PERVAPORATION SEPARATION OF WATER-ACETIC ACID MIXTURES THROUGH AN-co-AA MEMBRANES TREATED WITH RARE EARTH METAL IONS

Pervaporation separation of water-acetic acid mixtures through Poly (AN-co-AA)membranes and rare earth metal ions treated Poly(AN-co-AA)membranes was investigatedfor the first time. The results showed that the treatment with rare earth metal ions couldgreatly improve the characteristics of the separation of water-acetic acid mixtures.     

醇／水混合液分离用聚乙烯醇复合膜的渗透汽化特性

制备了聚乙烯醇（ＰＶＡ）／聚丙烯睛（ＰＡＮ）渗透汽化复合膜，研究了交联剂用量、底膜结构、进料液组成、操作温度等因素对膜的渗透汽化性能的影响．发现ＰＶＡ／ＰＡＮ复合膜对水／醇混合液表现为水优先透过，进料液中乙醇浓度在６０～９９ｗｔ％的范围内，渗透通量Ｊｔ与温度之间符合Ａｒｒｈｅｎｉｕｓ关系，选择分离系数αＷ／Ｅ也随温度上升而增大．进料液为９５ｗｔ％的乙醇／水混合液时，７５℃下Ｊｔ高达３００～４５０ｇ／ｍ２ｈ，αＷ／Ｅ为８００～１１００．对异丙醇／水、异丁醇／水及甘油／水混合体系，复合膜显示出更为优秀的透过、分离性能．就膜的化学、物理结构与其渗透汽化性能间的关系进行了讨论．     

PVA／PEG共混渗透蒸发膜的盐水分离机理研究

以聚乙烯醇（ＰＶＡ）和聚乙二醇（ＰＥＧ）共混,甲醛交联制备亲水性高分子膜,用于渗适蒸发过程进行海水脱盐。ＰＥＧ的引入使盐－水分离成为可能, 到钠的引入使膜的分离通量明显提高。通过溶用蔗、ＰＥＧ水溶液的粘度和膜形态分析等方法对ＰＶＡ－ＰＥＧ体系的高分子网络结构和膜中相分离作了研究,发现了膜结构与渗透蒸发脱盐性能的基本关系。影响膜分离的因素除了化学亲合性之外,主要是膜的溶胀性和微相分离程度。ＰＥＧ的作     

PREPARATION AND PROPERTIES OF ETHYL-CYANOETHYL CELLULOSE/POLYACRYLIC ACID COMPOSITE FILMS WITH REFLECTION COLORS*

Ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid (AA) becomes a cholesteric liquid crystalline solution withvivid colors when the (E-CE)C concentration is 42 wt%～52 wt%. (E-CE)C/polyacrylic acid (PAA) composites withcholesteric structure were prepared by polymerzing AA in (E-CE)C/AA liquid crystalline solutions. The layers of orderedpolymer chains in the cholesteric phase were inclined during polymerization and the degree of the inclination depended onthe polymerization temperature and the concentration of the solution before polymerization. The cholesteric structure in thecomposites could not be changed when temperature was lower than 100℃. Cross-linking of the PAA in compositesimproved their water-resistance. The cholesteric order of the composites without cross-linking was destroyed when theywhere immersed in water. The color derived from the selective reflection of the cholesteric phase of the cross-linkedcomposites turned from blue to red after the composites absorbed water. The color of the composites could be returned to theoriginal one when the absorbed water was removed from the swollen composites.     

FORMATION AND MICROSTRUCTURE OF POLYETHYLENE MICROPOROUS MEMBRANES THROUGH THERMALLY INDUCED PHASE SEPARATION*

Microporous membranes of low-high density polyethylene and their blends were prepared bythermally-induced phase separation of polymer/long-aliphatic chain alcohol (diluent) mixtures.The microstructures of this particular membrane, which depends on the diluent properties,polymer concentration and cooling rate, were observed by scanning electron microscopy."Beehive-type,"leafy-like, and lacy porous structure morphologies can be formed,depending onthe blend composition and phase separation conditions, which were discussed by the polymer anddiluent crystallization processes.     

GRAFTING OF HUMIC ACID ONTO COTTON CELLULOSE (Ⅱ)*

Cotton cellulose reacted with epichlorohydrin under the catalytic action of HClO_4 and H_2O to form 3-chloro-2-hydroxypropyl ether with a substitution degree of 0.61. The chlorine-containing product was treated with aliphatic diamines (ethylenediamine, propylenediamine, etc.) to produce nitrogen-containing cellulose which further reacted with humic acid to give black fiberous graft cellulose. This product contains 27—35% humic acid, 0.90 meq/g acidic groups, possesses 0.49 meq/g Cu~(2+)-complexing capacity and good mechanical strength, and can be used under pH12.     

