合成双酚AF的新方法

由六氟丙酮三水合物和苯胺,经缩合、重氮化、水解、Friedel-Crafts烷基化等4步反应在常压下合成了双酚 AF。首先,以五氧化二铌为催化剂,在 n (HFA•3H₂O) : n (aniline) : n (Nb₂O₅) = 2 : 1 : 0.1,回流 6 h 条件下,合成出中间体（Ⅰ）,收率高达96.3%。然后在重氮化温度为 ﹣2 ～ 2 ℃,硫酸质量分数为 14.7%,n (Ⅰ) : n (H₂SO₄) : n (NaNO₂) = 1 : 4.1 : 1.1,及水解时硫酸质量分数为 50%,n (H₂SO₄) : n (Ⅰ) = 11.0 : 1、108～112 ℃反应 1.5 ～ 2 h 的优化条件下,化合物Ⅰ经重氮化、水解后以 92.7%的高收率得到中间体 2-（4-羟基苯）六氟异丙醇（Ⅱ）;再在甲磺酸存在下,化合物Ⅱ与苯酚经Friedel-Crafts烷基化反应以 72.4% 的收率合成了目标产物双酚 AF（Ⅲ）,总收率为 64.6%（以苯胺为基准计算）。     

2-甲基-1,4-萘醌的绿色合成方法

以2-甲基萘(2-MN)为原料、H₂O₂为氧化剂,经不同酸(硫酸、氢溴酸、三氟乙酸等)催化合成2-甲基-1,4-萘醌(2-MNQ),其结构经¹H NMR和¹³C NMR确证,其纯度经HPLC检测。对反应条件进行了优化。最佳反应条件为：20 eq. CH₃COOH为溶剂,6 eq. H₂O₂为氧化剂,在10%mol H₂SO₄催化下,于75 ℃反应,2-MNQ纯度95%,收率67%。     

超声法合成3,4-二氢嘧啶-2(1H)-酮衍生物

以取代芳醛（1a~1h）,乙酰乙酸乙酯(2)和脲(3)为原料,MMT/CuCl₂为催化剂,乙醇为溶剂,在超声条件下经Beginelli反应合成了8个3,4-二氢嘧啶-2(1H)-酮衍生物（4a~4h）,其结构经¹H NMR和IR确证。以4a为例,分别采用单因素法和正交实验法研究了催化剂、溶剂、反应温度、超声时间和物料比r［n(1a): n(2) :n(3)］对4a产率的影响。结果表明：在最优反应条件(1a 2.4 mol, r=1.2 : 1.0 : 1.0, MMT/CuCl₂20 mol%, EtOH 1 mL,于90 ℃超声15 min)下,4a产率88.4%。 MMT/CuCl₂循环使用3次,产率基本不变。     

3-羟基-1-金刚烷甲基酮的合成

改进了沙格列汀中间体3-羟基-1-金刚烷甲基酮（1）的合成路线。以金刚烷甲酸（2）为起始原料,经二氯亚砜酰氯化后与N-氯代琥珀酰亚胺（NCS)反应制得3-氯-1-金刚烷甲酰氯（3）; 3依次经取代,脱羧和与碱反应合成1,其结构经¹H NMR, IR和MS(ESI)确证。采用星点设计-效应面法对1合成条件进行了优化。结果表明:在最佳反应条件[2 28 mmol, n(NCS)/n(2)/n(AIBN)=1/0.83/0.65,于65 ℃反应8 h]下,1收率70%。     

2-甲硫基-4-羟基-5-嘧啶甲酸乙酯的工艺优化

以S-甲基异硫脲半硫酸盐和乙氧基亚甲基丙二酸二乙酯为主要原料,乙醇为溶剂,合成出2-甲硫基-4-羟基-5-嘧啶甲酸乙酯,研究了2-甲硫基-4-羟基-5-嘧啶甲酸乙酯的工艺优化,考察了投料比、反应温度、反应时间等因素对产率的影响。 获得较好的反应条件:n(C₂H₆N₂S·1/2H₂SO₄):n(C₁₀H₁₆O₅):n(NaOH)=1.2:1:1.8,在室温下缓慢滴加NaOH溶液,搅拌反应6 h,酸化得白色固体产物,产率为81.1%。产物结构经熔点测定仪、¹H NMR、ESI-MS、FT-IR等技术手段得到验证。     

