再生纤维素膜对聚苯乙烯的截留性

本文用铜氨法以及微相分离和后处理技术制备了孔径30A至1000A的一系列再生纤维素膜。采用膜渗透计按流动速率法及静态渗透压法分别测定了它们的平均孔径2rf以及膜在甲苯溶液中对聚苯乙烯标样的截留率Re。得到膜平均孔径和所截留聚苯乙烯分子最Mw及其均方根末端距〈h~2〉~(1/2)之间的关系式分别为: lg2r?=lg0.155 0.59lgM_w lg2rf=lg0.589 0.96lg〈h~2〉~(1/2)     

再生纤维素／聚乙烯醇共混膜的研究

由纤维素铜氨溶液与不同体积比（１－１０％）的聚乙烯醇（ＰＶＡ）水溶液共混制备了一系列再生纤维素共混膜．扫描电镜结果表明ＰＶＡ含量大于８％时，该共混膜产生明显相分离．当ＰＶＡ低于５％时，共混膜相容性较好．膜的结晶度，抗张强度，直角撕裂强度，断裂伸长及耐热性均优于单独用钢氨液制备的再生纤维素膜．此外，用流动速率法和超滤法测定了膜的孔径，渗透性及纯水通量，结果表明共混膜的孔性没有明显变化．本文得出：再生纤维素与５％ＰＶＡ共混能改善力学性能，并且能保持其生物降解性．     

SIZE EXCLUSION CHROMATOGRAPHIC COLUMN PACKED WITH REGENERATED CELLULOSE GELS*

Microporous regenerated cellulose gel particles were prepared by mixing cellulose cuoxam with silk fibroin aspore former, and the mean pore size and pore volume of the pallicles were 525 nm and 7.27 mL g~(-1), respectively. Apreparative size-exclusion chromatography (SEC) column (550 mm×20 mm) packed with the cellulose gel particles wasused for the fractionation of two polysaccharides Dextran 07 (M_w = 7.14×10~4, d= 1.7) and Dextran 50(M_w = 50.5×10~4,d = 3.8) in water phase. The fractionation range of the stationary phase covered M_w from 3×10~3 to 1.1×10~6. The dailythroughput was 2.9 g for Dextran 07 (D07) and 4.3 g for Dextran 50 (D50) with a flow-rate of 1.5 mL min~(-1). The fractionsobtained by using the SEC were analyzed by an analytical SEC combined with laser light scattering (LLS), and thepolydispersity indices of fractions for Dextran 07 and Dextran 50 were determined to be 1.34-1.57 and 1.53-3.36,respectively. The preparative SEC is a simple, rapid, and suitable means not only for the fractionation of polysaccharides inwater but also for other polymers in organic solvents.     

PHOTOCOPOLYMERIZATION OF MALEIC ANHYDRIDE AND VINYL ACETATE

The charge-transfer complex of maleic anhydride and vinyl acetate was copolymerized under UV light. The chain composition and structure of the copolymer were analyzed with conductometry and NMR, and the chain sequence was determined as alternating. The copolymerization rates at different feed ratios, temperatures and in different solvents were investigated, giving evidence to the very active involvement of the CT complexes in the copolymerization. Terpolymerization with acrylonitrile also showed that the complex mechanism was a proper one for this system.     

BAND-LIKE TEXTURE OF ETHYLCYANOETHYL CELLULOSE MESOPHASE

In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough and merge with each other with increasing concentration. The band-like texture is composed of parallel equidistant bright and dark alternative strips which are about 0.2-2.0 μm in width. In the band-like texture, the layers of ordered polymer chains are perpendicular to the solution film and the axes of helicoids are parallel to it. The width of the strips is different in different zones. Under the effect of an external magnetic field, the strips in the band-like texture first become wider and then narrower gradually.Moreover, the axes of helicoids in the (E-CE) C/DCA mesomorphic solution change from the direction normal to the magnetic field to the agreement with the magnetic field direction.     

