High Temperature Gel Permeation Chromatography Research Articles

Microstructural design characteristics of high-density polyethylene for thick-walled pressure pipe applications

Advancements in process technology and structure-property relationship-based design of high-density polyethylene has led to development of high-performance bimodal polyethylene grades suitable for large diameter thick-walled pressure pipe applications. These high-density bimodal products have enhanced design life, high pressure rating and sag resistance for fabrication of large diameter thick-walled pipe. Achieving optimal balance of these performance properties require controlled microstructural characteristics. The design characteristics are intricately influenced by catalyst type and process technology employed in resin manufacturing. In this study, we systematically establish correlations between microstructural characteristics of seven commercially available bimodal PE resins, produced using dual slurry or gas phase reactors, and their most relevant performance properties. We conducted comprehensive microstructural characterization of all samples using GPC-IR (high-temperature gel permeation chromatography coupled with an infrared composition detector), 13C NMR (nuclear magnetic resonance), TREF (temperature rising elution fractionation) and DSC (differential scanning calorimetry) techniques. Additionally, we measured mechanical, thermal, and rheological properties, focusing on crystallization kinetics, density, slow crack growth resistance (PENT and strain hardening modulus SHM) and low-frequency shear rheology of these products. Comparisons were made between key properties of interest, including slow crack growth resistance and low-frequency rheology (relevant for sag resistance), and microstructural characteristics. Theoretical and empirical correlations based on phenomenological models were employed for this analysis. The detailed study contributes to determining the critical levels of short and long chain branching, as well as molecular weight distribution characteristics essential to produce bimodal PE-4710 certifiable high-density polyethylene resins with low sag resistance. These design principles may serve as a foundation for the efficient design of reactor recipes and post-reactor modification processes, contributing to the evolution of pressure pipe polyethylene resin development and paving the way for design of next-generation pressure pipe grades.

Biodegradation of low-density polyethylene film by two bacteria isolated from plastic debris in coastal beach

Low-density polyethylene (LDPE) conduces massive environmental accumulation due to its high production and recalcitrance to environment. In this study, We successfully enriched and isolated two strains, Nitratireductor sp. Z-1 and Gordonia sp. Z-2, from coastal plastic debris capable of degrading LDPE film. After a 30-day incubation at 30 ℃, strains Z-1 and Z-2 decreased the weight of branched-LDPE (BLDPE) film by 2.59 % and 10.27 % respectively. Furthermore, high temperature gel permeation chromatography (HT-GPC) analysis revealed molecular weight reductions of 7.69 % (Z-1) and 23.22 % (Z-2) in the BLDPE film. Scanning electron microscope (SEM) image showed the presence of microbial colonization and perforations on the film's surface. Fourier transform infrared spectroscopy (FTIR) analysis indicated novel functional groups, such as carbonyl and carbon-carbon double bonds in LDPE films. During LDPE degradation, both strains produced extracellular reactive oxygen species (ROS). GC-MS analysis revealed the degradation products included short-chain alkanes, alkanols, fatty acids, and esters. Genomic analysis identified numerous extracellular enzymes potentially involved in LDPE chain scission. A model was proposed suggesting a coordinated role between ROS and extracellular enzymes in the biodegradation of LDPE. This indicates strains Z-1 and Z-2 can degrade LDPE, providing a basis for deeper exploration of biodegradation mechanisms.

