在烃类溶剂中制备丁基橡胶的研究

<正> 关于多分散性对丁基橡胶加工行为的影响,有人进行了研究,近年来人们对丁基橡胶的分子量分布与加工性能的研究,又有新的报道,结果表明,丁基橡胶的分子量分布对其加工时收缩变形有很大的影响,我们曾用过渡金属卤化物和卤代烷基铝-加氢汽油催化体系合成了丁基橡胶,但在加工时收缩率大和不均匀,我们利用高聚物沉淀分级原理,在烷烃溶剂中添加氯代烃(CH_2Cl_2,CH_3Cl),混合溶剂制备的丁基橡胶,其分子量分布及加工收缩性能比单用汽油溶剂时有显著改进,其综合性能基本上达到了Polvsar 301水平。     

高聚物分级的基本研究 Ⅰ.分级曲线的绝对评价问题

对四个聚甲基丙烯酸甲酯级分用混合级分法分别进行淋洗柱分级和沉降速度法测定分子量分布的研究,以混合级分的分子量累积分布是否与单一级分累积分布的加和符合,作为分子量分布曲线绝对评价的判据.淋洗柱分级采用苯-甲醇体系,超速离心沉降在丙酮-乙醇体系的θ-温度附近测定.实验结果说明,混合级分的淋洗柱分级曲线与加和曲线比较,显得分子量分布偏窄,分子量小的部分低估,分子量大的部分高估;而用沉降速度法所得混合级分的分子量分布曲线则与加和曲线相符,因此可以用后法所得分子量分布曲线作为评价淋洗柱分级曲线的依据.可以认为淋洗柱分级曲线基本上真实反映试样的分子量分布,但是如用通常方法画出累积分布曲线,则使分布偏窄,对试样中高分子量尾端大大低估.因此如何用分级法分成较少的级分,而对分级数据作出更合理的处理,值得作进一步的研究.     

顺丁橡胶分子结构参数对其浓溶液流变性质的影响

对顺丁橡胶浓溶液作了较为深入的研究,主要讨论了分子量分布和支化因子与顺丁橡胶浓溶液流动行为的关系。用倒沉淀分级的方法进行了大量分级,得到分子量分布较窄的试样;对这些试样用GPC-自动粘度计联用的方法测定了分子量、分子量分布和支化因子,同时用同轴圆筒式粘度计及落球方法测定了这些试样的浓溶液粘度。     

高聚物的柱上溶解分级

高分子的分级是目前研究高聚物分子量分布的主要方法,但一般所用分级沉淀法费时甚久,往往需要三、四个星期完成一次实验,Fuchs用高聚物薄膜溶解分级的方法,可以在一天内得到分级曲线。本工作试用柱上溶解分级法测定了一个硝化纤维素试样([η]=379)的分子量分布,溶剂沉淀剂体系用丙酮-水,并与普通的分级沉淀法所得结果比较,两者是符合的如图1.实验所需试样约0.5克,可以在12小时内完成分级手续,分级损失极小,可以认为柱上溶解法是一个简单可行的良好分级方法。但是有一点值得指出溶解分级法所得最后几个级分往往[η]值较小,有次序倒置的现象,我们怀疑是否由于硝化纤维素含氮量不均一的影响,但     

醇酸树脂热炼过程中分子量分布的研究

<正> 涂料工业中醇酸树脂基料分子量分布的研究,通常采用萃取分级法和沉淀分级法,近年来发展了高速凝胶色谱法。我们曾报道了高效GPC法测定醇酸树脂的分子量分布的方法。本文就醇酸树脂热炼过程产物作了物性表征和研究。 实验所测试样系取自5吨反应釜热炼生产中酯化过程各阶段和反应终点的产物。各品种醇酸树脂的配方见表1。     

乙烯基单体／N-苯基马来酰亚胺共聚物组成分布测定原理及应用

共聚物分子量往往根据溶液性质来测定 ,而组成变化对高分子溶液的性质有影响 .如果共聚物组成不随分子量而变化 ,则认为组成分布均匀 .用化学或光谱方法得到的共聚物组成只是一个平均值 ,不能完全表征组成分布情况 .根据溶液性质差异进行分级 ,需选择合适的溶剂 沉淀剂体系 ,且操作时间长 .采用薄层色谱法所需时间亦长 ,且由于存在扩散效应而掩盖真实的共聚物组成分布 .自从凝胶渗透色谱 (ＧＰＣ)出现后 ,将紫外吸收光谱 (ＵＶ)或红外吸收光谱仪与示差折光仪 (ＤＲ)串联 ,一个对组成敏感 ,一个对浓度 (共聚物总量 )敏感 ,将组成变化和分子量…     

