The nitrile butadiene rubber(NBR)hardness effect on the sealing characteristics of hydraulic O-ring rod seals is analyzed based on a mixed lubrication elastohydrodynamic model.Parameterized studies are conducted to re...The nitrile butadiene rubber(NBR)hardness effect on the sealing characteristics of hydraulic O-ring rod seals is analyzed based on a mixed lubrication elastohydrodynamic model.Parameterized studies are conducted to reveal the mechanism of the influence of rubber hardness on the static and dynamic behavior of seals.The optimized selections of rubber hardness are then investigated under different conditions.Results show that the low hardness seal is prone to stress concentration due to the extrusion effect under high pressure conditions;it is also more prone to leaking.A high hardness seal can better prevent leakage by reducing film thickness but it will cause large frictional power loss and increase the probability of wear failure.The choice of low hardness is recommended to reduce friction with the premise that leakage requirements are met.展开更多
Upgrading of sustainable ethanol into C_(4)olefins by C-C coupling contributes to alleviating the dependency towards petroleum.The reaction network consists several key steps,whereas dehydration often competes with de...Upgrading of sustainable ethanol into C_(4)olefins by C-C coupling contributes to alleviating the dependency towards petroleum.The reaction network consists several key steps,whereas dehydration often competes with dehydrogenation over acidic catalyst.Herein,we report a designed bifunctional Co-YPO_(4)catalyst with balanced active sites for dehydrogenation and condensation that can directly catalyze ethanol to butadiene.The YPO4 can stabilize Co^(2+)species to form highly dispersed[Co-O-P]sites,which catalyze ethanol dehydrogenation to acetaldehyde.Additionally,the YPO4 surface exposed Y^(3+)site,as Lewis acid center,which can effectively catalyze C-C coupling reaction.The addition of cobalt enhances the ethanol dehydrogenation process while reducing the surface acidity,thus inhibiting the formation of dehydration products and promoting the formation of butadiene.Kinetic measurements suggest that the rate-limiting step is the dehydrogenation of ethanol to acetaldehyde.The synthesized Co-YPO4 shows a 68.5%selectivity of butadiene under a conversion of 78.2%at 350°C and a weight hourly space velocity of 1.0 gC_(2)H_(5)OH×gCat.^(-1)×h^(-1).展开更多
In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene p...In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile.The accuracy of five prediction methods,UNIFAC(UNIQUAC Functional-group Activity Coefficients),UNIFAC-LL,UNIFAC-LBY,UNIFAC-DMD and COSMO-RS,applied to the butadiene extraction process was verified using partial phase equilibrium data.The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system.COSMO-RS-predicted multiple systems showed good accuracy,and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method.The predicted phase equilibrium data were checked for consistency.The NRTL-RK(non-Random Two Liquid-Redlich-Kwong Equation of State)and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data.Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process.The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2%compared to that using the commercial simulation software,Aspen Plus and its database.The average deviation was much smaller than that of the simulations using the Aspen Plus database(>10%),indicating that the obtained phase equilibrium data are highly accurate and reliable.The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided.This improves the accuracy and reliability of the design,optimization and control of the process,and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.展开更多
A comprehensive single particle model which includes the mesoscale and microscale models was developed to study the influence of particle diameter on mass and heat transfer occurring within a ferrite catalyst during t...A comprehensive single particle model which includes the mesoscale and microscale models was developed to study the influence of particle diameter on mass and heat transfer occurring within a ferrite catalyst during the oxidative dehydrogenation of butene to butadiene process. The verified model can be used to investigate the influence of catalyst diameter on the flow distribution inside the particle. The simulation results demonstrate that the mass fraction gradients of all species, temperature gradient and pressure gradient increase with the increase of the particle diameter. It means that there is a high intraparticle transfer resistance and strong diffusion when applying the large catalysts. The external particle mass transfer resistance is nearly constant under different particle diameters so that the effect of particle diameter at external diffusion can be ignored. A large particle diameter can lead to a high surface temperature, which indicates the external heat transfer resistance. Moreover, the selectivity of reaction may be changed with a variety of particle diameters so that choosing appropriate particle size can enhance the production of butadiene and optimize the reaction process.展开更多
Abstract Two series of trans-1,4-poly（butadiene-co-isoprene） copolymers （TBIR） were prepared using the catalyst system TiCl4/MgCl2-Al（i-Bu）3 at different reaction temperatures. All dyad and triads sequence distr...Abstract Two series of trans-1,4-poly（butadiene-co-isoprene） copolymers （TBIR） were prepared using the catalyst system TiCl4/MgCl2-Al（i-Bu）3 at different reaction temperatures. All dyad and triads sequence distributions, the number-average sequence length and the sequence concentration of the copolymers were calculated according to 13C-NMR spectra. The influences of temperature and initial molar ratio of butadiene to isoprene （Bd to Ip） on the distribution of the chain segments in the TBIR copolymers were discussed. The correlation of copolymer compositions and thermal properties were also evaluated, which facilitated the understanding of controlling the degree of crystallinity and the transition tempera^re by changing Bd content and temperature.展开更多
