Universal calibration in GPC: A new approach for the calculation of molecular weights

A method has been developed for determining simultaneously the molecular weight of a broad-distribution polymer and the Mark-Houwink coefficients for that polymer type by using only GPC and intrinsic viscosity data. Standardized samples of poly(vinyl chloride), polystyrene, polybutadiene, and an experimental cycloolefin polymer were analyzed by this method. Shear-corrected intrinsic viscosities were used in all cases because of the high molecular weights involved. Molecular weight data for all samples were found to be in good agreement with molecular weight data obtained by membrane osmometry and from other GPC techniques. The proposed technique provides a means for calculating the molecular weight of a single polymer sample through universal calibration of GPC without knowledge of the Mark-Houwink coefficients for that polymer type.     

从特性粘数和GPC图谱获得重均分子量的新方法

本文提出了从未知样品的特性粘数和GPC图谱计算重均分子量的新方法,该方法可用于计算窄分布和宽分布的未知Mark-Houwink 常数的样品的重均分子量。用七个不同分子量和不同分布的实例验证了所提出的方法。结果与已知Mark-Houwink常数用普适校准法得到的结果一致。     

从特性粘数和GPC图谱获得数均分子量的新方法

本文提出了从未知K和a的样品的特性粘数和GPC图谱计算数均分子量的新方法。该法对窄分布或宽分布的样品都适用,并用不同分子量和分子量分布的样品进行了验证,和已知K和a的计算值进行比较,得到非常满意的结果。该法是计算M_n的近似解法,但计算简便。     

聚辛烯-1Mark-Houwink常数的确定及其分子量分布研究

本文用GPC结合特性粘度的方法,对聚辛烯-1四氢呋喃体系的Mark-Houmink常数进行订定。数据处理采用了Weiss法和流体力学平均分子量(?)_x两种方法,α值分别为0.701和0.625,相对误差10％左右,所得Mark-Hon-Wink方程Weiss法为:[η]_(THF)~(25℃)=3.89×10~(-4)[M]~(0.701)(?)_x法为[η]_(THF)~(℃25)=4.14×10~(-4)M~(0'625)。本文还研完了聚合反应条件对聚辛烯-1分子量及分子量分布的影响。发现三种TiCl_3为主催化剂,三乙基铝为助催化剂时,其GPC谱图均为双峰型,两个峰的比例随聚合反应条件不同而变化。表明聚合体系至少有两种不同性质的活性中心,有着不同的形成和增长速率。     

聚硅烷亚芳弹性体的凝胶渗透色谱测量

用简易GPC柱研究了在未知合适的Mark-Houwink 系数的情况下,通过GPC和特性粘度的数据,同时计算出宽分布硅烷亚芳弹性体聚合物的分子量和这种类型聚合物的 Mark-Houwink 系数的方法。装柱填料为多孔硅胶球,理论塔板数 4200—5500块/米以上,塔板高度 0.7—0.9毫米。其分子量分布宽度指数在2左右。素炼后,分子量分布变窄,分子量下降。     

Characterization of Copolymers and Polymer Mixtures by Gel Permeation Chromatography

Abstract

Estimation of molecular weights from GPC data is complicated when the polymer sample consists of a mixture of homopolymers or of statistical copolymers with nonuniform compositions. This is because sizes of solvated polymer coils depend on solvent interaction with both the homo-and hetero-units of the copolymers and because the extent of solvation of different homopolymers can differ. The overall degree of solvation may change effectively with composition and use of a single “average” set of Mark-Houwink constants in calibration procedures will then produce false molecular weight data from the GPC data. A new molecular weight average, M _x, is defined to overcome this problem. This average can be determined from the GPC chromatogram and intrinsic viscosity of the sample in the GPC solvent. Mark-Houwink coefficients are not needed. M _x lies between M _w and M _z.     

Molecular weight determinations by gel-permeation chromatography and viscometry

The hydrodynamic volume concept can be used effectively with gel-permeation chromatographic (GPC) and viscosity data to estimate the molecular weight of a variety of polymers. Agreement is within ±5–10% of the absolute values and thus is satisfactory for many purposes. An iterative computer technique and a method developed by Funt and Hornof for analyzing GPC–viscosity data were found to be equivalent with respect to estimating the molecular weights for the five cases studied. The latter is easily employed but restricted to the case where the sample of interest and the GPC calibration standards have approximately equal Mark-Houwink parameters. Since GPC measurements are commonly performed in thermodynamically good solvents, the general applicability of the method is not impaired. Using the unperturbed dimensions of the polymer chain to estimate the molecular weight of a variety of polymers was not as satisfactory as the above techniques. This approach generally gave biased molecular weight values (consistently low or consistently high). Agreement with the absolute values ranged from 10 to 30%. We therefore believe that either of the techniques based on the hydrodynamic volume concept can be used more effectively to estimate the molecular weight of a series of polymers than the treatment based on the unperturbed dimension.     

