Short Chain Branching Research Articles

Tearing properties, crystallization behavior, microstructure, and morphology of LLDPE with different short branched chain distributions

Abstract The length and distribution of comonomers with short-chain branching (SCB) have a significant influence on the crystallization behavior and crystal structure of polymers, as well as the mechanical properties of the material. This study investigates the crystallization behavior and properties of linear low-density polyethylene (LLDPE) samples with similar density, molecular weight, and branching degree but varying SCB distributions. The results show that LLDPE with butene as the comonomer has a stronger ability to suppress crystallization compared to LLDPE with hexene as the comonomer due to its more uniform SCB distribution. Additionally, among LLDPEs with comonomers of octene, hexene, and butene, the LLDPE with the most uniform SCB distribution exhibits the weakest crystallization ability. Small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) results indicate that LLDPE with more uniform distribution of SCB has smaller long-period and more regular lamellar structure. Therefore, LLDPE with more uniform SCB distribution exhibits weaker inhibition ability towards crystallization, leading to less agglomerated phases and weaker phase separation, resulting in higher tear strength.

Impact of molecular architecture and draw ratio on enhancement of targeted mechanical properties of machine direction oriented polyethylene films produced after blown film extrusion

Conventional multi-material multi-layer flexible packaging offers excellent properties. However, it has recycling challenges, necessitating a shift to mono-material multi-layer flexible packaging for example all-polyethylene (PE) packaging which can be tailored through various synthesis and processing methods for different layers. In this work, we study how the key molecular properties (number-average molecular weight ( Mn), weight-average molecular weight ( M w), molecular weight distribution (MWD), comonomer content (short chain branching)) and machine direction orientation (MDO) process draw ratio (MDX) influence the final morphology and mechanical properties of MDO-PE films which are intended as the outer layer of mono-material all-polyethylene multi-layer flexible packaging. Five PE grades and various blends were extruded and blown into films. Selected blown films were machine direction oriented to obtain the final MDO-PE films. Furthermore, one selected PE blown film was processed at different MDO process draw ratios while keeping other process parameters constant. From the molecular properties point of view, the higher molecular weight fractions provide a higher possibility for uniform stretching whereas lower molecular weight fractions provide a higher natural draw ratio and therefore higher modulus and stiffness enhancement. Further, the results show that increasing MDO process draw ratio leads to more fibrillation and increased crystallinity. Consequently, the tensile modulus and stiffness at the higher draw ratios increase as well and are comparable to conventionally used polymers in outer layers of multilayer flexible packaging. Thus, this work demonstrates that MDO-PE films with enhanced modulus can provide sufficient stiffness for the design of outer layer of mono-material multi-layer all-PE packaging which presents higher potential for mechanical recyclability.

Relationship between microstructure changes and embrittlement during chemo-oxidative degradation of bimodal HDPE with short chain branches

Relationship between microstructure changes and embrittlement during chemo-oxidative degradation of bimodal HDPE with short chain branches

Synthesis of linear low-density polyethylene waxes through chain-walking benzocycloalkyl nickel-catalyzed ethylene polymerization

Polyethylene wax is a highly useful material, and its diverse topological structures may have a significant impact on its applications. In this study, we have devised and synthesized a series of unilateral benzocycloalkyl α-diimine nickel catalysts. These nickel catalysts exhibited very high activities (1.06 to 10.25 × 106 g mol-1·h-1) and yielded branched (37–97/1000 C) polyethylene waxes with low molecular weights (Mn = 0.49 to 2.01 kg mol-1) and variable molecular weight distributions (1.79–35.05) in ethylene polymerization. Polymerization conditions such as pressure and temperature and catalyst structure such as backbone and axial substituents have an important influence on the polymerization activity and the properties of the resulting polyethylene waxes. High-temperature NMR reveals that these branched polyethylenes primarily feature short-chain branches, such as the methyl group, and exhibit a topology resembling that of low-molecular-weight linear low-density polyethylene (LLDPE).