A series of trans-1,4-butadiene/isoprene copolymers were prepared using the catalyst system TiCl4/MgCl2-Al（i- Bu）3 with bulk precipitation technology at different temperatures. Monomers reactivity ratios were calcul...A series of trans-1,4-butadiene/isoprene copolymers were prepared using the catalyst system TiCl4/MgCl2-Al（i- Bu）3 with bulk precipitation technology at different temperatures. Monomers reactivity ratios were calculated based on the Kelen-Tiid6s （K-T） method and the Mao-Huglin （M-H） method. The influence of temperature on copolymer composition and polymerization rate was discussed in detail. The increase of reaction temperature brought the decrease of butadiene reactivity ratio rBd and supplied an effective adjustment on copolymers＇ composition distribution.展开更多
A series ofbutadiene-isoprene copolymers （BIR） with various compositions were synthesized with a neodymiumbased catalyst system. The microstructure, composition and sequence of copolymers were characterized by FTIR ...A series ofbutadiene-isoprene copolymers （BIR） with various compositions were synthesized with a neodymiumbased catalyst system. The microstructure, composition and sequence of copolymers were characterized by FTIR and ^13C-NMR spectroscopy. The crystallization behavior of the BIR copolymers was investigated by DSC analysis. The results demonstrate that the content of cis-1,4 configuration in both butadiene （Bd） and isoprene （Ip） units are around 98% when Bd content in feed （fBd） covering the range from 55.7 mol% to 96.0 mol%. The reactivity ratios of Bd and Ip were determined to be 1.40 and 0.48 respectively. The random copolymers of Bd and Ip show only one glass transition temperature （Tg） from -107.4℃ to -80.5℃, which is dependent on the composition and fits nicely with Fox equation. The sequence distribution followed the first-order Markov statistical model. It is found that the copolymer chains with higher Bd content contain longer polybutadiene （PBd） segments, and the sequence length of PBd segments （NBd） exhibits great influence on the crystallization behavior of the copolymer. The copolymers with NBd ≥ 11.8 could crystallize at low temperatures （-71℃ to -43℃）. The crystallization temperature and enthalpy values decreased gradually with decreasing NBd. The copolymers with NBd ≤ 7.9 are amorphous even at very low temperatures （0℃ to -150℃） due to the short PBd segments.展开更多
Liquid carboxyl-terminated poly（butadiene-co-acrylonitrile）（CTBN）-epoxy resin（EP） prepolymers were prepared with different contents of CTBN.The chemical reactions between EP and CTBN were characterized by Fourie...Liquid carboxyl-terminated poly（butadiene-co-acrylonitrile）（CTBN）-epoxy resin（EP） prepolymers were prepared with different contents of CTBN.The chemical reactions between EP and CTBN were characterized by Fourier ransform infrared（FTIR） spectroscopy and gel permeation chromatography（GPC）.The scanning electron micrograph（SEM） and dynamic mechanical analysis（DMA） of curing films showed phase separation,and the rubber particles were finely dispersed in the epoxy matrix.Mechanical properties analysis of curing films showed that impact strength and elongation at break increased significantly upon the addition of CTBN,indicating good toughness of the modified epoxy resins.Thermogravimetric analysis（TGA） showed that the incorporation of CTBN had little effect on the thermal stability of EP.Fusion-bonded-epoxy（FBE） powder coatings modified with CTBN-EP prepolymers were prepared.The experimental results demonstrate the ability of CTBN-EP prepolymers,toughening technology to dramatically enhance the flexibility and impact resistance of FBE coatings without compromising other key properties such as corrosion protection.展开更多
Coordinative chain transfer polymerization(CCTP)is a newly developed strategy that features similarly,but superiorly,to classical living polymerization,in other words,precise molecular weight controlling,narrow molecu...Coordinative chain transfer polymerization(CCTP)is a newly developed strategy that features similarly,but superiorly,to classical living polymerization,in other words,precise molecular weight controlling,narrow molecular weight distribution,atom economy and so on,and has been quickly grown as a powerful tool to prepare the target polymer materials[1].As an extension of this concept,the present study discloses our recent progresses on CCTP of butadiene(Bd)and isoprene(Ip)to prepare precisely controlled Bd/Ip copolymers.展开更多
A new kind of multifunctional macromolecular initiator with Sn-C bonds and polydiene arms was synthesized by living anionic polymerization. At first, polydiene-stannum chloride （PD-SnCl3） was prepared by the reactio...A new kind of multifunctional macromolecular initiator with Sn-C bonds and polydiene arms was synthesized by living anionic polymerization. At first, polydiene-stannum chloride （PD-SnCl3） was prepared by the reaction of n-butyl-Li （n-BuLi）, stannic chloride （SnCl4） and diene. Then PD-SnCl3 was used to react with the dilithium initiator to prepare the multifunctional organic macromolecular initiators. The result suggested that the initiators had a remarkable yield by GPC, nearly 90%. By using these multifunctional macromolecular initiators, styrene and butadiene were effectively polymefized via anionic polymerization, which gave birth to novel miktoarm star copolymers. The relative molecular weight and polydispersity index, microstructure contents, copolymerization components, glass transition temperature （Tg） and morphology of the miktoarm star copolymers were investigated by GPC-UV, ~H NMR, DSC and TEM, respectively. 2009 Xing Ying Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
