Phase equilibrium data prediction and process optimizationin butadiene extraction process

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.

Preparation and Characterization of Carboxyl-terminated Poly(butadiene-co-acrylonitrile)-epoxy Resin Prepolymers for Fusion-bonded-epoxy Powder Coating

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.

IN SITU MONITORING OF COORDINATION COPOLYMERIZATION OF BUTADIENE AND ISOPRENE VIA ATR-FTIR SPECTROSCOPY

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.

Synthesis and characterization of miktoarm star copolymer of styrene and butadiene using multifunctional macromolecular initiator

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.

Computational Study on the Hetero-Diels-Alder Reactions between Phosphonodithioformate and Butadienes

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.

Synthesis of polystyrene-styrene/butadiene diblock copolymers via reversible addition-fragmentation chain transfer miniemulsion polymerization

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.

CHARACTERIZATION OF IRON COMPLEXES SUPPORTED ON POLYMER AND THEIR CATALYTIC ACTIVITY IN BUTADIENE POLYMERIZATION

Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum suggested that the complex SAAC·Fe possesses a structure of(C)and the Fe-O bond is higher in covalency.The complex SAAC·Fe with the structure of(C)shoved a higher catalytic activity in butadiene polymerization. When Fe/-COOH molar ratio in SAAC·Fe was about 0.2 the complex gave optimum catalytic activity. The catalytic activity of SAAC·Fe with the higher content of long sequence of acrylic acid units was low. When the content of the short sequence of acrylic acid units was predominant and at the same time the content of the short sequence was approximately equal to that of the long sequence for stryrene, the activity of the complex was high.

Performance of CTBN(carboxyl-terminated poly (butadiene-co-acrylonitrile))-EP(diglycidyl ether of bisphenol-A (DGEBA)) Prepolymers and CTBN-EP/polyetheramine (PEA) System

CTBN-EP prepolymers were synthesized from CTBN and epoxy resin under the catalysis of HTMAB. FTIR analyses indicate the formation of ester group between the carboxyl group of CTBN and the oxirane group of epoxy resin. The viscosity of modified prepolymer increases with CTBN content increasing, but the epoxy value of the prepolymer decreases greatly. DSC analyses verify that CTBN affects the curing process of CTBN-EP/PEA system. Mechanical testing presents the improved toughness of CTBN-EP/PEA curings for the decrease of tensile strength, flexural strength and compressive strength, and increase of impact strength and elongation-at-break with the CTBN content increasing. SEM micrographs show the rubber phase with many holes in diameter about 0.5-1.5 μm is formed when CTBN content is lower than 10 phr. However, the pattern of SEM graph shows some stalactite-like strips when CTBN content is higher than 15 phr. Furthermore, the SEM image of 25 phr CTBN sample forms a kind of co-continuous structure.

Comparison between Pigment Printing Systems with Acrylate and Butadiene Based Binders

Pigment printing was carried out on lab scale by simple screen-printing techniques. By the application of acrylate and butadiene based binder, the crocking fastness, formaldehyde release and PVC migration of fabric printed with Imparon red KB pigment was evaluated. The effect of curing time on K/S values was also investigated. It has been found that butadiene based binder shows good performance in terms of crocking fastness, formaldehyde release and PVC migra-tion. It has also been observed that by increasing the binder concentration, the release of formaldehyde decreased and by increasing the curing time, the K/S values of printed fabric were decreased.

Coordinative chain transfer copolymerization of 1,3-butadiene and isoprene by neodymium precatalyst

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.

Reinforcement of Styrene-Butadiene Rubber with Silica Modified by Silane Coupling Agents: Experimental and Theoretical Chemistry Study

The properties of styrene-butadiene rubber (SBR) reinforced by modified silica was investigated according to national standards. Silica was modified by silane coupling agents KH-570, KH-590, and KH-792. The optimized geome-tries of molecular modified silica reinforced SBR were obtained by using B3LYP calculation of density functional theory with the 6-31+G basis sets. The natural bond orbital analyses were carried out. The Si—O bond length of silica modified by KH-792 was the shortest and the electronegative of O was the highest. It indicated that the connection between silica and KH-792 was the tightest. Higher tensile strength and elongation of reinforced SBR was obtained by silica modified with the KH-792. It was caused by large delocalization of lone pair electrons of the two N atoms in KH-792. The S—C bond length in silica modified by KH-590 was longer than the ordinary S—C bond length. Then the sulfur free radical (·S·) was produced more easily in vulcanization. The degree of crosslink was increased by the cross-linkage of the rubber molecule and the sulfur free radical. That was why the highest stress and tear strength of reinforced SBR was produced when silane coupling agent KH-590 was used. The calculation results was in accord with experimental data.

