Crystallization Analysis Fractionation Research Articles

Crystallization analysis fractionation of poly(ethylene-co-styrene) produced by metallocene catalysts

Ethylene homo polymer and ethylene–styrene copolymers were synthesized using Cp2ZrCl2 (1)/methyl aluminoxane (MAO) and rac-silylene-bis (indenyl) zirconium dichloride (2)/MAO catalyst systems by varying styrene concentration and reaction conditions. Crystallization analysis fractionation (CRYSTAF), DSC, FTIR and 1H NMR spectroscopy were used for characterizing the synthesized polymers. Interestingly, styrene was able to increase the activity of 1/MAO and 2/MAO catalyst systems at low concentrations, but at higher concentrations the activity decreases. The 1/MAO system at low and high pressure was unable to incorporate styrene, and the final product was pure polyethylene. On the other hand, with 2/MAO polymerization of ethylene and styrene yielded copolymer containing both styrene and ethylene. Results obtained from CRYSTAF and DSC reveal that on using 1/MAO system at high pressure, the resulting polymer in the presence of styrene has similar crystallinity as the polymer produced without styrene. Using both 1/MAO at low pressure and 2/MAO leads to decrease in crystallinity with increase in styrene concentration, even though the former does not incorporate styrene.

Linear low density polyethylene: Microstructure and sealing properties correlation

The microstructures of four commercial linear low density polyethylenes (LLDPE) were evaluated and correlated with their sealing properties. Atomic Force Microscopy (AFM), Temperature Rising Elution Fractionation (TREF), Differential Scanning Calorimetry (DSC) and Crystallization Analysis Fractionation (CRYSTAF) experiments revealed that the comonomer distribution is one of the main factors that influence the sealing properties. The superior sealing performance showed by metallocene LLDPE samples in comparison to Ziegler-Natta LLDPE samples can be attributed to their well balanced chemical composition distribution.

Separation of High‐Impact Polypropylene Using Interactive Liquid Chromatography

AbstractFractionation techniques such as temperature rising elution fractionation or crystallization analysis fractionation fail to fractionate the ethylene–propylene (EP) copolymers, which are a component of high‐impact polypropylene (hiPP), according to their chemical composition. High‐temperature high‐performance liquid chromatography separates blends of EP‐copolymers and polypropylene. The elution volume of the EP‐copolymers depends linearly on the average content of ethylene. The separation according to the chemical composition was hyphenated with size exclusion chromatography. In this way, the relationship between the distribution with regard to chemical composition and molar mass, that is, the full chemical heterogeneity of hiPP, was revealed for the first time.

Crystallization Elution Fractionation of LLDPEs Made with Metallocene Catalysts

AbstractSummary: Temperature rising elution fractionation (TREF) and crystallization analysis fractionation (CRYSTAF) fractionate semicrystalline polymers according to their crystallizabilities from dilute solution and have been widely used to measure the CCD of LLDPE. A new fractionation technique, known as crystallization elution fractionation (CEF), has been developed recently. The main difference between CEF and TREF and CRYSTAF is that the crystallization cycle in CEF is performed dynamically under solvent flow in a long column that contains an inert support material. In this paper, several metallocene‐LLDPE resins have been analyzed by CEF to investigate the effect of cooling cycle parameters, comonomer fraction, polymer molecular weight, and blend cocrystallization on the fractionation. This new technique can be used to obtain CCDs with better resolution and in shorter times than TREF and CRYSTAF.

Crystallization Elution Fractionation and Thermal Gradient Interaction Chromatography. Techniques Comparison

AbstractSummary: The chemical composition distribution has been shown to be the most critical and discriminating parameter in understanding the performance of industrial polyolefins with non homogeneous comonomer incorporation. The chemical composition distribution is being analyzed by well known techniques such as temperature rising elution fractionation, TREF, crystallization analysis fractionation, CRYSTAF and crystallization elution fractionation, CEF. These techniques separate according to crystallizability and provide a powerful and predictable separation of components based on the presence of branches, irregularities or tacticity differences, independently of the molar mass. TREF, CRYSTAF and CEF can not be used, however, for the separation of more amorphous resins, and may not always provide the best solution for complex multi‐component resins due to the existence of some co‐crystallization. The application of high temperature interactive HPLC to polyolefins opened a new route to characterize these types of polymers. The use of solvent gradient HPLC for separation of polyethylene and polypropylene and the developments in HPLC on carbon based columns extended further the application of high temperature HPLC in polyolefins. A new approach has been developed recently using the carbon based column but replacing solvent gradient by a thermal gradient which facilitates the analysis of polyethylene copolymers and provides a powerful tool for the analysis of elastomers. Thermal gradient interaction chromatography (TGIC) is being compared with TREF and CEF with the analysis of model samples. The advantages/disadvantages of each technique are being investigated and discussed. The combination of TGIC and TREF/CEF provides an extended range of separation of polyolefins.

