The Fractionation of Copolymers by Chemical Composition

Abstract

Phase diagrams for the system of methyl ethyl ketone, cyclo-hexane, and styrene-acrylonitrile copolymer were determined. The phase diagrams indicate that the copolymer may be fractionated by chemical composition in this system. Discussions of the thermodynamics are also presented, to show that copolymers can effectively be fractionated into fractions of different compositions if a system can be found in which the difference between the Flory interaction parameters (x parameters) of two constituents of the copolymer with solvent is sufficiently large. Theoretically, the fractionation of copolymer must always occur to a certain extent, depending both on chemical composition and molecular weight. The composition fractionation results of styrene-acrylonitrile copolymers are given to confirm the discussions.     

Simultaneous Deconvolution of Molecular Weight Distribution and Chemical Composition Distribution of Ethylene/1-Olefin Copolymers Synthesized with Multiple-Site-Type Catalytic Systems

Summary: Ethylene/1-olefin copolymers synthesized with multiple-site-type catalytic systems typically exhibit broad molecular weight distribution (MWD) and chemical composition distribution (CCD). These microstrucral characteristics can be described by the presence of several active site types, each of which produces chains with distinct chain microstructures. In this work, a new approach to identify the number of active site types and chain microstructures produced on each active site type was developed based on simultaneous deconvolution of the bivariate MWD/CCD information. Chain microstructures produced on each active site type are assumed to follow Stockmayer's bivariate distribution. The proposed approach was validated with simulated data of model ethylene/1-butene and ethylene/1-octene copolymers.     

Chemical Composition Distribution of Multicomponent Copolymers

The number and weight chemical composition distributions in random terpolymers were derived using a statistical approach. The solution was then generalized to comprise higher multicomponent copolymers. The analytical solution was verified with Monte Carlo simulations and by considering limiting cases. Chemical composition distributions for fractions of random terpolymers of various kinetic chain lengths were also investigated. In a similar way to the results for binary copolymers described by Stockmayer's distribution, broadening of the distribution is observed for low‐molecular‐weight chains.

Comparison of chemical composition distributions from Stockmayer (Equation ( 3 )) and statistical approach (Equation ( 4 )).     

双亲三嵌段共聚物PEO-PPO-PEO在水溶液中相行为的理论研究

用自洽平均场理论的谱方法研究了双亲三嵌段共聚物PEO-PPO-PEO的分子量对其在水溶液相行为的影响. 理论预测了各种溶致液晶相的稳定区域. 通过系统地改变聚合物的分子量, 我们给出了各种PEO-PPO-PEO三嵌段共聚物在水溶液中的相图. 此外, 也研究了分子量对自组装结构各组分浓度分布的影响. 发现在给定的温度下, 聚合物的分子量是体系发生相分离的一个重要驱动力. 我们的理论结果与相关的实验很好地符合.     

Effect of Ethylene-Propylene Copolymer Composition on Morphology and Surface Properties of Impact Poly(propylene) Copolymer

Summary: Impact poly(propylene) copolymers (IPC) having various ethylene-propylene rubber (EPR) compositions were prepared using a high activity Ziegler-Natta catalyst. EPR composition was characterized by temperature rising elution fractionation (TREF) analysis and FT-IR spectroscopy. Effect of EPR composition on the morphology and surface properties of IPC was investigated by scanning electron microscopy (SEM), 3D profiler, and gloss meter. Composition and amount of amorphous and crystalline EPR were quantified by TREF and found to be dependent on the ethylene content in EPR. From the SEM result, it was found EPR composition has a strong influence on its shape and size. IPCs containing propylene-rich EPR exhibited a finer dispersion of EPR phase. The surface roughness decreased with decreasing ethylene content in EPR. The comparison of EPR composition and morphology and surface properties exhibited strong correlations.     

Copolymers of Wheat Starch and Polyacrylonitrile. Effect of Aqueous-Organic Solvent Systems on Copolymer Composition

Starch-polyacrylonitrile graft copolymers prepared in a number of aqueous-organic solvent systems with ceric ammonium nitrate as the initiator had more grafted chains than those prepared in water alone, and these were of lower molecular weight. Substitution of methanol for 80% of the water produced grafted chains with a molecular weight of 15,700 and a grafting frequency of 253 anhydroglucose units per graft. The influence of catalyst concentration, increased reaction temperature, and sodium sulfate on the composition of the copolymer were investigated for the methanol-water system.     