Polystyrene-styrene/butadiene diblock copolymers were synthesized via reversible addition-fragmentation chain transfer （RAFT） miniemulsion polymerization.During the polymerization process,the molecular weight distri...Polystyrene-styrene/butadiene diblock copolymers were synthesized via reversible addition-fragmentation chain transfer （RAFT） miniemulsion polymerization.During the polymerization process,the molecular weight distribution was narrow and the numerical molecular weight of the copolymers increased with increasing conversion of monomers,which was close to the theoretical.FT-IR and ^1H NMR results indicated that the microstructure of the polymer was mainly 1,4-trans-butadiene with small amount of 1,2-units,and composition in the copolymers was obtained.展开更多
FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance （ATR） immersion probe was utilized to study in situ the copolymerization of butadiene （Bd） and isoprene （Ip） with neodymium-bas...FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance （ATR） immersion probe was utilized to study in situ the copolymerization of butadiene （Bd） and isoprene （Ip） with neodymium-based catalyst in hexane. The relationship between the signal intensity of monomer and its concentration was investigated. The kinetic study of copolymerization of Bd and Ip was further conducted, and the monomer reactivity ratios were determined via in situ ATR FTIR. The signal band at 1010 cm^-1 was assigned to wagging vibration of Bd and its intensity was proportional to Bd concentration （[Bd]） in the range of 0.46-3.88 mol.L^-1. The signal bands at 890 and 989 cm^-1 were assigned to wagging vibration of Ip and the signal intensity was also proportional to Ip concentration （[Ip]） in the range of 0.08-4.73 mol·L^-1 at 890 cm^-1 and 0.08-7.49 mol·L^-1 at 989 cm^-1, respectively. Thus the signal band at 1010 cm^-1 was chosen to monitor Bd concentration and bands at 989 and 890 cm^-1 to monitor Ip concentration during the copolymerization, respectively. It was demonstrated that the conversions of Bd and Ip calculated from FTIR data agreed very well with those obtained gravimetrically. The poiymerization rates were first order with respect to both [Bd] and [Ip], respectively at different polymerization temperatures. The apparent propagation activation energy for Bd and Ip could be determined to be 54.4 kJ·mol^-1 and 57.7 kJ·mol^-1, respectively. The monomer reactivity ratios were calculated to be 1.08 for Bd （rBd） and 0.48 for IP （rIp） based on FTIR data. The Bd-Ip copolymer products with random sequence could be obtained with only one glass transition temperature.展开更多
An experimental apparatus composed of microscope, video camera. image-processing, and mini reactor which can be used for real-time measurement of the growth of polymer particle in gas phase polymerization was built up...An experimental apparatus composed of microscope, video camera. image-processing, and mini reactor which can be used for real-time measurement of the growth of polymer particle in gas phase polymerization was built up to carry out dynamic study of gas phase polymerization of butadiene by heterogeneous catalyst based on neodymium(Nd). The studies of the shape duplication of polymer particles and catalyst particles and the growth rate of polymer particle were made. Results show that the apparatus and procedure designed can be well utilized to make dynamic observation and data collection of the growth of polymer particle in gas phase polymerization. A phenomenon of shape duplication of polymer particles and catalyst particles was observed by the real-time measurement. The result also concludes that the activity of individual catalyst particle is different, and the effect of reaction pressure on the growth of polymer particle is significant.展开更多
The mechanism, catalytic effect and substituent effect of the hetero-Diels-Alder reactions between phosphonodithioformate and butadienes have been investigated theoretically using density functional theory at the B3LY...The mechanism, catalytic effect and substituent effect of the hetero-Diels-Alder reactions between phosphonodithioformate and butadienes have been investigated theoretically using density functional theory at the B3LYP/6-31G（d） level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C and opposite result is found in other reactions. The BF3 catalyst and trimethylsilyloxy group may lower the activation barriers by changing the energies of FMOs for reactant molecules. With the BF3-catalyzed reactions, the complete regioselectivity observed experimentally has well been reproduced by theoretical calculation and these results originate probably from blue-shifting C-H...F hydrogen bond interaction in some transition states.展开更多
Selective hydrogenation of 1,3‐butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector.Catalyst design is crucial to achieve a virtually alkadiene‐free product while...Selective hydrogenation of 1,3‐butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector.Catalyst design is crucial to achieve a virtually alkadiene‐free product while avoiding over‐hydrogenating valuable olefins.In addition to the great industrial relevance,this demanding selectivity pattern renders 1,3‐butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia.Nonetheless,critical reviews on the catalyst development are extremely lacking in literature.In this review,we aim to provide the reader an in‐depth overview of different catalyst families,particularly the precious metal‐based monometallic catalysts(Pd,Pt,and Au),developed in the last half century.The emphasis is placed on the development of new strategies to design high‐performance architectures,the establishment of structure‐performance relationships,and the reaction and deactivation mechanisms.Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.展开更多
