双全氟丙酰过氧化物的合成

简述了双全氟丙酰过氧化物的的合成,并对全氟丙酰氟的制备工艺条件及相应的过程作了详细的介绍。     

全氟羧酸酯乙烯基醚的合成研究

全氟羧酸酯乙烯基醚用于多种含氟聚合物的改性,合成全氟羧酸离子交换树脂等高性能含氟聚合物,也可以合成含氟醚类的绿色可降解表面活性剂。采用3-羧酸甲酯全氟丙酰氟与六氟环氧丙烷进行加成反应,然后脱羧制备全氟羧酸酯乙烯基醚。     

哈龙替代品全氟己酮及中间体全氟丙酰氟合成综述

全氟己酮是哈龙灭火剂的清洁替代品,具有优异的环境和使用性能。对其合成方法进行了介绍和分析,指出了以六氟丙烯为原料的合成工艺具有工业化前景。并对六氟丙烯工艺的重要中间体全氟丙酰氟的合成方法进行了综述。     

五氟丙酰氟的制备及应用

综述了以六氟环氧丙烷及其低聚物、三氟甲基三氟乙烯基醚、全氟丙酸全氟丙酯及丙酸丙酯、丙酸酐为原料制备五氟丙酰氟的方法及其优缺点,概述了五氟丙酰氟下游含氟精细化学品的的应用前景,为五氟丙酰氟的制备及应用提供参考。     

全氟异丁烯的性能及利用

介绍了全氮异丁烯(PFIB)的物理、化学性质，以及如何将其转化为有用的化学物质，如全氟丙酮、六氟丙烷、五氟丙烯、全氟叔丁醇等，重点介绍了由PFIB制备全氟丙酮的工艺路线。     

全氟丙酰氟制备方法及应用

总结了几种制备全氟丙酰氟的方法,比较了各种方法的优缺点,介绍了其在不同领域的应用情况。认为采用化学合成法,鼓泡反应器,工艺简单,三废排放少,原料的转化率及产品收率高,是较理想的制备方法。     

电化学氟化法制备全氟丁磺酸钾

本文分别介绍了以环丁烯砜或丁磺酰氯为原料经电解氟化等过程制取全氟丁磺酸钾的方法。首先，二种原料各自在Simons电解槽中转变为全氟丁磺酰氟，然后将生成的酰氟除酸分离提纯，再与氢氧化钾水溶液反应，过滤和干燥由碱解反应生成的沉淀物，便制得最终产品。此外，本文还对采用这两种原料制成最终产品工艺路线的优缺点进行了比较。     

环丙羧酸合成新工艺

介绍一种合成环丙羧酸的新工艺。以固体光气为原料,与2,4-二氯氟苯反应制得2,4-二氯-5-氟苯甲酰氯,然后与3-乙氧基丙烯酸乙酯偶联,后经环丙胺置换、在DMF中环合、水解制得环丙羧酸,总收率为39.1%。该工艺流程缩短、操作简单,环境污染小,值得进一步研究和推广。     

氟硅乳液的合成

从全氟辛酸出发制备了含氟单体;用甲基二氯硅烷和二甲基二氯硅烷合成出七甲基环四硅氧烷;将含氟单体与七甲基环四硅氧烷进行加成反应,合成出含全氟辛基的环硅氧烷;以含全氟辛基的环硅氧烷、八甲基环四硅氧烷和乳化剂制得了氟硅乳液。探讨了含氟单体的合成路线、氟硅乳液的合成工艺条件及性能,并用红外光谱对氟硅乳液进行了表征。采用十二烷基苯磺酸和OP-10为复合乳化剂,偶氮二异丁腈为引发剂,调压搅拌器的搅拌速度保持在1500r/min,反应温度65℃,反应时间6h时合成的氟硅乳液性能稳定,固体质量分数为20%,全氟辛基环硅氧烷的质量分数为15%。经氟硅乳液整理后的棉布憎水憎油性能良好。     

全氟二(2,5,8-三甲基-11-氟磺酰基-3,6,9-三氧杂十一酰基)过氧化物的合成

以全氟-2,5,8-三甲基-11-氟磺酰基-3,6,9-三氧杂十一酰氟、氢氧化钠和双氧水为原料,全氟-2-甲基四氢呋喃和全氟-2-乙基四氢呋喃的混合物为溶剂,合成了1种新的全氟酰基过氧化物:全氟二(2,5,8-三甲基-11-氟磺酰基-3,6,9-三氧杂十一酰基)过氧化物(FAP),用红外光谱法对产物结构进行了表征,测定了FAP分解反应的动力学数据,并推算出较低温度下的分解反应速率常数和半衰期.通过正交实验得到最佳条件为:氢氧化钠的浓度为6 mol/L,n(H2O2)∶n(NaOH)=1.4∶1,反应温度-8℃,反应时间30 min.FAP的平均收率为52.6%,可在-30℃以下较长时间贮存.     

