Effect of Molecular Weight and Molecular Distribution on Skin Structure and Shear Strength Distribution near the Surface of Thin-Wall Injection Molded Polypropylene

In this study, the relationship between skin structure and shear strength distribution of thin-wall injection molded polypropylene (PP) molded at different molecular weight and molecular distribution was investigated. Skin-core structure, cross-sectional morphology, crystallinity, crystal orientation, crystal morphology and molecular orientation were evaluated by using polarized optical microscope, differential scanning calorimeter, X-ray spectroscopic analyzer and laser Raman spectroscopy, respectively, while the shear strength distribution was investigated using a micro cutting method called SAICAS (Surface And Interfacial Cutting Analysis System). The results indicated that the difference of molecular weight and molecular weight distribution showed own skin layer thickness. Especially, high molecular weight sample showed thicker layer of the lamellar orientation and molecular orientation than low molecular weight sample. In addition, wide molecular distribution sample showed large crystal orientation layer.

Study on Enzymatic Hydrolysis of Gadus morrhua Skin Collagen and Molecular Weight Distribution of Hydrolysates

Process parameters on enzymatic hydrolysis and molecular weight （MW） distribution of collagen hydrolysates from Gadus morrhua skin were investigated. The optimal process parameters were obtained by the single-factor and orthogonal experiments. The molecular weight distribution of hydrolysates was determined using both Sephadex G25 partition and high speed liquid chromatography electricity spray mass spectrum （HPLC-ESI-MS）. Collagen hydrolysates were first gained by an alkaline protease ＂alcalase＂ for 3 h at temperature （50~C）, pH （10.0）, substrate concentration （75 g L-~）, and E/S （3%）. The molecular weight distribution of collagen hydrolysates ranged from 300 to 1 500 Da, and most of peptides were under 1 200 Da. Sephadex G25 partition and HPLC-ESI-MS should be successfully employed to determine the molecular weight distribution of collagen hydrolysates.

A HIGHLY ACTIVE NEODYMIUM CHLORIDE ISOPROPANOL COMPLEX/MODIFIED METHYLALUMINOXANE CATALYST FOR PREPARING POLYISOPRENE WITH HIGH CIS-1,4 STEREOSPECIFICITY AND NARROW MOLECULAR WEIGHT DISTRIBUTION

Neodymium chloride isopropanol complex （NdCl3.3＇prOH） activated by modified methylaluminoxane （MMAO） was examined in isoprene polymerization in hexane, with regards to Nd compounds, aluminum （Al） compounds, [Al]/[Nd] ratio, polymerization temperature and time. NdCl3＇3iprOH exhibited high activity producing polymers feasting high cis-l,4 stereospecificity （〉 96%）, very high molecular weight （Mn 〉 1.0 × 10^6） and fairly narrow molecular weight distribution （MWD, Mw/Mn 〈 2.0） simultaneously. In comparison, neodymium isopropoxide also showed high activity providing polymers with narrow MWD （Mw/Mn = 2.07）, but somewhat low cis-1,4 content （ca. 92%）, while neodymium chloride had no activity under present polymerization conditions. The Al compounds affected the polymer yield in the order of Al（i-Bu）3 〉 MMAO 〉 Al（i-Bu）2H. MMAO as cocatalyst afforded polyisoprene with high Mn over 1.0 × 10^6, whereas as stronger chain transfer agent than MMAO, AI（i-Bu）3 and AI（i-Bu）EH yielded polymers with low Mn （1.0 × 10^5-8.0 × 10^5）. NdCl3·3＇PrOH/MMAO catalyst showed a fairly good catalytic activity even at relatively low [Al]/[Nd] ratio of 30, and the produced polymer remained high cis-1,4 content of 95.8% along with high Mn over 1.0× 10^6 even at elevated temperatures up to 70℃. The polymerization rate is of the first order with respect to the concentration of isoprene. The mechanism of active species formation was discussed preliminarily.