This paper presents the influence of graphene on the vulcanization kinetics of styrene butadiene rubber （SBR） with dicumyl peroxide. A curemeter and a differential scanning calorimeter were used to investigate the c...This paper presents the influence of graphene on the vulcanization kinetics of styrene butadiene rubber （SBR） with dicumyl peroxide. A curemeter and a differential scanning calorimeter were used to investigate the cure kinetics, from which the kinetic parameters and apparent activation energy were obtained. It turns out that with increasing graphene loading, the induction period of the vulcanization process of SBR is remarkably reduced at low graphene loading and then levels off; on the other hand, the optimum cure time shows a monotonous decrease. As a result, the vulcanization rate is suppressed at first and then accelerated, and the corresponding activation energy increases slightly at first and then decreases. Upon adding graphene, the crosslinking density of the nanocomposites increases, because graphene takes part in the vulcanization process.展开更多
This paper determined the association degree of n-BuLi and polybutadinyllithium(PBLi)by UV spec-trometry and viscometry.The experimental results of UV spectrometric analysis showed that the associationdegree of n-BuLi...This paper determined the association degree of n-BuLi and polybutadinyllithium(PBLi)by UV spec-trometry and viscometry.The experimental results of UV spectrometric analysis showed that the associationdegree of n-BuLi as well as PBLi is dependent mainly on their concentration in solutions;there may be specieswith three and two degrees of association in cyclohexane solvent respectively for n-BuLi and PBLi,i.e.the asso-ciation degree for the former is equal to 2,4 and 6;and for the latter it equals to 2 and 4.Similarly,the experi-mental results obtained by viscometric measurement showed that the average association degree N of PBLiin cyclohexane changed from 2 to 4 with increasing of its concentration in solution and decreased with addi-tion of a small amount of polar additive into the above mentioned system.Furthermore,in pure polar solvent,such as dimethoxyethane(DME),tetrahydrofuran(THF)or dioxane(DOX),PBLi is completely dissociatedinto monomeric species;however,in pure diethyl ether,due to its weak polarity a part of associated species stillcan be found.Generally speaking,all of the above results were consistent with the results of kinetic studies in-vestigated by us before.展开更多
A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling mode...A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling models and the buried volume percentages,obviously longer bond distances of Co―N and Co―O are revealed from those complexes.Moreover,because of these well-protected active species,the cobalt complexes are able to catalyze 1,3-butadiene polymerization in high yields at extreme low catalyst concentrations,revealing a ultra high catalytic efficiency.At a ratio of 50000,all the complexes can afford polybutadiene with yields higher than 90%.Furthermore,the highly steric bulkiness of the ligand can also significantly enhance the thermostability of the active species.At temperature of 80-120°C,the complexes are able to successfully maintain high activities,giving polymer yields up to 90%.展开更多
Rare earth catalysts possessing characteristics of cation-anion ion pair show advantages of adjusting electronegativity and steric hindrance of metal active sites, which can control the catalytic performance and stere...Rare earth catalysts possessing characteristics of cation-anion ion pair show advantages of adjusting electronegativity and steric hindrance of metal active sites, which can control the catalytic performance and stereoselectivity better than those of traditional metallocene and Ziegler-Natta catalysts in diene polymerization. In this work, a series of neodymium organic sulfonate complexes,Nd(CF_3SO_3)_3·x H_2O·y L(x, y: the coordination number; L refers to an organic electron donating ligand, such as acetylacetone(acac), isooctyl alcohol(IAOH), tributyl phosphate(TBP), etc.), have been synthesized to form the cationic active species in the presence of alkylaluminum such as Al(i-Bu)_3, AlEt_3, and Al(i-Bu)_2H, which display high activities and distinguishing cis-1,4 selectivities(up to99.9%) for the polymerization of butadiene. The microstructures, yield, molecular weight, and molecular weight distribution of the resulting polymer are well controlled by adjusting electronegativity/steric hindrance of the complexes. In addition, the kinetics, active species, and the possible process of polymerization are also discussed in this article.展开更多
Surface-modified poly(butadiene)urethane (PBTU) films with silk fibroin (SF) were prepared by simple chemical method under the normal temperature. The physical properties and biological behaviour of the SF-modified PB...Surface-modified poly(butadiene)urethane (PBTU) films with silk fibroin (SF) were prepared by simple chemical method under the normal temperature. The physical properties and biological behaviour of the SF-modified PBTU film were evaluated. The results showed that the SF-modified PBTU films kept the tenacity and pliability very well, and could overcome rigid and brittle weaks of silk fibroin films. The morphology of SF in the PBTU film was dendritic aggregations, and the water-contact angle measurement indicated that the surface hydrophilicity of modified films was apparently enhanced. The biocompatibility of PBTU films was improved due to the change of surface components. The degree of platelet adhesion and the cell viability of rat embryo dermal fibroblasts seeded on PBTU films, SF films, and SF-modified PBTU films were measured by counting platelets before and after they contacted the films and MTT assay, respectively. The results indicated that platelet adhesion resistance and cell viability on the modified film were greatly superior to those on the PBTU film and the compound interface had good stability in the air.展开更多
基金supported by the National Natural Science Foundation of China(No.52005470)the Natural Science Foundation of Zhejiang Province(No.LQ21E050020)the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.2021YW17),China.