Attaching the fluorine atom to organic molecules using BrF3 and other reagents directly derived from F2

Elemental fluorine is a starting point for nucleophilic fluorinations (e.g., BrF3), radical fluorinations (e.g., F2 under irradiation), and electrophilic fluorinations (e.g., AcOF). All three categories are represented in this Account. Bromine trifluoride, although commercially available, can be readily made from the elements and is a very good source for naked nucleophilic fluoride ions. To minimize radical reactions, an anchor has to be installed in the molecules with which it reacts. Such an anchor is constituted of a soft base such as nitrogen and especially sulfur atoms. This reagent was used for constructing compounds with a CF2, CF3, CHF2, or CF2COOH group in specific sites. F2 itself was used for completing perfluorination of various polyfluoroethers, while the electrophilic acetyl hypofluorite is an excellent tool for introducing a single fluorine atom into organic molecules such as carboxylic acids and nitro compounds.     

1-溴-5-氯戊烷的合成方法研究

报道了采用无水氯化锌和硫酸复合催化剂 ,正庚烷作为卤代反应的分水剂 ,将 1,5 戊二醇同时用氯化氢和溴化氢卤化反应一步制取 1 溴 5 氯戊烷的实验结果。实验考察了反应温度、催化剂用量、原料气配比、卤化反应时间等因素对产物收率的影响。实验确定 :在反应温度为 95℃左右 ,采用浓硫酸 (0 5 % )和无水氯化锌 (2 0 % )复合催化剂 ,用HCl∶HBr(mol)为 3 0～ 3 5的原料气将 1,5 戊二醇卤化 ,反应 14h后产物中 1 溴 5 氯戊烷的含量达到 80 %以上。     

Mechanical,gamma rays and neutron radiation transmission properties for some ZnO–TeO2–P2O5-ZnX glasses

Oxyhalide glasses are utilized in the process of immobilizing nuclear waste and function as scintillating agents for the purpose of radiation detection. The objective of this study is to examine the enhanced mechanical and radiation attenuation characteristics of newly developed oxyhalide glasses by incorporating zinc-iodide. This study investigates the synthesis process, mechanical properties, and experimental gamma-neutron radiation transmission properties. A halogen-free base glass, consisting of an oxide mixture of P₂O₅, TeO₂, and ZnO, was synthesized. Following that, the initial glass composition was further strengthened by the addition of zinc bromide (ZnBr₂), zinc chloride (ZnCl₂), zinc fluoride (ZnF₂), and zinc iodide (ZnI₂) in a successive manner. The experimental configuration entailed positioning circular glass samples between a 133Ba radioisotope and a Canberra High Purity Germanium (HPGe) detector. The determination of attenuation coefficients is achieved through the measurement of individual attenuation properties. Afterwards, theoretical approaches are utilized to determine the mechanical characteristics of halogenated glasses, including Young's modulus (Y), Bulk modulus (K), Shear modulus (G), Longitudinal modulus (L), and Poisson's modulus (v). The results of the study suggest that the implementation of the halogenation process on the P₂O₅–TeO₂–ZnO base composition led to a significant enhancement in the examined properties. The incorporation of zinc-iodide in the halogenation process resulted in a significant improvement in the gamma absorption properties. The utilization of zinc in the halogenation process demonstrates multifunctional capabilities, which involve the potential to enhance various glass properties, including durability and gamma-ray absorption properties. It can be concluded that zinc-iodide demonstrates enhanced halogenation capabilities in comparison to zinc bromide, zinc chloride, and zinc fluoride.     

