Molecular Weight Distribution Research Articles

Micronization induced gelatinization of tapioca starch and its effects on starch physicochemical and structural properties.

The vibrating superfine mill (VSM) is a machine that belongs to the micronization technique. In this study, VSM was employed to produce micronized tapioca starch by varying micronization times (15, 30, 45, and 60min). The structural and physicochemical properties of the micronized starch were then examined. Scanning electron microscopy studies revealed that micronized starch was partially gelatinized, and the granule size dramatically increased when micronization time increased. X-ray diffraction patterns showed that the relative crystallinity was decreased from 24.67% (native) to 4.13% after micronization treatment for 15min and slightly decreased after that. The solubility of micronized starch significantly increased as the micronization time increased, which was associated with the destruction of the starch crystalline structure. Differential scanning calorimetry investigations confirmed that micronized starch was "partly gelatinized," and the degree of gelatinization increased to 81.27% when the micronization time was 60min. The weight-average molar mass was reduced by 15.0% (15min), 30.9% (30min), 55.7% (45min), and 70.5% (60min), respectively, indicating that the molecular structure was seriously degraded. The results demonstrated that the physicochemical changes of micronized starch granules were related to the destruction of the starch structure. These observations would provide details on micronized starch and its potential applications. PRACTICAL APPLICATION: These observations would provide details on micronized starch and its potential applications. Moreover, we believe that when the structures of starches were known, it is probable that the effect of VSM on the structural and physicochemical properties change of other starches might be predicted by adjusting the processing time.

Scaling of the linear viscoelasticity of entangled poly(ethylene oxide) aqueous solutions

The dynamic modulus of polymer solutions and melts can be expressed as a universal function of reduced frequency when the modulus is scaled by a characteristic value according to the scaling theory of polymer physics. Although the plot of the scaled modulus as a function of the scaled frequency supports the theory, it suffers from considerable scattered distribution of data points around the hypothetical master curve. Compared with the master curve of the time–temperature superposition (TTS) of polymer melts, the master curve of polymer solutions has poor quality. Furthermore, the scale factors of polymer solutions may not show a clear dependency on molecular weight and concentrations. Experimental errors and molecular weight distribution appear to enhance the inaccuracy of the master curve. Therefore, we apply a global optimization for the superposition of the viscoelastic data of polymer solutions with various molecular weights and concentrations. The global optimization resulted in the superposition of data as accurate as that of TTS. Furthermore, the numerically determined shift factors, which were relative scale factors, showed clear dependences on molecular weight and concentrations. We compared our global optimization with previous scaling methodologies.

Preparation and Characterization of H-Shaped Polylactide.

An H-polymer has an architecture that consists of four branches symmetrically attached to the ends of a polymer backbone, similar in shape to the letter "H". Here, a renewable H-polymer efficiently synthesized using only ring-opening transesterification is demonstrated. The strategy relies on a tetrafunctional poly(±-lactide) macroinitiator, from which four poly(±-lactide) branches are grown simultaneously. 1H NMR spectroscopy, size exclusion chromatography (SEC), and matrix-assisted laser desorption/ionization (MALDI) spectrometry were used to verify the macroinitiator purity. Branch growth was probed using 1H NMR spectroscopy and SEC to reveal unique transesterification phenomena that can be controlled to yield architecturally pure or more complex materials. H-shaped PLA was prepared at the multigram scale with a weight-average molar mass Mw > 100 kg/mol and low dispersity Đ < 1.15. Purification involved routine precipitations steps, which yielded products that were architecturally relatively pure (∼93%). Small-amplitude oscillatory shear and extensional rheology measurements demonstrate the unique viscoelastic behavior associated with the H-shaped architecture.