文摘The nitrile butadiene rubber(NBR)hardness effect on the sealing characteristics of hydraulic O-ring rod seals is analyzed based on a mixed lubrication elastohydrodynamic model.Parameterized studies are conducted to reveal the mechanism of the influence of rubber hardness on the static and dynamic behavior of seals.The optimized selections of rubber hardness are then investigated under different conditions.Results show that the low hardness seal is prone to stress concentration due to the extrusion effect under high pressure conditions;it is also more prone to leaking.A high hardness seal can better prevent leakage by reducing film thickness but it will cause large frictional power loss and increase the probability of wear failure.The choice of low hardness is recommended to reduce friction with the premise that leakage requirements are met.
文摘Upgrading of sustainable ethanol into C_(4)olefins by C-C coupling contributes to alleviating the dependency towards petroleum.The reaction network consists several key steps,whereas dehydration often competes with dehydrogenation over acidic catalyst.Herein,we report a designed bifunctional Co-YPO_(4)catalyst with balanced active sites for dehydrogenation and condensation that can directly catalyze ethanol to butadiene.The YPO4 can stabilize Co^(2+)species to form highly dispersed[Co-O-P]sites,which catalyze ethanol dehydrogenation to acetaldehyde.Additionally,the YPO4 surface exposed Y^(3+)site,as Lewis acid center,which can effectively catalyze C-C coupling reaction.The addition of cobalt enhances the ethanol dehydrogenation process while reducing the surface acidity,thus inhibiting the formation of dehydration products and promoting the formation of butadiene.Kinetic measurements suggest that the rate-limiting step is the dehydrogenation of ethanol to acetaldehyde.The synthesized Co-YPO4 shows a 68.5%selectivity of butadiene under a conversion of 78.2%at 350°C and a weight hourly space velocity of 1.0 gC_(2)H_(5)OH×gCat.^(-1)×h^(-1).
基金supported by the National Natural Science Foundation of China(22178190)。
文摘In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile.The accuracy of five prediction methods,UNIFAC(UNIQUAC Functional-group Activity Coefficients),UNIFAC-LL,UNIFAC-LBY,UNIFAC-DMD and COSMO-RS,applied to the butadiene extraction process was verified using partial phase equilibrium data.The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system.COSMO-RS-predicted multiple systems showed good accuracy,and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method.The predicted phase equilibrium data were checked for consistency.The NRTL-RK(non-Random Two Liquid-Redlich-Kwong Equation of State)and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data.Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process.The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2%compared to that using the commercial simulation software,Aspen Plus and its database.The average deviation was much smaller than that of the simulations using the Aspen Plus database(>10%),indicating that the obtained phase equilibrium data are highly accurate and reliable.The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided.This improves the accuracy and reliability of the design,optimization and control of the process,and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.
基金The National Science Foundation of China(No.2157604921576050)the Fundamental Research Funds for the Central Universities(No.2242014K10025)
文摘A comprehensive single particle model which includes the mesoscale and microscale models was developed to study the influence of particle diameter on mass and heat transfer occurring within a ferrite catalyst during the oxidative dehydrogenation of butene to butadiene process. The verified model can be used to investigate the influence of catalyst diameter on the flow distribution inside the particle. The simulation results demonstrate that the mass fraction gradients of all species, temperature gradient and pressure gradient increase with the increase of the particle diameter. It means that there is a high intraparticle transfer resistance and strong diffusion when applying the large catalysts. The external particle mass transfer resistance is nearly constant under different particle diameters so that the effect of particle diameter at external diffusion can be ignored. A large particle diameter can lead to a high surface temperature, which indicates the external heat transfer resistance. Moreover, the selectivity of reaction may be changed with a variety of particle diameters so that choosing appropriate particle size can enhance the production of butadiene and optimize the reaction process.
基金financially supported by the National Basic Research Program of China(No.2015CB654700(2015CB654706))Shandong Province Natural Science Fund for Distinguished Young Scholars(No.JQ201213)the National Natural Science Foundation of China(No.51473083)
文摘Abstract Two series of trans-1,4-poly（butadiene-co-isoprene） copolymers （TBIR） were prepared using the catalyst system TiCl4/MgCl2-Al（i-Bu）3 at different reaction temperatures. All dyad and triads sequence distributions, the number-average sequence length and the sequence concentration of the copolymers were calculated according to 13C-NMR spectra. The influences of temperature and initial molar ratio of butadiene to isoprene （Bd to Ip） on the distribution of the chain segments in the TBIR copolymers were discussed. The correlation of copolymer compositions and thermal properties were also evaluated, which facilitated the understanding of controlling the degree of crystallinity and the transition tempera^re by changing Bd content and temperature.