含氰侧基联苯型聚芳醚醚酮酮的合成及表征

通过一种反应条件较为温和的反应新工艺,合成联苯二甲酰氯,即4,4’-二氯甲酰基联苯(BC IBP)。然后,在无水A lC l3及N-甲基吡咯烷酮(NMP)/1,2-二氯乙烷(DCE)复合溶剂的存在下,将2,6-二苯氧基苯甲腈(DPOBN)与BC IBP进行低温缩聚反应,合成了一类新型含氰侧基联苯型聚芳醚醚酮酮。用IR,DSC,TG,WAXD及元素分析等方法对其结构和性能进行了表征。结果表明,所合成的聚合物具有预期结构且为非晶态聚合物;其玻璃化转变温度(Tg)为211℃,在氮气气氛中及在空气气氛中的热分解5%的温度(Td)分别为523℃及498℃,说明其具有突出的耐高温性能;聚合物除了能在浓H2SO4,CF3COOH/CHC l3等强质子性溶剂当中溶解外,对其他的溶剂均不溶解,说明聚合物具有优异的耐化学腐蚀性能。     

含磺酰胺桥类染料中间体的合成与表征

合成了两种磺酰替苯胺类染料中间体3′-甲基-4,4′-二氨基苯磺酰替苯胺(Ⅳ)和2′-甲氧基-4,5′-二氨基苯磺酰替苯胺(Ⅶ)。合成步骤如下:(1)邻甲苯胺、对甲氧基苯胺的氨基保护后,分别与氯磺酸反应得3-甲基-4-乙酰氨基苯磺酰氯(Ⅰ)和2-甲氧基-5-乙酰氨基苯磺酰氯(Ⅴ);(2)对氨基乙酰苯胺(Ⅱ)分别与Ⅰ、Ⅴ在w(CH3COOH)=5%的醋酸中反应,所得缩合物水解得产品Ⅳ、Ⅶ。产品经过IR1、HNMR1、3CNMR、MS表征确定了结构。胺化反应优化条件均为:n(Ⅰ或Ⅴ)∶n(Ⅱ)=1.1∶1,反应温度45℃,反应时间2 h,产率分别为89.37%、87.68%。     

兰索拉唑合成新工艺研究

报道了以兰索拉唑羟基物（2-羟甲基3-甲基-4（2,2,2-三氟乙氧基）-吡啶）为起始原料进行兰索拉唑合成的新工艺。新工艺中用PBr₃替代SOCl₂作为卤化剂,用H₂O₂—（NH₃）₂MoO₄体系替代间氯过氧苯甲酸作为氧化剂,卤化与缩合工艺合并成一步。试验结果表明,该新工艺操作简单,能有效降低生产成本,可满足工业化生产要求。     

由铵盐制备高纯氟化钡的工艺研究

以氟化铵和氯化钡为原料,采用沉淀法制备了氟化钡。反应温度为25 ℃,反应时间为60 min,氯化钡初始质量分数为10%,氟化铵与氯化钡物质的量比为2.2,m(洗水)∶m(滤饼)=10∶1,可制备出纯度达99%以上的氟化钡。XRD谱图表明,样品氟化钡的所有衍射峰均与标准立方相氟化钡吻合,属立方晶系。该工艺流程简单,经济效益好。     

Adsorption behavior of fluoride ions using a titanium hydroxide-derived adsorbent

The removal behavior of fluoride ions was examined in aqueous sodium fluoride solutions using a titanium hydroxide-derived adsorbent. The adsorbent was prepared from titanium oxysulfate (TiOSO₄·xH₂O) solution, and was characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry-differential thermal analysis, Fourier transform infrared spectrum and specific surface area. Batchwise adsorption test of prepared adsorbent was carried out in aqueous sodium fluoride solutions and real wastewater containing fluoride ion. The absorbent was the amorphous material, which had different morphology to the raw material, titanium oxysulfate, and the specific surface area of the adsorbent (96.8 m²/g) was 200 times higher than that of raw material (0.5 m²/g). Adsorption of fluoride on the adsorbent was saturated within 30 min in the solution with 200 mg/L of fluoride ions, together with increasing pH of the solution, due to ion exchange between fluoride ions in the solution and hydroxide ions in the adsorbent. Fluoride ions were adsorbed even in at a low fluoride concentration of 5 mg/L; and were selectively adsorbed in the solution containing a high concentration of chloride, nitrate and sulfate ions. The adsorbent can remove fluoride below permitted level (< 0.8 mg/L) from real wastewaters containing various substances. The maximum adsorption of fluoride on the adsorbent could be obtained in the solution at about pH 3. After fluoride adsorption, fluoride ions were easily desorbed using a high pH solution, completely regenerating for further removal process at acidic pH. The capacity for fluoride ion adsorption was almost unchanged three times after repeat adsorption and desorption. The equilibrium adsorption capacity of the adsorbent used for fluoride ion at pH 3 was measured, extrapolated using Langmuir and Freundlich isotherm models, and experimental data are found to fit Freundlich than Langmuir. The prepared adsorbent is expected to be a new inorganic ion exchanger for the removal and recovery of fluoride ions from wastewater.