小角激光散射法研究聚苯基喹噁啉在稀溶液中的缔合现象

聚[2,2’-(1,4-苯撑)-6,6’-双(3-苯基喹噁啉)](PPQ)是一种耐高温材料,其合成方法、机械性能及应用方面的研究已有很多报道,但是有关其溶液性质和分子形态的研究还甚少。我们用小角激光散射法研究了PPQ的稀溶液性质。本文报道PPQ在溶液中的缔合现象。实验 PPQ试样由本系孙猛提供。以体积比为3比2的四氯乙烷-苯酚混合溶剂为良溶剂,正庚烷为沉淀剂对样品进行分级,所得狭分布样品按分子量由大到小排列,依次记为PPQ-1,PPQ-2和PPQ-3。     

分子量分布对双烯类聚合物粘弹性能的影响—Ⅰ.分子量分布对顺-1,-4聚丁二烯粘弹性能的影响

本文采用沉淀分级和溶液混合的方法制备分子量相近但分子量分布不同的顺-1,4-聚丁二烯样品,通过凝胶渗透色谱(GPC)和应力松弛的方法,研究分子量分布宽度对生胶粘弹性能的影响,并考察低分子量级份对缠结网络密度的作用和高分子量级份对生胶粘弹性能的影响。结果表明,聚合物本体的稳流切变粘度对分子量分布最为敏感。随分子量分布的变宽,低分子量级份增多,缠结网络密度变小,当高分子量级份增加时,生胶的弹性记忆效应加强。     

聚对羟基苯甲酸酯分子量分布的理论研究

本文从理论上研究了聚对羟基苯甲酸酯(简称PHB或PHBA)的分子量分布。理论分析表明,由对羟基苯甲酸酯缩聚制得的PHB的分子量分布与Flory分布稍有不同,可以认为是修正的Flory分布;而由对羟基苯甲酸制得的PHBA仍可用Flory分布表征。由于未发现上述聚合物的溶剂,故不可能对其分子量分布进行实验研究。     

分子量分森的简易测定与分级数据的处理

本文对作者等以前提出的应用溶度函数的简易分级法,和应用董履和函数处理沉淀分级数据作了进一步的简化和考验。用在良溶剂和θ溶剂中测定两个特性粘数值来决定 级分的分布参数,在一般的实验条件下不可能达到所要求的精确度,因此改用分相参数Q=R的近似来决定简易分级法中两个级分的分布参数,实际的计算说明Q的取值可以有相当大的变化范围而对结果的影响不大,这样对简易分级法提供了一个简便的权宜办法。对应用董履和函数计算普通分级法的分级数据时,除第一级分和最后级分外,其他各级分的累积分布均可采用直綫近似,此直綫通过M(I=1/2)=(?)_η,M(I=0)=1/2(?)_η两点,可以简省计算,而对结果的影响极小。本文中对一个聚甲基丙烯酸甲酯试样的两种分级数据进行计算的结果,说明上面两种方法都比习惯应用的Schulz-Dinlinger法计算结果更接近于用沉降速度法测定的分子量分布。     

等规聚苯乙烯的分子量分级

Fractionation of isotactic polystyrene based on phase equilibrium was preformed by using o-dimethylphthalate (DMP) as a solvent and cyclohexanol (CHA) as a nonsolvent. Fractionation with semi-preparative GPC was also preformed. The effect of fractionation based on phase equilibrium is limited, but the result obtained from semi-preparative GPC is quite well.     

