML] [PDF 0KB](0)
Abstract:
Original chitosan with Mv of 2.7 105 was degraded by irradiation with -rays and a series of low molecular weight O-carboxymethylated chitosans (O-CMCh) were prepared based on the irradiated chitosan. A kinetic model of the irradiation of chitosan was put forward. Results show that the irradiation degradation of chitosan obeys the rule of random degradation and the degree of deacetylation of irradiated chitosan is slightly raised. The antibacterial activity of O-CMCh is significantly influenced by its MW, and a suppositional antibacterial peak appears when Mv is equal to 2 105.
ADSORPTION OF 2,4-DICHLOROBENZOXYACETIC ACID ONTO HYPERCROSSLINKED RESIN MODIFIED BY PHENOLIC HYDROXYL GROUP (AM-1)
Zheng-hao Feia.b , Jin-long Chena* , Jian-guo Caia , Yu-ping Qiua , Ai-min Lia.b , Quan-xing Zhanga
2004, 22(6): 529-533
[Abstract](610) [FullText HTML] [PDF 0KB](0)
Abstract:
An experimental comparison of the adsorption properties of hypercrosslinked resin AM-1 modified by phenolic hydroxyl group with Amberlite XAD-4 toward 2,4-dichlorobenzoxyacetic acid was performed. This paper focuses on the static equilibrium adsorption behaviors and the adsorption thermodynamics. Two isotherm models were used to explain the results. It is seen that the Langmuir equation can give a perfect fit. The adsorption capacities from the different ranges of temperature, the adsorption enthalpy change value and the comparison of desorption conditions lead to the same conclusion that the adsorption of 2,4-dichlorobenzoxyacetic acid from water onto AM-1 is a type of physical and chemical transition.
THERMODYNAMIC STUDY ON ADSORPTION OF AROMATIC SULFONIC ACIDS ONTO MACROPOROUS WEAK BASE ANION EXCHANGER FROM AQUEOUS SOLUTIONS
Chao Long* , Quan-xing Zhang , Ai-min Li , Jin-long Chen
2004, 22(6): 535-542
[Abstract](668) [FullText HTML] [PDF 0KB](0)
Abstract:
The adsorption equilibrium isotherms of three aromatic sulfonic acid compounds, 2-naphthalenesulfonic acid, p-toluenesulfonic acid and p-chlorobenzenesulfonic acid, from aqueous solutions by macroporous weak base anion exchanger within the temperature range of 293 K?313 K were obtained. Several isotherm equations were correlated with the equilibrium data, and the experimental data was found to fit the three-parameter Redlich-Peterson equation best within the entire range of concentrations. The study showed that the hydrophobicity of solute has distinct influence on adsorption capacity of the anion exchanger for the aromatic sulfonic acid. Moreover, estimations of the isosteric enthalpy, free energy, and entropy change of adsorption were also reported. The positive isosteric enthalpy and entropy change for adsorption indicate an endothermic and entropy driven process in the present study.
KINETICS OF SUSPENDED EMULSION POLYMERIZATION OF METHYL METHACRYLATE
Yong-zhong Bao , Cheng-xi Wang , Zhi-ming Huang and Zhi-xue Weng
2004, 22(6): 543-548
[Abstract](629) [FullText HTML] [PDF 0KB](0)
Abstract:
The kinetics of suspended emulsion polymerization of methyl methacrylate (MMA), in which water acted as the dispersed phase and the mixture of MMA and cyclohexane as the continuous phase, was investigated. It showed that the initial polymerization rate (Rp0) and steady-state polymerization rate (Rp) were proportional to the mass ratio between water and oil phase, and increased as the polymerization temperature, the potassium persulphate concentration ([I]) and the Tween20 emulsifier concentration ([S]) increased. The relationships between the polymerization rate and [I] and [S] were obtained as follows: Rp0 μ [I]0.73[S]0.32 and Rp μ [I]0.71[S]0.23. The above exponents were close to those obtained from normal MMA emulsion polymerization. It also showed that the average molecular weight of the resulting poly(methyl methacrylate) decreased as the polymerization temperature, [I] and [S] increased. Thus, MMA suspended emulsion polymerization could be considered as a combination of many miniature emulsion polymerizations proceeding in water drops and obeyed the classical kinetics of MMA emulsion polymerization.