基金financially supported by the National Key Technology R&D Program of China(No.2011BAE26B05)the Shandong Province Natural Science Fund for Distinguished Young Scholars(No.JQ201213)+2 种基金National Natural Science Foundation of China(No.21174074)Shandong Province Science and Technology Development Plan(No.2012GGA05042)the Major Projects of Independent Innovation Achievements Transformation in Shandong Province(No.2013ZHZX1A0207)
文摘A series of trans-1,4-butadiene/isoprene copolymers were prepared using the catalyst system TiCl4/MgCl2-Al（i- Bu）3 with bulk precipitation technology at different temperatures. Monomers reactivity ratios were calculated based on the Kelen-Tiid6s （K-T） method and the Mao-Huglin （M-H） method. The influence of temperature on copolymer composition and polymerization rate was discussed in detail. The increase of reaction temperature brought the decrease of butadiene reactivity ratio rBd and supplied an effective adjustment on copolymers＇ composition distribution.
基金supported by the National 863 program(No.2006AA03Z552)China Petroleum Chemical Corp. (SINOPEC) and Program for Changjiang Scholars and Innovative Research Teams in Universities(IRT0706)
文摘A series ofbutadiene-isoprene copolymers （BIR） with various compositions were synthesized with a neodymiumbased catalyst system. The microstructure, composition and sequence of copolymers were characterized by FTIR and ^13C-NMR spectroscopy. The crystallization behavior of the BIR copolymers was investigated by DSC analysis. The results demonstrate that the content of cis-1,4 configuration in both butadiene （Bd） and isoprene （Ip） units are around 98% when Bd content in feed （fBd） covering the range from 55.7 mol% to 96.0 mol%. The reactivity ratios of Bd and Ip were determined to be 1.40 and 0.48 respectively. The random copolymers of Bd and Ip show only one glass transition temperature （Tg） from -107.4℃ to -80.5℃, which is dependent on the composition and fits nicely with Fox equation. The sequence distribution followed the first-order Markov statistical model. It is found that the copolymer chains with higher Bd content contain longer polybutadiene （PBd） segments, and the sequence length of PBd segments （NBd） exhibits great influence on the crystallization behavior of the copolymer. The copolymers with NBd ≥ 11.8 could crystallize at low temperatures （-71℃ to -43℃）. The crystallization temperature and enthalpy values decreased gradually with decreasing NBd. The copolymers with NBd ≤ 7.9 are amorphous even at very low temperatures （0℃ to -150℃） due to the short PBd segments.
基金Funded by the National Science and Technology Pillar Program of China(No.2007BAE15B02)
文摘Liquid carboxyl-terminated poly（butadiene-co-acrylonitrile）（CTBN）-epoxy resin（EP） prepolymers were prepared with different contents of CTBN.The chemical reactions between EP and CTBN were characterized by Fourier ransform infrared（FTIR） spectroscopy and gel permeation chromatography（GPC）.The scanning electron micrograph（SEM） and dynamic mechanical analysis（DMA） of curing films showed phase separation,and the rubber particles were finely dispersed in the epoxy matrix.Mechanical properties analysis of curing films showed that impact strength and elongation at break increased significantly upon the addition of CTBN,indicating good toughness of the modified epoxy resins.Thermogravimetric analysis（TGA） showed that the incorporation of CTBN had little effect on the thermal stability of EP.Fusion-bonded-epoxy（FBE） powder coatings modified with CTBN-EP prepolymers were prepared.The experimental results demonstrate the ability of CTBN-EP prepolymers,toughening technology to dramatically enhance the flexibility and impact resistance of FBE coatings without compromising other key properties such as corrosion protection.
基金Supported by Jilin Provincial Science and Technology Development Program(20190103122JH).
文摘Coordinative chain transfer polymerization(CCTP)is a newly developed strategy that features similarly,but superiorly,to classical living polymerization,in other words,precise molecular weight controlling,narrow molecular weight distribution,atom economy and so on,and has been quickly grown as a powerful tool to prepare the target polymer materials[1].As an extension of this concept,the present study discloses our recent progresses on CCTP of butadiene(Bd)and isoprene(Ip)to prepare precisely controlled Bd/Ip copolymers.
