THE SYNTHESIS AND CHARACTERIZATION OF SOME POROUS CROSS-LINKED POLY (VINYLACETOPHENONE) RESINS AND THEIR CAPACITIES IN ADSORBING GYPENOSIDES

In search of a suitable adsorbent used for the enrichment and separation of natural saponins from an aqueous solution, a series of porous cross-linked poly (vinylacetophenone) resins Ⅰ-Ⅸ were synthesized via the. Friedel-Crafts acylation of styrene-divinyl-benzene copolymer beads. Their carbonyl contents were characterized by infrared spectra and elemental analysis. Their physical properties such as bulk densities, skeleton densities, and specific surface areas were also determined. The tests for the resins adsorption of gypenosides showed that only those resins with high carbonyl contents and large specific surface areas could favorably adsorb gypenosides from an aqueous solution with much higher capacities.     

SYNTHESIS AND CHARACTERIZATION OF POLY（STYRENE—ETHYLENE OXIDE）DIBLOCK COPOLYMERS

Well-defined diblock copolymers of styrene(St) and ethylene oxide(EO) have been prepared by sequential living anionic polymerization of the two comonomers in THF.Diphenyl methyl potassum has been used as initiator.The block copolymers were characterized in detail by methods of size exclusion chromatography(SEC),^1H-NMR,FT-IR,dynamic mechanical analysis(DMA) and WAXD.     

PREPARATION AND CHARACTERIZATION OF SHISH-KEBAB TYPE LIQUID CRYSTALLINE POLY（p-PHENYLENEVINYLENE）

Novel shish-kebab type liquid crystalline poly（p-phenylenevinylene） derivatives were synthesized by Stille coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer l） and 1,2-bis（tributylstannyl） ethylene （monomer 2）. The polymers with alkoxy groups are soluble in common organic solvents and exhibit blue fluorescence. Both the cast film and the annealed film have large red-shifts in fluorescence spectra and show yellow fluorescence. The polymers with CN and NO2 groups show poor solubility and green fluorescence. All the polymers possess liquid crystalline smectic phases. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The polymers are easily aligned under a magnetic field of 10 Tesla. It is found that the conjugated backbone and LC side chain are aligned perpendicular and parallel to the magnetic field, respectively. The polymers show optical dichroism in fluorescence spectra, suggesting that they are available for advance materials with linear optical polarization.     

SURFACE MODIFICATION OF BLEND FILMS COMPOSED OF SILK FIBROIN AND POLY（ETHYLENE GLYCOL） MACROMER AND THEIR IN VITRO ANTITHROMBOGENICITY

In order to improve the blood compatibility of silk fibroin (SF), poly(ethylene glycol) macromer (PEGM) in different amounts was added to the SF film to incorporate C=C group into the surface of blend films which were then modified by SO2 gas plasma treatment. ATR-FITR and XPS were used to analyze the chemical change which had occurred on the film‘s surface. When the content of sulfur on the surface of blend films surpasses 1.59%, the antithrombogenicity of plasma treated films increases remarkably due to surface sulfonation. This result implies that SF with blend of PEGM after SO2 plasma treatment have potential use for making blood-contacting biomaterials.     

THE SYNTHESIS AND CHARACTERIZATION OF POLY—L—LACTIDE USED FOR THE INTERNAL FIXATION OF BONE FRACTURE

A high Mw of PLLA was synthesized,it intended to be used in the manufacture of bioabsorbable screw applied in bone fracture internal fixation.The optical reaction conditions have been discussed.     