Simulation of 1,3-Butadiene Production Process by Dimethylfomamide Extractive Distillation

现在，引得出的蒸馏是主要技术生产 1,3 丁二烯。这研究由白杨随 DMF 引得出的蒸馏模仿了 1,3 丁二烯生产过程加。溶剂比率是引得出的蒸馏过程的最重要的参数。文章给出合适的溶剂比率，倒流比率，精华比率，和列的底部产品比率。它也讨论热大量几列。模拟的结果因而与植物数据，它与对方一起显示出好一致相比。

SOME THEORETICAL PROBLEMS OF ANIONIC POLYMERIZATION OF BUTADIENE——A Study on the Association Degree of n-BuLi and Polybutadienyl-Li

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.

Study of Mechanical and Physical Properties of Palm Fiber Reinforced Acrylonitrile Butadiene Styrene Composite

Palm fiber (PF) reinforced acrylonitrile butadiene styrene (ABS) composite matrix was prepared by employing Injection Moulding Machine (IMM). Palm fiber was collected from ten different trees of different age group from Comilla region in Bangladesh. Three sets of samples were prepared for three different wt% (5%, 10% and 20%) of fiber contents. The mechanical (tensile strength, flexural stress, micro hardness, Leeb’s rebound hardness) and physical (bulk density and water absorption) properties were measured. The observed result reveals that the tensile strength (TS) and flexural stress (FS) were decreased with increasing fiber contents in the PF-ABS composites except 10% fiber content.

The Effects of Build Parameters and Strain Rate on the Mechanical Properties of FDM 3D-Printed Acrylonitrile Butadiene Styrene

In this paper, the effects of build parameters on the mechanical properties of 3D-printed acrylonitrile butadiene styrene (ABS) produced using fused deposition modeling (FDM) are investigated. Full factorial experimental design incorporating a 2-level, 3-factor design with raster angle, layer thickness and interior fill style was carried out. Tensile tests were performed at four different strain rates to determine how the build parameters influence the mechanical properties of the 3-D printed ABS and to assess its strain rate sensitivity under quasi-static loading. It was found that the modulus of toughness of ABS material is most influenced by raster angle, while the interior fill style is the most dominant build parameter that dictates the specimen’s modulus of resilience, yield strength and ultimate tensile strength. At all strain rates, it is further revealed that higher mean values of yield strength, ultimate tensile strength and modulus of resilience were obtained when the interior fill style is solid as opposed to high density. This can be attributed to the denser structure and higher effective cross-sectional area in solid interior fill style in comparison with high density interior fill style. However, the influence of the layer thickness on the investigated mechanical properties was found to be inconsistent. It was noted that specimens built with both 0.254 mm layer thickness and the cross [0°/90°] raster angle had superior mechanical properties when compared to those built with the 0.3302 mm layer thickness and cross [0°/90°] raster angle. This suggests that there is a key interaction between the layer thickness and the raster angle. At any FDM build parameter, it was found that all the mechanical properties investigated in this work exhibited modest sensitivity to strain rates. This study has provided a platform for an appropriate selection of build parameters combinations and strain rates for additive manufacturing of 3D-printed ABS with improved mechanical properties.

Analysis and optimization of nitrile butadiene rubber sealing mechanism of ball valve

An approach for analyzing and optimizing sealing mechanism of ball valve made of nitrile butadiene rubber(NBR) with finite element method was presented. The Mooney-Rivlin hyperelastic material model was chosen to characterize NBR sealing, as it has been recommended in the similar applications. That is, NBR sealing was modeled as incompressible hyperelasticity, as well as the assumption of isotropic flow. The results illustrate the structural pressure and contact pressure on the contact surface, which shows that the NBR sealing mechanism is very suitable for sealing after dimension optimization.

Dynamic Study of Polymer Particle Growth in Gas Phase Polymerization of Butadiene

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.

Copolymerization of Butadiene and Isoprene by NdC_6H_6(AlCl_4)_3-AlR_3 System

This paper reported the copolymerization results of butadiene and isoprene catalyzed by NdC_6H_6(AlCl_4)_3-AlR_3 system.The results show that the catalytic activity is dependent on the weight ratio of butadiene and isoprene,the concentration of comonomers,the nature of alkylaluminium and the polymerization temperature as well.High contents of 1,4 microstructure of copolymer are obtained by the novel catalyst system.

Influence of Poly(methylmethacrylate) Dopant on Butadiene Derivative Electroluminescence

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Silk Fibroin-modified Poly(butadiene) urethane Films and Their Effects on Fibroblast Viability

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.