基金supported by National Natural Science Foundation of China(No.50573005)
文摘A new kind of multifunctional macromolecular initiator with Sn-C bonds and polydiene arms was synthesized by living anionic polymerization. At first, polydiene-stannum chloride （PD-SnCl3） was prepared by the reaction of n-butyl-Li （n-BuLi）, stannic chloride （SnCl4） and diene. Then PD-SnCl3 was used to react with the dilithium initiator to prepare the multifunctional organic macromolecular initiators. The result suggested that the initiators had a remarkable yield by GPC, nearly 90%. By using these multifunctional macromolecular initiators, styrene and butadiene were effectively polymefized via anionic polymerization, which gave birth to novel miktoarm star copolymers. The relative molecular weight and polydispersity index, microstructure contents, copolymerization components, glass transition temperature （Tg） and morphology of the miktoarm star copolymers were investigated by GPC-UV, ~H NMR, DSC and TEM, respectively. 2009 Xing Ying Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金supported by Major Program of National Natural Science Foundation of China(No. 20836007)National Natural Science Foundation of China(No.20806067).
文摘Polystyrene-styrene/butadiene diblock copolymers were synthesized via reversible addition-fragmentation chain transfer （RAFT） miniemulsion polymerization.During the polymerization process,the molecular weight distribution was narrow and the numerical molecular weight of the copolymers increased with increasing conversion of monomers,which was close to the theoretical.FT-IR and ^1H NMR results indicated that the microstructure of the polymer was mainly 1,4-trans-butadiene with small amount of 1,2-units,and composition in the copolymers was obtained.
基金supported by the National 863 program(No.2006AA03Z552)the National Natural Science Foundation of China(No.50903003)China Petroleum Chemical Corp.(SINOPEC)and Program for Changjiang Scholars and Innovative Research Teams in Universities(IRT0706)
文摘FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance （ATR） immersion probe was utilized to study in situ the copolymerization of butadiene （Bd） and isoprene （Ip） with neodymium-based catalyst in hexane. The relationship between the signal intensity of monomer and its concentration was investigated. The kinetic study of copolymerization of Bd and Ip was further conducted, and the monomer reactivity ratios were determined via in situ ATR FTIR. The signal band at 1010 cm^-1 was assigned to wagging vibration of Bd and its intensity was proportional to Bd concentration （[Bd]） in the range of 0.46-3.88 mol.L^-1. The signal bands at 890 and 989 cm^-1 were assigned to wagging vibration of Ip and the signal intensity was also proportional to Ip concentration （[Ip]） in the range of 0.08-4.73 mol·L^-1 at 890 cm^-1 and 0.08-7.49 mol·L^-1 at 989 cm^-1, respectively. Thus the signal band at 1010 cm^-1 was chosen to monitor Bd concentration and bands at 989 and 890 cm^-1 to monitor Ip concentration during the copolymerization, respectively. It was demonstrated that the conversions of Bd and Ip calculated from FTIR data agreed very well with those obtained gravimetrically. The poiymerization rates were first order with respect to both [Bd] and [Ip], respectively at different polymerization temperatures. The apparent propagation activation energy for Bd and Ip could be determined to be 54.4 kJ·mol^-1 and 57.7 kJ·mol^-1, respectively. The monomer reactivity ratios were calculated to be 1.08 for Bd （rBd） and 0.48 for IP （rIp） based on FTIR data. The Bd-Ip copolymer products with random sequence could be obtained with only one glass transition temperature.
基金the National Natural Science Foundation of China (No. 29876035).
文摘An experimental apparatus composed of microscope, video camera. image-processing, and mini reactor which can be used for real-time measurement of the growth of polymer particle in gas phase polymerization was built up to carry out dynamic study of gas phase polymerization of butadiene by heterogeneous catalyst based on neodymium(Nd). The studies of the shape duplication of polymer particles and catalyst particles and the growth rate of polymer particle were made. Results show that the apparatus and procedure designed can be well utilized to make dynamic observation and data collection of the growth of polymer particle in gas phase polymerization. A phenomenon of shape duplication of polymer particles and catalyst particles was observed by the real-time measurement. The result also concludes that the activity of individual catalyst particle is different, and the effect of reaction pressure on the growth of polymer particle is significant.
文摘The mechanism, catalytic effect and substituent effect of the hetero-Diels-Alder reactions between phosphonodithioformate and butadienes have been investigated theoretically using density functional theory at the B3LYP/6-31G（d） level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C and opposite result is found in other reactions. The BF3 catalyst and trimethylsilyloxy group may lower the activation barriers by changing the energies of FMOs for reactant molecules. With the BF3-catalyzed reactions, the complete regioselectivity observed experimentally has well been reproduced by theoretical calculation and these results originate probably from blue-shifting C-H...F hydrogen bond interaction in some transition states.
基金supported by Zhejiang Normal University (YS304320035, YS304320036)
文摘Selective hydrogenation of 1,3‐butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector.Catalyst design is crucial to achieve a virtually alkadiene‐free product while avoiding over‐hydrogenating valuable olefins.In addition to the great industrial relevance,this demanding selectivity pattern renders 1,3‐butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia.Nonetheless,critical reviews on the catalyst development are extremely lacking in literature.In this review,we aim to provide the reader an in‐depth overview of different catalyst families,particularly the precious metal‐based monometallic catalysts(Pd,Pt,and Au),developed in the last half century.The emphasis is placed on the development of new strategies to design high‐performance architectures,the establishment of structure‐performance relationships,and the reaction and deactivation mechanisms.Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.