羟丙基醋酸纤维素的合成及其膜的反渗透性

研究了羟丙基纤维素和羟丙基醋酸纤维素的合成。制备羟丙基纤维素的较佳反应温度为40℃左右和2小时或稍长,羟丙基含量随环氧丙烷浓度的增加而增加。在制备羟丙基醋酸纤维素时,随羟丙基含量的增加,所需醋化和水解的时间减少。以甘油-正丙醇或磷酸为添加剂,丙酮为溶剂经30～60s蒸发后制得了羟丙基醋酸纤维素反渗透膜。后者在20kg/cm~2下对氯化钠脱盐率可达95～98％,水通量1.0～2.1mL/cm~2·h,其使用温度上限比醋酸纤维素反渗透膜提高10℃以上。     

THERMAL ACTIVATION OF IMMOBILIZED PAPAIN

Papain (Papainase, EC 3.4.22.2) was immobilized on porous silica beadsby cross linking with glutaraldehyde. The thermal activation of this immobilized papainin aqueous system was found at a temperature range from 50 to 90℃. The higher thetemperature, the more active the immobilized papain will possess. At the same time,the durability of the immobilized papain on heating was greatly improved. The effect ofadditives and salts on the activity of the immobilized papain were also studied. The resultsshowed that the additives and some of the salts studied could markedly enhance the activityof the immobilized papain at elevated temperature.     

纤维素中空纤维膜气体加湿性能的研究

采用纤维素N甲基吗啉N氧化物(NMMO)水三元纺丝体系,以去离子水为芯液,自来水为凝胶浴,湿法纺制了纤维素中空膜.经自然干燥后该膜的轴向、径向都明显收缩,断面呈现均质致密结构.干膜在水中会明显溶胀,重新润湿后具有气密性.考察了加湿水温、水气压力差等因素对膜的水渗透通量的影响,并初步测试了膜对质子交换膜燃料电池(PEMFC)反应气体H2和O2的加湿性能.实验结果表明该膜透水性能较优,气体加湿效果明显,具有应用于PEMFC反应气体加湿系统的潜力.     

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.     

聚醚砜/纤维素晶体共混膜材料及其超滤性能

聚醚砜与纤维素晶体等共混成铸膜液,采用浸没沉淀相转化法制备聚醚砜/纤维素晶体共混膜材料.通过超滤装置检测复合膜的水通量、截留率、平均孔径、孔隙率、抗污染性等超滤性能,从而讨论了纤维素晶体含量对共混膜超滤性能的影响.采用抗张测试机、热重分析仪(TGA)、原子力显微镜(AFM)对共混膜的力学性能、热稳定性能、形貌结构进行表征.结果表明,随着纤维素晶体的含量的增加,共混膜的纯水通量先升高后有所降低,截留率均保持在91%～95%,抗张强度、断裂伸长率先增大后有所下降,抗污染性较纯聚醚砜膜显著提高.当纤维素晶体质量分数为1%时,纯水通量达到最大为813.3L·m-2·h-1,孔隙率为88.8%,平均孔径达为70.9nm,抗张强度为7.25MPa,断裂伸长率为11.6%,平均污染度FR值为22.0%,衰减系数m值为35.8%.共混膜具有由纤维素晶体、聚醚砜热降解分别引起的两个失重阶段.共混膜为典型非对称膜结构,表皮层较为致密,多孔支撑层孔径较大.     

THERMAL BEHAVIOR OF THERMOTROPIC HYDROXYETHYL CELLULOSE ACETATE/POLYETHYLENE BLENDS

The thermal behavior of thermotropic hydroxythyl cellulose acetate (HECA)/polyethy-lene (PE) blends has been studied by DSC. It is found that the blends of HECA and PEare immiscible but the crystallization of PE is affected by HECA chains in the blends withmore than 50% HECA, which results in the subordinate crystallization of PE and the for-mation of imperfect structures in the PE crystals. The imperfection of PE crystals in theblends can be eliminated after annealing at 393K.     

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.     

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.     

