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....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.展开更多
[Objective] The aim of this work was to identify molecular weight (MW) distribution and antioxidant activity of fish skin col agen hydrolysates. [Method] The MW distribution of hydrolysates was determined using both...[Objective] The aim of this work was to identify molecular weight (MW) distribution and antioxidant activity of fish skin col agen hydrolysates. [Method] The MW distribution of hydrolysates was determined using both size exclusion chromatography and matrix-assisted laser desorption ionization time-of-flight mass spec-trometry (MALDI-TOF-MS). Fish skin were treated by the alkaline protease 2709. [Result] The optional conditions for hyerolysis were time 3 h, temperature 55 ℃, pH 10.0, substrate concentration 80 g/L and E/S 4%. The results of both methods indi-cated that the molecular weight of col agen hydrolysates was from 400 to 1 800 Da, and the peptides’ molecular weight was less than 1 400 Da mostly. The reducing power and antioxidant/radical scavenging activity [1, 1-diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging activity] were determined. [Conclusion] The results reveal that the fishskin hydrolysate is a potential source of antioxidants.展开更多
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...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.展开更多
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...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.展开更多
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-...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 ...展开更多
[ 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 vi...[ 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.展开更多
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 s...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.展开更多
A starved feed reactor (SFR) is a semi-batch polymerization reactor where initiator and monomer are fed slowly into a fixed amount of solvent. The polymerization is carried out isothermally at elevated temperatures. T...A starved feed reactor (SFR) is a semi-batch polymerization reactor where initiator and monomer are fed slowly into a fixed amount of solvent. The polymerization is carried out isothermally at elevated temperatures. The added initiator decomposes instantaneously and the added monomer polymerizes immediately. The molecular weight (MW) and molecular weight distribution (MWD) of the product polymer can be effectively controlled by the feed ratio of monomer to initiator. This paper presents a study on the MWD of styrene polymerization in a SFR. The MWD model parameters are regressed with experimental data. Although the solids fraction in the SFR is high (higher than 50%), viscosity is not too high and the 'gel effect' is weak due to the low molecular weight of the products. It is found that the termination rate constant is a power function of molecular weight, radicals terminate via 100% combination, the thermal initiation can be neglected even at high reaction temperature studied. And calculated results indicate that in the SFR, the validity of the long chain assumption becomes doubted. It appears that other alterative assumption should be found for an improved model.展开更多
The lumped time distribution functions were proposed, which can be used for describing the dynamicsystems with two or more than two states of the end of growing polymer chain during chain addition polymerization.Numer...The lumped time distribution functions were proposed, which can be used for describing the dynamicsystems with two or more than two states of the end of growing polymer chain during chain addition polymerization.Numerical analysis of the lumped time distribution functions was carried out. The method for calculating molecularweight distribution of polymer in the stable free radical polymerization and more general cases was developed basedon the lumped time distribution functions.展开更多
In last paper, the average molecular weight of a control cotton fabric and cotton fabrics treated with the polycarboxylic acid at different pH were measured. The result doesnt support the hypothesis that the pH of the...In last paper, the average molecular weight of a control cotton fabric and cotton fabrics treated with the polycarboxylic acid at different pH were measured. The result doesnt support the hypothesis that the pH of the finishing bath can affect the depolymerization of the finished cotton fabric. In order to understand more about it, the molecular weight distributions of the control and finished cotton fabrics were measured and the reason was fund. From the ratio and the molecular weight of the low molecular part one can see that the pH of the finishing bath can affect the depolymerization of the finished cotton fabrics. The phenomenon that the average molecular weights of the cotton fabric crosslinked with BTCA at different pH are almost same is attributed to that the crosslinks are not broken completely when treated with 0.5 M NaOH solution at 50℃ for 144 h.展开更多