Cascadic degradation of selected polyolefin grades in a simulated closed-loop recycling process

AbstractReintroducing recycled plastics into production processes can lead to irreversible degradation and changes in their properties, thereby limiting their recycling potential to a finite number of loops. This study investigates the impact of process-induced degradation resulting from multiple reprocessing cycles on specific material properties and aims to establish structure–property relationships. Four different polyolefins, including two polypropylenes, high-density polyethylene, and low-density polyethylene, were selected for the study. The materials underwent extrusion, pelletizing, injection molding, and milling before being reintroduced into the reprocessing cycle. This sequence of processing steps was repeated six times on each material. Various characterization techniques, including high-temperature gel permeation chromatography, melt mass flow rate, parallel-plate rheology, differential scanning calorimetry, gas chromatography–mass spectrometry, and optical defect control system, were performed to evaluate the molecular structure, rheological behavior, thermal stability, and the resulting contaminants and defects after each reprocessing step. The reprocessing of polypropylene resulted in a gradual decrease in the average molecular weights accompanied by a shift to lower viscosities and higher melt mass flow rates, whereas the polyethylene grades showed the opposite trend with a less pronounced effect in high-density polyethylene. The volatile organic compounds rose in polypropylene and sank in polyethylene after reprocessing. Additionally, all four materials exhibited an increase in degradation-related defects based on optical defect analysis. Graphical abstract

Identification of plastic-degrading bacteria in the human gut

Environmental pollution caused by the excessive use of plastics has resulted in the inflow of microplastics into the human body. However, the effects of microplastics on the human gut microbiota still need to be better understood. To determine whether plastic-degrading bacteria exist in the human gut, we collected the feces of six human individuals, did enrichment cultures and screened for bacterial species with a low-density polyethylene (LDPE) or polypropylene (PP)-degrading activity using a micro-spray method. We successfully isolated four bacterial species with an LDPE-degrading activity and three with a PP-degrading activity. Notably, all bacterial species identified with an LDPE or PP-degrading activity were opportunistic pathogens. We analyzed the microbial degradation of the LDPE or PP surface using scanning electron microscopy and confirmed that each bacterial species caused the physical changes. Chemical structural changes were further investigated using X-ray photoelectron spectroscopy and Fourier-transform-infrared spectroscopy, confirming the oxidation of the LDPE or PP surface with the formation of carbonyl groups (C=O), ester groups (CO), and hydroxyl groups (-OH) by each bacterial species. Finally, high temperature gel permeation chromatography (HT-GPC) analysis showed that these bacterial species performed to a limited extent depolymerization. These results indicate that, as a single species, these opportunistic pathogens in the human gut have a complete set of enzymes and other components required to initiate the oxidation of the carbon chains of LDPE or PP and to degrade them. Furthermore, these findings suggest that these bacterial species can potentially biodegrade and metabolize microplastics in the human gut.

Influence of various pretreatments on molecular and rheological properties of a linear and a long-chain branched polypropylene

The influence of a mechanical or a thermal pretreatment of a linear (L-PP) and a long-chain branched polypropylene (LCB-PP) in the molten state was studied. The molar mass distributions and the branching structure were determined by high-temperature gel permeation chromatography HT-GPC coupled with laser-light scattering. The samples were extruded through long or short capillaries of various geometries corresponding to a predominant shear or elongational deformation. As a rheological probe, the extrudate swell at low stresses was measured for the differently pretreated samples. For the L-PP, neither molecular nor rheological changes were observed. However, the extrudate swell of the LCB-PP was found to decrease with increasing volume throughput. It was more strongly affected by shear in the capillary than by molecule stretching in the entry region. The smaller extrudate swell was accompanied by a decrease of the high molar mass tail of the LCB-PP, which could be the reason for the decay of swell, in principle. However, a comparable degradation of the high molar mass tail was obtained by a pure thermal treatment that was shown to leave the extrudate swell unchanged. This result and the unaffected branching structures found by high-temperature gel permeation chromatography (HT-GPC) support the hypothesis of a change of the branching topography by the mechanical pretreatment.

