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.     

SYNTHESIS, CHARACTERIZATION, THERMAL DEGRADATION AND ELECTROCHEMICAL PROPERTIES OF OLIGO-4-m-TOLYLAZOMETHINEPHENOL

The oxidative polycondensation reaction conditions of 4-m-tolylazomethinephenol （4-TAMP） in the presence of air O2 and NaOCl as oxidants were studied in an aqueous alkaline medium between 50 and 90℃. The structures of the obtained monomer and oligomer were confirmed by FT-IR, UV-Vis, ^1H- and ^13C-NMR and elemental analysis techniques. The physical characterization was made by TG-DTA, size exclusion chromatography （SEC） and solubility tests. At the optimum reaction conditions, the yield of oligo-4-m-tolylazomethinephenol （O-4-TAMP） was found to be 62.50% （for air O2 oxidant） and 90.0% （for NaOCl oxidant）, respectively. According to the SEC analysis, the number-average molecular weight （Mn）, weight-average molecular weight （Mw） and polydispersity index （PDI） values of O-4-TAMP were found to be 2310, 2610 g tool 1 and 1. 13, respectively, using air O2, and 1390, 1710 g mol^-1 and 1.23, using NaOCl, respectively. According to TG-DTA analyses, O-4-TAMP was more stable than 4-TAMP against thermal decomposition. The weight losses of 4-TAMP and O-4-TAMP were found to be 68% and 58% at 1000℃. Electrical conductivity of the O-4-TAMP was measured, showing that the polymer is a typical semiconductor. Electrochemically, the highest occupied molecular orbital （HOMO）, the lowest unoccupied molecular orbital （LUMO） and electrochemical energy gaps （E＇g） for 4-TAMP are -5.96, -3.22 and 2.74 eV, respectively. The HOMO, LUMO and （E＇g） for O-4-TAMP are -5.78, -3.44 and 2.34 eV, respectively. According to UV-Vis measurements, optical band gaps （Eg） of 4-TAMP and O-4-TAMP were found to be 3.45 and 3. 1 0 eV, respectively.     

Synthesis, Crystal Structure and Fluorescent Properties of 1-（4-（Dimethylamino）benzylidene）- 4-（naphthalen- 1-yl） Thiosemicarbazide

1 INTRODUCTION Recently, for the fluorescent properties, Schiff base has been more and more important and widely studied in density optical memories, nonlinear op- tics (NLO), organic light-emitting diodes (OLED), polymer LED and electrogenerated chemilumines- cence (ECL)[1~5]. Thiosemicarbazones are a kind of Schiff bases with thiourea and good ligands easily chelating with transition metal ions. Although they have been studied extensively for a long time due to their chemical and b…     

SYNTHESIS AND CHARACTERIZATION OF COPOLYMER OF 2,5-BIS[（4-METHOXYPHENYL）OXYCARBONYL]STYRENE AND STYRENE WITH HIGH MOLECULAR WEIGHT

The random copolymers of styrene and 2,5-bis[(4-methoxyphenyloxycarbonyl)styrene] (MPCS) with different copolymerization ratio were synthesized by conventional free radical polymerization. The copolymer having high molecular weight was experimentally elucidated using a combination of proton nuclear magnetic resonance spectroscopy and gel permeation chromatography. The liquid crystalline behavior of the copolymer was studied using differential scanning calorimetry, X-ray diffractometry and polarized optical microscopy. It was found that the liquid crystalline behavior was dependent on the content of styrene. Experimental results show that the copolymer could turn into a liquid crystalline phase at about 180℃ when the content of styrene was less than 20%. The mechanical properties of the copolymer were also studied. Preliminary results indicate that the tensile strength decreases while the tensile modulus increases as the content of MPCS is increased.     

Synthesis, Crystal Structure and Antibacterial Activities of 3-[（2-Hydroxy-4-diethylamino-phenyl）methylenehydrazinocarbonyl]-4-hydroxy-6-methyl-2（1H）-pyridinones

1 INTRODUCTION Recently, compounds containing pyrazole, imida- zole, triazole (including benzotriazole), pyridine, tetrazole and indole have attracted much interest because of their fungicidal activity, plant-growth regulating activity and antibacterial activity[1～3]. Schiff bases also constitute a good type of biolo- gically active substructures[4～7]. Studies of pyri- dine Schiff base-type fungicides have been repor- ted[8]. However, some structures of pyridine com- pounds containing h…     