Liquid-Liquid Equilibrium of Copolymer Solutions with Broad and Asymmetric Chemical Distributions

ABSTRACT

A solution of a random copolymer showing polydispersity only with respect to chemical composition is considered. A model distribution very flexible in its breadth and in its asymmetry is used to describe the polydispersity. Based on continuous thermodynamics, equations for the cloud-point curve, the shadow curve, the spinodal, the critical point, and the heterogeneous double critical point are derived. the activity coefficients are calculated with the aid of Huggins' χ-parameter concept assuming χ to depend linearly on the average chemical composition of the copolymer. the influence of the breadth and the asymmetry of the distribution on the liquid-liquid equilibrium of the copolymer solution is discussed.     

用NMR分析可生物降解的两亲性嵌段共聚物的相对分子质量和组成

凝胶渗透色谱(GPC)法是根据聚合物分子链流体力学体积大小的比较来测定聚合物相对分子质量(以下简称分子量)的,测得的聚合物分子量与聚合物分子链在溶剂中的构象有关[1]。两亲性嵌段共聚物分子链中亲水链段和亲油链段的极性差异很大,几乎在任何溶剂中它们的构象都不相同,因此可     

Molecular Weight Distributions of Polymer Solutions: Combination of Field Flow Fractionation (FFF) and Analytical Ultracentrifugation (AUC)

Molecular weight, distribution, as well as other molecular characteristics are important drivers in determining the potential behaviors and hence applications of polymeric materials. Out of different methods available for the determination of molecular weight and its distribution, field flow fractionation (FFF) provides absolute molecular weight values and accurate molecular weight distributions. Analytical ultracentrifugation (AUC), on the other hand, relies on the exact density of the polymer materials in solution to determine the accurate molecular weight and its distribution and in the absence of knowledge of exact density, AUC is less accurate than the FFF method. However, combination of the two methods can be achieved to gain insights into the other molecular characteristics of swollen polymer chains. One such example is the determination of the exact density of the swollen polymer chains by the incorporation of the molecular weight information from FFF into AUC analysis. Based on the comparison of the optimized polymer chain density with the bulk density, it was observed that the polyacrylic acid and polyacrylamide chains were swollen in the range of 27 to 29%. Moreover, the FFF and AUC can also complement each other in enhancing the range of characterization possible with the two methods when used separately.     

三元多嵌段共聚物分子链结构的统计表征

本文根据三元多嵌段共聚反应的一般模型,运用母函数方法,严格推导出了型三元多嵌段共聚物的分子量分布及平均分子量的解析表达式.对几种具有特殊分布的预聚体进行了讨论.     

Comparison of Fractionation Methods for the Characterisation of Short Chain Branching as a Function of Molecular Weight in Ethylene 1-Olefin Copolymers

Summary: Rapid and automated analysis of polyolefins is becoming essential for product development in industry. Quantifying short chain branching in ethylene 1-olefin copolymers is common practice. Several different methods are available to perform this type of analysis. Preparative fractionation followed by subsequent analysis of the fraction by SEC and NMR, SEC-FTIR and SEC-IR were studied towards their applicability in polyolefin research and product development environment. The method of choice is defined by prerequisites such as accuracy, labour and time demands but also in versatility and practicability. The most accurate method is limited in terms of sample throughput and the most practical method is limited towards resolution of very low branching. SEC-FTIR is capable to measure even heterogeneous low branched samples like bimodal high density polyethylene in rapid and satisfactory matter.     

Ultrahigh Molecular Weight Ethene Copolymers from Metallocene and Ziegler Catalysts

In this study, ultrahigh molecular weight polyethene homopolymer and copolymer were successfully produced with the metallocene and the Ziegler catalyst system. In case with the metallocene catalyst system, viscosity average molecular weight of the homopolymer was controlled from 2 million to 10 million. Also, the molecular weight of the copolymer was reached up to 6 million. In case with the Ziegler catalyst system, the molecular weight of the copolymer was reached up to 4 million. The transparency of the copolymer by the Ziegler catalyst, with which the copolymer with better uniformity was produced, could be comparable with that by the metallocene catalyst.     