NOVEL AMPHIPHILIC FLUORESCENT GRAFT COPOLYMER： SYNTHESIS, CHARACTERIZATION AND ENCAPSULATION OF A HYDROPHOBIC AGENT

Novel amphiphilic fluorescent graft copolymer （PVP-PyAHy） was successfully synthesized by the free radical copolymerization of hydrophobic monomer N-（1-pyrenebutyryl）-N＇-acryloyl hydrazide （PyAHy） with hydrophilic precursor polymers of vinyl-functionalized poly（N-vinylpyrrolidone） （PVP） in DMF. The copolymer is amphiphilic and has intrinsic fluorescence. FT-IR, ^1H-NMR, TEM, gel permeation chromatography-multi-angle laser light scattering, UV-Vis spectroscopy and fluorescence spectroscopy were used to characterize this copolymer. The TEM observation shows that the copolymer PVP-PyAHy forms micelles in aqueous solution. Results of fluorometric measurements illustrate that the critical micelle concentration （CMC） value of PVP-PyAHy in aqueous solution is about 0.90 mg/mL. To examine the encapsulation ability of the copolymer in aqueous media, methyl yellow was employed as a model hydrophobic agent. The loading level of the polymer to methyl yellow is 8.8 mg/g. The cytotoxicity assays for Madin Darby Canine Kidney （MDCK） cells shows good biocompatibility of PVP-PyAHy in vitro. These results suggest the potential of this copolymer PVP-PyAHy as drugs delivery carrier and fluorescent tracer.     

SYNTHESIS AND PROPERITIES OF SHISH-KEBAB-TYPE LIQUID CRYSTALLINE POLY（p-PHENYLENE）S

Abstract The novel shish-kebab-type liquid crystalline poly（p-phenylene）s were synthesized through Suzuki coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer 1） and 1,4-benzenediboronic acid bistrimethylene cyclic ester （monomer 2）. Their structure and properties were characterized by GPC, DSC, X-ray diffraction and polarizing optical microscope （POM）. It was found that the polymers turned to liquid crystalline phase above their melting point. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. The polymers could dissolve in common organic solvents and show strong blue fluorescence. The maximum absorption bands of polymers prepared from annealed films have large red-shift due to the spontaneous orientation of the liquid crystalline side chains. The same phenomena were also observed in the fluorescence spectra.     

SYNTHESIS AND CHARACTERIZATION OF HYBRID PROTON CONDUCTING MEMBRANES OF POLY（VINYL ALCOHOL） AND PHOSPHOMOLYBDIC ACID

Hybrid proton conducting membranes of poly（vinyl alcohol） （PVA） and phosphomolybdic acid （PMA） were prepared by solution casting method. The effect of PMA doping and PVA crosslinking density on the membrane properties and proton conductivity were investigated. The crosslinking reaction between the hydroxyl group of PVA and the aldehyde group of glutaraldehyde （GA） was characterized by IR spectroscopy. Proton conductivity of the membranes increases with an increase in concentration of the doped PMA and also with an increase in crosslinking density of the membranes. Proton conductivity results indicate that a significant amount of PMA was maintained in the membranes even after several hours of immersion in water. A maximum conductivity of 0.0101 S cm^-1 was obtained for the membrane with 33.3 wt% PMA and crosslinking density of 5.825 mol%. X-ray diffraction studies were carried out to investigate the influence of PMA doping and crosslinking density on the nature of the membranes. These properties make them very good candidates for polymer electrolyte membranes for direct methanol fuel cell application.     

SYNTHESIS OF POLY（3,4-AZOPYRIDYLENE） AND OXYGEN-BINDING AFFINITY OF ITS COMPLEX WITH COBALTPORPHYRIN

Synthesis and characteristics of poly(3,4-azopyridylene) (PAP), conductivity and oxygen-binding affinity of its complex with meso-α,α,α,α-tetrakis(o-pivalamidophenyl) porphyrinatocobalt(Ⅱ) (CoP) were studied. PAP was prepared by oxidative polymerization of 3,4-diaminopyridine (DAP) in DMF solution using CuCl/pyridine as the catalyst. IR and NMR results showed that the peak of amido group in DAP was converted to the azo group in PAP and a π conjugated polymer was synthesized. The average molecular weight of PAP was determined to be 5.0 × 103. The PAP-CoP complex was prepared by complexing the pyridyl group of PAP with the fifth coordination site of CoP in DMF solution. In comparison with the CoP complex with a non-π conjugated polymer, the PAP-CoP complex shows good electroconductivity of 5.8 × 10-6 Scm-1. The PAP-CoP complex displays a reversible change in the UV-Visible absorption spectrum from the deoxy form to the oxy or oxygen-binding one with an isosbestic point, in response to the partial oxygen pressure of the atmosphere. The oxygen-response behavior was monitored at the absorbance ascribed to the oxy form at 548 nm to give the oxygen-binding affinity.The oxygen-binding equilibrium curves of PAP-CoP complex obey a Langmuir isotherm. DMF has great effects on the oxygen-binding properties of the PAP-CoP complex. The oxygen-binding affinity of PAP-CoP complex in the solid state is higher than that in DMF solution. With decreasing temperature, the oxygen-binding affinity of the PAP-CoP complex increases.     