SYNTHESIS AND OPTICAL-ELECTRONIC PROPERTIES OF POLY [METHYLTETRAPHENYLPHENYLSILYLENE-CO- BIS（METHYLPHENYLSILYL）ACETYLENE]

Poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)acetylene) (PSA) was synthesized by the cocondensation reaction of methyltetraphenylphenyldichlorosilane and bis(chloromethylphenylsilyl)acetylene with sodium in toluene. The PSA thus obtained was soluble in most organic solvents, and its molecular weight was smaller than that of poly[(disilanylene)acetylenes] with alkyl- or aryl-substitution because of the great steric congestion of tetraphenylphenyl groups. The optical and electronic properties of the polymer were investigated. The results show that PSA has strong UV absorption and fluorescence emission, the maximum UV absorption wavelength of PSA is 330 nm, which shows a considerable red-shift in comparison with that of poly(methylphenylsilylene-co-methylphenylsilylacetylene) (PSI) and alkylsubstituted poly[(disilanylene)acetylenes]. A strong photoluminescence band at 470 nm in THF and 432 nm in benzene can be observed in the visible region, respectively. Treatment of the films of PSA with I2 vapor afforded conducting films. The conductivity of PSA thin film doped with I2 was measured to be 0.35 Scm-1 in the air which is lower than that of poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)phenylene), but higher than that of σ-π polymers without tetraphenylphenyl groups. As an explanation, the tetraphenylphenyl group is a large π-electron-conjugated group; after being introduced to the Si atoms of the polysilanes, the interaction between π-electrons of the tetraphenylphenyl groups and the σ-electrons conjugated along the Si-Si bonds is increased strongly, and the σ-electrons can be conjugated more extensively along the main chain of the polysilanes.     

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 Structure Characterization of N-Phenyl-（2S）-hydroxy-3-[（2-hydroxybenzylidene）amino]propionamide

1 INTRODUCTION Schiff bases can be conveniently prepared from the corresponding aldehyde and primary amine, which, as multidentate ligands, have already received great attention. Many metal complexes of this kind of ligands have been used successfully in various re- actions, such as Diels-Alder and hetero-Diels-Alder reactions[1], kinetic resolution of racemic epoxides[2], and Nozaki-Hiyama-Kishi (NHK) reaction[3]. Recen- tly Berkessel et al. have reported that the Cr- complex of sal…     

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 AND CHARACTERIZATION OF NOVEL SOL-GEL DOPED ORGANIC／INORGANIC HYBRID NONLINEAR OPTICAL MATERIALS

4-hydroxy-4 ‘-nitro azobenzene (NHA) and 4-amino-4 ‘-nitro azobenzene (DO3) were prepared respectively from p-nitrophenylamine as a precursor compound. Two kinds of doped organic/inorganic hybrid nonlinear optical (NLO) materials containing NHA and DO3 were synthesized by Sol-Gel process. The preparation and properties of two NLO materials were studied and characterized by FTIR, IH-NMR, UV-VIS, SEM, DSC and SHG measurements. The results show that the maximum doping amounts of NHA and DO3 in two doped hybrid NLO materials are 7.2(wt)% and ll.3(wt)% respectively, and the corresponding second-order NLO coefficients (d33values) are 2.91 ×l0^-3esu and 6.14×10 -8 esu. Two doped NLO materials have relatively good RT stability, after 90 days at RT the d33 values can maintain about 85% of their initial values, but after l0h at 100℃ can only maintain about 50% of their initial values. In this report, the reasons for high-temperature instability of doped materials were discussed, and the possible improvements were also suggested.     

SYNTHESIS, CHARACTERIZATION, THERMAL DEGRADATION AND ELECT-RICAL CONDUCTIVITY OF OLIGO[2-(2-HYDROXYPHENYLIMINOMETHYL-BENZYLIDENE)AMINOPHENOL] AND OLIGOMER-METAL COMPLEXES

The oxidative polycondensation reaction conditions of 2-[(2-hydroxyphenyliminomethylbenzylidene)amino- phenol](2-HPIMBAP)has been accomplished by using air O_2 and NaOCl oxidants in an aqueous alkaline medium between 50-90℃.The optimum reaction conditions of the oxidative polycondensation and the main parameters of the process were established.At the optimum reaction conditions,yield of the products were found to be 67.72% and 61.49% for air O_2 and NaOCl oxidants respectively.The structures of the monom...     