Physicochemical Properties and Fine Structure of Starch in Jinong Xiangruan 1 and DGR1 Soft Rice Varieties Cultivated in Different Regions of China

Rice, a staple food for billions around the globe, is cultivated in numerous forms. Among them, soft rice is well known, which is characterized by its tender, creamy consistency and desirable texture. In this study, we examined the physicochemical properties and fine structure of starch from two soft rice varieties, Jinong Xiangruan 1 and DGR1, cultivated in different regions in China (Baodi District, Tianjin City; Liaoning Province; and Fengyang City, Anhui Province). The aim was to understand how amylopectin content (AC) influences rice quality. This research aims to bridge the knowledge gap regarding the role of amylopectin in determining rice’s adhesive consistency and viscosity. Significant regional differences were observed in yield components such as the number of grains per panicle, seed setting rates and 1000-grain weight, with Liaoning generally showing higher performance metrics compared to other regions. Physicochemical analysis highlighted that though glue consistency and taste values showed little regional variation, AC significantly influenced rice hardness and viscosity. Rapid Visco Analyzer (RVA) profile analysis further demonstrated distinct differences in viscosity characteristics, underscoring the regional impacts on starch behavior. Additionally, molecular weight distribution and amylopectin chain length analysis, conducted via SEC-MALLS-RI and ICS ion chromatography, revealed notable differences in starch composition across varieties and locations. The findings suggest that environmental conditions play a crucial role in defining starch characteristics and, consequently, the eating quality of rice. This provides valuable insights for breeding high-quality japonica rice with broad adaptability.

Synergy of metallic Co and oxygen vacancy sites in Co/Ce-MOF catalysts for efficiently promoting lignin derived phenols and macromolecular lignin hydrodeoxygenation

The enhanced utilization of biomass-derived chemicals for the generation of high value aromatics through an advanced catalytic strategy has captured considerable attention within the realm of eco-friendly manufacturing. This work presented four innovative three-dimensional rod-shaped mesoporous Ce-based MOF materials, which were coupled with a H-donor solvent to facilitate vanillin hydrodeoxygenation and macromolecular lignin. Under the optimized conditions (30 mg CoCe@C catalyst, 2 MPa N2 pressure, 15 mL isopropanol, 190 °C, and 5 h), the CoCe@C catalyst achieved nearly complete conversion of vanillin and demonstrated 87.8 % selectivity in the hydrogen-donor solvent. The characterization findings suggested that the synergy between metallic Co and oxygen vacancy sites enabled the effective activation of CHO group in vanillin, leading to formation of reactive product MMP. In addition, the optimal CoCe@C catalyst could also achieve macromolecular lignin hydrodeoxygenation to obtain high yield of lignin oil products with narrower molecular weight distribution. This study presented a viable approach for the concurrent utilization of lignin derivatives in the generation of high value fuels and chemicals.

Experimental Tensile Strength Analysis of Different Manufacturer Oring

Importance and Purpose of Tensile Testing on ORings The tensile test on rings and especially on O-rings is primarily carried out for quality assurance reasons. The tensile test provides information about the formulation quality (evaluation of the absolute values, strength of the material, and determination of formulation changes). For example, it is not possible to detect an exchange of the polymer of compounds with different molecular weights and/or a different molecular weight distribution (e.g. highviscosity press mix by low-viscosity spray mix) by infrared spectroscopy (IR), but only by tensile testing and possibly by long-term compression set tests. Furthermore, the tensile test provides information on subsequent changes compared to the prototype condition. The Influence of Processing In the case of some O-rings, due to poor processing, it is not the strength value of the material that is determined, but the lower strength of the joining line (= confluence point of the rubber compound in the production of the O-ring in the injection mold) at which the O-ring tears. This problem depends on the material (e.g. certain acrylate rubbers), the tool and the process parameters. The joining line can usually be detected in advance by a visual and strain test or by relatively large scatter in a tensile test. Typical for the scatter in tensile tests of O-rings are 5-10%-points standard deviation related to the mean value of the elongation at break or the tensile strength. An important characteristic of good processing is the achievement of the optimum degree of vulcanization. However, there is no generally valid optimum, but this must be determined depending on the intended application of the elastomeric component. If, for example, the tear resistance is the most important material parameter for the finished product, a different degree of crosslinking or a different cross linking density must be aimed for than if, for example, a low