Effect of Chain Microstructure and Cooling Rate on Crystaf Calibration Curves: An Experimental Study

AbstractSummary: Crystallization analysis fractionation (Crystaf) is a polymer characterization technique based on differences in chain crystallizabilities in a dilute solution during non‐isothermal crystallization. Crystaf profiles, a weight distribution function of chains crystallized at each temperature, can be used to infer the chemical composition distribution (CCD) of copolymers when a Crystaf calibration curve, a relationship between peak crystallization temperature and average comonomer content, is known. In this investigation, the effect of the number average molecular weight, comonomer type, and cooling rate on Crystaf calibration curves were experimentally investigated. It was found that the cooling rate and comonomer type may strongly affect Crystaf calibration curves, while the influence of molecular weight is relatively subtle.

Production of Ethylene/α-Olefin/1,9-Decadiene Copolymers with Complex Microstructures Using a Two-Stage Polymerization Process

Ethylene was copolymerized with 1,9-decadiene using methylaluminoxane-activated rac-Et(Ind)2ZrCl2 at 120 °C to produce macromonomers with pendant and terminal vinyl groups with a maximum of 6.5 vinyl groups per polymer chain. The macromonomers were copolymerized with ethylene and 1-butene or 1-octene using a constrained geometry catalyst (dimethylsilyl(N-tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride) at 120 °C in toluene. The resulting branched polymers showed three distinct populations during crystallization analysis fractionation, indicating the formation of a new fraction produced by the incorporation of macromonomer chains into ethylene/1-butene or ethylene/1-octene copolymer chains. These novel polyolefins have complex branched structures consisting of three main components: a high-crystallinity fraction (macromonomers), a low-crystallinity (or amorphous) fraction (α-olefin copolymer), and a third component resulting from the cross-linking of the two previous components (cross-prod...

Bimodality Criterion for the Chemical Composition Distribution of Ethylene/1‐Olefin Copolymers: Theoretical Development and Experimental Validation

AbstractEthylene/1‐olefin copolymers with controlled bimodal molecular weight distributions (MWDs) and chemical composition distributions (CCDs) have improved mechanical and rheological properties. In this work, the Stockmayer's distribution was used to develop a criterion for CCD bimodality. The proposed criterion was validated theoretically using simulation data and experimentally using crystallization analysis fractionation (CRYSTAF) and crystallization elution fractionation (CEF) of ethylene/1‐octene copolymer blends. The effect of mass fraction and number average molecular weight of copolymer produced with each metallocene catalyst on CCD bimodality was also examined. The proposed criterion was then used as a benchmark for describing cocrystallization effects in both CRYSTAF and CEF techniques. magnified image

Cocrystallization of ethylene/1‐octene copolymer blends during crystallization analysis fractionation and crystallization elution fractionation

AbstractBlending of ethylene/1‐octene copolymers can be used to achieve a well‐controlled broad chemical composition distribution (CCD) required in several polyolefin applications. The CCD of copolymer blends can be estimated using crystallization analysis fractionation (CRYSTAF) or crystallization elution fractionation (CEF). Unfortunately, both techniques may be affected by the cocrystallization of chains with different compositions, leading to profiles that do not truly reflect the actual CCD of the polymer. Therefore, understanding how the polymer microstructure and the analytical conditions influence copolymer cocrystallization is critical for the proper interpretation of CRYSTAF and CEF curves. In this investigation, we studied the effect of chain crystallizabilities, blend compositions, and cooling rates on cocrystallization during CEF and CRYSTAF analysis. Cocrystallization is more prevalent when the copolymer blend has components with similar crystallizabilities, one of the components is present in much higher amount, and fast cooling rates are used. CEF was found to provide better CCD estimates than CRYSTAF in a much shorter analysis time. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011

Separation of ethylene‐propylene copolymers and ethylene‐propylene‐diene terpolymers using high‐temperature interactive liquid chromatography

AbstractEthylene‐propylene‐diene terpolymers (EPDM) are generally amorphous and, therefore, do not crystallize from solution. Consequently, fractionation techniques based on crystallization, such as crystallization analysis fractionation or temperature rising elution fractionation, cannot be used to analyze their chemical composition distribution. Moreover, no suitable chromatographic system was known, which would enable to separate them according to their chemical composition. In this study, two different sorbent/solvent systems are tested with regard to the capability to separate EPDM‐terpolymers and ethylene‐propylene (EP)‐copolymers according to chemical composition. While porous graphite/1‐decanol system is selective towards ethylene and ethylidene‐2‐norbornene, carbon coated zirconia/2‐ethyl‐1‐hexanol is preferentially selective towards ethylene. Consequently, the earlier system enables to separate both EP copolymers and EPDM according to the chemical composition and the latter mainly according to the ethylene content. The results prove that the chromatographic separation in both sorbent/solvent systems is not influenced by molar mass of a sample or by its long chain branching. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Characterization of Ethylene methyl methacrylate and Ethylene butylacrylate Copolymers with Interactive Liquid Chromatography