SYNTHESIS, CHARACTERIZATION AND ANTIMICROBIAL PROPERTIES OF 4-[（4-HYDROXYBENZYLIDENE） AMINO] PHENOL AND ITS POLYMER

The oxidative polycondensation reaction conditions of 4-[(4-hydroxybenzylidene)amino]phenol(4-HBAP)were studied with H_2O_2,air oxygen and NaOCl in an aqueous alkaline medium between 50 and 90℃.The structures of the obtained monomer and polymer were confirmed by FT-IR,UV-Vis,~1H-and ~(13)C-NMR and elemental analysis.The characterization was made by TG-DTA,size exclusion chromatography(SEC)and solubility tests.At the optimum reaction conditions,the yield of poly[4-(4-hydroxybenzylidene amino)phenol](P-4-HBAP)was found to be 48.3%(for H_2O_2 oxidant),80.5%(for air O_2 oxidant)and 86.4%(for NaOCl oxidant).According to the SEC analysis,the number-average molecular weight(M_n),weight-average molecular weight(M_w)and polydispersity index(PDI)values of P-4-HBAP was found to be 8950,10970 g mol~(-1) and 1.225,respectively,using H_2O_2;and 11610,15190 g mol~(-1) and 1.308 respectively, using air O_2 and 7900,9610 g mol~(-1) and 1.216,respectively,using NaOCl.According to TG-DTA analyses,P-4-HBAP was more stable than 4-HBAP against thermal decomposition.The weight loss of P-4-HBAP was found to be 49.27% at 1000℃. The highest occupied molecular orbital(HOMO)and the lowest unoccupied molecular orbital(LUMO)values calculated from electrochemical measurement.Electrochemical energy gaps(E′_g)of 4-HBAP and P-4-HBAP were found to be-5.46, -5.28;-2.26,-2.67;3.20 and 2.61 eV,respectively.According to UV-Vis measurements,optical band gap(E_g)of 4-HBAP and P-4-HBAP were found to be 3.34 and 3.01 eV,respectively.Also,antimicrobial activities of 4-HBAP and P-4-HBAP were examined against selected some bacteria.The electrical conductivity of the polymer was measured after doping with iodine.     

SYNTHESIS OF SOLUBLE POLY（3,4-DIHYDROXY-o-TOLYLENE）： REDOX POLYMER

Conventional chloromethylation, paraformaldehyde/hydrogen chloride in acetic acid medium, was applied to 1,2- dimethoxybenzene. Chloroform-soluble poly（3,4-dimethoxy-o-tolylene） was obtained with an intrinsic viscosity of 0.034 dL g^-1. The polymer was evaluated as a condensation redox polymer precursor formed by a Friedel-Crafts reaction. Cleavage of the methoxy groups present in this polymer resulted in poly（3,4-dihydroxy-o-tolylene） which manifested a great air-oxidation resistance. The redox property of the latter polymer was found to be 1017 mV by potentiometric titration with 0.05 N ceric ammonium nitrate at 25℃. This midpotential was compared to that of catechol, a monomeric analogue, under the same titration conditions.     

NUCLEATION MECHANISM OF PEO BLOCK IN DOUBLE-CRYSTALLINE POLY（ETHYLENE-co-BUTENE）-b-POLY（ETHYLENE OXIDE） BLOCK COPOLYMERS

In this paper, we proposed a method to determine the nucleation effect of pre-existing crystals on crystallization of the second block in double crystalline block copolymers, which is usually covered by the suppression effect. The nucleation mechanism of poly（ethylene oxide） （PEO） block from the pre-crystallized polyethylene （PE） block in poly（ethylene-cobutene）-b-poly（ethylene glycol） （EmEOn） diblock copolymers was investigated under variable crystallization environments. The crystallization environment for the PEO block was altered by cooling at different cooling rates or successive selfnucleation （SSN） to the PE block. It was found that the presence of nucleation effect is strongly dependent on composition of the block copolymers. The crystallization temperature （Tc） of PEO block in E174EO90 increases as cooling rate applied to the PE block decreases, indicating that PE block can nucleate the crystallization of PEO block and more perfect PE crystals have stronger nucleation effect. In E182EO41 crystallization of the PEO block is confined, shown by the disappearance of selfnucleation domain, and the PE block has no nucleation effect on the crystallization of PEO block. Double crystallization peaks are observed for the PEO block in E182EO41 and the intensity of the crystallization peak at higher temperature increases as the PE crystals become more perfect. After exclusion of homogeneous nucleation mechanism, the higher temperature crystallization peak of the PEO block in E182EO41 is tentatively ascribed to surface nucleation.     