SUPPORTED ZIEGLER-NATTA CATALYSTS FOR ETHYLENE SLURRY POLYMERIZATION AND CONTROL OF MOLECULAR WEIGHT DISTRIBUTION OF POLYETHYLENE

The effect of chemical composition of highly active supported Ziegler-Natta catalysts with controlled morphology on the MWD of PE has been studied.It was shown the variation of transition metal compound in the MgCl_2-supported catalyst affect of MWD of PE produced in broad range:Vanadium-magnesium catalyst(VMC)produce PE with broad and bimodal MWD(M_w/M_n=14-21).MWD of PE,produced over titanium-magnesium catalyst(TMC)is narrow or medium depending on Ti content in the catalyst(M_w/M_n=3.1-4.8).The oxidation ...

Molecular Weight and Distribution of Cellulose and Cellulose Microspheres

[ Objective ] This study aimed to provide basic data for studying the relationship between structure and property of cellulose microspheres by measuring molecular weight of cellulose and cellulose microspheres with viscosity method and gel permeation chromatography （GPC） method. [ Method] In viscosity method, cadmium ethylenediamine was used as the solvent, intrinsic viscosity η of the solution was determined at 25 ℃ by using a Ubbelohde viscometer, to calculate the molecular weight of cellulose; in GPC method, 8% LiC1 / N, N-dimethylacetamide （LiC1/DMAc） was used as the solvent and 0.5% LiC1/DMAc was used as the mobile phase to determine the relative molecular weight and distribution of cellulose and cellulose microspheres. In addition, the determination results were analyzed to compare these two methods. [ Result ] Viscosity-average molecular weight Mr/ of cellulose and cellulose microspheres determined with viscosity method were 224,532 and 16,686, respectively; weight-average molecular weight Mw of cellulose and cellulose microspheres determined with GPC method were 284,196 and 22,345, respectively. [ Conclusion] The determination results of （;PC method are relatively close to the actual value and could truly reflect the characteristics of molecular weialat distribution of eellulose and cellulose mierosr, heres.

THE RELATION OF SEQUENCE DISTRIBUTIONS OF S-SBR TO ITS MOLECULAR WEIGHT DISTRIBUTIONS

The relationship between sequence distributions and molecular weight distributions of S-SBR, obtained from styrene and butadiene anionic copolymerization at various conversions with THF/Li^+ as an initiator has been studied by ^(13)C-NMR,GPC. The results showed that the molecular weight distributions of the copolymer couldbe correlated sophisticatedly to the binary sequcne distributions or the monomer unit distributions of the copolymer in a corrected Poisson's distribution from.

Molecular photoelectron momentum and angular distributions of N_(2) molecules by ultrashort attosecond laser pulses

The ultrafast photoionization dynamics of N_(2) molecules by x-ray/XUV laser pulses is investigated.The molecular frame photoelectron momentum distributions(MF-PMDs) and the molecular frame photoelectron angular distributions(MF-PADs) are obtained by numerically solving 2D time-dependent Schrodinger equations within the single-electron approximation(SEA) frame.The results show that the molecular photoionization diffraction appears in 5 nm laser fields.However,when the laser wavelength is 30 nm,the molecular photoionization diffraction disappears and the MF-PMDs show four-lobe pattern.The ultrafast photoionization model can be employed to describe the MF-PMDs and MF-PADs of N_(2) molecules.

The Relationship between Bulk Property and Property Distribution in Thin-Wall Injection Molded PP at Different Molecular Weight and Molecular Weight Distribution

Thin-wall injection molded parts have been paid much attention to the lightweight saving from viewpoints of natural resources saving. In the injection molding, skin-core structure can be found in the parts. This skin-core structure affects the property of completed injection molding parts (bulk property) even if in thin-wall injection molding. However, there is a few research about the relationship between bulk property and internal property distribution in the injection molding specimen. In this study, thin-wall injection molded parts of polypropylene (PP) were prepared by 4 different molecular weight and molecular weight distribution to reveal the relationship between bulk property and property distribution. These characteristics were investigated by using tensile test, fracture toughness characterized by Essential Work of Fracture (EWF) method for bulk property and film tensile test by sliced sample for tensile property distribution. The property distribution test results revealed that the highly bulk property sample had thicker highly mechanical property layer on its surface.