Influence of chain entanglements and melt memory effect on the crystallization behavior of polyphenylene sulfide

Polyphenylene sulfide (PPS) has a prospective application in high-frequency communication due to its excellent dielectric properties. However, owing to the strong melt memory effect, the crystalline structure of PPS is very sensitive to the processing conditions and difficult to be controlled. To date, the melt memory effect of polymer cannot be detected directly and quantitatively. In this work, four PPS samples were successively prepared via polymerization, extrusion and dissolution treatment. The Fourier infrared transform spectroscopy (FTIR), high-temperature gel permeation chromatography (HT-GPC) and dynamic rheological tests disclose that these four PPS samples have analogous molecular structure and only differ in entanglement density. The molecular weight between entanglements (Me) decreases gradually from 1188 to 354 g/mol. Furthermore, differential scanning calorimetry (DSC) and polarized optical microscopy (POM) measurements were carried out to study the effect of entanglement density on the crystallization kinetics of PPS. It is found that entanglement density is a key indicator to characterize the melt memory effect of PPS semi-quantitatively, and the residual local ordered structures in PPS melt is proportional to Me. In addition, the crystallization kinetics of PPS is determined by the cooperation of melt memory effect (nucleation) and entanglement density (growth). Accordingly, the relationship of “chain entanglements” → “melt memory effect” → “crystallization behavior” of PPS is established, constructing a roadmap for the precise control of crystalline structures of PPS products during practical processing.

Influence of Cooling Rate on the Temperature Rising Elution Fractionation of One Poly(1‐butene‐co‐ethylene) Resin and Microstructure of Its Fractions

AbstractTREF (temperature rising elution fractionation) is a method to separate resins based on crystallizability. The influence of TREF cooling rate (V0) on the fractionation process is still unclear. Herein, a poly(1‐butene‐co‐ethylene) resin is fractionated by the TREF method at three different cooling rates (1, 2, and 4 °C h−1), and then the fractions are analyzed by high‐temperature gel permeation chromatography (HT‐GPC), differential scanning calorimetry (DSC), and 13C‐nuclear magnetic resonance spectroscopy (13C‐NMR). The cooling rate V0 affects the crystallization process of the PB‐1 resin, resulting in different fraction contents at the same elution temperature. Furthermore, the cooling rate also affects the chain microstructure of fractions obtained from the same elution temperatures, i.e., the content of 1‐butene and ethylene monomer units, average sequence length and isotacticity. The lower cooling rate is beneficial to the effective separation of the fractions with weak crystallizability. These results have important guidance for optimizing fractionation conditions and obtaining different narrow distribution fractions of poly(1‐butene) (PB‐1) resin.

Comparative study on the degradation of HDPE, LLDPE and LDPE during multiple extrusions

Stricter regulations of plastics waste and the enforcement of higher recycling quotas has led to an increasing interest in recycling. One of the most prominent recycling strategies is mechanical recycling, which is based on sorting, pre-treatment and remelting of plastics waste. As repeated reprocessing, may be associated with a reduced quality of the obtained recyclates, approaches for the characterization of these materials by analytical techniques need to be developed. These should help to identify recyclates that will not fulfil the requirements but also to provide data allowing to take countermeasures (such as addition of a certain percentage of virgin material and/or polymer stabilizers). Three different polyethylene (PE) types (high-density (HDPE), linear low-density (LLDPE) and low-density (LDPE)) were subjected to long-time extrusion experiments in order to gain a better understanding of degradation occurring during multiple recycling steps (as expected in a circular economy). Unstabilized material as well as PE with two different stabilizers, Irganox 1010 (IX1010) and Irgafos 168 (IF168) were investigated, employing high temperature gel permeation chromatography with infrared spectroscopic detection (HT-GPC-IR), thermo desorption gas chromatography-mass spectrometry (TD-GC-MS) and high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (HPLC-qTOF-MS) (the latter primarily used for analysing stabilizer degradation). The direct comparison of the PE types revealed significant differences regarding the degradative behaviour. One main conclusion is the possible use of short n-alkanes (below 30 carbon atoms) as a quality markers in the recycling process, as unique trends in the breakdown of polymer chains were found for each PE type. Both HDPE and LLDPE showed an increase in odd numbered n-alkanes, but only HDPE showed a constant decrease in the even numbered ones. For LDPE odd and the even numbered n-alkanes were increasing during extrusion. Focusing on the effect of the added stabilizers, IF168 alone had little to no impact, whereas the presence of IX 1010 showed a beneficial influence on polymer degradation – a trend that was even intensified when both stabilizers were combined. Also, in this case differences between the three PE types could be observed. In HDPE and LDPE stabilizers were consumed during extrusion to a higher extent than in LLDPE.