4-氧代-3（4H）-喹唑啉-5-羧酸的合成

以2-氨基-6-甲基苯甲酸为起始原料,通过合环反应生成两种4-氧代-3(4H)-喹唑啉-5-羧酸衍生物(1a, 1b), 1a, 1b分别经高锰酸钾氧化合成了4-氧代-3(4H)-喹唑啉-5-羧酸（2a, 2b）,其结构经¹H NMR, ¹³C NMR和MS表征。研究了投料比｛r［n(高锰酸钾) :n(5-甲基-3(4H)-喹唑啉-4-酮)］｝和反应温度等对收率的影响。结果表明：在最佳反应条件（r=7:1,中性高锰酸钾氧化,于90 ℃反应）下合成2总收率可达66%。     

3-氟-6-碘吡嗪-2-羧酸甲酯的合成及晶体结构

以3-氨基吡嗪-2-羧酸为原料，经酯化反应、亲电反应和重氮化反应合成了3-氟-6-碘吡嗪-2-羧酸甲酯（1），总收率62.34%，其结构经¹H NMR、¹³C NMR和MS确证，用X-单晶衍射法测定了化合物的晶体结构。结果表明：1（CCDC: 1986368）属单斜晶系，空间群C2/c，晶胞参数a=17.6566(5) Å, b=4.74850(10) Å，c=19.6368(6) Å，β=95.6540(10)°，V=1638.39(8) ų，Z=8，R_gt(F)=0.0173，wR_ref(F²)=0.0465，F(000)=1056，μ=3.885 mm^-1。      

新型5-取代吲哚-3-甲酰胺化合物的合成

以5-取代吲哚为原料,经维尔斯迈尔-哈克反应制得5-取代吲哚-3-甲醛(2a~2e); 2a~2e在DMF催化下,与盐酸羟胺反应制得5-取代吲哚-3-甲腈（3a~3e）; 3a~3e在H₂O₂和NaOH溶液中水解合成了5-取代吲哚-3-甲酰胺（4a~4e, 4b~4e为新化合物）,产率62.0%~75.0%,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。     

合成E-10-羟基-2-癸烯酸的新方法

以1,8-辛二醇（1）为起始原料,经4步反应合成了（E）-10-羟基-2-癸烯酸,其结构经¹H NMR, ¹³C NMR和MS确证。考察了乙酰氯、缚酸剂种类及其用量［r=n（1）: n（乙酰氯）: n（缚酸剂）］对8-乙酰氧基-1-辛醇（2）收率的影响以及反应温度、三乙胺滴加温度、低温停留时间对8-乙酰氧基辛醛（3）收率的影响。结果表明：以三乙胺为缚酸剂,r=1.0 : 1.1 : 2.0时,2产率达78%;反应温度为-65 ℃、三乙胺滴加温度低于-50 ℃、低温反应3 h, 3产率达97%。     

高碱煤含钠矿物沉积层的高温熔融及多相反应过程分析

采用纯矿物试剂模拟燃用高碱煤时炉内受热面典型的灰沉积层化学组成,利用热机械分析（TMA）、TG-DSC分析、高温煅烧实验结合XRD、SEM-EDS表征方法研究了不同Na₂SO₄含量灰沉积层的高温熔融过程及矿物间的多相反应机理。结果表明,掺混Na₂SO₄后沉积层熔化特征温度显著降低,Na₂SO₄的主要反应途径与掺混比例有关,当掺混比低于20%时,Na₂SO₄与SiO₂、CaO、Al₂O₃反应主要转变为CaSO₄和钠的硅铝酸盐;掺混比大于40%时则主要与CaSO₄生成低熔点的钠钙复合硫酸盐。富Na₂SO₄沉积层颗粒在800℃时开始黏结;900-950℃时,霞石、钠长石等钠的硅铝酸盐发生低温共熔,同时Na₂SO₄和CaSO₄生成的复合硫酸盐开始熔融,逐渐形成液相;1200-1250℃时,镁黄长石与含钙矿物发生强烈共熔,温度超过1300℃后矿物完全熔融成为自由液相。     

Mechanism of Lithium and Cobalt Recovery from Spent Lithium-ion Batteries by Sulfation Roasting Process

Different from the traditional pyrometallurgical recovery process of Li and Co from spent lithium-ion batteries, a new recovery method for Li and Co was established by converting LiCoO₂ into water-soluble metal sulfates by roasting a mixture of LiCoO₂ and NaHSO₄·H₂O. The evolution law of the mixture with increased roasting temperature was investigated by thermogravimetry-differential scanning calorimetry(TG-DSC), in situ X-ray diffraction(XRD), XRD, and X-ray photoelectron spectroscopy(XPS). The results show that the phase transition of LiCoO₂ mixed with NaHSO₄·H₂O with increased temperature proceeded as follows:LiCoO₂, NaHSO₄·H₂O→LiCoO₂, NaHSO₄→Li_1-xCoO₂, LiNaSO₄, Na₂S₂O₇, Na₂SO₄→Li_1-xCoO₂, Co₃O₄, LiNaSO₄, Na₂SO₄→Co₃O₄, LiNaSO₄. The reaction mechanism of this roasting process may be as follows:LiCoO₂+NaHSO₄·H₂O→1/2Li₂SO₄+ 1/2Na₂SO₄+1/3Co₃O₄+1/12O₂+3/2H₂O, Li₂SO₄+Na₂SO₄=2LiNaSO₄.     