SYNTHESIS OF SOLUBLE POLY(3-HEXYL-2,5-THIENYLENE VINYLENE) FROM THIOPHENE*
2004, 22(6): 549-557
[Abstract](694) [FullText HTML] [PDF 0KB](0)
Abstract:
Soluble poly(3-hexyl-2,5-thienylene vinylene) (PHTV) was readily synthesized from thiophene in a yield better than that of the precursor method to prepare poly(thienylene vinylene) (PTV). The bandgap of the polymer is about 1.8 eV,which is comparable with that of PTV. Owing to the introduction of alkyl side groups onto the backbone of the polymer, it can be dissolved in common organic solvents such as chloroform, THF and toluene. The synthesis of soluble PHTV is a very important approach to preventing oxidation and to improving the properties and the processbility of the PTV. The existence of alkyl side groups in PHTV does not affect its, bandgap and thermal properties as compared with PTV. After doping with FeCl3, the conductivity of PHTV is as high as 1.1 10-2S/cm. The soluble PHTV can be easily transformed into thin film with much better quality than that of the PTV film prepared by the traditional precursor method, which is very important for fabricating devices with good properties.
SURFACE STRUCTURE AND BULK PROPERTIES OF FLUORINATED POLY(ETHER URETHANE)S AND POLY(ETHER URETHANE) BLENDS*
2004, 22(6): 559-566
[Abstract](592) [FullText HTML] [PDF 0KB](0)
Abstract:
It has been well known that fluorinated polyurethanes exhibit uniquely low surface energy, biocompatibility and biostability, thermal and oxidative stability and nonsticking behavior. Consequently, these polymers have attracted considerable interest. However, the mechanical properties of fluorinated polyurethanes usually decline with increasing fluorine contents. The blending of fluorinated polyurethanes with normal polyurethane was carried out to achieve balanced mechanical and surface properties. It was found that polyurethane with good mechanical properties and low surface energy can be obtained by adding a small amount of fluorinated polyurethane. The fluorinated side chains can easily migrate to uppermost surfaces of the blends untill the fluorine level at the surface becomes almost saturated. It has been shown from contact angle, XPS and AFM measurements that only as little as 0.34 wt% of fluorine level is enough to produce a surface saturated with fluorine, and the fluorine level at the uppermost surface is one hundred times higher than that in the blend bulk. The final outer surface structures of the polyurethane blend were independent of the content of the fluorinated polyurethane in the blends due to the surfaces saturated by fluorine.
SCATTERING FUNCTION OF POLYMER BLENDS*
2004, 22(6): 567-572
[Abstract](634) [FullText HTML] [PDF 0KB](0)
Abstract:
For a system of flexible polymer molecules, the concepts of two concentrations, namely the segmental and the molecular concentrations, have been proposed in this paper. The former is equivalent to the volume fraction. The latter can be defined as the number of the gravity centers of macromolecules in a unit volume. The two concentrations should be correlated with each other by the conformational function of the polymer chain and should be discussed in different thermodynamic equations. On the basis of these concepts it has been proved that the Flory-Huggins entropy of mixing should be the result of the mixing "ideal gases of the gravity centers of macromolecules". The general correlation between the free energy of mixing and the scattering function (structural factor) of polymer blends has been studied based on the general fluctuation theory. When the Flory-Huggins free energy of mixing is adopted, the de Gennes scattering function of a polymer blend can be derived.
SCATTERING FUNCTION OF POLYMER BLENDS
2004, 22(6): 567-572
[Abstract](578) [FullText HTML] [PDF 0KB](0)
Abstract:
For a system of flexible polymer molecules, the concepts of two concentrations, namely the segmental and the molecular concentrations, have been proposed in this paper. The former is equivalent to the volume fraction. The latter can be defined as the number of the gravity centers of macromolecules in a unit volume. The two concentrations should be correlated with each other by the conformational function of the polymer chain and should be discussed in different thermodynamic equations. On the basis of these concepts it has been proved that the Flory-Huggins entropy of mixing should be the result of the mixing “ideal gases of the gravity centers of macromolecules”. The general correlation between the free energy of mixing and the scattering function (structural factor) of polymer blends has been studied based on the general fluctuation theory. When the Flory-Huggins free energy of mixing is adopted, the de Gennes scattering function of a polymer blend can be derived.
