Investigation of grafted impact-resistant polypropylene by temperature rising elution fractionation

The goal of the present work is the examination of maleic anhydride (MAn) grafted impact-resistant polypropylene (I-PP), consisting of amorphous rubber and semicrystalline matrix. A special instrument to separate the rubber from the matrix is preparative temperature rising elution fractionation (TREF). Investigations of the isolated fractions permit conclusions on the course of the grafting reaction and side reactions during the modification. The present work has shown that the fractionation is just as possible in the modified products as in the raw material. It has also shown that a grafting reaction occurs mainly in the rubber phase of this two-phase polypropylene. During the grafting reaction, only small degrees of radical degradation of the homopolymeric polypropylene matrix could be detected. © 1997 John Wiley & Sons, Inc.     

Investigation of the composite molecular structure of LDPE by using temperature rising elution fractionation

In the synthesis of low-density polyethylene there is a direct relationship between the synthesis conditions, molecular structure, and technical properties of the product. The evaluation of the molecular structure of the polymer is therefore important. The most important structure parameters in low-density polyethylene are molecular weight distribution (MWD), degree of long-chain branching (LCB), and short-chain branching distribution (SCBD). Through chain transfer to polymer it is possible to get composite molecules made up of chains with different amounts of short-chain branching. By using temperature rising elution fractionation (TREF) and plotting the methyl contents or the DTA melt temperature of the fractions as functions of the elution temperature, the SCBD within composite molecules can be evaluated. The deviations from linear relationships are caused by such SCBD within composite molecules. In order to demonstrate the buildup of composite molecules, samples from different parts of a reactor were investigated.     

Microstructural characterization of propylene–butene-1 copolymer using temperature rising elution fractionation

Propylene–butene-1 copolymer (PBC) prepared with a titanium catalyst system was fractionated by temperature rising elution fractionation (TREF) over a temperature range of 5–80°C. PBC was shown to have a wide composition distribution ranging between 12–47 mol % of butene-1. Most of the fractions showed nearly the same crystallinity regardless of the butene-1 content. However, the solubility of the crystalline parts, which turned out to be the driving force for the fractionation, varied over the butene-1 content. Evidence that PBC shows isomorphism was obtained by the analysis of fractionated polymers, using ¹³C nuclear magnetic resonance spectrometry, X-ray diffraction, differential scanning calorimetry, and gel permeation chromatography. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1493–1501, 1998     

Studies of thermal oxidative degradation of polypropylene impact copolymer using the temperature rising elution fractionation method

Thermal oxidative degradation of polypropylene impact copolymer has been studied with its fractions obtained using the temperature rising elution fractionation method. The fractions were analyzed using ¹³C NMR, Fourier transform infrared and differential scanning calorimetry measurements, and the chemical structure, isotacticity, conformation and melting point were investigated. It is found that these fractions are composed of a homopolymer or a polymer blend of polypropylene, polyethylene and ethylene–propylene copolymer. The thermal oxidative degradation of each fraction was carried out at 130 °C, and the degradation progress was estimated by the change of molecular weight distribution (from gel permeation chromatography curves). The rate of degradation is found to be dominated by the content of tertiary C? H bonds (propylene unit) and the existence of 3₁ helix conformation corresponding to a crystalline polypropylene part in each fraction. The latter is more evident leading to the degradation reaction path with a lower activation energy. Copyright © 2007 Society of Chemical Industry     

A temperature rising elution fractionation study of short chain branching behavior in ultra low density polyethylene

The properties of ultralow-density polyethylenes (ULDPE) have been studied using temperature rising elution fractionation (TREF) as both an analytical and preparative process. TREF was employed to determine the short chain branch distribution and to fractionate the polymer into fractions that enabled further properties studies, including carbon-13 nuclear magnetic resonance, differential scanning calorimetry, dynamic mechanical thermal analysis, density gradient studies, gel permeation chromatography, analytical TREF, and some simple tensile tests. The results of these studies are reported here.     