PREPARATION AND CHARACTERIZATION OF INCLUSION COMPLEXES OF TWO-ARM LINEAR AND FOUR-ARM STAR-SHAPED POLY（ε-CAPROLACTONE）S WITH α-CYCLODEXTRIN

Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs） formed between the PCL polymers and α-CD were characterized by ^1H-NMR, DSC, TGA, WAXD, and FT-1R, respectively. Both branch ann number and molecular weight of the PCL polymers have apparent effect on the stoichiometry （CL：CD, mol：mol） of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic α-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-ann linear or four-ann star-shaped PCL polymers and α-CD not only enhances the thermal stability of the guest PCL polymers but also improves that of α-CD.     

CHARACTERIZATION OF NOVEL POLYMERIC INTERMEDIATE POLY（p-BROMOACETYL STYRENE） CROSSLINKED BY DIVINYLBEZENE

Acetyl crosslinked polystyrene (EPS) and crosslinked bromoacetyl polystyrene (BEPS)beads were synthesized by Fridel-Crafts acetylation of polystyrene (PS) and bromination of EPS respectively. FTIR, XPS, and TG-TDG were employed to characterize their structures. The results revealed there are two types of bromine in the BEPS molecule. One is in the main chain of polystyrene and the other is in the acetyl. The results of TG-DTG showed that the rates of loss weight of PS, EPS, and BEPS were 92.7%, 92.2%, and 81.3% among the 300 ℃～500 ℃; 7.3%, 7.8%, and 18. 7% in 594 ℃, 660 ℃, and 584.8 ℃, respectively.     

SYNTHESIS, CHARACTERIZATION OF CHIRAL POLY（ESTER AMIDE）S DERIVED FROM L-ISOLEUCINE

A series of new optically active aromatic poly(ester arnide)s containing a chiral group in the side chain prepared from the p-toluenesulfonic acid salt of o,o‘-bis(leucyl)-hexanediol (TS^- LHD^ TS^-) and p-phthaloyl chloride and styrene-2,5-dicarbonyl chloride styrene have been synthesized by interfacial polymerization. The structure of the monomer is elucidated by FT-IR and elemental analysis. The thermal properties of the polymers were studied by DSC and TGA. The chiroptical properties of the above polymer have also been studied by circular dichroism (CD) spectroscopy. Results indicated that these polymers form helical structures.     

THERMAL PROPERTY, MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF POLY（3-HYDROXYBUTYRATE-co- 3-YDROXYHEXANOATE） AND POLY（BUTYLENE SUCCINATE-ADIPATE） （PHBHHX/PBSA） BLENDS

Blends of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) and poly(butylene succinate-adipate) (PBSA), both biodegradable semicrystalline polyesters, were prepared with the ratio of PHBHHx/PBSA ranging from 80/20 to 20/80 by melt mixing method. Differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), dynamic mechanical thermal analysis (DMA), polarizing optical microscopy (POM) and wide angle X-ray diffractometer (WAXD) were used to study the miscibility and crystallization behavior of PHBHHx/PBSA blends. Experimental results indicate that PHBHHx is immiscible with PBSA as shown by the almost unchanged glass transition temperature and the biphasic melt.     

SYNTHESES OF RESINS IMPREGNATED WITH POLYETHER OR POLYTHIOETHER OLIGOMERS AND THEIR EXTRACTION FOR GOLD（Ⅲ） and palladium（Ⅱ）

Six novel resins impregnated with polyether or polythioether oligomers have been synthesized and their extraction properties have also been investigated.Gold(Ⅲ） and /or palladium (Ⅱ） coulld be extracted repidly by the resins with high percentage and capacities from aqueous solution but most of the co-existing base metal ions were remained.The extraction capacities and stripping percentage were approximately unchanged after four extraction-elution cycles and the resins also showed excellent column extraction-elution properties.