Determination and Temperature Dependence of Plateau Modulus for Polymerization of Propylene to Isotactic Polypropylene with Ultra-high Molecular Weight under Catalysis of Ziegler-Natta Catalyst

The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G″) plots at 180 and 200 ℃ versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0.01-100 rad/s for Ziegler-Natta catalyzing ethylene-propylene random copolymerization(PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G″(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus(G 0_N) of UHPPH from a certain experimental temperature G″(ω) curve directly. For UHPPH, the G 0_N determined to be 4.28×10 5 and 3.62×10 5 Pa at 180 and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G 0_N has no relation to the molecular weight.

Laser phase effect on asymmetric harmonic distribution in H_2^+

The laser phase effect on the spatial distribution of the molecular high-order harmonic generation（MHHG） spectrum from H_2~＋ is theoretically investigated through solving the Non-Bohn-Oppenheimer（NBO） time-dependent Schrodinger equation（TDSE）.The results are shown as follows,（i） The generated harmonics from the two nuclei each present an asymmetric distribution.Particularly,when the laser phases are chosen from 0.0π to 0.6π and from 1.7π to 2.0π,the contribution from the negative-H plays a main role in harmonic generation.When the laser phases are chosen from 0.7πto 1.6k,the contribution from the positive-H to the harmonic generation is remarkably enhanced and becomes greater than that from the negative-H.The electron localization,the time-frequency analyses of the harmonic spectrum and the time-dependent wave function are shown to explain the asymmetric harmonic distribution in H_2~＋,which provides us with a method to control the electron motion in molecules,（ⅱ） As the pulse duration increases,the asymmetric distributions of the MHHG in two H nuclei decrease,（ⅲ） Isotope investigation shows that the asymmetric harmonic distribution can be reduced by introducing the heavy nucleus（i.e.,D_2~＋）.

Preparation of Hydroxypropyl Methylcellulose Acetate Succinate with a Narrow Molecular Weight Dispersion

Hydroxypropyl methylcellulose acetate succinate(HPMCAS)was successfully synthesized from the reaction of hydroxypropyl methylcellulose with succinic anhydride and acetic anhydride in an acetone/pyridine system.Products with different contents of succinyl groups and acetyl groups were prepared by varying the reaction conditions.In the acetone/pyridine system,equipment corrosion does not occur,the product is easy to wash,and the solvent can be recycled.By varying the concentration of the esterifying agents,products with different ratios of acidic groups can be obtained.Under the optimum conditions,the obtained products had an average molecular weight between 5.39×104 and 5.41×104,a number average molecular weight from 4.97×104 to 5.13×104,and a polydispersity index from 1.05 to 1.08.The products dissolved well in acetone and methanol,and formed films on a mold.The films had good pH-sensitivity,tensile strength,and thermal stability.The formed films could dissolve in solutions with a pH value ranging from 5.4 to 6.4,and are therefore suitable for use as an enteric coating for pharmaceutical dosage forms.

Tuning Polymer Molecular Weight Distribution in Cationic RAFT Polymerization by Mixing Chain Transfer Agents

Polymer dispersity (Đ) or molecular weight distribution (MWD) is a basic but vital parameter for the properties of polymeric materials. Developing new methodologies for controlling polymer MWD is emerging as a research hotspot. However, the methods to tune polymer MWD in cationic polymerization are still not well explored. Herein, we present a simple method to control the dispersity of poly(isobutyl vinyl ether) (PIBVE) by mixing two different chain transfer agents in batch visible light induced cationic RAFT polymerization. A broad dispersity range (Đ ≈ 1.16—1.80) was successfully achieved while maintaining monomodal MWD. Moreover, chain extension of PIBVE through both cationic polymerization and radical polymerization has been studied, which also provides a method to tune polymer MWD in mechanism transformation polymerization.

Characteristics of molecular weight distribution of dissolved organic matter in bromide-containing water and disinfection by-product formation properties during treatment processes

The characteristics of dissolved organic matter（DOM） and bromide ion concentration have a significant influence on the formation of disinfection by-products（DBPs）. In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight（MW）, trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes（pre-chlorination, coagulation, sand filtration,disinfection） were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW 1 k Da and fraction with MW 3-10 k Da, and the DBP＇s generation ability of lower molecular weight DOM（ 10 k Da） was higher than that of higher molecular weight DOM. During different processes,pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes（THMs） were mainly generated in pre-chlorination and disinfection, while haloacetic acids（HAAs） were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration.