Characterization of linear low density polyethylene by temperature rising elution fractionation and by differential scanning calorimetry

In this article we consider characterization of the branching distribution of LLDPE by analytical TREF and by DSC techniques. Qualitatively, both methods yield parallel information, provided that the DSC samples are prepared at very slow cooling rates. Analytical TREF provides more quantitative information, however, in that the mass fraction of material with different branch levels can be estimated. Full characterization of a polyethylene requires the use of a preparative TREF technique, in which fractions dissolved at preselected temperatures are investigated for branching with high resolution ¹³C NMR and for molecular weight distribution, with high temperature SEC analyses.     

升温淋洗分级研究聚丙烯流延膜专用料的微观结构及热学表征

采用升温淋洗分级技术分离了2种聚丙烯流延膜(CPP)专用料(CPP1、CPP2),通过红外光谱仪、差示扫描量热仪和高温凝胶色谱对2种样品的链结构、熔融和结晶行为进行了表征,确定了产品各级分的分子结构信息.结果表明,对于低温(<100℃)级分,CPP1样品中其含量为9.29％(质量分数,下同),CPP2样品中其含量为26...     

Influence of the short‐chain branch length on the calibration of temperature rising elution fractionation systems

The effects of short‐chain branch (SCB) length on the calibration of temperature rising elution fractionation (TREF) were examined. Samples of ethylene–hexene, ethylene–octene, and a novel polyolefin produced using Eastman Chemical Company's Gavilan catalyst technology were used to prepare TREF calibration curves. Preparative TREF was used to collect fractions of the materials based on their crystallizability, and the branching frequencies of the fractions were determined by NMR. Calibration curves were generated by plotting the branching frequency as a function of the TREF elution temperature. The results indicate that the calibration curves shift to lower TREF elution temperatures as the length of the SCB increases from methyl to butyl to hexyl. Other factors that may contribute to this shift include chain microstructural differences from variations in catalyst structure and process conditions. The shift can be decreased by plotting the data in “number of branches per 1000 backbone carbons” versus TREF elution temperature instead of the more traditional “number of branches per 1000 total carbons.” These data indicate that the branch type must be known a priori to calculate SCB averages and SCB distributions and that unique calibration curves exist for copolymers made using different α‐olefin comonomers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 722–728, 2003     

Studies of the comonomer distributions in low density polyethylenes using temperature rising elution fractionation and stepwise crystallization by DSC

The comonomer distributions of commercial linear low density polyethylenes (LLDPE) and linear very low density polyethylenes (VLDPE) produced with traditional high activity Ziegler–Natta (Z–N) catalysts were characterized by temperature rising elution fractionation (TREF). In order to develop faster characterization methods the polymers were also characterized using a segregation fractionation technique (SFT) based on a stepwise crystallization by differential scanning calorimetry (DSC). Comparative studies of SFT and TREF demonstrated that SFT provides an alternative tool for the relative qualitative analysis of the chemical composition distribution (CCD) and the technique is useful to characterize the heterogeneity in comonomer unit distribution. Lamellar thickness distributions can be calculated from the DSC endo-therms by applying the Thomson–Gibbs equation. The SFT technique was also applied to commercial single-site (metaliocene) LLDPE and VLDPE polymers. In spite of their more homogeneous structure compared with the Z–N copolymers, which contain many active sites, these single site copolymers also gave thermograms resolved into several peaks.     

Structural evaluation of copolymers of ethylene and 1‐octadecene by using the temperature rising elution fractionation technique

Three samples of ethylene‐octadecene copolymers having different quantitative composition were analyzed structurally and in terms of their thermal behavior. The samples were fractionated by temperature rising elution fractionation, presenting different chemical composition distributions (CCD) that are essentially the result of the proportion of incorporated octadecene. The CCD profiles were relatively wide for samples generated by metallocene catalysts. The analyses of the fractions showed that the melting and crystallization temperatures decrease with increasing comonomer incorporation, but this relation is affected by the average molecular weight of the chains. The melting thermograms of those fractions having higher proportions of octadecene may be divided into two characteristic regions: the first one, at a higher temperature, originates from the melting of the least modified chains, which crystallize more perfectly. The second one is formed by the melting of chains having a high degree of comonomer incorporation, which melt in a diffuse manner over a wide range of temperatures. It is probable that the morphology of the crystals formed in this region does not follow the folded chain model, and are better represented by a model involving the alignment of chain segments (bundling). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 221–227, 2001     