Unraveling the comonomer distribution in ethylene – vinyl ester terpolymers through liquid chromatography with infrared detection

Polyolefins are the most commercially relevant polymers by volume. A readily available feedstock and their tailor-made microstructure allow to adapt polyolefins to many fields of application. Important molecular design features of olefin copolymers are the molar mass distribution (MMD) with the corresponding average values, comonomer type, chemical composition distribution (CCD) with the corresponding average and the tacticity distribution (TD). Advanced separation techniques i.e., high-temperature gel permeation chromatography (HT-GPC) as well as its hyphenation with high-temperature high performance liquid chromatography (HT-HPLC) in the form of high-temperature two-dimensional liquid chromatography (HT 2D-LC) have been successfully applied in this work. This allowed to deeply analyze the molecular heterogeneities of complex polyolefin terpolymers consisting of ethylene, vinyl acetate and branched vinyl ester monomers. By using filter-based infrared detection, the capabilities of HT-GPC are further extended so that the distribution of methyl- and carbonyl groups could be obtained along the molar mass axis. Using porous graphitic carbon (PGC) as a stationary phase for HT-HPLC separation provided information about the CCD of these complex polyolefins from experimental data as part of the hyphenated approach of HT 2D-LC. The latter revealed the full MMD x CCD distribution function, which is the key for a comprehensive analysis of the bivariate molecular structure of the polyolefin terpolymers.

Biodegradation of additive-free polypropylene by bacterial consortia enriched from the ocean and from the gut of Tenebrio molitor larvae

Accumulation of highly recalcitrant PP wastes has caused a serious environmental pollution. We evaluated the biodegradation of two types of additive-free PP polymers by microbial degraders from different environments. Two bacterial consortia, designated as PP1M and PP2G, were enriched from the ocean and from the guts of Tenebrio molitor larvae. Both consortia were able to utilize each of two different additive-free PP plastics with relatively low molecular weights (low molecular weight PP powder and amorphous PP pellets) as the sole carbon source for growth. After a 30-day incubation, several plastic characterization methods, including high-temperature gel permeation chromatography, scanning electron microscopy, Fourier transform infrared spectroscopy, and differential scanning calorimetry, were used to characterize the PP samples. The bio-treated PP powder was covered with tight biofilms and extracellular secretions with significantly increased hydroxyl and carbonyl groups and slightly decreased methyl groups. This suggested that degradation and oxidation had occurred. The altered molecular weights and the increased melting enthalpy and average crystallinity of the bio-treated PP samples all suggested that both consortia preferred to depolymerize and degrade the fractions with molecular weights of ≤34 kDa and the amorphous phase fractions of the two types of PP. Furthermore, low molecular weight PP powder was more susceptible to bacterial degradation compared to amorphous PP pellets. This study provides a unique example of different types of additive-free PP degradation by different culturable bacteria from the ocean and insect guts as well as a feasibility of PP waste removal in different environments.