Benchtop-Stable Carbyl Iminopyridyl NiII Complexes for Olefin Polymerization.

Design of catalysts for Ni-catalyzed olefin polymerization predominantly focuses on ligand design rather than the activation process when attempting to achieve a broader scope of polyolefin micro- and macrostructures. Air-stable alkyl-or aryl-functionalized NiII precatalysts were designed which eliminate the need of in situ alkylating processes and are activated solely by halide abstraction to generate the cationic complex for olefin polymerization. These complexes represent an emerging class of olefin polymerization catalysts, enabling the study of various cocatalysts forming either inner- or outer-sphere ion pairs. It is demonstrated that an organoboron cocatalyst activation produces a well-defined ion pair, which in contrast to ill-defined organoaluminum cocatalysts, can directly activate the complex by halide abstraction to yield comparatively higher molecular weight homo/copolymers. Under high ethylene pressure, broader branching densities and the gradual incorporation of short-chain branches were achieved, circumventing the need for elaborate ligand design and copolymerization with α-olefins. The underlying chain-walking mechanism and ion pair interactions were further elucidated by DFT calculations. A phenyl group on the bridging carbon functioned as a rotational barrier, producing higher molecular weight polymers compared to methyl-substituted analogs. Here, we provide a perspective to manipulate the iminopyridyl NiII system, leveraging ion pair interactions and ligand design to govern polyolefin molecular weights and microstructures.

Unraveling the Mechanical Response of Short-Chain Branched Amorphous Polyethylene: Insights from Molecular Dynamics Simulations

The deformation behavior of short-chain branched, amorphous polyethylene (PE) was investigated using united atom molecular dynamics (MD) simulations under uniaxial stretching. Our research reported in this paper examined the internal mechanisms underlying the mechanical response of the PE by analyzing potential energies, dihedral angle distributions, chain orientation and entanglements. The findings indicated that the short-chain branching generally enhanced Young’s modulus, except for sample B60 with a critical ethyl branch content of 60/1000 (60 ethyl branches per 1000 backbone carbons). The Young’s modulus of B60 was the local minimum value in the various samples. Analysis of the evolution of dihedral angles shows that the short-chain branching hinders the transition from gauche to trans configurations, leading to a decrease in the trans population as the branch content increases. Regarding the sample B60 with critical branch content 60/1000, the orientation parameter and entanglement parameter of the molecular chains along the backbone were lowest in the initial structure, and the efficiency of chain disentanglement was at its lowest during deformation. The simulation results elucidated the deformation mechanism related to the conformational evolution of the molecular chains, which can provide atomic-scale insights into the mechanical properties and processability of branched polyethylene, thereby allowing for optimization in its design and application.

Structural and physicochemical characteristics of starches from sorghum varieties with varying amylose content.

Six sorghum varieties containing different amylose were selected to investigate the structural and physicochemical characteristics of starches and endosperm texture of grains. The results showed that the outer layer endosperm of sorghum grain changed from waxy to corneous, and its starch granules were more compactly packed and exhibited the spindle-shaped holes with the increase of amylose content. Higher amylose starch granules exhibited fewer and smaller micropores on the surface and were more likely to deform and agglomerate into larger amorphous particles after heated. Amylose content of sorghum starches was negatively correlated to granule size, relative crystallinity, and the proportion of the long branch chains (DP = 25-36 and > 36), whereas positively correlated to the proportion of the short branch chains (DP = 6-12 and 13-24). Amylose content had negative correlations with T o , T p , ΔH, PV, and SDS (p < .05), positive corrections with FV, SB, and RDS (p < .05), and no correlations with T c , HPV, BD, and RS. It could be concluded that amylose content affected the endosperm texture of sorghum grain and had strong correlations with structural and physicochemical properties of sorghum starch. These findings may help identify uses for these sorghum varieties in baijiu production.