Effects of different extraction methods on the structure and function of blackberry seed polysaccharides

SummaryThe different extraction methods including hot‐water extraction, ultrasound‐assisted extraction, and microwave‐assisted extraction, enzyme‐assisted extraction, ultrasound and microwave‐assisted extraction, and ultrasound and enzyme‐assisted extraction (UEE) methods were carried out to extract blackberry seed polysaccharides (BSPs). The extraction yield, structure, antioxidant capacity, and glucometabolic enzyme inhibition activities of BSPs were determined in this work. Extraction methods have no influence on the monosaccharide composition of BSPs but affected the molar ratio of monosaccharides. Fourier transform infrared spectroscopy and X‐ray diffraction results showed that the extraction method cannot effect on the functional groups and crystal forms of BSPs. The findings also revealed that UEE led to the highest BSP extraction yield (4.56%), highest antioxidant capacities, and highest α‐amylase (48.49%) and α‐glucosidase (67.33%) inhibitory rates, which may because of the dispersed molecular weight distribution and loose microstructure of BSPs. These results suggest that UEE may be used in the industry to obtain BSPs with high functional activities.

Sequence of monomers and position of stereocenters matter for thermal properties of stereocontrolled oligourethanes.

Polyurethanes are commodity materials used for multiple applications. In recent years, a new category of polyurethane material has emerged, characterized by the lack of polymer molar mass distribution, control of the monomer arrangement in the chain, and even full stereocontrol. Various multistep synthesis strategies have been developed to fabricate sequence-defined polyurethanes. However, synthesizing stereocontrolled polyurethanes with a controlled sequence is still a challenge. Polyurethanes with structural precision, as represented by biopolymers, i.e. proteins or nucleic acids, have opened new application directions for these groups of materials. It has been shown that polyurethanes can be used as biomimetics, information carriers, molecular tags, and materials with strictly controlled properties. Precise synthesis of macromolecules allows us to fine-tune the properties of polymers to specific needs. Therefore, it is essential to collect information on the sequence-structure relationship of polymers. In our work, we present synthetic pathways to make sequence and stereo-defined oligourethanes. We demonstrate that structural details, i.e., the monomer sequences and position of the stereocenter, have a tremendous effect on the thermal properties of model oligourethanes. We show that the introduction of chirality by constitutional isomerization can be used to program the thermal characteristics of polymers, which are key features for material applications.

Crystallographic Texture Evolution in 3D Printed Polyethylene Reactor Blends.

In this work, crystallographic texture evolution in 3D printed trimodal polyethylene (PE) blends and high-density PE (HDPE) benchmark material were investigated to quantify the resulting material anisotropy, and the results were compared to materials made from conventional injection molded (IM) samples. Trimodal PE reactor blends consisting of HDPE, ultrahigh molecular weight PE (UHMWPE), and HDPE_wax have been used for 3D printing and injection molding. Changes in the preferred orientation and distribution of crystallites, i.e., texture evolution, were quantified utilizing the wide angle X-ray diffraction through pole figures and orientation distribution functions (ODFs) for 3D printed and IM samples. Since the change in weight-average molecular weight (Mw) of the blend was expected to significantly affect the resulting crystallinity and orientation, the overall Mw of the trimodal PE blend was varied while keeping the UHMWPE component weight fraction to 10% in the blend. The resulting texture was analyzed by varying the overall Mw of the trimodal blend and the process parameters in 3D printing and compared to the texture of conventional IM samples. The printing speed and orientation (defined with respect to the axis along the length of the samples) were used as the variable process parameters for 3D printing. The degree of anisotropy increases with an increase in the nonuniform distribution of intensities in pole figures and ODFs. All the highest intensity major texture components in IM and 3D printed samples (0° printing orientation) of reactor blends are observed to have crystals oriented in [001] or [001̅]. Overall, for the same throughput, 3D printed samples in the 0° orientation showed greater texture evolution and higher anisotropy compared to IM samples. Most notably, an increase in 3D printing speed increased the crystalline distribution closer to the 0° direction, increasing the anisotropy, while deviation from this printing orientation reduced crystalline distribution closer to the 0° direction, thus increasing isotropy. This demonstrates that tailoring material properties in specific directions can be achieved more effectively with 3D printing than with the injection molding process. Change in the overall Mw of the trimodal PE blend changed the preferential orientation distribution of the crystal planes to some degree. However, the degree of anisotropy remained the same in almost all cases, indicating that the effect of molecular weight distribution is not as significant as the printing speed and printing orientation in tailoring the resulting properties. The 3D printing process parameters (speed and orientation) were shown to have more influence on the texture than the material parameters associated with the blend.