A systematic study on the effect of co-catalysts composition on the performance of Ziegler-Natta catalyst in ethylene/1-butene co-polymerizations

Effect of the type and composition of conventional co-catalysts on the catalytic performance of Ziegler-Natta catalysts has been investigated by means of a combined experimental and theoretical study. Two fully alkylated co-catalysts (triethylaluminium, TEA, and triisobuthylaluminium, TIBA) and their combinations with two chlorinated ones, DEAC (diethylaluminiumchloride) and EADC (ethylaluminiumdichloride), were employed in ethylene/1-butene co-polymerization using a commercial TiCl4/MgCl2 catalyst. The highest co-polymerization rate was found for TEA and TIBA, without the addition of chlorinated co-catalysts. According to the high temperature gel permeation chromatography and the rheometric mechanical spectrometer analyses, the composition of DEAC with TEA and TIBA lead to the production of polymers with the highest molar mass and longer relaxation times. The promising influence of chlorinated Al-alkyl co-catalysts was on the comonomer incorporation since the combination of TIBA + DEAC could promote it up to 34%. Eventually, to elucidate the role of the co-catalysts on the comonomer response, density functional calculations were performed using ethylene and propylene as monomers. Lower energy barrier was observed in propylene insertions in the presence of DEAC and TIBA co-catalysts, demonstrating their positive impact on comonomer response, in comparison to TEA and EADC, which confirm the experimental evidence.

Evaluation of the Dielectric and Insulating Properties of Newly Synthesized Ethylene/1-Hexene/4-Vinylcyclohexene Terpolymers

Terpolymerizations of newly synthesized ethylene (E), vinylcyclohexene (VCH), and 1-hexene were carried out with symmetrical metallocene catalysts rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (catalyst A) and rac-Et(Ind)2ZrCl2 (catalyst B). X-ray diffractometry (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), high-temperature gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy were used to evaluate the behavior and microstructure of the polymers. The activity of catalyst B was 1.49 × 106 gm/mmolMt·h), with a Tm of 73.45 (°C) and ΔHm of 43.19 (J/g), while catalyst A produced first higher 1-hexene, 19.6 mol %, and VCH contents with a narrow molecular weight distribution (MWD). In previous reports, ethylene propylene monomer dienes (EPDM) had a low content and were used for dielectric and insulating properties with nanomaterials. Second, this paper presents a kind of elastomeric polymers based on E/1-hexene and VCH with a high dielectric constant (k = 6–4) and mechanical properties. In addition, low dielectric loss suggests the suitable application potential of these polymeric materials for the fabrications of capacitors. Also, this work reveals that these polymers can be a better candidate for high-voltage electrical insulation due to their enhanced dielectric, mechanical, and thermal characteristics. To examine the insulating property, the interface characteristics of the polymer were evaluated using electrochemical impedance spectroscopy (EIS) with a frequency range of 1 × 105–0.01 Hz and an amplitude of 5.0 mV. EIS is an effective method to investigate the polymers’ interfacial electron transfer characteristics. The EIS Nyquist plot showed high Warburg impedance features in the low-frequency domain with straight lines without a semicircle, suggesting that the property of the polymer owing to the high electrical resistance and poor conductivity for ionic kinetics in the electrolyte may have surpassed that of the semicircle. Although the slope of low frequencies in polymers holding potent exoelectrogenic bacteria (Shewanella oneidensis MR-1) as a charge carrier in the electrolyte could significantly reduce the Warburg resistance, it still could not improve the conductivity, which demonstrated that the external charge supply could not alter the insulating property in the used polymers.

Thermal Diffusivity and Conductivity of Polyolefins by Thermal Lens Technique.

A mode-mismatched thermal lens spectrometry (TLS) technique, in a pump–probe two-laser-beam configuration, was employed for the experimental determination of the thermal properties of four selected well-characterized polyolefin homopolymer films. We investigated the thermal diffusivity (D) and thermal conductivity (κ) of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene. We also measured the structural properties (i.e., average molecular weight, polydispersity index, branching number), along with the rheological and thermal properties (i.e., melting point, specific heat capacity Cp, degree of crystallinity) of samples by high-temperature gel permeation chromatography (HT-GPC), rheometric mechanical spectrometry (RMS), differential scanning calorimetry (DSC), and densitometry. The relationship between microstructural properties such as degree of crystallinity, D, and κ was investigated. The results show that there is good correlation between the degree of crystallinity and D. The TL technique enables measurement of D in semitransparent thin films within an uncertainty of 4%.