Fast quantitative analysis of high density polyethylene using adiabatic-refocused INEPT spectroscopy

Quantitative 13C NMR serves as a potent tool for determining the microstructure of polyolefin, but it generally requires long experiment times to achieve reliable quantification, for its low natural abundance and sensitivity. We utilized refocused insensitive nuclei enhanced by polarization transfer (RINEPT) here to characterize high-density polyethylene (HDPE) with very low branch contents. Compared with the standard quantitative experiment, this approach drastically reduces the experiment time from more than 20 h to several minutes, and boosts the signal to noise ratio by fivefold per unit of time. We have effectively applied this optimized method to determine short chain branching (SCB) in HDPE with various comonomer incorporations. Using 5 mm prodigy cryoprobe can further reduce the experiment time to approximately one-tenth that obtained by conventional probes. It means the total experiment time saved could be up to 225 times. We have quantified an SCB concentration of 7 branches per 10000 CH2 in just 2 h. Furthermore, our results demonstrated excellent concordance between RINEPT and traditional 13C NMR techniques in quantifying the branch content of HDPE, thereby validating the reliability of this method.

Effect of solvent type on chemical composition distribution analysis of polyolefins using crystallization elution fractionation (CEF)

For microstructure characterization of polyolefin by separation-based techniques with infrared detector, either 1,2-dichlorobenzene (o-DCB) or 1,2,4-trichlorobenzene (TCB) is commonly selected as a dissolution solvent and mobile phase. Herein, we studied the effects of o-DCB and TCB on the comonomer detection and chemical composition distribution (CCD) by crystallization elution fractionation (CEF) with a filter-based IR detector. We first compared the detector sensitivity on methyl group content or short chain branching (SCB) in polyethylene-co-butene with varied sample concentrations in o-DCB and TCB. TCB demonstrated superior comonomer detection in the IR detector with a single linear calibration across a wide range of sample concentrations. In contrast, o-DCB displayed stronger concentration dependent methyl group response, requiring a more complex equation in the calibration. Furthermore, o-DCB provided better separation of comonomer distribution with less peak broadening and co-crystallization effects, as observed with various polyolefins, including high density polyethylene (HDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), and ethylene-propylene copolymer (EP).

Improving Environmental Stress Cracking Resistance of High-Density Polyethylene Grades by Comonomer Addition and Nanocomposite Approach.

The aim of this paper is to determine the effect of polymer density, correlated to the comonomer content, and nanosilica addition on the mechanical and Environmental Stress Cracking Resistance (ESCR) characteristics of high-density polyethylene (HDPE). In this regard, five HDPE samples with similar Melt Flow Index (MFI) and molar mass but various densities were acquired from a petrochemical plant. Two polymerization reactors work in series and differ only in the amount of 1-buene comonomer fed to the second reactor. To ascertain the microstructure of the studied samples, GPC and SSA (successive self-nucleation and annealing) analyses were accomplished. All samples resulted having similar characteristics but slightly various SCB/1000 C=7.26-9.74 (SCB=Short Chain Branching). Consequently, meanwhile studied HDPEs reveal similar notched impact and stress at yield values, the tensile modulus, stress-at-break, and elongation-at-break tend to demonstrate different results with the SCB content. More significantly, ESCR characteristic varied considerably with SCB/1000 C extent, so that higher amount of SCB acknowledged advanced ESCR. Notably, blending HDPE sample containing higher amount of SCB/1000 C, with 3 wt.% of chemically modified nanosilica enhanced ESCR characteristic by 40 %. DFT (Density Functional Theory) calculations unveiled the role of the comonomer, quantitatively by binding energies and qualitatively by Non Covalent Interaction (NCI) plots.

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.