A New Concept for Interpretation of the Viscoelastic Behavior of Aqueous Sodium Carboxymethyl Cellulose Systems.

Viscoelastic behaviors of aqueous systems of commercially available sodium carboxymethyl cellulose (NaCMC) samples with the degrees of substitution (DS) of approximately 0.68 and 1.3, and the weight-average molar masses (Mw) higher than 200 kg mol-1 dissolved in pure water and aqueous sodium chloride solutions were investigated over a wide concentration (c) range of NaCMC samples. The dependencies of the specific viscosity (ηsp), the average relaxation time (τw), and the reciprocal of the steady-state compliance (Je-1) on c were discussed. The relationships ηsp ∝ c3, τw ∝ c2, and Je-1 ∝ c, characteristic of the rod particle suspensions, were clearly observed in a range lower than the c where the critical gel behavior was observed. Thus, a new concept based on the rheology of rod particle suspensions was employed to interpret the viscoelastic behaviors obtained in the c range. In this context, NaCMC polymer molecules are assumed to behave as extended rod particles with length (L) and diameter (d), including effective electrostatic repulsive distances, due to the dissociation of Na+ in aqueous systems. Thus, the number density of polymer molecules is given to be ν = c/Mw, and viscoelastic parameters such as ηsp, τw, and Je-1 are calculated using the theoretical model for rod particle suspensions proposed by Doi and Edwards. This concept reasonably described not only the viscoelastic data obtained in this study but also those from other groups using NaCMC samples with different DS and Mw values.

RELAXATION BEHAVIOR OF 3D PRINTED NBR-BASED RUBBER O-RINGS AS INNER PART OF ROD SEALS

ABSTRACT The viscoelastic properties of rubber polymer-based compounds are crucial for further applications but challenging in the manufacturing process using additive manufacturing techniques. The fact that the first layer is attached to the printing bed restricts free relaxation after extrusion, that the part shows a strong contraction along the printing direction after release and especially after vulcanization. In this study, the molar mass distribution and acrylonitrile (ACN) content of an NBR-based compound for the fabrication of O-rings for rod seal applications was varied to demonstrate the different degree of contraction resulting from 3D printing. An ACN content of 34% and an average molar mass Mw of 2.47·105 g·mol−1 with a dispersity index D of 2.6 was found to be a suitable compromise between the degree of contraction and compression set as a criterion for the application as O-ring as inner part of rod seals.

Peculiar Behavior of Methyl Methacrylate Emulsion Polymerization-Induced Self-Assembly Mediated by RAFT Using Poly(Methacrylic Acid) Macromolecular Chain Transfer Agent.

Reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of methyl methacrylate (MMA) is successfully performed in water in the presence of a poly(methacrylic acid) (PMAA) macromolecular chain transfer agent (macroCTA) leading to the formation of self-stabilized PMAA-b-PMMA amphiphilic block copolymer particles. At pH3.7, the reactions are well-controlled with narrow molar mass distributions. Increasing the initial pH, particularly above 5.6, results in a partial loss of reactivity of the PMAA macroCTA. The effect of the degree of polymerization (DPn) of the PMMA block, the solids content, the nature of the hydrophobic segment, and the pH on the morphology of the obtained diblock copolymer particles is then investigated. Worm-like micelles are formed for a DPn of PMMA of 20 (PMMA20), while "onion-like" particles and spherical vesicles are obtained for PMMA30 and PMMA50, respectively. In contrast, spherical particles are obtained for the DPns higher than 150. This unusual evolution of particle morphologies upon increasing the DPn of the PMMA block seems to be related to hydrogen bonds between hydrophilic MAA and hydrophobic MMA units.