SEMI-QUANTITATIVE CHARACTERIZATION OF SEGMENT DISTRIBUTION IN LLDPE BASED ON THERMAL SEGREGATION

Based on successive multiple-step isothermal crystallization and self-nucleation annealing methods, a novel semi-quantitative method for the characterization of segment distribution in linear low density polyethylene (LLDPE) wasestablished by treating the thermal analysis data using the Gibbs-Thomson equation. The method was used to describe thesegment distribution of Ziegler-Natta catalyzed LLDPE (Z-N LLDPE), metallocene catalyzed LLDPE (m-LLDPE) and twoconunercial LLDPEs with wide molecular weight distribution. The differences of the results obtained from the two thermallytreated samples were compared. The results of segmeni distribution of the polymers were discussed according to theirmicrostructure data and were compared with their characteristics. It can be deduced from the results that this characterizationmethod is effective to characterize the sequence structure of the branched ethylene copolymers.     

细菌纤维素/聚丙烯酰胺水凝胶的制备及性能表征

通过自由基聚合在细菌纤维素(BC)网络中引入聚丙烯酰胺(PAM),制备了细菌纤维素/聚丙烯酰胺(BC/PAM)复合水凝胶,并采用扫描电子显微镜(SEM)、红外光谱(IR)、热失重分析(TGA)、X射线衍射(XRD)和力学测试等手段对复合凝胶的结构和性能进行了研究.研究结果显示在复合水凝胶中,虽然PAM自身没有交联,但由...     

CHARACTERIZATION OF BLEND ACRYLIC FIBER''''S STRUCTURES

The fine structures, paracrystal, porous and phase structures of blend acrylic fibers have bencharacterized using techniques based on X-ray diffraction, gas adsorption, density, electron and opticalmicroscopy, mercury penetration method and IR spectroscopic analysis. The existence of a fibril-void structure, with voids and fibrils of the order of 10~2.to 10~3A diameter has been confirmed for thewet-spun blend fibers. It was found that the blend acrylic fiber in the present work is a kind of ma-trix-fibril fiber; phase separation takes place in it. Further studies about the effects of composition andsequence distribution of copolymers on structure of the blend fibers were made; and it was discoveredthat void volume in the blend fibers largely depends on the interface area between two polymer phases,and pore size and number on the particle size and number of the dispersing phase. An appropriatestructural model about the blend fibers has been described.     

凝固浴温度对纤维素中空纤维膜结构及气体渗透分离性能影响研究

利用新型溶解工艺,在不同的凝固浴温度(0～60℃)下制备了纤维素中空纤维膜,考察了凝固浴温度对纤维素中空纤维膜结晶结构、机械性能和气体渗透分离性能的影响.扫描电镜表征表明凝固浴温度的升高使得纤维素中空纤维膜更加疏松,并且内侧的指状孔变大变多;膜的机械性能随凝固浴温度的升高而变差;XRD谱图显示凝固浴温度对纤维素中空纤维...     

THERMAL ANALYSIS OF ACRYLIC FIBERS

This is a comprehensive survey of our work during the past thirteen years on the thermal analysis of acrylic fiber, including some recent, unpublished results.     

SYNTHESIS AND CHARACTERIZATION OF COMB-SHAPED POLYBUTADIENES

Polybutadiene (PB) was chlorinated with t-BuOCl without chain crosslinking and degradation togive chlorinated polybutadiene (Cl--PB) with active allylic chlorine atoms on the backbone. Comb-shaped PB was prepared by coupling of Cl--PB with "living" PB anions in a mixed solvent of cyc-lohexane and tetrahydrofuran. Characterization by GPC and osmometry showed that purifiedproducts were welldefined comb-shaped PB composed of low polydispersity backbone chain andrandomly distributed grafts of uniform length. The averagr number of branches could be variedin a wide range to meet the needs of structure-properties relationship studies.     

ORIENTED TEXTURE OF MESOMORPHIC SOLUTIONS OF CYANOETHYL CELLULOSE/DIMETHYL ACETAMIDE

Textures of the oriented mesomorphic solutions of cyanoethyl celluloss/dimethyl acetamide were studied by polarized light microscopy, small angle light scattering and depolarized light transmission. If the mesomorphic solutions were sheared, they could form the band-like texture. Molecular chains in the solutions highly oriented almost along the shear direction. But the orientation directions of the molecular chains in the bands neighbouring each other were slightly different.