关于聚电解质浓溶液的粘度-浓度幂律方程中指数(α)的探讨

在含有0.07 mol NaNO_3外加盐和无外加盐的二甲基甲酰胺/甲苯(体积比:3/1)的两类混合溶剂中,采用RN50-1型落球粘度仪研究了不同磺化度(IEC=0～0.93mmol/g)的磺化聚砜(S-PSF)浓溶液的零剪切粘度(η)-浓度(C)的幂律关系式,η=K·C~α。实验结果显示:磺化度不同的试样在舍有外加盐溶剂中的指数(α=4.29～3.52)值均分别大于无外加盐溶剂中的指数(α=4.09～3.03)值,且它们都随试样磺化度的增加而下降。文中,应用标度的分析方法对浓度指数(α)的变化规律作了解释。     

STUDIES ON THE SORPTION OF MACROPOROUS PHOSPHONIC ACID RESIN FOR LANTHANUM

The influences of Medium pH,sorption temperature,sorption time,etc.on the sorption capacity of macroporous phosphonic acid resin for La^3+ were determined.The sorption rate constant was k298=7.64×10^-5 s^-1. The complex ratio of phosphonic groups of the resin to La^3+ was 3:1.The basic sorption parameters were determined. The sorption mechanism of macroporous phosphonic acid resin for La^3+ was examined by chemical analysis and IR-spectrometry.     

REMOVAL OF GLUCORAPHENIN FROM THE EXTRACT OF RADISH PIGMENT BY ANION EXCHANGE RESIN 201×7

A method for removimg glucoraphenin from the extract of Radish pigment by anion exchange resin 201×7 was studied.The adsorption capacity of 201×7 resin for glucoraphenin was 72.8mg/ml resin,the equilibrium time 55 minutes,and the optinum pH5.5.All glucoraphenin that had been adsorbed on 201×7 resin was eluted by 1.5BV.hr^-1, eluent in whinc concentration of NaOH was 0.05mol·L^-1 at the flow rate of 1.5BV/h.Extracting solution of deglucoraphenin was enriched by vacuum and spray drying.A powder product of Radish pigment was obtained and E1cm^1%=4.30.     

Sulfonated and sulfoacylated poly(styrene-divinylbenzene) copolymers as packing materials for cation chromatography

Three different types of cation exchangers were produced from four basic poly(styrene-divinylbenzene) substrates with different properties. Porous PS-DVB resin beads were functionalized by sulfonation and sulfoacylation under various conditions to produce sulfonated resins with exchange capacities of 0.03-1.80 mM g(-1). The matrix with 50% of cross-linking is most suitable for updating by the proposed technique. Sulfuric and chlorosulfonic acids were used as the reagents for sulfonation. The sulfonating conditions, capacities, and the technique of the synthesis are given. The effects of parameters of the sulfonation reaction and the composition of the reactionary mixture on ion-exchange capacity of the sorbents were investigated. Selectivity and efficiency of the separation of some inorganic cations and derivatives of amines and hydrazines on the resins obtained are compared by ion chromatography with conductometric detection. As a result, the sulfoacylated resin was proved more efficient for the separation of these analytes. The resolution of the analytes strongly depends on the degree of functionalization. The best performance about 19,000 plates m(-1) was obtained using the sulfopropionylated beads with an ion-exchange capacity of 0.3 mM g(-1). The prepared sulfoacylated cation exchanger was compared with the commercially available Dionex CS-12 packing material. It was found that the separation of alkaline ions and 1,1-dimethylhydrazine (UDMH) were much better that those for the commercial material.     

磺化间规聚苯乙烯的表征

间规聚苯乙烯(sPS)是一种新型结晶性工程塑料,熔点达270℃,具有结晶速度快、耐热性好、耐化学腐蚀性优良等特点,可广泛用于汽车、电子、机械等行业,极具开发意义,但是由于sPS脆性大,抗冲击性差,故通过化学改性在sPS的苯环上引入极性基团,用于制成共混合金与复合材料,是提高材料韧性,开拓sPS用途的重要途径。     

高交联大孔苯乙烯-二乙烯苯共聚物的磺化反应

研究了高交联大孔苯乙烯－二乙烯本共聚物在有溶胀剂和无溶胀剂条件下,反应温度、 反应时间及共聚物合成时所用致孔剂对其磺化反应的影响．结果显示,当磺化反应在不同溶胀 剂介质中进行时,共聚物的交换容量随交联度变化可是现不同的关系．与低交联大孔共聚物（交 联度７％）比较,高文联大孔共聚物（交联度６０％）磺化反应速度更快,反应能在低得多的温度下 进行,同时溶胀介质对磺化产物的交换容量的影响变得很小．６０％交联的共聚物于３５Ｃ反应３ｈ, 可获得接近于表面磺化的产物．     