Characterization and microstructure study of low‐density polyethylene by Fourier transform infrared spectroscopy and temperature rising elution fractionation

Infrared spectroscopy is a powerful technique for studying the microstructure and determining the short‐chain branch distribution of polyethylene. In this work, the types and amounts of short‐chain branches in low‐density polyethylene were investigated with Fourier transform infrared spectroscopy, and a new and simple method for the determination of butyl short branches was discovered. The amount of each unsaturated species in low‐density polyethylene was also determined with Fourier transform infrared after the bromination of samples. Furthermore, the resin was fractionated by preparative temperature rising elution fractionation, and the branch distribution and melting endotherm of each fraction were analyzed with attenuated total reflectance/Fourier transform infrared and differential scanning calorimetry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study on molecular chain heterogeneity of linear low‐density polyethylene by cross‐fractionation of temperature rising elution fractionation and successive self‐nucleation/annealing thermal fractionation

The molecular chain heterogeneity of commercial linear low‐density polyethylene (LLDPE) was investigated by cross‐fractionation of temperature rising elution fractionation (TREF) and successive self‐nucleation/annealing (SSA) thermal fractionation by use of DSC. The results indicate that the linear relationships between crystallinity or melting temperature and the elution temperature are confirmed by TREF fractions. Intermolecular heterogeneity exists in the original LLDPE, whereas there is less intermolecular heterogeneity in the TREF fractions. After SSA thermal fractionation, the multiple endothermic peaks for both LLDPE and their TREF fractions are mainly attributed to the heterogeneities of ethylene sequence length (ESL) and lamellar thickness. The statistical terms, including weighted mean L _w, arithmetic mean L _n, and broad index L _w/L _n, were introduced to evaluate the heterogeneities of ESL and lamellar thickness of polyethylene. The difference of broadness index indicates that TREF fractions of LLDPE have less inter‐ and intramolecular heterogeneities of both ESL and lamellar thickness than those of the original LLDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1710–1718, 2004     

High resolution solution and solid state NMR characterization of ethylene/1-butene and ethylene/1-hexene copolymers fractionated by preparative temperature rising elution fractionation

Preparative TREF was used to fractionate 2 commercial LLDPE polymers. These polymers had similar MFI values, density and comonomer content, but differed in comonomer type, 1-butene vs 1-hexene. High resolution solution NMR and solid state NMR was used to characterize the copolymer fractions. Distinct differences in chemical composition distribution could be observed from solution NMR results, and these correlated well with solid state analyses. Conclusions regarding the molecular make-up and crystallization phenomena are made.     

The compatibilizing effect of poly(styrene-co-4-vinylpyridine) copolymers on the polystyrene–polyethylene-based ionomer blends

The compatibilizing effect of styrene-co-4-vinylpyridine (SVP) random copolymers on the immiscible polystyrene (PS)–polyethylene-based ionomer (Surlyn) blends was examined by means of scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and tensile test. For the binary SVP–Surlyn and ternary PS–Surlyn–SVP blends, the domain size of dispersed phase decreases dramatically with the increase in the vinyl pyridine (VP) content of the SVP copolymers. The mechanical properties are improved with increasing the VP content in copolymers. FTIR results suggest that the compatibilization in this blend system is attributed to the ion–dipole interaction between the polar VP groups of SVP copolymer and ionic groups of Surlyn. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 807–816, 1998     

Influence of electron donors on the initial stage of cyclopolymerization of 1,5‐hexadiene with MgCl2‐supported Ziegler catalysts analyzed by temperature rising elution fractionation

