Modeling the continuous melt transesterification of bisphenol-A and diphenyl carbonate in a continuous stirred tank reactor

A model of continuous melt transesterification of bisphenol-A and diphenyl carbonate in a continuous stirred tank reactor is developed using phase equilibria assumption and the method of molecular weight moments. The model equations can be simplified into a polynomial system that has 17 equations and 17 unknowns. Solution of the polynomial system gives out almost every aspects of the continuous transesterification process. Molecular weight and polydispersity index, end group ratio of hydroxyl to phenyl carbonate, contents of molecular species, and lost diphenyl carbonate fractions are studied in different operation parameters.     

The properties of equimolar copolycarbonates of bisphenol A with bisphenol S and 1,4-bis(hydroxymethyl)cyclohexane

Ranges of both alternating and random 1:1 copolycarbonates of Bisphenol-A (2,2-bis(4-hydroxyphenyl)propane) and Bisphenol-S (4,4′-dihydroxydiphenyl sulphone) and of Bisphenol-A and 1,4-dimethanoylcyclohexane have been synthesized in order to test the hypothesis that, other things being equal, a more random structured polymer should exhibit superior thermal ageing characteristics. Studies on these materials' mechanical and thermal properties establish that within each pair they are extremely similar and hence the original hypothesis is disproved.     

一种高弹性改性环氧道路修补胶的研制

通过添加合适的增韧剂对双酚A环氧树脂进行改性,得到改性环氧树脂;同时筛选合适的韧性固化剂,固化得到高弹性道路修补胶。     

Thermally induced redistribution and degradation of bisphenol-A polycarbonate fractions in open and closed systems

Thermally induced chain-scission and redistribution reactions in as-polymerized and fractionated bisphenol-A polycarbonate (PC) materials made by melt-transesterification and interfacial polymerization were studied at temperatures between 200 and 300 °C in open systems, where volatile reaction products are continuously removed, and in closed systems, where these products are retained. Under the applied conditions, PC made via interfacial polymerization shows no measurable susceptibility towards redistribution. This is the result of an extremely low concentration of hydroxyl end-groups. Upon similar thermal treatment, PC made by melt-transesterification undergoes fast redistribution which leads to post-condensation in open systems and strong changes of molecular weight distributions (MWDs) for fractions in all cases. Redistribution effects were visualized through changes in the MWD of mixed fractions. The initial stages of redistribution were simulated using a Monte Carlo method based on a random sampling technique. From comparison between experimental and simulation results, it can be concluded that approximately half a percent of all carbonate linkages is involved in a redistribution reaction per minute at 250 °C for the studied samples.     

储油罐环氧基钛纳米复合导静电涂层耐蚀性能

目的研究钛纳米填料粒径和含量对环氧基钛纳米复合导静电涂层耐蚀性能的影响。方法将不同粒径的钛纳米粉(经聚乙烯基吡咯烷酮表面预处理)按不同量加入双酚A(E)型环氧树脂中,之后涂覆在Q235钢表面形成导静电复合涂层。通过表面电阻测试、截面形貌观察、电化学极化曲线和阻抗谱测试,分别评价复合涂层的导静电性能、截面结构和耐蚀性。结果钛纳米粉添加量(占涂层质量百分比)为28%时,随着钛纳米粉粒径从40 nm增大到200 nm,环氧基复合导静电涂层的表面电阻降低,截面结构更加杂乱,添加100 nm钛纳米粉的涂层阻抗和极化曲线阳极电流分别出现最大值和最小值。添加的钛纳米粉粒径为100 nm时,随着添加量从7%增至28%,环氧基复合导静电涂层的表面电阻降低,截面孔洞增大,阻抗值降低,极化曲线阳极电流增大。结论钛纳米填料的加入可以有效提高涂层的导静电性能、致密性和耐蚀性。当添加量为28%时,钛纳米粒径大于100 nm后,涂层截面形貌更加杂乱,耐蚀性降低。对于100 nm粒径的钛纳米填料,当其添加量大于7%时,复合涂层的致密性和耐蚀性降低。     

Dynamic experiments with high bisphenol-A concentrations modelled with an ASM model extended to include a separate XOC degrading microorganism

The perspective of this work is to develop a model, which can be used to better understand and optimize wastewater treatment plants that are able to remove xenobiotic organic compounds (XOCs) in combination with removal of traditional pollutants. Results from dynamic experiments conducted with the endocrine disrupting XOC bisphenol-A (BPA) in an activated sludge process with real wastewater were used to hypothesize an ASM-based process model including aerobic growth of a specific BPA-degrading microorganism and sorption of BPA to sludge. A parameter estimation method was developed, which simultaneously utilizes steady-state background concentrations and dynamic step response data, as well as conceptual simplifications of the plant configuration. Validation results show that biodegradation of BPA is sensitive to operational conditions before and during the experiment and that the proposed model structure is capable of capturing important characteristics of the observed BPA removal, thus increasing the potential for generalizing knowledge obtained from plant specific experiments.     