NETWORK ENCAPSULATION OF NANOMETER CaCO3
2004, 22(6): 573-579
[Abstract](597) [FullText HTML] [PDF 0KB](0)
Abstract:
The encapsulation of stearic acid coated nanometer CaCO3 by a polystyrene (PS) network via emulsion polymerization is described, where -methacryloxypropyltrimethoxysilane (MPS) was used as an efficient crosslinker. The important factors such as the type and amount of surfactant and initiator and the content of CaCO3 are investigated as well as the role of MPS. It has been shown that little PS was extractable with only 0.6 wt% of MPS (relative to styrene). The cationic surfactant cetyl trimethylammonium bromide (CTAB) proved more effective than the anionic surfactant sodium dodecyl sulfonate (SDS). The yield rises, particles become smaller and size distribution broadens with increased amount of CTAB. It is also found that either 2,2'-azobis(isobutyronitrile) (AIBN) or ammonium persulfate (APS) is suitable for attaining high monomer conversion. With increased amount of CaCO3, the encapsulation ratio can be varied from 17.9 to 3.6, while monomer conversion and yield decrease slightly. FT-IR spectra of the products after extraction indicate tight encapsulation between PS and CaCO3, and TEM photographs of composite particles with well-defined core-shell structure give direct evidence of encapsulation.
INTERACTION OF POLYVINYLPYRROLIDONE WITH METAL CHLORIDE AQUEOUS SOLUTIONS*
2004, 22(6): 581-584
[Abstract](671) [FullText HTML] [PDF 0KB](0)
Abstract:
Interactions of polyvinylpyrrolidone (PVP) with metal chlorides (MgCl2, CaCl2, KCl and BaCl2) have been investigated by viscometric and spectrophotometric techniques in aqueous solutions. Intrinsic viscosity [] of (PVP) has shown a discontinuity with varying concentration of metal chlorides. The decreasing order of effectiveness of cation is K1+ Ca2+ Mg2+ Ba2+ for poly(vinylpyrrolidone) solution. Changes in the absorption spectra of the cosolutes were observed in the presence of PVP in the lower limit of the UV-visible region i.e. 200-210 nm. These changes were attributed to interaction of PVP molecules with the cosolute molecules. As the concentration of the cosolute increased, a red shift in the peaks was observed, indicating an increase in interaction between PVP and cosolutes.
STUDY ON THE POST-CURE KINETICS OF EPOXY RESIN IRRADIATED BY AN ELECTRON BEAM*
2004, 22(6): 585-588
[Abstract](624) [FullText HTML] [PDF 0KB](0)
Abstract:
The post-cure kinetics of electron beam (EB) curing of epoxy resin initiated by diaryiodinium was investigated.The post-cure reaction fits first order reaction kinetics. The reaction rate constant increases with increasing treatment temperature of post-cure. The reaction rate of post-cure is much lower than the rate of its reaction on electron beam treatment.
A COMPARATIVE STUDY OF CHAIN DYNAMICS OF DI-AND TRI-BLOCK COPOLYMERS IN SEMIDILUTE SOLUTION IN A NON-SELECTIVE SOLVENT*
2004, 22(6): 589-598
[Abstract](608) [FullText HTML] [PDF 0KB](0)
Abstract:
The chain dynamics of a pair of diblock poly(styrene-b-butadiene) (PS210-b-PB960) and triblock poly(styrene-b-butadiene-b-styrene) (PS200-b-PB1815-b-PS200) copolymers in both dilute and semidilute toluene solutions has been comparatively studied by dynamic laser light scattering. As expected, the mutual diffusion of individual chain changes into a fast cooperative diffusion of the chain segments (blobs) between two neighboring entanglement points for both the copolymers as the solution changes from dilute to semidilute. Further increases of the concentration lead to a second slow relaxation mode. For the triblock chains, there exists an additional middle relaxation between the fast and the slow modes.The concentration (c) dependent study of the average characteristic decay time of the fast mode (f) reveals that 1/f ~ c-with 0.33 0.44, much smaller than 0.75 predicted or 0.72 observed for linear homopolymer chains in good solvent. It implies that the solvent quality of toluene for PB might not be as good as that for PS. Due to such a difference in solubility, it is reasonable to speculate that the PB and PS blocks are transiently segregated in semidilute solution. The relaxation of these transient PB and PS richer domains leads to the observed slow relaxation. Such a speculation is supported by the appearance of an additional slow relaxation mode in the study of polyisoprene-b-polystyrene-b-polyisoprene in semidilute solution in cyclohexane, a non-selective solvent, in which we alternated the solubility difference by a variation of the solution temperature.
STUDY ON HYDROLYSIS OF MACROMOLECULAR GELATIN WITH ENZYMES IN COMBINATION MODE*
2004, 22(6): 599-602
[Abstract](645) [FullText HTML] [PDF 0KB](0)
Abstract:
The enzymatic hydrolysis of macromolecular gelatin with AS 1.398 neutral protease, bromelain and their combinations was studied by estimating the molecular weights of their hydrolytic products. It was discovered that the products hydrolyzed by using combination enzymes had lower molecular weight than those obtained by using single ones,and the kind of enzymes, their combination mode and addition sequence are effective ways to control the molecular weights of gelatin hydrolyzates.
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