Analytical and semi-preparative HPLC enantioseparation of novel pyridazin-3(2H)-one derivatives with α-aminophosphonate moiety using immobilized polysaccharide chiral stationary phases

The direct HPLC enantioseparation of a novel series of chiral pyridazin-3(2H)-one derivatives with α-aminophosphonate moiety was performed on two immobilized polysaccharide chiral stationary phases (Chiralpak IA, Chiralpak IC) using n-hexane (n-Hex)/dichloromethane (DCM) mobile phase with 5% alcohol additive. Good baseline separation of the enantiomers was achieved using amylose tris-(3,5-dimethylphenylcarbamate) chiral stationary phases (Chiralpak IA) on analytical scale. The analytical method was further scaled up to semi-preparative loading to obtain small amounts of both the enantiomers of pyridazin-3(2H)-one derivative. The semi-preparative resolution of all compounds was successfully achieved with n-hexane/dichloromethane/ethanol (EtOH) as mobile phase using a semi-preparative Chiralpak IA column. The first fractions were isolated with purities of >99.9% (enantiomeric excess (e.e.), and the second fractions were obtained with purities of >98.2% (enantiomeric excess). The assignment of the absolute configuration was established for the F1 fraction of compound a-2 by single-crystal X-ray diffraction method.     

Comparison of the binary equilibrium isotherms of the 1-indanol enantiomers on three high-performance liquid chromatography columns of different sizes

The competitive isotherm data for the enantiomers of 1-indanol were measured on three columns, a microbore column (15 cm x 0.1 cm), a conventional analytical column (15 cm x 0.46 cm), and a semi-preparative column (20 cm x 1.0 cm), packed with Chiralcel OB. The sets of isotherm data measured on each one of these three columns could be fitted well by a bi-Langmuir isotherm model. The experimental elution band profiles of mixtures of the 1-indanol isomers were recorded on the three columns. The isotherm model, combined with the equilibrium dispersive model of chromatography, gave calculated profiles that are in excellent agreement with the experimental profiles in all cases investigated. It was found that the value of the inner diameter of the column is an important parameter in the calculation of the isotherm parameters from the measured isotherm data. In order to use isotherm data obtained on one column to account for the phase equilibrium on another one, the inner diameters of these columns must be measured accurately. The diameters of the three columns were all slightly off their nominal value. Without correction, an important systematic error was made on the isotherm data obtained with the microbore column while only negligible errors were made on the data obtained with the other two columns. After due correction for this effect, the relative difference between the isotherm data for the microbore and the semi-preparative column is still, on the average, about 10%, a difference that might be explained by the limited precision of the measurement of the microbore column diameter. The relative difference between the isotherm data for the analytical and the semi-preparative columns was about 1%, a reasonable value, since the two columns came from different batches of the same packing material.     

Comparison of analytical and semi-preparative columns for high-performance liquid chromatography-solid-phase extraction-nuclear magnetic resonance

The application of analytical and semi-preparative columns in reversed-phase liquid chromatography-solid-phase extraction-nuclear magnetic resonance (HPLC-SPE-NMR) was compared. The work was aiming at separating a higher sample amount in a single run and in this way to reduce the necessary NMR measurement time of separated compounds. Several parameters for compound separation and trapping procedures were optimised: flow rate of HPLC and make-up water pumps, choice of stationary phase cartridges and drying time. The separation and loadability of nine model compounds on analytical and semi-preparative columns was determined, as well as the focussing capacity of SH-type SPE cartridges. It was found that a semi-preparative column--or multiple peak trapping on analytical columns--gave better results than a standard 4.6mm analytical column for non-polar compounds (e.g. flavonoid aglycones, sesquiterpene lactones, non-polar terpenes, logP>2), but for polar compounds (logP<-2) did not offer any advantage over an analytical column, or was even disadvantageous. For intermediately polar compounds (-2相似文献   

Continuous chromatographic separation of a baclofen precursor (N-Boc-4-[p-chloro-phenyl]-2-pyrrolidone) in a simulated moving bed using a polysaccharide carbamate as chiral stationary phase

Liquid chromatography is known as one of the most flexible, efficient and cost-effective methods to resolve racemic mixture in order to attend the growing demand of the pharmaceutical industry for pure enantiomeric compounds. Cellulose tris(3,5-dimethylphenylcarbamate) is frequently used as a stationary phase for enantiomeric separations because of its attractive properties, including high enantioselectivity, high loading capacity and good mechanical stability. In this study, we investigated the usefulness of cellulose tris(3,5-dimethylphenylcarbamate) as the stationary phase and of ethanol and hexane mixtures as the mobile phases for the chromatographic separation of potential pharmaceutical intermediates. Using adsorption equilibrium data, we determined the optimal operational conditions for the separation of the N-Boc-4-[p-chloro-phenyl]-2-pyrrolidone enantiomers - a baclofen precursor - in a semi-preparative scale simulated moving bed unit. This unit was used to obtain high purity enantiomers on a scale of 1g/day. The outlet streams were analyzed by an on-line system that consisted of a UV-vis spectrophotometric unit, a polarimeter, and HPLC. Enantiomeric purities of up to 97% were obtained for the raffinate stream and up to 90% for the extract stream.     

