1,1,1,4,4,4-六氟-2-丁烯的合成及应用

1,1,1,4,4,4-六氟-2-丁烯（HFO-1336）的ODP（臭氧消耗潜能值）为零,GWP（全球变暖潜能值）很低（GWP100=9.4）,是发泡剂HCFC-141b等的理想替代品之一,是新一代理想的环保发泡剂,属于第四代发泡剂,HFO-1336也可用于制冷剂、溶剂、灭火剂等其他领域。对其合成方法进行了研究,并对其应用也进行了总结,认为HFO-1336这一产品具有良好的应用前景和广阔的市场前景,同时对其专利情况也进行了分析。     

(顺)-1,1,1,4,4,4-六氟-2-丁烯的合成研究进展

作为氢氟烯烃（HFO）类物质,顺-1,1,1,4,4,4-六氟-2-丁烯（Z-HFO-1336）的臭氧消耗潜值（ODP）为零,温室效应潜值（GWP）极低,对环境影响很小,因其性能与前几代发泡剂相近,被看作新一代绿色环保发泡剂,其合成方法受到氟化工界的广泛关注。至今,Z-HFO-1336的合成方法主要可分为：①直接氟化C4化合物合成;②氟利昂类化合物CFC-113、HCFC-123经偶联反应制备;③由卤代甲烷与卤代烯烃经调聚反应制备。其中直接氟化法虽然路线短,但产物选择性低、催化剂稳定性差;而氟利昂类化合物偶联法污染大,调聚合成存在工艺复杂、收率低等问题。提出了两种具有学术和工业价值的研究路线：①HCFC-123自偶联一步合成Z-HFO-1336,反应涉及C—Cl键的活化、单电子转移（SET）等过程,极具理论研究意义;②以乙烯、三氟丙烯为原料经调聚反应合成,原料来源广泛,催化合成可连续进行,具有很强的工业价值。     

催化氟化合成反式-1,1,1,4,4,4-六氟-2-丁烯的工艺研究

在氟化镁基催化剂作用下,以催化氟化1,1,1,3-四氯-4,4,4-三氟丁烷(HCFC-343jfd)合成反式-1,1,1,4,4,4-六氟-2-丁烯(E-HFO-1336mzz)为研究对象,开展了反应温度、物料比、接触时间及催化剂的寿命实验。结果表明,最佳反应条件为反应温度300℃,HF与HCFC-343jfd的摩尔比为15∶1,停留时间6 s,在该条件下,HCFC-343jfd的转化率为100%,E-HFO-1336mzz的选择性为95.1%,且连续反应300 h后,HCFC-343jfd的转化率>99.0%,E-HFO-1336mzz的选择性>94.5%。采用新型无铬催化剂,获得了最佳E-HFO-1336mzz反应工艺,具有较高的氟化工业应用前景。     

相转移催化合成六氟-2-丁炔

在相转移催化剂作用下,2-氯-1,1,1,4,4,4-六氟-2-丁烯(HCFO-1326mxz)在碱液中脱氯化氢合成六氟-2-丁炔。研究表明,以四丁基氯化铵(摩尔分数2%)为相转移催化剂,反应温度为40℃、HCFO-1326mxz与氢氧化钠摩尔比为1∶4、反应时间为6 h, HCFO-1326mxz转化率为96.3%,六氟-2-丁炔选择性为91.4%。     

浅谈六氟-2,3-二丁酮的合成方法

浅谈了六氟-2,3-二丁酮的合成方法,并对其路线进行了比较和评价。使用三氧化铬(CrO_3)作为氧化剂,以顺反六氟二氯丁烯(R1316)混合物为原料,其目标产物的收率最高为31%;以1,1,1,4,4,4-六氟-2-丁烯为原料,其目标产物的收率为26.6%。充分利用生产三氟二氯乙烷(HCFC-123)过程中产生的废弃物六氟二氯丁烯(R1316)混合物制备六氟-2,3-二丁酮的方法最有工业化前景和研究价值。     

2-溴七氟丙烷合成与应用

叙述了2-溴七氟丙烷的性质及其制备方法,1种是六氟丙烯先和溴反应制得1,2-二溴六氟丙烷,1,2-二溴六氟丙烷与KF反应得到2-溴七氟丙烷;另1种是六氟丙烯先与HF反应制备1,1,1,2,3,3,3-七氟丙烷(HFC-227ea),HFC-227ea与溴反应得到2-溴七氟丙烷。目前实现工业化的方法实质上都是六氟丙烯法。介绍了2-溴七氟丙烷在医药农药中间体领域的应用情况。认为今后研究重点是将2-碘七氟丙烷参与的反应尽可能地用2-溴七氟丙烷代替,以合成更多的医药农药关键中间体;2-溴七氟丙烷制备的医药农药关键中间体主要是4-七氟异丙基苯胺衍生物,而其中2-甲基-4-七氟异丙基苯胺是合成氟虫酰胺的关键中间体,应重点关注。     