AbstractSummary: Copolymers of ethylene with methyl methacrylate (EMMA) and butyl acrylate (EBA), which are of different average chemical composition and block lengths according to NMR analysis, were analyzed by size exclusion chromatography (SEC), differential scanning calorimetry (DSC), Crystallization Analysis Fractionation (CRYSTAF), and high performance liquid chromatography at high temperature (HT‐HPLC). With CRYSTAF and DSC crystallizing fractions were detected only in some samples. HT‐HPLC fractionated all the samples irrespective of their crystallinity. Homopolymers, PMMA and PE were also found in the copolymer samples of EMMA. EMMA and EBA were separated in HPLC according to the content of polar comonomer. A linear correlation between the MMA content and elution volume could not be established due to the presence of homopolymers as admixtures. In such a case the average chemical composition obtained by NMR does not correspond to the real chemical composition of the copolymers. Unlike EMMA the EBA samples eluted in single peaks, which was used for evaluation of their chemical composition distribution. The comparison of results obtained by fractionation via CRYSTAF and HT‐HPLC clearly demonstrates the advantages of the chromatographic approach to study the chemical heterogeneity of olefin based copolymers.

Characterization of polypropylene–polyethylene blends by temperature rising elution and crystallization analysis fractionation

The introduction of single-site catalysts in the polyolefins industry opens new routes to design resins with improved performance through multicatalyst-multireactor processes. Physical combination of various polyolefin types in a secondary extrusion process is also a common practice to achieve new products with improved properties. The new resins have complex structures, especially in terms of composition distribution, and their characterization is not always an easy task. Techniques like temperature rising elution fractionation (TREF) or crystallization analysis fractionation (CRYSTAF) are currently used to characterize the composition distribution of these resins. It has been shown that certain combinations of polyolefins may result in equivocal results if only TREF or CRYSTAF is used separately for their characterization.

Simultaneous Deconvolution of the Molecular Weight and Chemical Composition Distribution of Polyolefins Made with Ziegler‐Natta Catalysts

AbstractHeterogeneous Ziegler‐Natta catalysts produce polyolefins that have broad distributions of molecular weight (MWD) and chemical composition (CCD). For such broad distributions, mathematical models are useful to quantify the information provided by polyolefin analytical techniques such as high‐temperature gel permeation chromatography (GPC), temperature rising elution fractionation (TREF), and crystallization analysis fractionation (CRYSTAF). In this paper, we developed a mathematical model to deconvolute the MWD and CCD of polyolefins simultaneously, using Flory's most probable distribution and the cumulative CCD component of Stockmayer's distribution. We have applied this procedure to “model” polyolefin resins and to one industrial linear low‐density polyethylene (LLDPE) resin. The proposed methodology is able to deconvolute theoretical distributions even when random noise is added to the MWDs and CCDs, and it can be used to calculate the minimum number of active site types on heterogeneous Ziegler‐Natta catalysts.

Comparison of High‐Temperature HPLC, CRYSTAF and TREF for the Analysis of the Chemical Composition Distribution of Ethylene‐Vinyl Acetate Copolymers

AbstractThe chemical composition distribution (CCD) is a fundamental molecular parameter of copolymers. High‐temperature interactive liquid chromatography (HT‐HPLC) has recently emerged as a new analytical technique for determination of the CCD of semicrystalline copolymers of ethylene and polar comonomers. With the aim of comparing the results of HT‐HPLC with those from the traditionally used temperature rising elution fractionation (TREF) and crystallization analysis fractionation (CRYSTAF) techniques, three ethylene‐vinyl acetate (EVA) copolymers were fractionated by TREF and the fractions were analyzed by HT‐HPLC. HT‐HPLC‐Fourier transform‐infrared (FT‐IR) spectroscopy showed that individual fractions of different VA‐content coelute in the HPLC. While the separation in TREF and CRYSTAF is mainly the result of the overall effect of alkyl branches and VA‐comonomer units, in HT‐HPLC it is the polar comonomer that selectively contributes to the adsorption. Thus, HT‐HPLC leads to a much more detailed knowledge of the distribution of the structured units; in addition, it saves time.magnified image

Estimation of Average Comonomer Content of Ethylene/1‐Olefin Copolymers Using Crystallization Analysis Fractionation (Crystaf) and Artificial Neural Network (ANN)

AbstractSummary: An artificial neural network (ANN) with a 4‐3‐3‐1 architecture was developed to estimate average comonomer content of ethylene/1‐olefin copolymers from crystallization analysis fractionation (Crystaf) results. The ANN was trained with a back propagation algorithm. It was found that average comonomer contents predicted from ANN agree well with experimental results for both training and testing data sets. The developed ANN was also used to systematically investigate the effects of chain microstructures and Crystaf operating conditions on Crystaf calibration curves.