Synthesis of sulfonated poly(diphenylacetylene)s with high CO2 permselectivity

High‐molecular‐weight poly[1‐phenyl‐2‐(4‐t‐butylphenyl)acetylene], poly[1‐phenyl‐2‐(4‐trimethylsilylphenyl) acetylene], and their copolymers were synthesized by the polymerization with TaCl₅–n‐Bu₄Sn. The obtained polymers were sulfonated by using acetyl sulfate to give sulfonated poly(diphenylacetylene)s with different degrees of substitution. The degrees of sulfonation of poly[1‐phenyl‐2‐(4‐t‐butylphenyl)acetylene] and copolymers were in the range of 0.57–0.85. When poly[1‐phenyl‐2‐(4‐trimethylsilylphenyl)acetylene] was sulfonated, the sulfonated poly(diphenylacetylene) with the highest degree of sulfonation was obtained among all the polymers in this study. Its degree of sulfonation was 1.55. All the sulfonated polymers exhibited high CO₂ permselectivity, and their CO₂/N₂ separation factor were over 31. The sulfonated poly(diphenylacetylene) with the highest degree of sulfonation showed the highest CO₂/N₂ separation factor of 75. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6463–6471, 2009     

Preparation of silica-based cation-exchangers for use in ion chromatography

Summary A low exchange-capacity, silica-based cation-exchanger for use in ion chromatography has been synthesized. (p-Trimethylsilyl)benzyl-dimethylchlorosilane (TBDCS) reacts with trimethylsilyl chlorosulfonate (TMCS) to produce a compound sulfonated in the para position of the type ArSO₂OSi (CH₃)₃, which is bonded to 5 μm porous silica beads and hydrolysed to the corresponding arylsulfonic acid. The product is hydrophilic and has a high degree of sulfonation, efficiencies of packed columns reaching about 40,000–50,000 plates per meter for the separation of the Mn²⁺ ion. The new stationary phase has been applied to the ion chromatography of some organic and inorganic ions. It is notable that 14 lanthanides can be separated by isocratic elution about one hour on a 150×4·6 mm column, with 4 mM ethylenediamine and 6 mM α-hydroxyl-isobutanoic acid (pH 3.67) as mobile phase. The work was supported by the National Science Foundation of China.     

Pervaporation separation of water/ethanol mixture by sulfonated polysulfone membrane

For dehydrating a water/ethanol mixture by pervaporation, a sulfonated polysulfone membrane was prepared. The separation performance of water and ethanol are shown to strongly depend on the degree of substitution of polysulfone membrane. The degree of substitution increased with increasing chlorosulfonic acid in the casting solution, and the substitution reaction was achieved within 2 h. The water permeation rate and separation factor increased with increasing substitution of polysulfone membrane up to a substitution of 2.0. The effect of sulfonation on separation performance was due to the improvement of hydrophilicity of sulfonated membrane. It was found that the solubility of water/ethanol in the membrane was not the dominant factor for separation but it was rather the diffusion difference in the membrane. The diffusion difference between permeate through sulfonated membrane was the dominant factor for separating the water/ethanol mixture. The high performance of pervaporation membrane can be prepared by sulfonated polysulfone.     

Controlled drug release studies of atenolol using differently sulfonated acryloxyacetophenone and methyl methacrylate copolymer resins as drug carriers

2-Acryloxyacetophenone(AAP) was prepared and subjected to suspension polymerization with methyl methacrylate(MMA) using azobisisobutyronitrile(AIBN) as free radical initiator.The differently sulfonated AAP-MMA cross-linked copolymer cationic exchange resins were prepared by sulfonation with concentrated sulphuric acid at 70 °C.Several characteristics of the prepared resins were evaluated,i.e.FTIR,the ion-exchange capacity(IEC),thermo gravimetric analysis(TGA),particle size distribution and microscopic morphology.The resin characteristics were altered with degree of sulfonation,providing that differently sulfonated resins could be prepared.The behavior of atenolol(ATL) loading and in vitro release in the USP stimulated gastric and intestinal fluids of the obtained resins were evaluated.The drug loaded in the resin increased with increasing degree of sulfonation and hence the drug binding site in resin employed.The drug release was lower from the resins with higher content of sulfonic group due to the increase in the diffusive path depth.The drug release was a little lower in stimulated gastric fluid(SGF) than in stimulated intestinal fluids(SIF).The basic groups,ionized to a little greater extent in SGF and preferred binding with the resin rather than releasing.Hence,the differently sulfonated resins could be utilized as novel carriers for drug delivery.     