LDPE (low-density polyethylene) photo degraded through various accelerated weathering tests has the molecular weight distribution curves unlike that through outdoor exposure. The authors therefore developed new weat...LDPE (low-density polyethylene) photo degraded through various accelerated weathering tests has the molecular weight distribution curves unlike that through outdoor exposure. The authors therefore developed new weathering test condition based on the existing accelerated weathering test using a xenon arc lamp. Samples of LDPE were photo degraded using various accelerated weathering test conditions and outdoor exposure. The physical properties and chemical structures of the photo degraded samples were studied through a tensile test, infrared spectroscopy, and gel chromatography. The authors found that the molecular weight distribution curve of a sample photo degraded using a xenon lamp at a higher BPT (black panel temperature) (73 ~C) was more similar to that of an outdoor-exposed sample than that of a sample photo degraded at the standard BPT (63 ~C). It is considered that higher temperature accelerates radical recombination, consequently recreating molecular enlargement similar to the outdoor-exposed sample. Multiple regression analysis using newly introduced Mp (peak-top molecular weight) and Mw (weight-average molecular weight) as explanatory variables was conducted, which successfully enabled the authors to provide a simple explanation for the decrease in polymer tensile strength.展开更多
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 distr...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.展开更多
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-...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.展开更多
Molecular dynamics simulations were carried out to study the internal energy and microstructure of potassium dihydrogen phosphates (KDP) solution at different temperatures. The water molecule was treated as a simple...Molecular dynamics simulations were carried out to study the internal energy and microstructure of potassium dihydrogen phosphates (KDP) solution at different temperatures. The water molecule was treated as a simple-point-charge model, while a seven-site model for the dihydrogen phosphate ion was adopted. The internal energy functions and the radial distribution functions of the solution were studied in detail. An unusually large local particle number density fluctuation was observed in the system at saturation temperature. It has been found that the specific heat of oversaturated solution is higher than that of unsaturated solution, which indicates the solution experiences a crystallization process below saturation temperature. The radial distribution function between the oxygen atom of water and the hydrogen atom of the dihydrogen phosphate ion shows a very strong hydrogen bond structure. There are strong interactions between potassium cation and oxygen atom of dihydrogen phosphate ion in KDP solution, and much more ion pairs were formed in saturated solution.展开更多
To improve the naphtha composition prediction model based on molecular type homologous series matrix (MTHS), this paper puts forward a novel molecular matrix to characterize the naphtha composition and the norreal d...To improve the naphtha composition prediction model based on molecular type homologous series matrix (MTHS), this paper puts forward a novel molecular matrix to characterize the naphtha composition and the norreal distribution hypothesis to better describe the molecular composition distribution within each homologous series of the molecular matrix. Through prediction calculation of eight groups of naphtha samples and eight groups of gasoline samples, it is verified that the normal distribution hypothesis is more applicable than gamma distribution hypothesis for the prediction model. According to the prediction results of the samples, the restrain range of normal distribution parameters during model computing process is summarized. With the bulk properties of naphtha samples and the value range of distribution parameters as input conditions, this study utilizes the improved novel molecular matrix to predict the composition of naphtha samples. As the results show, the novel molecular matrix can predict more detailed composition information of naphtha and improve prediction accuracy with less unknown parameters.展开更多
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 ...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.展开更多
Novel MgCl2-supported Ziegler-Natta (Z-N) catalysts prepared using a new one-pot ball milling method can effectively control the amounts of Ti-loading in the catalysts. Complex GPC data on polypropylene synthesized by...Novel MgCl2-supported Ziegler-Natta (Z-N) catalysts prepared using a new one-pot ball milling method can effectively control the amounts of Ti-loading in the catalysts. Complex GPC data on polypropylene synthesized by these novel catalysts were analyzed using the method of fitting the molecular weight distribution (MWD) curves with a multiple Flory-Schulz function. It was found that multiple active centers exist in these novel catalysts. Detailed study of the effects of the Ti-loadings in the catalysts on the distribution of the active centers showed that the Ti-loadings in the novel MgCl2-supported Z-N catalysts might affect the proportion of each type of active centers; and might be the main factor responsible for the effect of the Ti-loadings on the microstructure, the molecular weight and molecular weight distribution width of the resultant polymer, the catalytic activity and polymerization kinetics.展开更多
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-depend...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~+).展开更多
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.Product...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.展开更多
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 researc...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.展开更多
文摘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.