基金financially supported by the National Natural Science Foundation of China(No.51203096)the Ph.D.Programs Foundation of Ministry of Education of China(No.20100181120020)Sichuan University
文摘This paper presents the influence of graphene on the vulcanization kinetics of styrene butadiene rubber （SBR） with dicumyl peroxide. A curemeter and a differential scanning calorimeter were used to investigate the cure kinetics, from which the kinetic parameters and apparent activation energy were obtained. It turns out that with increasing graphene loading, the induction period of the vulcanization process of SBR is remarkably reduced at low graphene loading and then levels off; on the other hand, the optimum cure time shows a monotonous decrease. As a result, the vulcanization rate is suppressed at first and then accelerated, and the corresponding activation energy increases slightly at first and then decreases. Upon adding graphene, the crosslinking density of the nanocomposites increases, because graphene takes part in the vulcanization process.
文摘This paper determined the association degree of n-BuLi and polybutadinyllithium(PBLi)by UV spec-trometry and viscometry.The experimental results of UV spectrometric analysis showed that the associationdegree of n-BuLi as well as PBLi is dependent mainly on their concentration in solutions;there may be specieswith three and two degrees of association in cyclohexane solvent respectively for n-BuLi and PBLi,i.e.the asso-ciation degree for the former is equal to 2,4 and 6;and for the latter it equals to 2 and 4.Similarly,the experi-mental results obtained by viscometric measurement showed that the average association degree N of PBLiin cyclohexane changed from 2 to 4 with increasing of its concentration in solution and decreased with addi-tion of a small amount of polar additive into the above mentioned system.Furthermore,in pure polar solvent,such as dimethoxyethane(DME),tetrahydrofuran(THF)or dioxane(DOX),PBLi is completely dissociatedinto monomeric species;however,in pure diethyl ether,due to its weak polarity a part of associated species stillcan be found.Generally speaking,all of the above results were consistent with the results of kinetic studies in-vestigated by us before.
基金financially supported by the National Natural Science Foundation of China(Nos.U1862206 and 21801236)。
文摘A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling models and the buried volume percentages,obviously longer bond distances of Co―N and Co―O are revealed from those complexes.Moreover,because of these well-protected active species,the cobalt complexes are able to catalyze 1,3-butadiene polymerization in high yields at extreme low catalyst concentrations,revealing a ultra high catalytic efficiency.At a ratio of 50000,all the complexes can afford polybutadiene with yields higher than 90%.Furthermore,the highly steric bulkiness of the ligand can also significantly enhance the thermostability of the active species.At temperature of 80-120°C,the complexes are able to successfully maintain high activities,giving polymer yields up to 90%.
基金the National Natural Science Foundation of China(Nos.51473156 and 51873203)Key Projects of Jilin Province Science and Technology Development Plan(Nos.2018020108GX and 20160204028GX)
文摘Rare earth catalysts possessing characteristics of cation-anion ion pair show advantages of adjusting electronegativity and steric hindrance of metal active sites, which can control the catalytic performance and stereoselectivity better than those of traditional metallocene and Ziegler-Natta catalysts in diene polymerization. In this work, a series of neodymium organic sulfonate complexes,Nd(CF_3SO_3)_3·x H_2O·y L(x, y: the coordination number; L refers to an organic electron donating ligand, such as acetylacetone(acac), isooctyl alcohol(IAOH), tributyl phosphate(TBP), etc.), have been synthesized to form the cationic active species in the presence of alkylaluminum such as Al(i-Bu)_3, AlEt_3, and Al(i-Bu)_2H, which display high activities and distinguishing cis-1,4 selectivities(up to99.9%) for the polymerization of butadiene. The microstructures, yield, molecular weight, and molecular weight distribution of the resulting polymer are well controlled by adjusting electronegativity/steric hindrance of the complexes. In addition, the kinetics, active species, and the possible process of polymerization are also discussed in this article.
基金Major State Basic Research Development Programof China (No.2005CB623906)
文摘Surface-modified poly(butadiene)urethane (PBTU) films with silk fibroin (SF) were prepared by simple chemical method under the normal temperature. The physical properties and biological behaviour of the SF-modified PBTU film were evaluated. The results showed that the SF-modified PBTU films kept the tenacity and pliability very well, and could overcome rigid and brittle weaks of silk fibroin films. The morphology of SF in the PBTU film was dendritic aggregations, and the water-contact angle measurement indicated that the surface hydrophilicity of modified films was apparently enhanced. The biocompatibility of PBTU films was improved due to the change of surface components. The degree of platelet adhesion and the cell viability of rat embryo dermal fibroblasts seeded on PBTU films, SF films, and SF-modified PBTU films were measured by counting platelets before and after they contacted the films and MTT assay, respectively. The results indicated that platelet adhesion resistance and cell viability on the modified film were greatly superior to those on the PBTU film and the compound interface had good stability in the air.