紫外高级还原技术还原降解水中N-亚硝基二甲胺

采用2种高级还原技术(UV/Na2SO3和UV/Na2S2O4)还原降解N-亚硝基二甲胺(NDMA),考察pH值、光照强度、还原剂质量浓度和溶解氧等因素对NDMA还原降解效果的影响,计算还原降解反应过程中的表观反应动力学常数,推断NDMA的还原降解机理.研究结果表明,弱酸性条件下有利于2种高级还原技术对NDMA的还原降...     

Chemical Evolution of LiCoO2 and NaHSO4·H2O Mixtures with Different Mixing Ratios During Roasting Process

Mixtures of NaHSO₄·H₂O and LiCoO₂ extracted from spent lithium-ion batteries were prepared with molar ratios of 1:1, 1:2 and 1:3. The chemical evolution of the LiCoO₂ and NaHSO₄·H₂O mixtures during the roasting process was investigated by means of thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray diffraction(XRD), scanning electron microscopy(SEM), and X-ray photoelectron spectroscopy (XPS). The results show that the chemical reactions in the LiCoO₂ and NaHSO₄·H₂O mixtures proceed during the roasting process. The Li element in the product of the roasting process is in the form of LiNa(SO₄). With the increase of the proportion of NaHSO₄·H₂O in the mixtures, the Co element evolves as follows: LiCoO₂→Co₃O₄→ Na₆Co(SO₄)₄→Na₂Co(SO₄)₂. The roasting products exhibit dense structures and irregular shapes, and the bonding energy of Co increases.     

Modelling of calcium sulphate solubility in concentrated multi-component sulphate solutions

The chemistry of several calcium sulphate systems was successfully modelled in multi-component acid-containing sulphate solutions using the mixed solvent electrolyte (MSE) model for calculating the mean activity coefficients of the electrolyte species. The modelling involved the fitting of binary mean activity, heat capacity and solubility data, as well as ternary solubility data. The developed model was shown to accurately predict the solubility of calcium sulphate from 25 to 95 °C in simulated zinc sulphate processing solutions containing MgSO₄, MnSO₄, Fe₂(SO₄)₃, Na₂SO₄, (NH₄)₂SO₄ and H₂SO₄. The addition of H₂SO₄ results in a significant increase in the calcium sulphate solubility compared to that in water. By increasing the acid concentration, gypsum, which is a metastable phase above 40 °C, dehydrates to anhydrite, and the conversion results in a decrease in the solubility of calcium sulphate. In ZnSO₄–H₂SO₄ solutions, it was found that increasing MgSO₄, Na₂SO₄, Fe₂(SO₄)₃ and (NH₄)₂SO₄ concentrations do not have a pronounced effect on the solubility of calcium sulphate. From a practical perspective, the model is valuable tool for assessing calcium sulphate solubilities over abroad temperature range and for dilute to concentrated multi-component solutions.     

The effect of CTAB on Na2SO4 nucleation in mixed Na2SO4/CTAB aerosols by FTIR-ATR technology

FTIR-ATR technology is used to study the efflorescence kinetic of Na_2SO_4 and mixed Na_2SO_4/CTAB aerosols.As the RH decreased linearly,the v_3-SO_4~2 band shifts from 1094 cm~1 to 1132 cm~1,suggesting the phase transition of Na_2SO_4 from solution to crystal phase(Ⅲ).For pure Na_2SO_4 aerosols,the ERH is 75.1%RH,whereas the efflorescence point of mixed Na_2SO_4/CTAB aerosols(74.2%) is lower.By further analysis of IR differential spectra,the ratio of Na_2SO_4 crystals in mixed aerosols is only 62.7%and the heterogeneous nucleation rate of Na_2SO_4 in Na_2SO_4/CTAB mixed aerosols is lower than that in pure Na_2SO_4 aerosols.They showed that CTAB assembled into reversed micelle and part Na_2SO_4 droplets are in the core to form core-shell structure,and CTAB shell prevents core Na_2SO_4 solutions from crystallizing.However,the counter ion Br for CTAB reversed micelle can interact with Na~+ ions,which decreases the crystallization rate of free Na_2SO_4 droplets and ERH is delayed.     