STUDY ON MEAN-SQUARE RADIUS OF GYRATION FOR POLYALKYLENEOXIDES

Taking account of the effect of heteroatoms in backbone, this article dealt with themean-square radii of gyration of polyalkyleneoxides by the approach of matrix algebrain accordance with the rotational isomeric state model. Numerical calculation with theparameters available in the literatures indicated that the dependence of on themolecular weight can be expressed by the general formula: = aM~b     

STUDY OF DYE-SENSITIZED SYSTEMS FOR PHOTOIMAGING*

 o-Chloro-hexaarylbiimidazole (o-C1-HABI) can be sensitized efficiently by cyanine dyes, the cyclopentanone and cyclohexanone dyes, when exposed to xenon lamp (use filter cut λ≤ 400 nm). The photoreaction between the photoinitiator and the dyes was completed through an electron transfer process. Excellent results have been obtained in photoimaging studies, e.g. the resolution of the image can reach 7 μm. The influence of the content of the dyes and the heat after the exposure on the resolution of the image was investigated.     

ASSOCIATION OF ETHYLENE—VINYL ACETATE COPOLYMER IN DILUTE SOLUTIONS Ⅲ. CRITICAL ASSOCIATION CONCENTRATION*

Association behavior of ethylene vinyl acetate (EVA) copolymer in foursolvents 1, 2-dichloroethane (DCE), cyclohexane (CYH), xylene (XYL) and chloroform(CF) has been investigated by dilute solution viscometry The critical association concen-tration (C_A) was determined at which the incipient decrease in slope of the η_(sp)/C～ Ccurve in solutions at the dilute regime. Our results showed that whether the CA couldexist depends on solvent property. The values of CA in DCE increase with increasing, oftemperature and vinyl acetate (VA) content in EVA and decreasing of molecular weight ofEVA.     

THERMALLY STIMULATED SHAPE MEMORY BEHAVIOR OF POLYMERS WITH PHYSICAL CROSSLINKS*

The shape memory effect of polymers was investigated for the purpose of improving the processingconditions of their preparation and broadening the list of polymers for shape memory applications. Emphasiswas put on the possibility of using polymers with physical crosslinks as shape memory materials and theirstructure-function relationships. Segmented block polyurethanes and polyethylene/nylon 6 graft copolymerswere used as examples of polymers with physical crosslinks. It was found that these copolymers can really beused as thermally stimulated shape memory materials with large recoverable strain and high final recoveryrate. The main advantage of using copolymers is their improved processing conditions as compared withpolymers with chemical crosslinks. As only physical crosslinks are introduced, all conventional processingtechniques for thermal plastics can be used, and the materials become easily reusable. The results indicatethat the high crystallinity of these copolymers at room temperature and the formation of stable physicalcrosslinks are the two prerequisites for these polymers to exhibit shape memory effect. The successful use ofblock and graft copolymers imply the possibility of using polymers of various structure and properties asshape memory materials.     

THE STRUCTURE AND OPTICAL PROPERTIES OF COPOLYMER OF CHOLESTERIC ESTER

The structure and switching properties of liquid crystalline side chain copolymers of cholesteric ester of 1,2-hydroxypropyl 2,4-di-isocyanatoluene methylmethacrylate (PHCPM) have been studied in detail. The cholesteric mesophase of PHCPM is shown by polarizing microscopy, X-ray diffraction and selective light reflection. Solution of PHCPM in CHCl_3 is optically anisotropic; its optical properties were determined by specific rotation [α], circular dichroism (CD) and wide-angle hght scattering (WALS) methods.     

STUDY ON HIGHLY ACTIVE ZIEGLERNATTA CATALYSTS FOR POLYMERIZATION OF OLEFINS

In this paper, highly active Ziegler-Natta catalysts of MgCl_2 supported TiCl_4 for synthesis ofpolyolefins, using di-n-butyl phthalate (DNBP) as internal donor and diphenyl dimethoxyl silane(DPDMS) as external donor, have been prepared. The conditions controlling the treatment ofsupport were studied. The interactions of various components present in the catalysts and theirinfluences on catalytic performance were investigated. It is found that by using DNBP and DPDMSas internal and external donors together the polymer products with higher isotactic index can beobtained. Plausible structure model and mechanism were proposed.     

STUDY ON SEGMENTED POLYURETHANE WITH MIXED SOFT SEGMENTS OF POLYCHLOROMETHYL METHYL SILOXANE AND POLYTETRAMETHYLENE OXIDE

Two series of polyurethanes based on mixed polychloromethyl methyl siloxane and poly-tetramethylene oxide in different weight fractions were synthesized. The phase separation ofsamples was studied using DSC and dynamic mechanical property analysis. The results showedthat the introduction of chloromethyl group into polysiloxane increased its polarity and henceimproved the miscibilities with polytetramethylene oxide and polyurethane hard segment.Particularly, in the case of N-methyldiethanolamine extended materials, the surface and tensileproperties of these samples can be adjusted by various ratios of two soft segments.     