八氟-2-丁烯的合成与应用研究进展

八氟-2-丁烯（octafluoro-2-butene）是一种不饱和全氟烯烃,消耗臭氧潜能值(ODP)为0,全球增温潜能值（GWP）为1.97。由于具有良好的环境性能和优异的工作性能,其在灭火、制冷、发泡、绝缘介质和集成电路等领域越来越受到人们的关注和重视,因此具有较大潜在市场需求和良好的发展前景。本文介绍了八氟-2-丁烯的合成研究进展,并较为详细地阐述了其在制冷、发泡、集成电路等领域的应用研究情况。     

2,3-二氯-1,1,1,4,4,4-六氟-2-丁烯的应用研究

综述了2,3-二氯六氟-2-丁烯的应用情况。     

制冷剂HFC-134a资源化利用制备六氟丁二烯

介绍了各国对HFC-134a高GWP制冷剂的政策、法规以及六氟丁二烯的制备方法;提出了利用HFC-134a为原料制备低GWP、高精度的蚀刻气体六氟丁二烯是一条HFC-134a资源化转化的有效途径。     

十氟戊烷的合成研究进展

介绍了十氟戊烷(HFC-310)的性能和用途,叙述了3种重要的同分异构体2,3-二氢十氟戊烷(HFC-4310mee),3,3-二氢十氟戊烷(HFC-4310mcf)和2,2-二氢十氟戊烷(HFC-4310mf)的合成方法.认为我国应利用四氟乙烯或六氟丙烯已实现大规模生产的基础上,深入研究HFC-4310的合成工艺,争取早日实现HFC-4310的工程化,满足国内市场需求.     

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。     

Catalytic hydrodehalogenation of halon 1211 (CBrClF2) over γ-alumina-supported Ni, Pd and Pt catalysts

The hydrodehalogenation of halon 1211 over Ni, Pd and Pt supported on γ-alumina was studied. The effect of reaction temperature and hydrogen/halon 1211 input ratio was examined. Steady state catalytic activities of Pd and Pt are very similar, and much higher than that of Ni. Hydrodehalogenation over Pd favours the formation of CH₂F₂, while Pt and Ni produce primarily CH₄ and CH₃F, respectively. Product profiles suggest that the hydrodehalogenation of halon 1211 over Pd and Pt follows a reaction mechanism which is similar to hydrodehalogenation of CFC-12. Over Ni catalysts, the primary hydrodehalogenation reactions are those which first remove one halogen (Cl or Br) and then remove two halogens (one F and either Br or Cl). The higher mobility of hydrogen atom on the surface of Pt is consistent with the observation that only trace amounts of C₂₊ hydrocarbons were detected when Pt was used compared with Pd and Ni. Increasing selectivity to CH₂F₂ with time on stream over Pd and Pt is mainly ascribed to the transformation of support alumina to partially fluorinated alumina.     

灭火剂发展现状与未来

合理选择灭火剂是即时有效扑灭燃烧火焰和防火防爆的关键。对常用的物理灭火剂和化学灭火剂的特点、灭火机理和适用范围作了归纳 ,着重介绍了哈龙和哈龙替代品的灭火机理 ,并对物理灭火剂和化学灭火剂之间的协同作用作了重点阐述     

EBM气溶胶灭火剂吸湿性的研究

烟火型气溶胶发生剂EBM是一种新型高效气溶胶灭火剂，其灭火效率高于哈龙类灭火剂。气溶胶生成物中固体微粒含量很高。吸湿后的固体微粒会对金属材料及线路板等有腐蚀性，影响保护物的正常使用。本文研究了温度和空气相对湿度对气溶胶生成物吸湿性的影响。     

A PROCESS FOR DISPOSAL OF HALON 1301 (CBrF3)

We report the results of an experimental and kinetic modeling study of gas-phase reaction between methane and halon 1301 (CBrF³). At 1000 K, with an equimolar feed of CH⁴ and CBrF³ and at a residence time of 1 second, CHF³ and CH³Br are produced at selectivities in excess of 90%. Other reaction products detected include C²H²F², C²H², C²H², and CHBrF². Very good agreement between kinetic modeling and experimental results was obtained.     