The influence of low-temperature shear on crystallization of shish-kebab of unimodal/ bimodal C4 short-chain branching polyethylene

The shish crystal, a crucial structure in the formation of shish-kebab crystals, has drawn widespread attention due to its highly oriented chain arrangement, significantly enhancing the mechanical properties of products. This study utilizes polyethylene samples with longer C4 short branches, employing in-situ synchrotron SAXS/WAXD to investigate the influence of short branch length and content on the formation of shish-kebab crystals in unimodal and bimodal polyethylene under low-temperature shear conditions (with supercooling degrees of 13.5 °C and 10.5 °C). The results reveal that the presence of C4 short-chain branching affects system crystallization, but low-temperature shear induces stronger mechanical action on the melt, resulting in better-oriented lamellar crystals compared to high-temperature shear (superheat degrees of 22.5 °C and 19.5 °C), achieving higher orientation. This achieves the control of shish-kebab crystal generation through the stretched network mechanism. Both types of samples with different C4 short-chain branching contents generate shish-kebab crystals during the shear stage, with relatively higher short-chain branching content inducing more shish crystal formation but with less regular structure. The bimodal polyethylene exhibit higher proportions and absolute amounts of final shish crystals compared to the unimodal polyethylene, indicating that high molecular weight portions are conducive to shish crystal generation under shear. The result demonstrates the feasibility of generating shish-kebab crystals during the low-temperature shear process of PE in the presence of C4 branches using the stretched network mechanism under shear flow conditions. Moreover, controlling the degree of entanglement of molecular chains by adjusting shear temperature, branch content, and branch length can modulate two formation mechanisms of shish crystals—coil-stretch transition mechanism at high temperature and stretched network mechanism at low-temperature.

Structural, topological, and rheological characteristics of entangled short-chain branched polymer melts under shear flow in comparison with the linear analog

We present a detailed analysis of the general influence of short branches on the structural, topological, and rheological behaviors of entangled short-chain branched (SCB) polyethylene (PE) melt systems under shear flow via direct comparison with the corresponding linear analogs using extensive atomistic nonequilibrium molecular dynamics (NEMD) simulations, for a wide range of flow strengths. In comparison with the linear melt, the SCB systems generally exhibit more compact chain structures and larger dynamic resistance, in response to an imposed flow field at all flow strengths. These features essentially arise from (i) the increased chain stiffness due to the torsional restriction of backbone atoms around the branch points and (ii) the fast random Brownian motion of short branches via their very short characteristic relaxation time. We analyzed various structural and rheological properties, such as anisotropic chain dimension and orientation and their detailed distributions, topological characteristics of the entanglement network, material functions, chain rotation dynamics, and flow birefringence. Distinctive physical characteristics of the entangled SCB systems exposed by these individual properties can be consistently understood based on the fundamental structural and dynamical roles of short branches. These findings are considered informative in our systematic understanding and prediction for the general rheological behaviors of long entangled SCB polymer systems under flow, and in tuning the material properties of SCB polymers in practical applications.

Architectural Editing of Polyesters and Polyurethanes via Palladium(II)-Catalyzed [3,3]-Sigmatropic Oxo-Rearrangements.

Architecture underlies the thermomechanical properties of polymers. Yet, few strategies are available to tune a polymer's architecture after it is prepared without altering its chemical composition. The ability to edit the architecture of a polymer would dramatically expand the accessible architecture-property space of polymeric materials. Herein, we disclose a backbone rearrangement approach to tune the short-chain branching of polymers. Specifically, we demonstrate that palladium(II)-catalyzed [3,3]-sigmatropic oxo-rearrangements can transform branched polyesters and polyurethanes to their linear counterparts. While the effects on materials properties are generally subtle in the case of polyesters, more dramatic changes are observed in the case of polyurethanes: two polyurethanes undergo a soluble-to-insoluble transition, and one exhibits a dramatic increase in both strain at break and toughness after rearrangement. Additionally, the incorporation of alkenes in the polymer backbone through the rearrangement enables facile deconstruction via ethenolysis. In all, we disclose a powerful and broad-scope strategy to edit the architecture of polymer backbones and thereby tune their physical and chemical properties.