Effect of complexones and tensides on selectivity of nitrogen dioxide determination in air with a chemiluminescence aerosol detector

Modification of the luminol solution by means of addition of various complexones and surfactants has been investigated to eliminate interferences from gaseous co-pollutants in the determination of ambient nitrogen dioxide using a chemiluminescence aerosol detector. The simultaneous presence of EDTA and triton X-100 or X-405 together with sulphite and iodide in the luminol solution suppressed interferences from ozone and peroxyacetyl nitrate to a negligible level and no scrubbers or corrections of the NO₂ measurements were needed.

In general, the best composition of the reagent solution included luminol, KOH, Na₂SO₃, KI, Na₂EDTA and triton X-100. From the point of view of selectivity of NO₂ determination, an optimum reagent solution consisted of luminol (0.002 M), KOH (0.5 M), Na₂SO₃ (0.2 M), KI (0.1 M), Na₂EDTA (0.05 M) and triton X-100 (0.5 vol.%). Interferences from ozone (170 ppb (v/v)) and peroxyacetyl nitrate (81 ppb (v/v)) were 0.2 and 1.2%, respectively, for nitrogen dioxide at a concentration of 50 ppb (v/v) and 0.25 and 1.7%, respectively, for 0.5 ppb (v/v) NO₂. The calibration graph was linear for NO₂ concentrations ranging from 3 to 665 ppb (v/v). Below 3 ppb (v/v) NO₂ the detector response to nitrogen dioxide can be fitted with a linear equation of the third order.     

Preparation and characterization of N,O-carboxymethyl chitosan (NOCC)/polysulfone (PS) composite nanofiltration membranes

N,O-carboxymethyl chitosan (NOCC) composite nanofiltration membranes having a polysulfone (PS) UF membrane as the substrate were prepared using a method of coating and cross-linking, in which a glutaraldehyde (GA) aqueous solution was used as the cross-linking agent. Attenuated total reflection infrared spectroscopy (ATR-IR) was employed to characterize the resulting membrane. The effects of the composition of the casting solution of the active layer, the concentration of the cross-linking agent, and the membrane preparation techniques on the performance of the composite membrane were investigated. At 13–15 °C and 0.40 MPa the rejections of the resulting membrane to Na₂SO₄ and NaCl solutions (1000 mg L⁻¹) were 92.7 and 30.2%, respectively, and the permeate fluxes were 3.0 and 5.1 kg m⁻² h⁻¹, respectively. The rejection of this kind of membrane to the electrolyte solutions decreased in the order of Na₂SO₄, NaCl, MgSO₄, and MgCl₂. This suggests that the membrane active layer acquires a negative surface charge distribution by the adsorption of anions from the electrolyte solution and this charge distribution mainly determines the membrane performance.     

光热效应增强的Au/RGO/Na2Ti3O7光催化加氢性能

将典型的光热等离激元石墨烯和纳米金简便地负载在钛酸钠(Na₂Ti₃O₇)载体上, 构建出具有较窄禁带宽度和较高光催化活性的Au/RGO/Na₂Ti₃O₇光热辅助光催化体系. 研究发现, 石墨烯片层与金纳米颗粒在光照下, 通过局域表面等离激元共振效应诱导产生大量的热电子, 以活化反应物并降低反应活化能, 其引发的光热效应还可精准提升光催化体系中反应位点附近的温度, 从而大幅提升光催化反应速率. 通过构建特殊微支结构, 进一步增强了Au/RGO/Na₂Ti₃O₇催化剂对光的捕获, 并限域锚定高表面能催化剂以增强体系的稳定性. 在光热、 光催化的高效协同增强下, Au/RGO/Na₂Ti₃O₇催化剂体系对对硝基苯酚和肉桂醛的加氢反应均表现出增强的光催化活性. 光热辅助下的Au/RGO/Na₂Ti₃O₇光催化剂在对硝基苯酚反应中的转换频率（TOF）值高达54.4 min^-1, 反应活化能显著降低至15.78 kJ/mol, 且其在长效测试中表现出良好的稳定性（4次循环催化后, 转化率的保持率近90%）.     

氧瓶法测定难燃烧高硼有机物中的硼含量

把有机硼定量地转变为硼酸是测硼的关键,常用氧瓶、氧弹和消化法进行分解。Gradskova,N.A.等用氧瓶法测硼,其准确性欠佳^[1]。