Application of a new chiral stationary phase containing the glycopeptide antibiotic A-40,926 in the direct chromatographic resolution of β-amino acids

A new enantioselective HPLC procedure for the direct resolution of β-amino acids is described, based on the use of a new chiral stationary phase (CSP) containing the macrocyclic glycopeptide antibiotic A-40,926, structurally related to teicoplanin, covalently bonded to silica gel microparticles. The new CSP shows higher enantioselectivity and broader applicability in this field compared to the parent teicoplanin phase. The potential for semi-preparative separations on the A-40,926-CSP is demonstrated for a selected cyclic β-amino acid.     

半制备型液相色谱法分离纯化茶叶鲜叶中7种儿茶素类化合物

建立了从茶叶鲜叶中分离纯化7种儿茶素类化合物(没食子儿茶素(GC)、表没食子儿茶素(EGC)、儿茶素(C)、表没食子儿茶素没食子酸酯(EGCG)、表儿茶素(EC)、表没食子儿茶素3-O-(3-O-甲基)没食子酸酯(EGCG3"Me)和表儿茶素没食子酸酯(ECG))的半制备色谱法。铁观音鲜叶经甲醇超声浸提、浓缩、氯仿萃取后,向水相中加入碱式醋酸铅沉淀,得到茶多酚粗品。分别以甲醇-水、乙腈-水作为流动相,采用半制备色谱法纯化7种儿茶素类化合物,纯度均达到90%。此外,利用同样的方法分离纯化另外两种茶叶鲜叶中的7种儿茶素类化合物,得到相似的结果。该方法以溶剂提取、离子沉淀结合半制备色谱,适于简单、高效地同时分离制备多种儿茶素类化合物。     

Computer-assisted optimization for the selection of mobile phase in semi-preparative HPLC

A computer-assisted method is presented for optimization for the selection of mobile phasecomposition in semi-preparative HPLC.The optimization for the expected separation is based ona polynomial estimation from five preliminary runs.Statistical scanning technique was used foroptimization.Double criteria simulation system (DCSS) is established for chromatographic perfor-mance measurement in this method.The validity of the optimization strategy is confirmed by applyingit to a technical Cypermethrin separation.Excellent agreement is obtained between the predictedand experimental results.     

COMPARISON OF GPC AND THERMAL FIELDFLOW FRACTIONATION METHODS FOR LINEAR AND STAR BRANCHED POLYSTYRENE SAMPLES

The Thermal Field-Flow Fractionation (TFFF) method was used to determine the elution volumeof a series of star branched polystyrene having different number of arms but the same arm molecularweigh and polystyrene standards with narrow distribution whose molecular weight ranged from5.0×10~4 to 8.6×10~5. Results were obtained by measuring at two temperature difference (△T=30℃and △T=50℃in THF. The same star branched samples were measured by means of GPC method.Comparison of Vr-Mrelationships obtained from TFFF and GPC showed that the displacement of V_r-M curves for star and linear polystyrene is larger than that in GPC. This difference is caused by theentirely different mechanism of separation for these two methods. As the controlling factor is hy-drodynamic volume of the polymer chain in solution for GPC, it is the diffusion coefficient of polymermolecules for TFFF. The experimental results indicate that the influence of variance of chain struc-ture on diffusion coefficient is stronger than that on the hydrodynamic volume and that TFFF tech-nique may be used as a method for characterizing branching of polymer molecules. For this pur-pose a proper theoretical model and more accurate experiments are needed.     

Arginine as an effective additive in gel permeation chromatography

A major problem in gel permeation chromatography (GPC) or size exclusion chromatography is non-specific binding of applied proteins to the column matrix (stationary phase). We have tested an aqueous arginine solution as the GPC mobile phase on silica-based and polymer-based columns, using mouse monoclonal antibody and recombinant human activin, interleukin-6, basic fibroblast growth factor, and interferon-gamma as model proteins. We observed that addition of arginine to the mobile phase improves separation of the proteins and their soluble aggregates from the GPC columns, which suggests that arginine is an effective additive for the GPC mobile phase.