基金Supported by Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi,China(2010127)~~
文摘[Objective] The aim of this work was to identify molecular weight (MW) distribution and antioxidant activity of fish skin col agen hydrolysates. [Method] The MW distribution of hydrolysates was determined using both size exclusion chromatography and matrix-assisted laser desorption ionization time-of-flight mass spec-trometry (MALDI-TOF-MS). Fish skin were treated by the alkaline protease 2709. [Result] The optional conditions for hyerolysis were time 3 h, temperature 55 ℃, pH 10.0, substrate concentration 80 g/L and E/S 4%. The results of both methods indi-cated that the molecular weight of col agen hydrolysates was from 400 to 1 800 Da, and the peptides’ molecular weight was less than 1 400 Da mostly. The reducing power and antioxidant/radical scavenging activity [1, 1-diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging activity] were determined. [Conclusion] The results reveal that the fishskin hydrolysate is a potential source of antioxidants.
基金supported by Tianjin Committee of Science & Technology, China (06YFGZSH02300)
文摘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.
基金supported by the Administration of Science and Technology of Jilin Province,China (No.200505254)
文摘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.
文摘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 ...
基金Supported by Natural Science Foundation of Guangxi(0991024Z)
文摘[ 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.
文摘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.
基金Supported by the State Key Polymerization Reaction Engineering Laboratory of Zhejiang University.
文摘A starved feed reactor (SFR) is a semi-batch polymerization reactor where initiator and monomer are fed slowly into a fixed amount of solvent. The polymerization is carried out isothermally at elevated temperatures. The added initiator decomposes instantaneously and the added monomer polymerizes immediately. The molecular weight (MW) and molecular weight distribution (MWD) of the product polymer can be effectively controlled by the feed ratio of monomer to initiator. This paper presents a study on the MWD of styrene polymerization in a SFR. The MWD model parameters are regressed with experimental data. Although the solids fraction in the SFR is high (higher than 50%), viscosity is not too high and the 'gel effect' is weak due to the low molecular weight of the products. It is found that the termination rate constant is a power function of molecular weight, radicals terminate via 100% combination, the thermal initiation can be neglected even at high reaction temperature studied. And calculated results indicate that in the SFR, the validity of the long chain assumption becomes doubted. It appears that other alterative assumption should be found for an improved model.
文摘The lumped time distribution functions were proposed, which can be used for describing the dynamicsystems with two or more than two states of the end of growing polymer chain during chain addition polymerization.Numerical analysis of the lumped time distribution functions was carried out. The method for calculating molecularweight distribution of polymer in the stable free radical polymerization and more general cases was developed basedon the lumped time distribution functions.
基金The Project Sponsored by SRF for ROCS,SEM and EYTP of MOE
文摘In last paper, the average molecular weight of a control cotton fabric and cotton fabrics treated with the polycarboxylic acid at different pH were measured. The result doesnt support the hypothesis that the pH of the finishing bath can affect the depolymerization of the finished cotton fabric. In order to understand more about it, the molecular weight distributions of the control and finished cotton fabrics were measured and the reason was fund. From the ratio and the molecular weight of the low molecular part one can see that the pH of the finishing bath can affect the depolymerization of the finished cotton fabrics. The phenomenon that the average molecular weights of the cotton fabric crosslinked with BTCA at different pH are almost same is attributed to that the crosslinks are not broken completely when treated with 0.5 M NaOH solution at 50℃ for 144 h.
