聚醚二醇钾盐引发D．L－丙交酯的开环聚合研究

以聚乙二醇－４０００钾盐为引发剂．合成了食不同长度聚醚链段的聚Ｄ．Ｌ－乳酸－聚乙二醇－聚Ｄ．Ｌ－乳酸（ＰＬＡ－ＰＥＧ－ＰＬＡ）三嵌段共聚物。考察了溶剂用量、引发剂用量、反应温度和时间、ＰＥＧ分子量、不同溶剂对聚合反应的影响。以１Ｈ－ＮＭＲ、ＩＲ、ＤＳＣ、ＧＰＣ对共聚物进行了表征。     

Electrochemical characteristics of phase-separated polymer electrolyte based on poly(vinylidene fluoride-co-hexafluoropropane) and ethylene carbonate

A polymer electrolyte based on microporous poly(vinylidene fluoride-co-hexafluoropropane) (PVdF-HFP) film was studied for use in lithium ion batteries. The microporous PVdF-HFP (Kynar 2801) matrix was prepared from a cast of homogeneous mixture of PVdF-HFP and solvents such as ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC). After evaporation of DMC and EMC, a sold film of the PVdF-HFP and the EC mixture was obtained. EC-rich phase started its formation in the PVdF-HFP/EC film at EC content of about 60 wt.% based on the total weight of PVdF-HFP and EC. The formation of the new phase resulted in the abrupt increase of the porosity of the PVdF-HFP matrix from 32 to 62%. The ionic conductivity of the film soaked in 1 M LiPF₆-EC/DMC=1/1 was significantly increased from order of 10⁻⁴ S/cm to order of 10⁻³ S/cm at the EC content of 60 wt.%. Thermal and spectroscopic investigations showed that most of the EC interact with PVdF-HFP with the EC content being below 60 wt.%. MCMB/polymer electrolyte/LiCoO₂ cells employing the microporous PVdF-HFP polymer film showed stable charging/discharging characteristics at 1C rate and good rate capability.     

Optimal reaction conditions for the minimization of energy consumption and by‐product formation in a poly(ethylene terephthalate) process

We determined the optimal reaction conditions to minimize the energy cost and the quantities of by‐products for a poly(ethylene terephthalate) process by using the iterative dynamic programming (IDP) algorithm. Here, we employed a sequence of three reactor models: the semibatch transesterification reactor model, the semibatch prepolymerization reactor model, and the rotating‐disc‐type polycondensation reactor model. We selectively chose or developed the reactor models by incorporating experimentally verified kinetic models reported in the literature. We established the model for the entire reactor system by connecting the three reactor models in series and by resolving some joint problems arising when different types of reactor models were interconnected. On the basis of the simulation results of the reactor system, we scrutinized the cause and effect between the reaction conditions and the final quality of the polymer product. Here, we set up the optimization strategy by using IDP on the basis of the integrated reactor model, and the process variables with significant influence on the properties of polymer were selected as control variables with the help of a simulation study. With this method, we could refine the reaction conditions at the end of each iteration step by contracting the spectra of control regions, and the iteration process finally stopped when the profile of the optimal trajectory converged. We also took the constraints on the control variables into account to guarantee polymer quality and to suppress side reactions. Constituting six different strategies by setting weighting vectors differently, we examined the differences in optimal trajectories, the trend of optimality, and the quality of the final polymer product. For each of the strategies, we conducted the optimization to examine whether the number‐average degree of polymerization approached the desired value. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 993–1008, 2002     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. I. Effect of orientation

The present study examined poly(ethylene terephthalate) (PET) and a series of statistical and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate by copolymerization and melt blending, respectively. Some level of transesterification during processing of melt blends resulted in blocky copolymers, as confirmed by NMR. Random and blocky copolymers exhibited similar properties in the glassy state, including a single glass transition, due to miscibility of the blocks. However, random copolymerization effectively retarded cold‐crystallization from the glass whereas blocky copolymers readily cold‐crystallized to a crystallinity level close to that of PET. The polymers were oriented at four temperatures in the vicinity of the T_g and characterized by oxygen transport, wide‐angle X‐ray diffraction, positron annihilation lifetime spectroscopy, and infrared spectroscopy. Orientation of all the copolymers resulted in property changes consistent with strain‐induced crystallization. However, blocky copolymers oriented more easily than random copolymers of the same composition and after orientation exhibited slightly lower oxygen permeability, higher density, and higher fraction trans conformers. Analysis of oxygen solubility based on free volume concepts led to a two‐phase model from which the amount of crystallinity and the amorphous phase density were extracted. Dedensification of the amorphous phase correlated with the draw temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1615–1628, 2005     