Improvement of thermal stability of sulfonated polyphosphazenes by introducing a self‐crosslinkable group

We prepared sulfonated polyphosphazenes having various aryloxy substituents, and studied their thermal stabilities and membrane properties. Sulfonated polyphosphazenes were synthesized by the reaction of polydichlorophosphazene with sodium aryloxides and subsequent sulfonation with fuming sulfuric acid. With increasing the degree of sulfonation, the polymers showed higher proton conductivity, but suffered more from swelling in an aqueous solution. We introduced a hydroxymethylphenoxy group onto the phosphazene backbone as a self‐crosslinkable group by reaction of poly(dichlorophosphazene) and a sodium salt of 4‐hydroxymethylphenol. When a film of a sulfonated polymer having a methylol group was heated at 80 °C under vacuum for 1 h, it became insoluble in NMP, indicating the formation of a network structure. We investigated the crosslinking reaction of the polymers by DSC and FTIR. The crosslinking reaction proceeded only in the sulfonated polymers. Because the sulfonated polymers provide acidic protons, the methylol groups became more electrophilic and reacted with neighboring aromatic rings. A condensation reaction between themselves could also occur. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5850–5858, 2008     

Preparation and characterizations of asymmetric sulfonated polysulfone membranes by wet phase inversion method

This paper presents an original approach to prepare the asymmetric sulfonated polysulfone membranes by using wet phase inversion method and their applications for dehydrating a water/ethanol mixture by pervaporation. The separation performances of sulfonated membranes were strongly affected by the degree of sulfonation and the degree of swelling of membranes. The substitution degree of sulfonic group enhanced the permselectivity of sulfonated polysulfone membranes by increasing the hydrophilicity of polymer backbone. Based on the observations of membrane morphology and light transmittance measurements, the degree of sulfonation of polysulfone presented less influence on the membrane formation pathway and the final structure of membrane in wet phase inversion process. It was also found that the sulfonated membranes showed well hydrophilic properties and facilitated water adsorption in the membranes. The sorption and permeation properties also showed that the permselectivity of asymmetric membrane was dominated by the permeate diffusion rather than the permeate sorption in the skin layer. The high separation performance of pervaporation membrane can be achieved by phase inverse method with sulfonated polysulfone.     

天然植物中生物碱的提取及树脂法在其纯化中的应用

总结了近期提取和分离纯化方法在天然植物中生物碱类有效成分研究中的应用,特别是对于吸附树脂法在生物碱纯化中的应用进行了系统综述,归纳了具有不同结构的大孔吸附树脂、凝胶型离子交换树脂和大孔型离子交换树脂对生物碱纯化效果的影响规律,进而为高效、高选择性纯化生物碱的专用吸附树脂结构设计和应用提供了可借鉴的研究思路.     

不同软段结构的双离子型聚氨酯离聚体

本文讨论了以聚环氧乙烷(PEO)、聚环氧丙烷(PPO)以及聚丁二烯(PBD)为软段,以4,4’-二异氰酸二苯甲烷(MDI)和N,N-二羟乙基甲胺(MDEA)为硬段的链段型聚氨酯的合成。并通过MDEA中的第三胺与Υ-丙磺内酯反应,转化为双离子型离聚体。用差示扫描量热、红外光谱、动态力学性能以及应力-应变等实验方法研究了化学组成和氨磺化程度对材料相分离程度,力学性能和形态结构的影响。结果表明,离子化后的材料力学性能有很大的改善。对PBD为软段的材料,离子化只能提高硬段“微区”的内聚能,而对PEO、PPO为软段的材料,还能大大提高软、硬相的相分离程度。     

SULFONATION OF A NEW POLYETHERETHERKETONE PREPARED FROM PHENOLPHTHALEIN

A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with concentrated sulfuric acid. Degree of sulfonation can be regulated by controlling the temmperature and time of sulfonation. The characterization of the sulfonated PEK-C in sodium salt form has been made by IR, ~1H NMR and ~(13)C NMR etc. It is shown that the sulfonation appears to take place exclusively in the ortho position to phenolic ether of phenolphthalein unit. The result is in agreement with theoretical deduction. Some properties of the sulfonated PEK-C, such as solubility, transition temperature, thermal degradation and hydrophilicity have also been discussed.     