On the number-average molecular weight of poly(1,4-trans isoprene) determined by conventional GPC

We became aware, in the course of our on-going research, that the number-average molecular weight of poly(1,4-trans isoprene) determined by conventional gel permeation chromatography (GPC) in tetrahydrofuran (THF) using polystyrene standards differs from its true value by a factor 2. As far as we know, the Mark-Houwink coefficients of this polymer in a widespread GPC eluent such as THF have never been determined. We provide in this contribution a simple relationship between the number-average molecular weight of poly(1,4-trans isoprene) determined by GPC in THF using polystyrene standards and its true value.     

高聚物各种平均相对分子质量的绝对测定——GPC和特性粘数法

从GPC数据和特性粘数能较准确迅速求出高聚物的数均、粘均、重均、Z均相对分子质量及相对分子质量与特性粘敷关联参数。该方法经聚甲基丙烯酸甲酯验证后,用其表征了聚碳酸亚乙酯(PEC)和聚碳酸亚丙酯(PPC)。     

Polymer characterization by coupling gel-permeation chromatography and automatic viscometry

A method is proposed for use of the universal calibration curve, i.e., the product of molecular weight and intrinsic viscosity versus retention volume, in calculating the molecular weight distribution of a polymer from gel-permeation chromatography (GPC) when the Mark-Houwink relation of the polymer in the solvent used for the GPC is unknown. This is achieved by measuring the viscosity of each fraction with an automatic capillary tube viscometer. Application of this technique to poly(vinyl chloride) and poly(vinyl acetate) proved to be successful.     

聚乙酸乙烯酯的溶液性质及长链支化度

用粘度法,GPC和LALLS测定了线型及不同转化率的PVAc分级级份的粘度与分子量。提出了以线型和支化聚合物的K,α计算临界分子量的方法。讨论了表征PVAc长链支化的各种参数与分子量和转化率之间的关系以及不同条件下迭代法计算的支化频率λ的差异。实验结果表明,特性粘数和数均分子量乘积所表示的流体力学体积更适合GPC的普适标定概念。     

GPC-多检测联用技术测定聚己内酯分子量及其分布

介绍一种用于生物可降解高分子材料聚已内酯(PCL)及其改性高分子的分子量和分子量分布测定的GPC-示差折光(RI)-示差黏度(DV)-直角光散射(RALLS)多检测联用技术.叙述了该方法的实验原理,并对测试过程中的有关技术及实验结果进行了讨论.该方法可准确测定聚己内酯(PCL)及其改性高分子的分子量及其分布、特性黏度分布、Mark-Houwink方程系数以及高分子尺寸等重要参数.通过对窄分布PS标样验证,分子量测定结果的相对误差在1%之内.     

Universal calibration in GPC

The M[η]-elution volume calibration curve for gel-permeation chromatography (GPC) is based on the implicit assumption that the hydrodynamic volume of a solvated polymer species in the GPC columns is that which pertains at infinite dilution. This is not true of highly solvated high molecular weight fractions and results in apparent failure of this calibration in some instances. A model is presented to estimate hydrodynamic volumes of polymers at finite concentrations. The parameters required are polymer concentration, molecular weight, amorphous density, and the Mark-Houwink constants for the particular polymer–solvent combination. The calculated log (hydrodynamic volume)–elution volume relation provides a universal GPC calibration. The model accounts for the occasional shortcomings of the infinite dilution calibration and is essentially equivalent to it in noncritical cases. The use of the proposed calibration method is illustrated.     

凝胶渗透色谱测定涤纶分子量分布

<正> 凝胶渗透色谱(GPC)是测定高聚物分子量分布的一种重要工具.GPC用于涤纶(PET)分子量分布的测定,所见报导不多,例如Sham以135—110℃,用间甲酚为淋洗液进行涤纶分子量分布测定.由于PET在高温的极性溶剂中易产生水解和酯交换反应,因此在样品的溶解和GPC的分析过程中必须采用氮气保护等措施,否则不能反映其真实分子量分布.Paschke等发展的溶剂体系,在室温,以硝基苯-四氯乙烷混合溶剂为淋洗液,此法虽可避免PET的降解,但在样品的配制过程中需用高温过滤设备和示差折射计操作比较麻烦.国内以苯酚-四氯乙烷为淋洗液,检测浊度.本文采用常温,新溶剂体系,以单一氯仿为淋洗液,测定涤纶的分子量分布.     