From laboratory to industrial use: Understanding process variation during enzymatic protein hydrolysis with dry film fourier-transform infrared spectroscopy

Industries are continuously looking for dedicated sensor solutions for evaluating the chemical composition of products that can provide valuable insights into process control, process optimization, and product quality. A rapid and robust analytical method, Fourier-Transform Infrared (FTIR) spectroscopy, holds significant potential in this regard as it provides detailed compositional values of food nutrients. The main aim of the present study was to use dry film FTIR spectroscopy as an analytical tool to characterize products from an industrial enzymatic protein hydrolysis process and link this to understand industrial process variations. For this purpose, 463 protein hydrolysate samples were obtained from an industrial enzymatic protein hydrolysis plant. In the same period, systematic variations in process parameters such as raw material composition, enzyme type, and water addition, were performed. All samples were analyzed using dry film FTIR spectroscopy. Two subsets containing 200 and 68 hydrolysate samples were chosen for measuring average molecular weight (AMW) and collagen content respectively, providing reference data for constructing calibration models based on partial least squares regression (PLSR). The percentage of low molecular weight constituents was derived from the molecular weight distribution of size exclusion chromatograms of protein hydrolysates and also used in the modeling. Calibration models for the prediction of AMW, low molecular weight constituents, and collagen content were obtained with a good fit and lower estimation errors. Principal component analysis (PCA) of protein hydrolysates' FTIR spectra effectively differentiated process variations (enzyme types and raw materials) without extensive reference analysis. One-factor analysis of variance (ANOVA) tests was used to observe the impact of process variation on product quality. FTIR proved to be a sensitive method for liquid protein analysis and process control with a significant potential in process optimization approaches. To the authors’ knowledge, this is the first time dry film FTIR spectroscopy has been used to evaluate an industrial bioprocess with designed process variations.

Leveraging Electron Push-Pull Effect for Catalytic Polymerization and Degradation of a Cyclobutane Monomer System.

Ring-opening polymerization (ROP) offers a striking solution to solve problems encountered in step-growth condensation polymerization, including precise control over molecular weight, molecular weight distribution, and topology. This has inspired our interest in ROP of cycloalkanes with an ultimate goal to rethink polyolefins, which clearly poses a number of challenges. Practicality of ROP of cycloalkanes is actually limited by their low polymerizability and elusive mechanisms which arise from significantly varied ring size and non-polar C-C bonds in monomers. In this work, by using Lewis acid/Brønsted base/C(sp3)-H initiator system previously developed in our laboratory, we focus on cyclobutanes and explore the positional and electronic effects of substituents on the ring, namely electron push-pull effect, in promoting controlled polymerization to afford densely functionalized poly(cyclobutanes), as well as catalytic degradation of obtained polymers for upcycling. More importantly, experiments and DFT calculations unveil considerable population of Lewis-acid-induced thermostabilized 1,4-zwitterions, which distinguish cyclobutanes from cyclopropanes and others. All these findings would shed light on catalytic synthesis and degradation of saturated all-carbon main-chain polymers, as well as small molecule transformations of cyclobutanes.