SYNTHESIS,CHARACTERIZATION,THERMAL DEGRADATION AND ELECTRICAL CONDUCTIVITY OF OLIGO[2-(THIEN-2-YL- METHYLENE)AMINOPHENOL] AND OLIGOMER-METAL COMPLEXES

The optimum reaction conditions of the oxidative polycondensation of 2-(thien-2-yl-methylene)aminophenol (2-TMAP) has been accomplished by using air O_2,H_2O_2 and NaOCl oxidants in an aqueous alkaline medium between 20℃and 90℃.The structures of the monomer and oligomer were confirmed by FT-IR,UV-Vis,~1H-NMR and ~(13)C-NMR and elemental analysis.TGA-DTA,size exclusion chromatography(SEC) techniques and solubility tests were applied for characterization.The ~1H-NMR and ~(13)C-NMR data show that the polyme...     

SYNTHESIS AND CHARACTERIZATION OF POLY{4-[2-(tert-BUTYLDIMETHYLSILOXY)ETHYL]STYRENE} AND ITS HYDROLYSIS DERIVATIVE

The living cationic polymerization of 4-[2-(tert-butyldimethylsiloxy)ethyl]styrene(TBDMES)was studied in methylcyclohexane(MeChx)/methylchloride(MeC1)(50/50 V/V)solvent mixture at-80℃.The initiator 1,1- diphenylethylene(DPE)capped 2-chloro-2,4,4-trimethylpentane(TMPCl)was formed in situ in conjunction with titanium tetrachloride(TiCl_4).The Lewis acidity of TiCl_4 was decreased by the addition of titanium(IV)isopropoxide(Ti(OiPr)_4)to accomplish living polymerization of TBDMES.Hydrolysis of poly(TBDMES)i...     

SYNTHESIS, CHARACTERIZATION, THERMAL ANALYSIS, CONDUCTIVITY AND BAND GAPS OF OLIGO {4-[(2-HYDROXYL-1-NAPHTHYL)METHYLENE]-AMINOBENZOIC ACID}

The oxidative polycondensation reaction conditions of 4-[(2-hydroxyl-1-naphthyl)methylene]aminobenzoic acid (4-HNMABA) with H_2O_2,air O_2 and NaOCl were studied in an aqueous alkaline medium between 40℃and 90℃.The structure of oligo {4-[(2-hydroxyl-1-naphthyl)methylene]aminobenzoic acid} (O-4-HNMABA) was characterized by using ~1H-NMR,~(13)C-NMR,FT-IR,UV-Vis,size exclusion chromatography (SEC) and elemental analysis techniques.At the optimum reaction conditions,the yield of O-4-HNMABA was found to be 70...     

Synthesis, characterization, thermal stability and electrochemical properties of poly-4-[(2-methylphenyl)iminomethyl]phenol

In this study, the reaction conditions of poly-4-[(2-methylphenyl)iminomethyl]phenol (P-2-MPIMP) were studied by using oxidants such as air O₂, H₂O₂ and NaOCl in an aqueous alkaline medium between 50 and 90 °C. The structures of the synthesized monomer and polymer were confirmed by FT-IR, UV-vis, 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-[(2-methylphenyl)iminomethyl]phenol (P-2-MPIMP) was found to be 20% (for air O₂ oxidant), 33% (for H₂O₂ oxidant), and 74% (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-2-MPIMP were found to be 3300, 4100 g mol⁻¹ and 1.242, using H₂O₂, and 4550, 5150 g mol⁻¹and 1.132, using air O₂ and 5300, 5850 g mol⁻¹ and 1.104, using NaOCl, respectively. According to TG analysis, the weight losses of 4-[(2-methylphenyl)iminomethyl]phenol (2-MPIMP) and P-2-MPIMP were found to be between 75.29% and 48.17% at 1000 °C, respectively. P-2-MPIMP was shown to have a higher stability against thermal decomposition. Also, electrical conductivity of the P-2-MPIMP was measured, showing that the polymer is a typical semiconductor. Electrochemically, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) and electrochemical energy gaps ( of 2-MPIMP and P-2-MPIMP were found to be −6.01, −6.03; −2.63, −2.82; 3.38 and 3.21 eV, respectively. According to UV-vis measurements, the optical band gap (E_g) of 2-MPIMP and P-2-MPIMP was found to be 3.40 and 2.97 eV, respectively.     