Additive effects of donors on the initial polymerization of 1,5‐hexadiene with the MgCl₂‐supported Ziegler catalysts were investigated by using the stopped‐flow method, temperature rising elution fractionation (TREF) analysis, and kinetic study. The cyclopolymerization of 1,5‐hexadiene proceeded within an extremely short period (≤ 0.2 s) and yielded a unique poly(methylene‐1,3‐cyclopentane). cis ring content and cis–cis unit in meso dyad of the resulting polymer were increased by the addition of electron donors. The influence of internal and external donors was examined by the estimation of kinetic parameters and TREF analysis. Because the addition of the internal donor caused an obvious change in one of the kinetic parameters and the microstructure, an isospecific active site was considered to be formed by the addition of the internal donor. In the case of the external donor, the additive effects on the stereospecificity were weaker than those of the internal donor. It was expected from TREF measurements that the external donor modified an aspecific active site into a lower isospecific active site. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2976–2983, 2002; DOI 10.1002/app.2326     

Carbon‐13 NMR,GPC, and DSC study on a propylene‐1‐butene copolymer fractionated by temperature rising elution fractionation

A random copolymer of propylene with small amounts of 1‐butene comonomer, synthesized with a Ziegler–Natta catalyst, was fractionated by temperature rising elution fractionation (TREF) to systemically investigate the fraction samples' molecular microstructure, as well as their relationship to the melting and crystallization behavior. First, TREF was employed to fractionate the sample, and then crystallization analysis fractionation (Crystaf) was used to check the effect of the TREF experiment. In the characterization of the molecular microstructure, carbon‐13 NMR spectroscopy (¹³C NMR) and gel permeation chromatography (GPC) experiments gave the following results: the fraction samples have relatively uniform molecular microstructure; with an increase in elution temperature, the 1‐butene content in the fraction samples decreases, but the molecular weight (M_n) and number average sequence length of propylene (n?_P) increase. In the study on melting and crystallization behavior, differential scanning calorimetry (DSC) experimental results show that the melting temperature increasingly decreases with an increase in 1‐butene content; however, dependence of the melting temperature on molecular weight becomes weaker and weaker with an increase in the number average molecular weight in the range of number average molecular weight below 1.82 × 10⁵ g/mol. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 845–851, 2006     

Study of the influence of the reaction parameters on the composition of the metallocene‐catalyzed ethylene copolymers using temperature rising elution fractionation and 13C nuclear magnetic resonance

Polyethylene copolymers prepared using the metallocene catalyst rac‐Et[Ind]₂ZrCl₂ were fractionated by preparative Temperature Rising Elution Fractionation (p‐TREF) and characterized by ¹³C nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC) to study the heterogeneity caused by experimental conditions. Two ethylene–1‐hexene copolymers with different 1‐hexene content and an ethylene–1‐octene copolymer all obtained using low (1.6 bar) ethylene pressure were compared with two ethylene–1‐hexene copolymers with different 1‐hexene content obtained at high ethylene pressure (7.0 bar). Samples obtained at low ethylene pressure and with low 1‐hexene concentration in the reactor presented narrow distributions in composition. Samples prepared with high comonomer concentration in the reactor or with high ethylene pressure showed an heterogeneous composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 155–163, 2002; DOI 10.1002/app.10284     

Molecular weight fractionation of poly(methyl methacrylate) using Gas Anti-Solvent techniques

The solubility of poly(methyl methacrylate) in acetone, expanded by carbon dioxide, was studied at 20 °C for a variety of molecular weights and architectures. The suitability of the Gas Anti-Solvent method for fractionation of poly(methyl methacrylate) was investigated with positive results. The threshold pressure for precipitation of various monodisperse molecular weights was investigated, and the effectiveness of this technique to fractionate a polymer with a broad molecular weight distribution was evaluated. The pressure required to precipitate polymers was found to be low, generally below 60 bar.     

The glass transition temperature of nitrated polystyrene/poly(acrylic acid) blends

Low-molecular-weight polystyrene was nitrated to different levels. The nitrated polystyrene was blended with different molecular weights of poly(acrylic acid), PAA. The glass transition temperatures (T_g) for the mixtures were investigated by differential scanning calorimetry. A single T_g was observed for all blends, indicating single-phase blends. In general, it was found that the T_g increases with molecular weight of PAA. The T_g values of the blends showed a positive deviation from the linear average T_g as a result of strong hydrogen bonding between the segments of the component polymers. The observed T_g values were not adequately represented by simple predictive equations or by single-parameter fitting equations. However, two-parameter fitting equations gave a reasonable representation of the data.