Effects of Lactobacillus plantarum fermentation on the structure, physicochemical properties, and digestibility of foxtail millet starches

This study investigated the effects of Lactobacillus plantarum fermentation on the structural, physicochemical, and digestive properties of foxtail millet starches. The fermented starch granules formed a structure with honeycomb-like dents, uneven pores, and reduced particle size. As the fermentation time extended, the amylose content of waxy (0.88 %) and non-waxy (33.71 %) foxtail millet starches decreased to the minimum value at 24 h (0.59 % and 29.19 %, respectively), and then increased to 0.85 % and 31.87 % at 72 h, respectively. Both native and fermented foxtail millet starches exhibited an A-type crystal structure. Compared with native samples, the fermented samples performed enhanced proportion of short-branched chain, crystallinity, and short-range ordered degree. After fermentation for 24 h, the solubility, adsorption capacity, and pasting viscosity of foxtail millet starches improved, whereas the swelling power, pasting temperature, breakdown, setback, and degree of retrogradation reduced. Additionally, fermentation increased the transition temperatures, enthalpy, and digestibility. Overall, Lactobacillus plantarum fermentation is considered a competent choice to regulate the characteristics of foxtail millet starch.

Relationship between Chalkiness and the Structural and Physicochemical Properties of Rice Starch at Different Nighttime Temperatures during the Early Grain-Filling Stage.

The chalkiness, starch fine structure, and physiochemical properties of rice starch were analyzed and their correlations were investigated under different nighttime temperatures during the early grain-filling stage. Compared to MT, medium temperature (MT) and low (LNT) and high (HNT) nighttime temperatures resulted in an increased chalky grain rate (CGR) and chalkiness degree (CD). LNT mainly affected the chalkiness by increasing peak1 (short branch chains of amylopectin), the branching degree, and the proportion of small starch granules but decreasing peak2 (long branch chains of amylopectin) and peak3 (amylose branches). This altered the pasting properties, such as by increasing the peak viscosity and final viscosity. However, HNT mainly affected the chalkiness by increasing peak2 and the crystallinity degree but decreasing peak1 and peak3. Regarding the thermal properties, HNT also elevated peak and conclusion temperatures. The CGR and CD were significantly and positively correlated with the proportions of small and medium starch granules, peak1, branching degree, gelatinization enthalpy, setback viscosity, and pasting time but markedly and negatively correlated with the proportion of large starch granules, amylose content, peak3, peak viscosity, and breakdown viscosity. These findings suggest that LNT and HNT disrupted the starch structure, resulting in increased chalkiness. However, their mechanisms of action differ.

Starch spectra of Ampelopteris prolifera (Retz.) Copel, a new addition to the existing lexicon and its comparison with a local potato cultivar (Solanum tuberosum L. cv. Kufri Jyoti)

Novel kinds of starch spectra were generated from a lesser-known plant, making this investigation unique. The recent trend of starch characterization shows the establishment of novel bioresources from nonconventional unexplored databases. The present endeavor was made to obtain the starch fingerprint of Ampelopteris prolifera (rhizome) belonging to seedless vascular plants. For comparison, a commercial local cultivar of potato (Kufri Jyoti) was taken. The starch particle of A. prolifera shows much uniqueness depicting its novelty viz., crystallinity index of 60.04 %, powder diffractogram at (2θ scale)17.57° to 39.78°; this diffractogram pattern is reported from this study as newer one i.e. R type(whereas potato starch is CB type); characteristic peak at 2θ = 20.07° suggests starch-lipid complex formation and V type crystallinity (i.e. RS 5 type); FTIR spectra showing the presence of more short chain branching; high gelatinization temperature(84.62 ± 0.10), particle size and zeta value of A. prolifera is 4.00 ± 0.81 μm and − 18.91 ± 3.58 mV respectively. Bragg's peak from the single crystal X-ray diffraction has been generated for the first time of A. prolifera. Extraction of the starch particle was performed in chilled water. Therefore, the present study suggests wide-spectrum commercial utility and cost-effective production.