Synthesis, characterization and thermal degradation of oligo-2-[(4-fluorophenyl) imino methylene] phenol and some of its oligomer-metal complexes

In this study, the oxidative polycondensation reaction conditions of 2-[(4-fluorophenyl) imino methylene] phenol (FPIMP) with air oxygen and NaOCl were studied in an aqueous alkaline medium between 60 and 90 °C. Synthesized oligo-2-[(4-fluorophenyl) imino methylene] phenol was characterized by ¹H-NMR, FT-IR, UV-Vis, size exclusion chromatography (SEC) and elemental analysis techniques. The yield of oligo-2-[(4-fluorophenyl) imino methylene] phenol (OFPIMP) was found to be 62.00% (for air O₂ oxidant) and 97.70% (for NaOCl oxidant) at the optimum reaction conditions. According to the SEC analysis, the number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of OFPIMP were found to be 1370 g mol⁻¹, 1979 g mol⁻¹ and 1.45, using NaOCl, 2105 g mol⁻¹, 2557 g mol⁻¹, and 1.22, using air O₂, respectively. During the oxidative polycondensation reaction, (2.88%) a part of -CHN group oxidized to carboxylic acid (-COOH). TG and TG-DTA analyses were shown to be more stable of oligo-2-[(4-fluorophenyl) imino methylene] phenol and its oligomer metal complexes than monomer against thermo-oxidative decomposition. The weight loss of OFPIMP was found to be 97.00% at 900 °C. The weight losses of OFPIMP-Co, OFPIMP-Ni OFPIMP-Cu oligomer-metal complex compounds were found to be 88.66%, 94.36% and 83.21%, respectively, at 1000 °C.     

聚(对乙烯基苯酚)的合成及其与重氮树脂的氢键自组装研究

带相反电荷的聚电解质,交替沉积在基片,形成超薄有序膜,通常称为静电自组装,自1991年由Decher首次阐明以来,静电自组装技术引起了广泛重视,利用氢键相互作用的氢键自组装1997年才有报道,沈家骢、张希等从聚丙烯酸和聚乙烯基吡啶通过氢键组装了有序超薄膜。和乙烯基吡啶通过氢键组装超薄膜的制备。由于静电力和氢键均很弱,此类膜对极性溶剂不稳定,如在DMF中会离解而遭破坏,我们曾报道重氮树脂（DR）与酚醛树脂间通过氢键的自组装,本文报道聚（对乙烯基苯酚）（PVPh）的制备及春与重氮树脂（DR）间的氢键相经作用,并结合光照,制备了对极性溶剂稳定的超薄膜。     

含亚甲基和双二氮杂萘酮结构的聚芳酮的合成与性能

聚芳醚酮是一类重要的具有优异综合性能的工程塑料 ,它具有高的热稳定性、尺寸稳定性、耐溶剂性、好的加工性能和电性能 ,因而它经常作为复合材料的基质、粘合剂等被广泛的应用于航空、航天和电子等领域 .近几十年来 ,人们付出了很大的努力去开发聚芳醚酮新品种[1,2 ] .本研究组以 4 (4′ 羟基苯氧基 ) 2 ,3 二氮杂萘 1 (2Ｈ) 酮为缩聚单体制备了一系列的性能优良的聚芳醚酮[3～ 6] ,在主链中引入高密度的氮杂萘酮结构是获得高热稳定性和良好溶解性的重要途径 .由单体中含有更多的氮杂萘酮结构获得可溶解且耐温等级更高的聚芳酮是人们期…     

Synthesis and characterization of oligo-4-[(pyridin-3-ylimino)methyl]phenol

The oxidative polycondensation of 4-[(pyridin-3-ylimino)methyl]phenol (4-PIMP) with O₂, H₂O₂, and NaOCl was studied in an aqueous alkaline medium between 50°C and 90°C. Oligo-4-[(pyridin-3-ylimino)methyl]phenol (O-4-PIMP) prepared was characterized by ¹H-NMR, ¹³C-NMR, FT-IR, UV-VIS, size-exclusion chromatography, and elemental and thermal analyses techniques. At the optimum reaction conditions, the yield of O-4-PIMP was 18.9%, 39.4%, and 46.8% using H₂O₂, O₂, and NaOCl oxidant, respectively. According to the TG analysis, the initial degradation temperature of O-4-PIMP was 218°C, which was by 50°C higher than that of 4-PIMP. Thermal analyses of 4-PIMP and O-4-PIMP were carried out in N₂ atmosphere at 15–1000°C. The highest occupied molecular orbital, the lowest unoccupied molecular orbital, and electrochemical energy gaps of 4-PIMP and O-4-PIMP were determined from the onset potentials for n-doping and p-doping, respectively. Also, optical band gaps of 4-PIMP and O-4-PIMP were determined according to UV-VIS measurements.