Kinetics of polycyclotrimerization of aromatic dicyanates

Polycyclotrimerization of 4,4′-thiodiphenylcyanate (TDPC) and bisphenol-A dicyanate (BADC) were studied and compared by means of differential scanning calorimetry. Samples of different impurity levels (most likely residual moisture) or different catalyst loadings (n-nonylphenol) were studied. Moisture absorbed may indeed function as a catalyst. In the absence of residual phenols or added catalyst, the polycyclotrimerization of identical species shared the same apparent activation energy and all followed an autocatalyzed first-order rate expression. The autocatalytic effect was justified by the cure behavior of partially cured monofunctional cyanate (p-diphenyl cyanate). The rate expression obtained by the dynamic method is still available for the isothermal method. In the presence of an externally added catalyst (n-nonylphenol, NP), the polycyclotrimerization proceeded at obviously lower temperature as compared with the uncatalyzed case. In addition to the expected lowering of activation energy (independent of the catalyst concentration), the cure reaction exhibited an autocatalyzed higher order kinetics (second order for TDPC system and 1.7-th power for BADC system). These kinetic observations were explained in terms of proposed mechanistic scheme in which the competition between hydroxyl-catalyzed and autocatalytic paths is considered. In particular, formation of NP aggregates ((NP)_m, where m = 7 for TDPC system and m = 5 for BADC system, respectively) is proposed to explain the less-than-additive catalytic capacity with increasing added NP level.     

Photodegradation of tetrahalobisphenol-A (X = Cl, Br) flame retardants and delineation of factors affecting the process

The photoassisted degradation (HPLC-UV absorption), dehalogenation (HPLC-IC) and mineralization (TOC decay) of the flame retardants tetrabromobisphenol-A (TBBPA) and tetrachlorobisphenol-A (TCBPA) were examined in UV-irradiated alkaline aqueous TiO₂ dispersions (pH 12), and for comparison the parent bisphenol-A (BPA, an endocrine disruptor) in pH 4–12 aqueous media to assess which factor impact most on the photodegradative process. Complete degradation (2.7–2.8 × 10⁻² min⁻¹) and dehalogenation (1.8 × 10⁻² min⁻¹) of TBBPA and TCBPA occurred within 2 h of UV irradiation, whereas only 45–60% mineralization (2.3–2.7 × 10⁻³ min⁻¹) was complete within 5 h for the flame retardants at pH 12 and ca. 80% for the parent BPA. Factors examined in the pH range 4–12 that impact the degradation of BPA were the point of zero charge of TiO₂ particles (pH_pzc; electrophoretic method), particle or aggregate sizes of TiO₂ (light scattering), and the relative number of OH radicals (as DMPO–OH adducts; ESR spectroscopy) produced in the UV-irradiated dispersion. Dynamics of BPA degradation (2.0–2.4 × 10⁻² min⁻¹) were pH-independent and independent of particle/aggregate size, but did correlate with the number of OH radicals, at least at pHs 4 to 8–9, after which the rates decreased somewhat at pH > 9 with decreasing adsorption owing to Coulombic repulsive forces between the very negative TiO₂ surface and the anionic forms of BPA (pK_as ca. 9.6–11.3), even though the number of OH radicals continued to increase at the higher pHs.     

Synthesis of polyarylate through interfacial polycondensation by use of glycolyzed products of poly(ethylene terephthalate) glycolysis with bisphenol-a

The glycolysis of poly (ethylene-terephthalate) with bisphenol-A at certain ratios of PET/BPA was carried out in an autoclave reactor at different temperatures for varying periods of time. Then the glycolyzed products were utilized together with bisphenol-A for the synthesis of polyarylates through interfacial polycondensation. The polyarylates obtained (referred to as b/g-polyarylates in this article) possess good thermal characteristics but have lower mechanical strength than typical polyarylate synthesized from pure bisphenol-A by use of the same method. Blending the b/g-polyarylate with polycarbonate improved the impact strength significantly. As a whole, glycolysis with bisphenol-A followed by synthesis of polyarylate through interfacial polycondensation provided a feasible route for the reuse of poly(ethylene terephthalate).