Copolymers of Starch and Polyacrylonitrile. Influence of Granule Swelling on Copolymer Composition under Various Reaction Conditions

Molecular weights and grafting frequencies of graft copolymers prepared with ferrous ammonium sulfate-hydrogen peroxide initiation showed a dependence on granule swelling similar to that found with ceric ammonium nitrate (increased swelling of starch granules decreased the number of grafted polyacrylonitrile chains and increased their average molecular weight). As with unswollen starch, the composition of the copolymer prepared from swollen starch was not influenced by granule size. Molecular weights of polyacrylonitrile branches grafted to swollen and unswollen starch were independent of reaction time; however, grafting frequencies with swollen and unswollen starch tended to converge toward a common value with increased reaction time and increased dilution. Data suggest that the influence of granule swelling on copolymer composition is due to a faster termination rate for growing polyacrylonitrile chains in unswollen starch.     

Melting Point and Composition Distribution of Polyolefins by Fractionation

The fractionation technique described in this paper was used to characterize the melting-point, monomer, and blocking distributions for polymers and copolymers. It is different from the molecular-weight fractionation technique in that the fractions are obtained by using a single solvent to extract the solid polymer below its melting point at stepwise-increasing temperatures. The reproducibility of this technique is excellent, and the technique is sufficient to distinguish pellet-to-pellet variation in a commercially available polypropylene. It was used to show the influence of preparation variables on the melting-point distributions of polyethylene and polypropylene and on the monomer and blocking distribution of copolymers, and to distinguish copolymers from blends.     

Fractionation of Regenerated Silk Fibroin and Characterization of the Fractions

The molecular weight (MW) of regenerated silk fibroin (RSF) decreases during degumming and dissolving processes. Although MW and the MW distribution generally affect polymer material processability and properties, few reports have described studies examining the influences of MW and the distribution on silk fibroin (SF) material. To prepare different MW SF fractions, the appropriate conditions for fractionation of RSF by ammonium sulfate (AS) precipitation process were investigated. The MW and the distribution of each fraction were found using gel permeation chromatography (GPC) and SDS-polyacrylamide electrophoresis (SDS-PAGE). After films of the fractionated SFs formed, the secondary structure, surface properties, and cell proliferation of films were evaluated. Nanofiber nonwoven mats and 3D porous sponges were fabricated using the fractionated SF aqueous solution. Then, their structures and mechanical properties were analyzed. The results showed AS precipitation using a dialysis membrane at low temperature to be a suitable fractionation method for RSF. Moreover, MW affects the nanofiber and sponge morphology and mechanical properties, although no influence of MW was observed on the secondary structure or crystallinity of the fabricated materials.     

Using Fractionation and Diffusion Ordered Spectroscopy to Study Lignin Molecular Weight.

Recent reports demonstrate that applications of the biopolymer lignin can be helped by the use of a fraction of the lignin which has an optimal molecular weight range. Unfortunately, the current methods used to determine lignin's molecular weight are inconsistent or not widely accessible. Here, an approach that relies on 2D DOSY NMR analysis is described that provides a measure of lignin's molecular weight. Consistent results were obtained using this well-established NMR technique across a range of lignins.     

Application of Continuous Thermodynamics to Polymer Fractionation

Continuous thermodynamics was developed in recent years and applied successfully to the liquid-liquid equilibrium of poly disperse polymer solutions. Continuous thermodynamics is based on the direct use of continuous distribution functions in the thermodynamic equations. There is no need for a reduction to pseudocomponents. This paper presents the application of continuous thermodynamics to successive polymer fractionation procedures based on solubility differences. In this way, simple equations for the distribution function of the different polymer fractions are obtained. Furthermore, the other equations describing the fractionation possess a lucid structure favorable for computer simulations of the fractionation procedures.     

High-Molecular-Weight Alternating Copolymers from Thermal Copolymerizations of N-Alkylcitraconimides with Styrene

Radical copolymerizations of eight N-alkylcitraconimides (1) and styrene (2) were carried out in the presence or absence of a radical initiator. Alternating copolymers with number-average molecular weights higher than 7 × 10⁵ were obtained from the thermal copolymerizations (monomer molar ratio = 1:1) in bulk at 60°C. The spontaneous copolymerization is considered to be by induced radicals produced via an intermediate Diels-Alder dimer and minary a contact-type charge transfer complex between N-alkylcitraconimide and styrene. Thermogravimetric analyses indicate the resulting copolymers have high thermal stabilities.