Leveraging Electron Push‐Pull Effect for Catalytic Polymerization and Degradation of a Cyclobutane Monomer System

Ring‐opening polymerization (ROP) offers a striking solution to solve problems encountered in step‐growth condensation polymerization, including precise control over molecular weight, molecular weight distribution, and topology. This has inspired our interest in ROP of cycloalkanes with an ultimate goal to rethink polyolefins, which clearly poses a number of challenges. Practicality of ROP of cycloalkanes is actually limited by their low polymerizability and elusive mechanisms which arise from significantly varied ring size and non‐polar C–C bonds in monomers. In this work, by using Lewis acid/Brønsted base/C(sp3)–H initiator system previously developed in our laboratory, we focus on cyclobutanes and explore the positional and electronic effects of substituents on the ring, namely electron push‐pull effect, in promoting controlled polymerization to afford densely functionalized poly(cyclobutanes), as well as catalytic degradation of obtained polymers for upcycling. More importantly, experiments and DFT calculations unveil considerable population of Lewis‐acid‐induced thermostabilized 1,4‐zwitterions, which distinguish cyclobutanes from cyclopropanes and others. All these findings would shed light on catalytic synthesis and degradation of saturated all‐carbon main‐chain polymers, as well as small molecule transformations of cyclobutanes.

Chain branching during the polycondensation of isophthalic aldehyde and 1,1′‐diacetylferrocene by the Claisen–Schmidt reaction

AbstractN‐methyl‐2‐pyrrolidone‐soluble ferrocene‐containing polychalcones, which are promising as a platform for the formation of ferromagnetic coatings after pyrolysis in an inert atmosphere is synthesized through the polycondensation of isophthalic aldehyde and 1,1′‐diacetylferrocene by the Claisen–Schmidt reaction. The structure and the molecular weight distribution of the polychalcones is characterized by NMR, IR spectroscopy, and size exclusion chromatography. It is shown that the formation of polychalcones is accompanied by chain branching via the Michael reactions and the aldol‐croton condensation. The structure of the linear fragments of the polychalcone chains is simulated with a tailored low‐molecular model compound, that is 1,3‐bis(3‐ferrocenyl‐1‐propen‐2‐one)benzene, which is characterized by the NMR and IR spectroscopy as well as the X‐ray diffraction analysis. The obtained results indicate an increasing tendency for polychalcone chain branching with the temperature growth during the Claisen–Schmidt reaction. The weight loss and the increase in magnetization under the conditions of pyrolysis of polychalcones at different temperatures is studied. The assumptions regarding the possible mechanisms of thermal destruction of ferrocene‐containing macromolecules are put forward.

Effect of enzymatic hydrolysis with Alcalase or Protamex on technological and antioxidant properties of whey protein hydrolysates

The aim of this study was to evaluate the effect of the enzymatic hydrolysis, performed using Alcalase and Protamex enzymes, on the technological functionalities and the antioxidant capacity of whey protein hydrolysates (WPHs) to identify the conditions allowing to obtain target functionality/ies. Samples were characterized for hydrolysis degree (DH), molecular weight distribution, structural properties, and food-related functionalities. Free sulfhydryl groups and surface hydrophobicity significantly decreased with the increase in DH, regardless of the used enzyme. The foaming and antioxidant properties of Alcalase WPHs were higher as compared to those of WPI, reaching the maximum value at DH = 18–20 %, while higher DH resulted in impaired functionality. Gelling properties were guaranteed when WPI was hydrolysed by Protamex at DH < 15 % while foaming and antioxidant abilities were fostered at 15 < DH < 21 %. These results were well correlated with MW distribution and were rationalized into a road map which represents a useful tool in the selection of proper hydrolysis conditions (time, DH, enzyme type) to obtain WPHs with tailored functionalities. Research outcomes highlighted the possibility to drive protein hydrolysis to optimize the desired functionality/ies.

Characterization and functional evidence for Orf2 of Streptomyces sp. 139 as a novel dipeptidase E