SILYLATION OF CELLULOSE WITH TRICHLOROSILANE AND TRIETHOXYSILANE IN HOMOGENEOUS LiCl/N,N-DIMETHYLACETAMIDE SOLUTION*

Silyl celluloses (SiC) were prepared by reacting cellulose with chloropropyltrichlorosilane (CPTCSi) andchloropropyltriethoxysilane (CPTESi) in LiCl/N,N-dimethylacetamide (DMAc). The Si content in the silyl cellulose could becontrolled by adjustment of the molar ratio of silane and cellulose. FT-IR spectra showed that cellulose was readily reactedwith the above two silane reagents, and the reactivity of CPTCSi is higher than that of CPTESi. It was presumed that thereaction process belongs to graft-polymerization. The results of differential thermal analysis (DTA) indicated that thethermostability of the materials produced increased with the increase of Si content in the sample. The acid resistance of thesamples SiC in 1 mol/L HCl aqueous solution was improved significantly. When Si content was ca. 20%, the silyl cellulosehas excellent thermostability, hydrophobicity, low density and stability in 1 mol/L HCl aqueous solution, owing tocrosslinking of cellulose chain with silane.     

高选择性透过SO_2气体分离膜研究 Ⅱ.丙基乙烯基亚砜改性聚乙烯醇功能高分子膜的分离性能

丙基乙烯基亚砜改性聚乙醇功能高分子膜对SO_2,N_2及SO_2-N_2混合气体的渗透性能研究表明,该膜具有高选择透过SO_2的优良性能.透过SO_2的速率随着亚砜基含量的增加而增加,当亚砜基含量为25(mol)％时,经一次分离能使混合气体中SO_2的含量从1.54％提高到78.8％.     

DILUTE SOLUTION BEHAVIOR OF CHITOSAN IN DIFFERENT ACID SOLVENTS

Dilute solution behavior of chitosan was studied in formic acid, acetic acid, lactic acid andhydrochloric acid aqueous solution under different pH values. The reduced viscosities, η_(sp)/C,ofchitosan solutions were dependent on the properties of acid and pH value of solvents. For a givenchitosan concentration, η~(sp)/C decreased with the increase of acid concentration, or decreasing pHof solvent, indicating shielding effect of excessive acid similar to adding salt into solution. Thestabilities of dilute chitosan solution in formic acid and lactic acid were better than that in acetic acid and hvdrochloric acid.     

THE ELECTROCHEMICAL PREPARATION OF POLYPHENOL WITH CONDUCTIBILITY

Polyphenol film deposited on platinum foil can continuously grow with time during the electrolysis of a phenolsolution consisting of 0. 1 mol L~(-1) phenol, 3 mol L~(-1) NaOH and 0.5 mol L~(-1) Na_2SO_4, as has been proved by the methods ofsweep potential, constant potential and constant current, and visible spectra during the electrolysis of phenol. A polyphenolfilm with thickness of 0.11 mm was obtained by the electrolysis of phenol at a constant potential of 0.70 V (versus Ag/AClwith saturated KCl solution). Polyphenol film is inactive and stable in 2 mol L~(-1) H_2SO_4 solution, neutral solution and3 mol L~(-1) NaOH solution and in the potential range between -0.95 and 1.35 V. The usable potential range is dependent onthe pH value. Polyphenol has an ESR signal with a g factor of 2.0049. The conductivity of polyphenol is 1.2×10~(-4) S cm~(-1). Inthe solution of polyphenol dissolved in DMSO, the mobility of polyphenol anions is 8×10~(-9) m~2 s~(-1) V~(-1) at 20℃.     

IN SITU INTERFEROMETRIC STUDY ON THE GELATION PROCESS OF POLYACRYLIC ACID GELS*

In situ interferometry was used to investigate the gelation process of polyacrylic acid (PAA) gels. The basicprinciple of the in situ interferometry technique is illustrated. It can give sufficient information for non-destructive andsuccessful investigation of the whole gelation process. The effect of initiator concentration on the gelation process wasstudied. The polymerization rate of AA increases with increasing initiator concentration. The error arising from the thermaleffect in the gelation process can be neglected.     

STUDY ON THE IMMOBILIZATION OF PAPAIN WITH A MACROPOROUS BEAD CARRIER OF COPOLYMER CONTAINING MONOMER UNITS OF NAMINOETHYL ACRYLAMIDE AND VINYL ALCOHOL*

 A kind of macroporous bead carrier of copolymer containing monomer units of N-aminoethyl acrylamide and vinylalcohol was synthesized, i.e. the MR-AA carrier. Papain was immobilized on the carrier using glutaraldehyde as the couplingagent. The enzymatic activity of the immobilized papain was compared with free papain using casein as a substrate, and theeffects of glutaraldehyde concentration, pH, temperature, time and papain amount added on the activity recovery were alsoinvestigated. The results show that the MR-AA carrier contains reactive primary amine groups,hydrophilic amido links and hydroxyl groups,as well as macroporous structures based on its matrix (MR-AV matrix),furthermore,the activity recovery of papain in the immobilization could reach 48%～58%.In comparison with free papain,the resulting immobilized papain exhibits a remarkable thermostability and better reusability.     

A COMPARATIVE STUDY OF CHAIN DYNAMICS OF DI-AND TRI-BLOCK COPOLYMERS IN SEMIDILUTE SOLUTION IN A NON-SELECTIVE SOLVENT

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.with 0.33 ＜α＜ 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.