Determination of the Influence of Multiple Closed Recycling Loops on the Property Profile of Different Polyolefins.

In a circular economy, polymeric materials are used in multiple loops to manufacture products. Therefore, closed-loops are also envisaged for the mechanical recycling of plastics, in which plastic is used for products that are in turn collected and reprocessed again and again to make further products. However, this reprocessing involves degradation processes within the plastics, which become apparent through changes in the property profile of the material. In the present paper, the influence of multiple recycling loops on the material properties of four different polyolefins was analyzed. Two different closed-loop cycles with industrially sized processing machines were defined, and each polyolefin was processed and reprocessed within the predefined cycles. For the investigation of the effect of the respective loops, samples were taken after each loop. The samples were characterized by high-pressure liquid chromatography coupled to a quadru-pole time-of-flight MS, high-temperature gel permeation chromatography, melt flow rate measurements, infrared spectroscopy, differential thermal analysis, and tensile tests. With increasing number of processing loops, the tested polyolefins showed continuous material degradation, which resulted in significant changes in the property profiles.

18.55% Efficiency Polymer Solar Cells Based on a Small Molecule Acceptor with Alkylthienyl Outer Side Chains and a Low-Cost Polymer Donor PTQ10

18.55% Efficiency Polymer Solar Cells Based on a Small Molecule Acceptor with Alkylthienyl Outer Side Chains and a Low-Cost Polymer Donor PTQ10

Effect of oxygen on the radiation of silicone rubber determined by gaseous chromatograph and DFT calculation

The radiation effects of silicone rubber under different atmospheres are of great significance to evaluate the aging behavior of materials, and to assess their practical application life. The radiation-induced cross-linking and degradation of polydimethylsiloxane rubber were confirmed firstly by 1H NMR and high-temperature GPC, respectively. By using the established gas collecting system and gaseous chromatography method, we systematically investigated the gaseous products of irradiated silicone rubber at different oxygen concentrations. With the increase of oxygen concentration, the yield of CH4 decreases sharply, while the yield of hydrogen changes slightly. It can be further demonstrated that the reduction of CH4 concentration in the irradiated silicone rubber system is mainly due to the inhibition of CH4 formation, instead of the CH4 degradation, indicating that oxygen directly influences the conversion process of methyl radicals. Similarly, by monitoring the oxygen consumption, it is proved that oxygen is directly involved in the degradation process of silicone rubber, and oxygen scavenged the methyl radicals, which supressed the conversion process of methyl radicals to CH4. Finally, the radiation-induced crosslinking and degradation mechanism of raw silicone rubber was deduced by combining the gaseous products analysis and DFT calculation. It is demonstrated that the release of CH4 can be used to assess the radiation effect of silicone rubber. This work provides a novel method to understand deeply the radiation-induced crosslinking and degradation mechanism of silicone rubber under different atmospheres.

Degradation of UV-pretreated polyolefins by latex clearing protein from Streptomyces sp. Strain K30

Plastic products made of polyethylene (PE), polypropylene (PP), and polystyrene (PS) are widely used in daily life and industrial production. Polyolefins—which have a very stable structure and do not contain any active molecular groups—are difficult to degrade and pose a serious global environment threat. This study selected latex clearing protein (LcpK30) derived from Streptomyces sp. Strain K30. The natural substrate of the enzyme is rubber (cis-1, 4-polyisoprene), and the site of action is the carbon‑carbon double bond. LcpK30 was incubated with UV-irradiated polyolefin PE, PP and PS (UV-PE, UV-PP, and UV-PS containing carbon‑carbon double bonds) for 5 d at 37 °C. The results showed that UV-PE-LcpK30 was more fragmented than UV-PE-blank; the Fourier transform infrared spectroscopy results showed that UV-PE-LcpK30 and UV-PP-LcpK30 produced new active groups (e.g., –OH and –C=O); however, the effect on UV-PS was not significant. Scanning electron microscopy results showed that the treated group had more obvious roughness, cracks, and pits than the control group. The results of high-temperature gel permeation chromatography showed that the average molecular weight (Mw) of UV-PE-LcpK30 and UV-PP-LcpK30 decreased; the Mw of UV-PE5-LcpK30 was reduced by 42.02%. The results of gas chromatography–mass spectrometry showed the production of ketones. Therefore, the LcpK30 latex clearing protein degrade UV-oxidized polyolefin plastics and has great potential for PE and PP degradation but may not be suitable for PS. Furthermore, other Lcps (such as LcpNRRL, LcpNVL3) can also degrade UV-PE.