Sulfonated Polyetherimide and Its Membranes

Polyetherimide(PEI) was sulfonated by chlorosulfonic acid for the first time. The sulfonated products were characterized by FT-IR, DSC, ion exchange capacity and water sorption measurement. The hydrophilicity of PEI was improved by the sulfonation. The PEI was blended with the sodium salt from of sulfonated PEI(SPEI) to prepare microporous membranes. The morphologies of the membranes were studied with Scanning Electron Microscope (SEM).     

磺化壳聚糖的制备及其对生长因子活性的保护作用

以壳聚糖为基材,分别以氯磺酸、三甲胺.三氧化硫和丙磺酸内酯为磺化试剂,制备了3,6-O-磺化壳聚糖(OCS)、2-N-磺化壳聚糖(NCS)和2-N-磺丙基壳聚糖(PCS)3种磺化壳聚糖.采用红外光谱、核磁共振谱证明了磺化壳聚糖的结构,元素分析测定了磺化壳聚糖的磺化率.以组织修复过程中一种重要的活性因子——碱性成纤维细胞生长因子(bFGF)为目标因子,通过体外成纤维细胞培养实验,评价了不同磺化壳聚糖对bFGF活性的保护能力.结果显示,相对于未改性壳聚糖(CS),磺化壳聚糖对成纤维细胞的形态无显著影响.细胞活性检测结果显示,OCS和PCS对bFGF活性无明显的保护能力;NCS能有效提高bFGF促进成纤维细胞活性的能力,其对bFGF活性的保护能力可达肝素70%左右.磺化壳聚糖的bFGF活性保护能力不随磺化率的改变而变化.     

Sulfoacylated poly(styrene-divinylbenzene) copolymers as resins for cation chromatography. Comparison with sulfonated, dynamically coated and silica gel cation exchangers

Most important properties of an ion chromatographic resin are influenced by the resin matrix, the type of functional group and the ion-exchange capacity. Highly crosslinked PS-DVB resins of 5 microm diameter have been functionalized by sulfoacylation, by sulfonation and by dynamic coating over a wide range of exchange capacities. These materials allow a study of the influence of different ion-exchange sites and capacities. The influence of the degree of functionalization on resin performance is completely reverse for sulfoacylated and sulfonated resins. The HETP values for all observed analytes (Cu, Pb, Zn, Ni, Co, Cd, Mn, Ca, Mg) in a tartaric acid elution system decrease for sulfoacylated resins with increasing capacity, for sulfonated resins with decreasing capacity. The performance of sulfoacylated exchangers is better than for dynamically coated ones and far better than for sulfonated resins. The performance of silica gel based cation-exchangers such as BioSil CAT is in most cases better than observed for sulfoacylated resins.     

竹浆黑液高效减水剂的结构表征及吸附研究

研究了竹浆黑液混凝土高效减水剂(GCL1-JB)的结构和吸附特征.将GCL1-JB先通过超滤和离子交换树脂提纯,再通过凝胶柱层析分级,然后选择4种窄分子量分布的GCL1-JB级分进行结构表征和吸附研究.结果表明,GCL1-JB具有高分子量和高磺化度的结构特征.不同分子量级分的GCL1-JB的化学分子结构相似,但其中磺酸基含量随着分子量增大而减少,而芳香环含量随着分子量增大而增大.GCL1-JB在阳离子表面能形成平整的自组装吸附膜,其中高分子量级分的GCL1-JB因磺酸基含量较低,分子较卷曲,故吸附量较大.     

Morphological studies and ionic transport properties of partially sulfonated diblock copolymers

The morphological behavior of partially sulfonated polystyrene-block-poly(ethylene-alt-propylene) (PS-PEP) membranes cast from tetrahydrofuran (THF) solutions were investigated by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM).The uptakes of methanol and water increase as the sulfonation degree increases, the methanol uptake being overwhelmingly greater than the water uptake. The conductivity increases almost exponentially with increasing sulfonation degree of polystyrene units. Clusters of sulfonated units that are formed in the solution used for casting membranes persist in the solid state after evaporation. In contact with water, swelling of the membranes proceeds predominantly in these clusters. The original lamellar morphology of the diblock copolymer is progressively deformed with increasing degree of sulfonation by the presence of the clusters containing ion-rich sequences of sulfonated polystyrene blocks.