Determination of the viscometric constants for chitosan and the application of universal calibration procedure in its gel permeation chromatography

The viscometric constantsa andK in the Mark-Houwink equation were determined in 0.5 M acetic acid-0.5 M.sodium acetate solution for chitosan fractionated by gel filtration. The weight-average molecular weight of each fraction was measured by the light-scattering method. The values obtained area=0.59 andK=0.119 cm³ g^–1.The molecular weightsMw andMn for fractionated chitosan were measured by GPC. The value ofMw by GPC was much different from that by light scattering and, therefore, a universal calibration procedure was applied to the data by GPC. It was concluded that, also in the case of a cationic polysaccharide such as chitosan, the universal calibration procedure is effective for obtaining the reliable molecular weight by GPC.     

Polymerization of vinyl chloride with organolithium compounds. V. Fractionation and solution properties of high molecular weight poly(vinyl chloride)

A sample of high molecular weight poly(vinyl chloride) (PVC) was fractionated by classical precipitation fractionation and gel-permeation chromatography (GPC) on a preparative scale. The fractions thus obtained were characterized by light scattering, viscometry, and by the GPC method. The measured weight-average molecular weights M?_w, intrinsic viscosity [η], and polydispersity index M?_w/M?_n values were used for the determination of the Mark-Houwink equation, [η] = KM^a, for PVC in cyclohexanone (CHX) at 25°C valid for molecular weights from 100,000 to 625,000.     

稀土三元催化体系合成聚异戊二烯的溶液性质

本文用粘度法,膜渗透压,GPC和光散射法研究了稀土三元催化体系合成的顺式1,4-聚异戊二烯(PIP)的溶液性质。结果表明这种聚合物的分子结构是线性的。测定了甲苯、氯仿、四氢呋喃和正己烷中的Mark-Houwink方程的参数K_w和α,PIP各参数的GPC实验曲线与从对数正态分布函数计算的理论曲线一致,从对数正态分布的多分散改正因子q_w,求得单分散的[η]-M关系式。从光散射得到的均方根末端距与用Flory关系式计算的值一致。用Stockmayer和Fixman方法求得的无扰均方根末端距与文献值基本一致。     

Solution properties of polyurethane

Polyurethane was fractionated and the fractions were characterized by gel permeation chromatography (GPC) and viscometry. The intrinsic viscosities of polyurethane in ten solvents varying in their polarity were determined and are in the order of mineral spirit < acetone < cyclohexane < cyclohexanone < xylene < ethyl benzene < toluene < benzene < methyl ethyl ketone < tetrahydrofuran. The Mark-Houwink relations suggested that solvent blend MEK: n-heptane (1:3) is a poor solvent with an a value of 0·52 and tetrahydrofuran is a good solvent with an a value of 0·78. The weight average molecular weight has been estimated by an extrapolation technique based on a linear relationship between the viscosity average molecular weight _v and the Mark-Houwink constant. The weight average molecular weights obtained from viscosity studies were used to evaluate the unpertureb dimension of the chain.     

Gel Permeation Chromatography of Polyethylene Terephalate

Abstract

This paper describes the development of the gel permeation chromatography (GPC) technique for the measurements of cyclic trimer content, molecular weights, and molecular weight distribution of polyethylene terephthalate (PET), utilizing a solvent system of o-chlorophenol-chloroform. Mark-Houwink constants for this solvent system are also described.

The GPC technique was applied to the study of the cyclic trimer content, molecular weights and molecular weight distribution of a variety of commercial PET resins. The results indicate that the cyclic trimer content in PET is dependent on molecular weight, polycondensation process and catalyst system. Solidstate polymerized PET contains less cyclic trimer than PET made by the melt-phase process of the same molecular weight. The cyclic trimer content in solid-stated PET appears to be dependent on the conditions of solid-state polymerization.

The polydispersity index determine for a variety of PET samples is higher than the theoretically predicted value of 2.0; however, there is no systematic dependence on molecular weight or polycondensation process.     

Evaluation of long chain branching of polyphenylene sulfide using gel permeation chromatography with triple detection

The increasing polyphenylene sulfide (PPS) world demand due to its unique mechanical and chemical properties has augmented the pressure on development of analytical methods to evaluate its molecular weight distribution and structure. This article presents gel permeation chromatography with triple detection (GPC3D) performed in chloronaphthalene at 210°C on a commercially available instrument as a possible method to elucidate the structure properties of linear and branched PPS. The procedure allows measurement in a single run of the true molecular weight distributions and intrinsic viscosities, the Mark-Houwink parameters, and the number of long chain branches.