Aspartyl dipeptidase (dipeptidase E) can hydrolyze Asp-X dipeptides (where X is any amino acid), and the enzyme plays a key role in the degradation of peptides as nutrient sources. Dipeptidase E remains uncharacterized in Streptomyces. Orf2 from Streptomyces sp. 139 is located in the exopolysaccharide biosynthesis gene cluster, which may be a novel dipeptidase E with “S134-H170-D198” catalytic triad by sequence and structure comparison. Herein, recombinant Orf2 was expressed in E. coli and characterized dipeptidase E activity using the Asp-ρNA substrate. The optimal pH and temperature for Orf2 are 7.5 and 40 ℃; Vmax and Km of Orf2 are 0.0787 mM·min−1 and 1.709 mM, respectively. Orf2 exhibits significant degradation activities to Asp-Gly-Gly, Asp-Leu, Asp-His, and isoAsp-Leu and minimal activities to Asp-Pro and Asp-Ala. Orf2 contains a Ser-His-Asp catalytic triad characterized by point mutation. In addition, the Asp147 residue of Orf2 is also proven to be critical for the enzyme’s activity through molecular docking and point mutation. Transcriptome analysis reveals the upregulation of genes associated with ribosomes, amino acid biosynthesis, and aminoacyl-tRNA biosynthesis in the orf2 mutant strain. Compared with the orf2 mutant strain and WT, the yield of crude polysaccharide does not change significantly. However, crude polysaccharides from the orf2 mutant strain exhibit a wider range of molecular weight distribution. The results indicate that the Orf2 links nutrient stress to secondary metabolism as a novel dipeptidase E.Key points• A novel dipeptidase E with a Ser-His-Asp catalytic triad was characterized from Streptomyces sp. 139.• Orf2 was involved in peptide metabolism both in vitro and in vivo.• Orf2 linked nutrient stress to mycelia formation and secondary metabolism in Streptomyces.

Surrogate-model-based optimization of a nonideal polymerization reactor for producing tailored molecular weight distribution

The optimization of polymerization reactors with nonideal mixing has been greatly hindered by a tremendous computation burden. In this study, a global optimization framework to integrate full MWD calculations and detailed reactor dynamics with nonideal mixing behaviors was developed by reducing the considerable computation time required for implementing full MWD. A combination of surrogate-model-based optimization and a computational fluid dynamics (CFD)-compartment reactor model was applied to produce the desired MWD in a nonideal reactor. A neural network (NN) surrogate model was trained using 3,000 MWD data produced from the mechanistic reactor model. The results showed that the model successfully described asymmetric MWD with bimodality resulting from the nonideal mixing behaviors in the reactor. The surrogate model was used to construct operation maps for the asymmetry and bimodality factors, with SHapley Additive exPlanations (SHAP) values showing that the flow rate of the chain transfer agent had the largest impact on the asymmetry factor, whereas temperature significantly influenced the bimodality factor. Finally, the optimization strategy based on the asymmetric and bimodality factors successfully determined operating conditions to produce four tailored MWDs, reported in actual polymerization reactors with R scores of 0.988–0.997.

Mechanism of the green coagulation processes on the construction of raw rubber network structure

AbstractAcid coagulation is the most traditional latex coagulation technology, but this coagulation process leads to delayed vulcanization, corrosiveness, and environmental pollution. Different coagulation processes significantly impact the raw rubber network structure, leading to differences in the properties of both raw rubber and rubber vulcanizates. Raw rubber was prepared by three acid‐free coagulation processes: freeze, microwave, and flash drying. The network density, molecular chain flexibility, molecular weight, processing fluidity, and plasticity retention of the raw rubber were characterized, and the vulcanization characteristics, viscoelasticity, mechanical properties, and dynamic mechanical properties of the cured rubber composites were investigated. Raw rubbers prepared by microwave drying and flash drying had higher crosslink density, more flexible molecular chains, larger molecular weight, and wider molecular weight distribution, thereby increasing the crosslink density of rubber vulcanizates. The crosslink density of the raw rubber prepared by microwave drying versus the acid coagulated raw rubber increased by 51% to 105.71 mol/m3, the tensile strength increased by 16% to reach 28.12 MPa, and the elastic modulus and rolling resistance under dynamic stress increased. This paper provides a new idea for analyzing the relationship between the raw rubber network structure and the properties of vulcanized rubber.Highlights Acid‐free raw rubbers are prepared by freeze, microwave, and flash drying. Coagulation processes significantly impact the raw rubber network structures. Effects of raw rubber network structures on properties are investigated. Crosslink density, plasticity retention, and tensile strength are improved.