碳酸二甲酯市场现状及技术进展

目前,全球碳酸二甲酯(DMC)的产量约为12万t/a。生产方法有光气法、酯交换法、甲醇氧化羰基法和二氧化碳-甲醇直接合成法。我国DMC产量不足3万t/a,主要采用酯交换法和甲醇液相氧化羰基法。DMC可作为羰基化试剂代替剧毒物质光气用于合成聚碳酸酯、异氰酸酯、杀虫剂西维因等,用作甲基化试剂代替致癌物硫酸二甲酯合成苯甲醚。     

Structural characterization of reactor blends of polypropylene and ethylene‐propylene rubber

Blends of isotactic polypropylene (PP), ethylene‐propylene rubber copolymer (EPR), and ethylene‐propylene crystalline copolymer (EPC) can be produced through in situ polymerization processes directly in the reactor and blends with different structure and composition can be obtained. In this work we studied the structure of five reactor‐made blends of PP, EPR, and EPC produced by a Ziegler‐Natta catalyst system. The composition of EPR was related to the ratio between ethylene and propylene used in the copolymerization step. The ethylene content in the EPR was in the range of 50–70 mol %. The crystallization behavior of PP and EPC in the blends was influenced by the presence of the rubber, and some specific interactions between the components could be established. By preparative temperature rising elution fractionation (P‐TREF) analysis, the isolation and characterization of crystalline EPC fractions were made. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2155–2162, 2004     

我国煤制乙二醇竞争力分析

介绍了我国乙二醇市场现状,截至2019年底,我国乙二醇总产能为1 159万吨/年,其中,煤制乙二醇产能达491万吨/年,2020年还将有近400万吨/年的产能释放。煤制乙二醇技术逐渐成熟,所以短期内市场存在产能增速较快但产量增速缓慢的不匹配状态。比较了石油制乙二醇和煤制乙二醇生产工艺路线的成本,从生产成本、产品质量和物流方式3个维度分析了煤制乙二醇的市场竞争力,得出了煤制乙二醇的发展具有广阔前景,并根据国内乙二醇市场的远期发展趋势,提出了发展建议。     

碳酸二苯酯技术发展现状及展望

综述了碳酸二苯酯多种合成技术的发展现状，重点介绍了碳酸二甲酯与苯酚酯交换法和氧化羰基化法技术，并对碳酸二苯酯技术在国内的发展进行了展望。     

Catalytic conversion of methane to benzene over Mo/ZSM-5

Dehydroaromatization of methane to benzene occurs over a 2 wt% Mo/ZSM-5 catalyst at 700C under non-oxidizing conditions. Following an initial induction period, during which CH₄ reactant reduces the original Mo⁶⁺ ions in the zeolite to Mo₂C and deposition of coke occurs, a benzene selectivity of 70% at a CH₄ conversion of 8–10% could be sustained for more than 16 h. X-ray photoelectron spectroscopy and X-ray powder diffraction measurements indicate that the reduced Mo is highly dispersed in the channels of the zeolite. Initial activation of CH₄ reactant occurs on Mo₂C sites, leading to the formation of C₂H₄ as the primary product. The latter then undergoes subsequent oligomerization reactions on acidic sites of the zeolite to form aromatic products.     

碳酸二苯酯的合成工艺新进展

碳酸二苯酯是合成聚碳酸酯的重要原料,具有广泛的用途和应用前景.其合成方法主要有酯交换法、尿素法和二硫化碳法等.本文介绍了国内外碳酸二苯酯的现有生产技术及合成路线,综述了国内外的最新进展,并对今后的发展趋势作了展望.