STUDIES ON MOLECULAR WEIGHT DISTRIBUTION OF CARBON FIBER POLYMER PRECURSORS SYNTHESIZED USING MIXED SOLVENTS

The molecular weight distributions were estimated for carbon fiber polymer precursors such as poly（acrylonitrile-co-itaconic acid） synthesized by semi batch solution polymerization in mixed solvents media with the azonitrile compounds as initiator under the different ratios of solvent and non solvent from 0.75 to 2.5 in weight. The copolymer was characterized by using Fourier transform infrared spectroscopy （FTIR） and nuclear magnetic resonance （1H-NMR） analyses. The molecular weight distributions were evaluated by Mv/Mn ratios estimated from viscosity and osmotic measurements, and Mw/Mn estimated from size exclusion chromatography. The molecular weight distributions of these polymers as determined from M, JMn and Mw/Mn are 2.9 to 3,2 and 2.0 to 2.5 respectively. The molecular distributions were close to a narrow distribution of 2.0 when the solvent/non-solvent ratio was varied between 1.4 and 2.0. Intrinsic viscosity [η] as a function of molecular weight of poly（acrylonitrile-co-itaconic acid） was evaluated by means of low angle laser light scattering with size exclusion chromatography （SEC-LALLS） and viscometry with SEC （SEC-VISCO）. The relationship between [η] and Mw for poly（acrylonitrile-co-itaconic acid） in DMF at 50℃ was [q] = 1.1×10-5 Mw0.79, where [η] is obtained in dL/g.

Fouling of nanofiltration membrane by effluent organic matter:Characterization using different organic fractions in wastewater

The UF membrane with molecular weight cutoff （MWCO） ranging from 2 to 100 kDa and XAD-8 resin were employed to identify the characteristic of molecular weight （MW） distribution of wastewater effluent organic matter （EfOM） in terms of TOC and UV254, as well as the amounts of the hydrophilic/hydrophobic organic fractions in different MW ranges. Then, the nanofiltration （NF） membrane fouling experiments were carded out using the above fractionated water to investigate the effect of MW distribution and hydrophihc/hydrophobic characteristics of EfOM on the membrane flux decline using the fractionated water samples. The experimental results have shown that 45.61% of the total organics belongs to the low MW one, among which the percentage of the hydrophilic organics with low MW （less than 2 kDa） was up to 28.07%, while that of the hydrophobic organics was 17.54%. In particular, the hydrophilic fraction was found to be the most abundant fraction in the effluents. MW distribution has a significant effect on the membrane fouling. When the MW was less than 30 kDa, the lower the MW, the larger was the specific flux decline, while in the case of MW higher than 30 kDa, the higher the MW, the larger was the specific flux decline, and the decline degree of low MW organics was larger than the high MW one. With the same MW distribution range, specific flux decline of the hydrophilic organic was considerably slower than that of the hydrophobic organic, which indicated that the hydrophobic organic fractions dominantly contribute to the flux decline.

Facile Control of Molecular Weight Distribution via Droplet-Flow Light-Driven Reversible-Deactivation Radical Polymerization

Molecular weight distribution(MWD)is fundamental for polymer analysis,which influences many important properties of polymeric materials.In this work,we demonstrate the development of a computer-aided droplet-flow system that combines photo-mediated reversible-deactivation radical polymerization(RDRP)and chain transfer agent(CTA)diffusion strategy to enable facile MWD control for the first time.Synthetic advantages of this photo-flow polymerization allow controlled chain-growth to yield a variety of polymers of tunable MWDs in a broad range(Ð≈1.1—1.9)with predetermined molecular weights(Mn≈4—30 kDa)and good chain-end fidelity.Notably,the computer-aided platform has streamlined an automatic and high-throughput pathway to prepare polymer libraries of tunable MWDs.For copolymers,chemical compositions could be readily regulated besides MWDs with the droplet-flow platform.We believe that this work should be attractive for polymer engineering,and informative to create more flow polymerization techniques toward on-demand control of diverse polymer characters.