CES2, ABCG2, TS and Topo-I Primary and Synchronous Metastasis Expression and Clinical Outcome in Metastatic Colorectal Cancer Patients Treated with First-Line FOLFIRI Regimen

Enzymatic activation of irinotecan (CPT-11) is due to carboxylesterase (CES), and its pharmacological behavior is influenced by drug resistance-related proteins. We previously reported that the clinical response and prognosis of metastatic colorectal cancer (mCRC) patients did not differ in tumors with different thymidylate synthase (TS) or topoisomerase-I (Topo-I) expression. Using immunohistochemistry (IHC), we evaluated the biological role of CES2 and the expression of breast cancer resistance protein (BCRP/ABCG2) in 58 consecutive mCRC patients, who had undergone a first-line CPT-11/5-FU/leucovirin (FOLFIRI) regimen. The expression of these proteins was also examined in a group of synchronous lymph nodes and liver metastases. Furthermore, all samples were revaluated for TS and Topo-I expression. High expression of CES2, ABCG2, TS and Topo-I was observed in 55%, 56%, 38% and 49% of patients, respectively. There was a significant association between high TS and high ABCG2 expression (p = 0.049). Univariate analysis showed that only TS expression significantly impacted on time to progression (p = 0.005). Moreover, Cox’ multivariate analysis revealed that TS expression was significantly associated with overall survival (p = 0.01). No significant correlation was found between investigated markers expression and clinical response. Topo-I expression resulted in being significantly higher in liver metastases with respect to the corresponding primary tumors (p < 0.0001), emphasizing the role of Topo-I expression in metastatic cancer biology. In primary tumor tissues, CES2 expression tended to be higher than that observed in liver metastasis tissues (p = 0.05). These preliminary data may suggest CES2 over-expression as a potential marker of malignant phenotype. In light of these findings, we suggest that Topo-I expression together with TS expression could be associated with metastatic progression of CRC. Further studies are warranted with the aim of evaluating the potential predictive and prognostic role of CES2 and ABCG2 in larger series of patients.     

气溶胶灭火剂pH值测量方法的研究

气溶胶灭火剂作为一种新型灭火剂具有优越的灭火性能，但燃烧后的气溶胶微粒如果酸碱度太强就会腐蚀电路和仪器，所以必需测量出燃烧后的气溶胶的pH值以改良配方，使其酸碱度接近中性，本文就介绍了一套实验装置用来测量气溶胶的pH值，并通过一系列实验数据的分析证明了此种方法的可行性。     

CdS nanoparticles decorated hexagonal Fe2O3 nanosheets with a Z-scheme photogenerated electron transfer path for improved visible-light photocatalytic hydrogen production

Photocatalytic water splitting for hydrogen production (H₂) is one of the main potential applications of photocatalytic technology, which can use solar energy as the energy required for chemical reactions to alleviate the energy crisis. In this work, zero-dimensional/two-dimensional (0D/2D) contact surface CdS/α-Fe₂O₃ (CF) heterojunction photocatalyst was synthesized via a simple solvothermal method. Photocatalytic hydrogen production experiments revealed that the CF-15 sample shows the optimal photocatalytic H₂ rate (1806 (μmol·h^-1·g^-1)) and apparent quantum efficiency (AQE = 13.7% at λ = 420 nm). The enhancement of photocatalytic performance is mainly attributed to the contact of 0D/2D interface and the synergistic effect of Z-scheme electron transfer mechanism. This work provides an effective way for modified composite semiconductor photocatalyst by constructing special interface heterojunction to achieve highly efficiently catalysis.     

全氟三乙胺热解机理的实验与理论研究

氟胺类物质是最有希望作为哈龙替代品的含氮化合物之一,全氟三乙胺作为典型的氟胺类物质具有良好的灭火效果。为研究全氟三乙胺热解机理,在管式加热炉内对全氟三乙胺进行热分解,通过GC-MS分析全氟三乙胺在不同温度条件下的热解产物,并用Gaussian软件对其热解反应路径进行理论计算。结果表明：保持停留时间为10 s,全氟三乙胺的初始热解温度为600℃,750℃完全热解,热解产物有C₄F₉N、C₃F₇N、C₂F₆和C₃F₈,热解温度较低时C₄F₉N体积分数最大,热解温度较高时C₃F₇N体积分数最大。在全氟三乙胺热解反应路径计算中,全氟三乙胺分子中的C—C键断裂后存在1条反应路径,可生成实验产物中的C₃F₈;全氟三乙胺分子的C—N键断裂后存在3条反应路径,可生成实验产物中的C₃F₇N、 C₄F₉N和C₂F₆。全氟三乙胺热解后产生的CF₃自由基可与H、OH自由基发生反应,从而产生灭火作用。此外,其热解产物C₄F₉N和C₃F₇N具有CN双键,更容易与燃烧活泼自由基·OH、·H发生化学作用,对研究全氟三乙胺的灭火机理具有十分重要的意义。