Systematic Investigation of Solution-State Aggregation Effect on Electrical Conductivity in Doped Conjugated Polymers

Systematic Investigation of Solution-State Aggregation Effect on Electrical Conductivity in Doped Conjugated Polymers

Investigations on the influence of multiple extrusion on the degradation of polyolefins

The importance of mechanical recycling of polymers has increased within the last decades, especially due to numerous regulations of governments all over the world. Hereby recycling quotas are enforced to pave the way towards a closed loop recycling. During its lifetime, polymers are exposed to multiple environmental factors, which can already induce degradation. However, a major factor that needs to be taken into account is the increased thermo-mechanical stress during the recycling process, which may have significant impact on the quality of recyclates as well. In the present work, polyolefins (high-density polyethylene and polypropylene) were artificially exposed to stress by continuous extrusion at varying speeds and absence or presence of stabilizers to analyze the extent to which the recycling contributes to degradation processes. These samples were analyzed for low-molecular-weight stress markers by thermodesorption gas chromatography and by high-performance liquid chromatography (both coupled to mass spectrometric detection). Depending on the extent of stress, the occurrence of odd-numbered linear alkane chains was revealed in polyethylene samples, and of oxidized branched alkanes in polypropylene samples. Correlations with molecular weight (determined by high temperature gel permeation chromatography) and with decreasing concentrations of stabilizers could be demonstrated.

Influence of isothermal crystallization temperature on the temperature rising elution fractionation for a poly(1-butene-co-ethylene) resin

Temperature Rising Elution Fractionation (TREF) is effective for separating polyolefin resins according to crystallizability. A relatively low isothermal crystallization temperature is necessary to fractionate poly(1-butene) (PB-1) resin because of its slow crystallization kinetics. This study aims to investigate the influence of isothermal crystallization temperature of TREF on the fractionation and chain microstructure of eluted fractions for one poly(1-butene-co-ethylene) with 5.8 mol% ethylene. The resin is fractionated using P-TREF under four different isothermal crystallization temperatures, i.e. 0 °C, −5 °C, −10 °C, and −30 °C, and then the fractions are characterized by high-temperature gel permeation chromatography (HT-GPC), 13C nuclear magnetic resonance spectroscopy (13C NMR), and differential scanning calorimetry (DSC) to acquire their chain microstructure information. The isothermal crystallization temperature significantly affects the nucleation and growth of the crystals, which consequently results in differences in the relative content of eluted fractions. With the decrease of isothermal crystallization temperature from 0 °C to −30 °C, the copolymer is fractionated more effectively since fractions are more evenly distributed among elution temperatures rather than concentrated at lower elution temperatures. Furthermore, the isothermal crystallization temperature influences the chain microstructure of fractions obtained at the same elution temperature, which are different in ethylene content, isotacticity, and average sequence length. The distribution of ethylene content and isotacticity becomes broader with the decrease in isothermal crystallization temperature. Lower isothermal crystallization temperature is conducive to effective separation of the fractions with weak crystallizability. These results are of great significance for the selection of fractionation conditions and chain microstructure analysis of poly(1-butene-co-ethylene) resins.