文摘LDPE (low-density polyethylene) photo degraded through various accelerated weathering tests has the molecular weight distribution curves unlike that through outdoor exposure. The authors therefore developed new weathering test condition based on the existing accelerated weathering test using a xenon arc lamp. Samples of LDPE were photo degraded using various accelerated weathering test conditions and outdoor exposure. The physical properties and chemical structures of the photo degraded samples were studied through a tensile test, infrared spectroscopy, and gel chromatography. The authors found that the molecular weight distribution curve of a sample photo degraded using a xenon lamp at a higher BPT (black panel temperature) (73 ~C) was more similar to that of an outdoor-exposed sample than that of a sample photo degraded at the standard BPT (63 ~C). It is considered that higher temperature accelerates radical recombination, consequently recreating molecular enlargement similar to the outdoor-exposed sample. Multiple regression analysis using newly introduced Mp (peak-top molecular weight) and Mw (weight-average molecular weight) as explanatory variables was conducted, which successfully enabled the authors to provide a simple explanation for the decrease in polymer tensile strength.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12074146,11974007,12074142,11904122,91850114,and 11774131)the Natural Science Foundation of Jilin Province of China(Grant No.20180101225JC)。
文摘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.
文摘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.
文摘Molecular dynamics simulations were carried out to study the internal energy and microstructure of potassium dihydrogen phosphates (KDP) solution at different temperatures. The water molecule was treated as a simple-point-charge model, while a seven-site model for the dihydrogen phosphate ion was adopted. The internal energy functions and the radial distribution functions of the solution were studied in detail. An unusually large local particle number density fluctuation was observed in the system at saturation temperature. It has been found that the specific heat of oversaturated solution is higher than that of unsaturated solution, which indicates the solution experiences a crystallization process below saturation temperature. The radial distribution function between the oxygen atom of water and the hydrogen atom of the dihydrogen phosphate ion shows a very strong hydrogen bond structure. There are strong interactions between potassium cation and oxygen atom of dihydrogen phosphate ion in KDP solution, and much more ion pairs were formed in saturated solution.
基金Supported by the National Natural Science Foundation of China(U1462206)
文摘To improve the naphtha composition prediction model based on molecular type homologous series matrix (MTHS), this paper puts forward a novel molecular matrix to characterize the naphtha composition and the norreal distribution hypothesis to better describe the molecular composition distribution within each homologous series of the molecular matrix. Through prediction calculation of eight groups of naphtha samples and eight groups of gasoline samples, it is verified that the normal distribution hypothesis is more applicable than gamma distribution hypothesis for the prediction model. According to the prediction results of the samples, the restrain range of normal distribution parameters during model computing process is summarized. With the bulk properties of naphtha samples and the value range of distribution parameters as input conditions, this study utilizes the improved novel molecular matrix to predict the composition of naphtha samples. As the results show, the novel molecular matrix can predict more detailed composition information of naphtha and improve prediction accuracy with less unknown parameters.
文摘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.
基金Project supported by the National Natural Science Foundation ofChina (No. 20172045) Science and Technology Plan Fund of Zhe-jiang Province (No. 001101116) and Foundation for Doctors ofNingbo City (No. 2003A62012) China
文摘Novel MgCl2-supported Ziegler-Natta (Z-N) catalysts prepared using a new one-pot ball milling method can effectively control the amounts of Ti-loading in the catalysts. Complex GPC data on polypropylene synthesized by these novel catalysts were analyzed using the method of fitting the molecular weight distribution (MWD) curves with a multiple Flory-Schulz function. It was found that multiple active centers exist in these novel catalysts. Detailed study of the effects of the Ti-loadings in the catalysts on the distribution of the active centers showed that the Ti-loadings in the novel MgCl2-supported Z-N catalysts might affect the proportion of each type of active centers; and might be the main factor responsible for the effect of the Ti-loadings on the microstructure, the molecular weight and molecular weight distribution width of the resultant polymer, the catalytic activity and polymerization kinetics.
基金Project supported by the National Natural Science Foundation of China(Grant No.11504151)the Doctoral Scientific Research Foundation of Liaoning Province,China(Grant No.201501123)the Scientific Research Foundation of Liaoning Provincial Education Department,China(Grant No.L2014242)
文摘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~+).
基金The authors are grateful for the financial supports of this research from the Science and Technology Program of Guangdong(2019A1515011890)National Key R&D Program of China(2017YFD0601003).
文摘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.
基金supported by the National Natural Science Foundation of China(No.22101196)the China Postdoctoral Science Foundation(No.2021M692348).
文摘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.