Advances in Crystallization Elution Fractionation

AbstractSummary: Crystallization Elution Fractionation has been optimized to improve resolution power and reduce co‐crystallization. Most important step to be optimized is the first separation cycle of Dynamic Crystallization which can be investigated with the help of Crystallization Analysis Fractionation experiments. A new approach to reduce co‐crystallization and improve resolution is presented by applying successive cooling and heating cycles in a long column. The new process known as Multiple Crystallization Elution Fractionation adds extended separation at each cooling and heating cycles.

Simultaneous Deconvolution of the Bivariate Distribution of Molecular Weight and Chemical Composition of Polyolefins Made with Ziegler‐Natta Catalysts

Polyolefins made with Ziegler-Natta catalysts have non-uniform distributions of molecular weight (MWD) and chemical composition (CCD). The MWD is usually measured by high-temperature gel permeation chromatography (GPC) and the CCD by either temperature rising elution fractionation (TREF) or crystallization analysis fractionation (CRYSTAF). A mathematical model is needed to quantify the information provided by these analytical techniques and to relate it to the presence of multiple site types on Ziegler-Natta catalysts. We developed a robust computer algorithm to deconvolute the MWD and CCD of polyolefins simultaneously using Flory's most probable distribution and the cumulative CCD component of Stockmayer's distribution, which includes the soluble fraction commonly present in linear low-density polyethylene (LLDPE) resins and have applied this procedure for the first time to several industrial LLDPE resins. The deconvolution results are reproducible and consistent with theoretical expectations.

High-temperature gradient HPLC and LC-NMR for the analysis of complex polyolefins

Abstract The synthesis and characterization of polyolefins continues to be one of the most important areas for academic and industrial polymer research. One consequence of the development of new "tailor-made" polyolefins is the need for new and improved analytical techniques for the analysis of polyolefins with respect to molar mass and chemical composition distribution. The present article briefly reviews different new and relevant techniques for polyolefin analysis. Crystallization analysis fractionation is a powerful new technique for the analysis of short-chain branching in linear low-density polyethylene (LLDPE) and the analysis of polyolefin blends and copolymers regarding chemical composition. For the fast analysis of the chemical composition distribution, a new high-temperature gradient high-performance liquid chromatography (HPLC) system has been developed. The efficiency of this system for the separation of various olefin copolymers is demonstrated. The correlation between molar mass and chemical composition can be accessed by on-line coupling of high-temperature size exclusion chromatography (HT-SEC) and 1H NMR spectroscopy. It is shown that the on-line NMR analysis of chromatographic fractions yields information on microstructure and tacticity in addition to molar mass and copolymer composition.

A Mathematical Model for the Kinetics of Crystallization in Crystaf

AbstractSummary: A series of ethylene homopolymers and ethylene/1‐hexene copolymers with different molecular weight distributions (MWD) and chemical composition distributions (CCD) was analyzed by crystallization analysis fractionation (Crystaf) at several cooling rates to investigate the effect of MWD, CCD, and cooling rate on their Crystaf profiles. Using these results, we developed a mathematical model for Crystaf that considers crystallization kinetic effects ignored in all previous Crystaf models and can fit our experimental profiles very well.

Characterization of Ethylene‐1‐Hexene Copolymers Made with Supported Metallocene Catalysts: Influence of Support Type

AbstractSummary: It is known that the nature of the support, as well as the technique used to anchor the metallocene onto it, play important roles on catalytic activity and on the properties of the polymers produced with supported metallocenes. In the present work, the effect of different support types on the microstructure of ethylene/1‐hexene copolymers made with supported metallocene catalysts has been investigated through the analysis of molecular weight and chemical composition distributions using high temperature gel permeation chromatography (GPC) and crystallization analysis fractionation (Crystaf). The copolymer samples obtained using commercial carriers (silica and silica‐alumina) had unimodal chemical composition distributions and were used to create a linear calibration curve relating the peak crystallization temperature from Crystaf and the comonomer content as determined by 13C NMR. This calibration curve is useful to determine the 1‐hexene fractions for each peak in the resins showing bimodal chemical composition distributions, such as those obtained with catalysts supported on MCM‐41 and SBA‐15 materials. The structure and chemistry of the support used had a large influence on comonomer incorporation and the shape of the chemical composition distribution of the polymer, which suggests that the supporting process creates different types of active sites.