KINETIC ANALYSIS OF CO-CONDENSATION POLYMERIZATION OF AB_2 AND AB MONOMERS

This work deals with the kinetics of co-condensation polymerization of AB2 and AB monomers, giving expressions of the two-dimensional molecular weight distribution function and the number/weight average molecular weights of the resulting copolymers. The two-dimensional molecular weight distribution depends on two indices, n and l, which are the respective numbers of AB2 and AB units in a copolymer species. The evolution of the two-dimensional weight and z distributions during the co-condensation polymerization has been evaluated systematically. Finally, the two-dimensional distribution was transformed into a one-dimensional molecular weight distribution with only one variable (the molecular weight of the products instead of the degree of polymerization). The calculated results show that the highly branched copolymer has a very broad molecular weight distribution when the co-condensation polymerization approaches completion.

Fouling of organic fractionation on ultrafiltration membrane for drinking water treatment:a case study

The aim of this study was to obtain a better understanding of the range of organic molecular weight(MW)causing membrane fouling through the comparison between direct UF and in-line coagulation(without settling)/UF process.The experimental results indicated that,when raw water with organics was treated and the MW of more than half of the organics was less than 1 kDa,membrane fouling was rather serious by only UF and coagulation could improve the fouling for the treatment of raw water.Besides,coagulation/UF could remove organics in each region,and organics with MW greater than 30 kDa were the most possible matters causing membrane fouling,while organics with MW less than 1 kDa were impossibly responsible for membrane fouling due to few organics removed.Therefore,organics with MW greater than 30 kDa were the major factor of membrane fouling.

EFFECTS OF AMINO GROUPS AND MICROSTRUCTURE OF ORGANIC MESOPOROUS SILICA SUPPORTED METALLOCENE CATALYSTS ON ETHYLENE POLYMERIZATION

Mesoporous silica （MS）, 3-aminopropyltriethoxysilane （APTES） modified mesoporous silica （AMS）, bis（3- trimethoxysilylpropyl）amine modified mesoporous silica （BAMS） and APTES modified solid spherical silica （AS） were prepared and used to immobilize metallocene catalysts for ethylene polymerization. Gel permeation chromatography results showed that polyethylenes （PEs） catalyzed by AMS （or BAMS） supported metallocene catalysts at the molar ratios of Al/Zr = 100, 300 and 500 were of bimodal molecular weight distribution （BMWD）; while PEs catalyzed by the above catalysts at the molar ratios of Al/Zr 〉 800 were of monomodal molecular weight distribution （MMWD）. However, MS （or AS） supported metallocene catalysts could only produce PEs with MMWD in spite of the molar ratio of Al/Zr. It was because that AMS （or BAMS） supported catalysts possessed two active sites for ethylene polymerization at low molar ratios of Al/Zr due to the combination effects of mesopore geometrical constraint and amino groups of the supports, which was confirmed by X-ray photoelectron spectroscopy. This brings forward a novel and easy method for the synthesis of polyolefin with BMWD.

Purification and molecular weight distribution of a key exopolysaccharide component of Bacillus megaterium TF10

Extracellular polymeric substances（EPS） are organic metabolic compounds excreted by microorganisms. They largely impact microbial aggregate structures and functions.Extracellular polysaccharides（EP） in EPS are responsible for the formation of microbial aggregates. In this work, we successfully separated and characterized EP from EPS of the bacterium Bacillus megaterium TF10. Extraction of EP from EPS was optimized using Sevag＇s reagent. Chemical characteristics, functional groups, and molecular weight（MW） distribution of EP were compared with the harvested EPS and soluble microbial products（SMP）. We found that the polymers of lower MW and free proteins were successfully removed by Sevag＇s reagent. The higher MW components of EPS were predominantly polysaccharides,while the polymers of lower MW tended to secrete to the supernatant and were described as SMP. A part of the proteins in the EP was polysaccharide-bonded. Our results can be further used in elucidating the complex flocculation mechanisms in which EP play a major role.