Effect of short-chain branches in high-molecular-weight component on tensile properties of polyethylene solids

The effects of short-chain branches (SCBs) in the high-molecular-weight (MW) chains on the solid-state tensile properties of polyethylene (PE) have been investigated using blend samples of linear PE with a polydisperse MW distribution and PE with very narrow MW distribution and SCBs with four carbons. The introduction of SCBs in the high-MW chains had almost no effect on the crystalline structure, but relaxation of the interlamellar amorphous chains was only activated by blending the high-MW chains with a large fraction of SCBs (2.0 wt%). The blends of PE with 0.4 wt% SCBs resulted in significant increases in the strain-hardening modulus and strength without greatly decreasing the strain at break. The improvement in the strain-hardening modulus and strength by adding a small amount of SCBs (0.4 wt%) was significant compared with the improvement by adding linear PE or branched PE with a large amount of SCBs (2.0 wt%). For a small amount of SCBs, the SCBs will be incorporated into the crystalline structure, which enhances the fragmentation and subsequent orientation of the crystalline structure under yielding deformation. Consequently, blending the branched PE with a small amount of SCBs in the high-MW chains leads to significant improvement of the tensile properties.

Exploring the relationship between starch structure and physicochemical properties: The impact of extrusion on highland barley flour

Highland barley (HB) is an intriguing plateau cereal crop with high nutrition and health benefits. However, abundant dietary fiber and deficient gluten pose challenges to the processing and taste of whole HB products. Extrusion technology has been proved to be effective in overcoming these hurdles, but the association between the structure and physicochemical properties during extrusion remains inadequately unexplored. Therefore, this study aims to comprehensively understand the impact of extrusion conditions on the physicochemical properties of HB flour (HBF) and the multi-scale structure of starch. Results indicated that the nutritional value of HBF were significantly increased (soluble dietary fiber and β-glucan increased by 24.05%, 19.85% respectively) after extrusion. Typical underlying mechanisms based on starch structure were established. High temperature facilitated starch gelatinization, resulting in double helices unwinding, amylose leaching, and starch-lipid complexes forming. These alterations enhanced the water absorption capacity, cold thickening ability, and peak viscosity of HBF. More V-type complexes impeded amylose rearrangement, thus enhancing resistance to retrogradation and thermal stability. Extrusion at high temperature and moisture exhibited similarities to hydrothermal treatment, partly promoting amylose rearrangement and enhancing HBF peak viscosity. Conversely, under low temperature and high moisture, well-swelled starch granules were easily broken into shorter branch-chains by higher shear force, which enhanced the instant solubility and retrogradation resistance of HBF as well as reduced its pasting viscosity and the capacity to form gel networks. Importantly, starch degradation products during this condition were experimentally confirmed from various aspects. This study provided some reference for profiting from extrusion for further development of HB functional food and “clean label” food additives.

A comparative Monte Carlo simulation of HDPE synthesis with bimodal molecular weight distribution: evaluating slurry and solution processes using dual-site metallocene catalyst

ABSTRACT This research employed Monte Carlo simulation as a computational technique to investigate the copolymerization of ethylene and 1-butene in the presence of hydrogen, utilizing slurry and solution processes. A dual-site metallocene catalyst was utilized to synthesize high-density polyethylene (HDPE) with a bimodal molecular weight distribution (MWD). The solution process accelerated copolymerization rates and hydrogen transfer compared to the slurry. Furthermore, under equivalent conditions, the solution process exhibited a twofold higher level of 1-butene incorporation into copolymer chains. Elevating 1-butene partial pressure by 50% increased weight average molecular weight ( M ¯ w ) of copolymers by 15% in solution process and 5% in slurry process. Increasing 1-butene partial pressure expanded and shifted the bimodal distribution towards higher molecular weights in both processes. Elevated hydrogen partial pressure enhanced peak heights and shifted towards lower molecular weights, with the slurry process showing stronger effects. The solution process had a range of short-chain branching per 1000 carbon atoms (SCB/1000C) (15-40), approximately twice as large as the slurry process. The slurry process resulted in more regular chains with higher crystallinity (68.7%) compared to the solution process (66.4%).