硅烷基团再分配技术及其进展

围绕硅烷中不同烃基之间，烃基与卤素，经基与氢，氢与氯，氟与氯，烷氧基与烃基，氢，氯，氟等的交换，介绍了基团再分配技术的基本原理，方法，应用及进展。     

印刷线路板制造中应用水剂清洗

现已证实电子工业是氟氯烃化合物的主要用户之一。这种化合物能破坏臭氧层。氟氯烃化合物为主的化学商品如得利芬(Delifrene)、氟里昂(Freon),TMJ和阿克隆(Arklone)已广泛用于电子工业、特别是用于清洗印刷线路板。氟氯烃也用于印刷线路板表面装配的蒸气相焊接中以及清洗由于焊药糊堵塞的丝网。根据一个主要氟氯烃制造厂的统计,在电子工业中每年要用7500吨氟氢烃-113,而这只是世界消费量的3.5％。自从蒙特里尔环保议定书号召要明显地减少氟氯烃的使用后,电子工业部门已经着眼于在制造工艺中减少氟氯烃基溶剂的需用     

氟系表面活性剂的市场展望

氟系表面活性剂的市场展望１特点氟系表面活性剂系一般表面活性剂亲油基之氢被氟取代而生成的全氟烃基化合物，其表面活性格外地强。与一般表面活性剂相比，氟系表面活性剂具有如下特点：（１）一般表面活性剂溶于水时，水的表面张力可降至约３０ｄｙｎ／ｃｍ，而氟系表面...     

氟系清洗剂的现状与展望

介绍了替代CFC-113使用的氟系溶剂氢氯氟烷烃、氢氟烷烃、全氟烷烃、氢氟醚、氢氟醇的主要性能特点,同时介绍了氟系溶剂的发展状况及存在问题。     

气相催化合成氢氟烃和氢氟烯烃催化剂研究进展

随着氯氟烃(CFCs)制冷剂逐步被淘汰,市场上使用的制冷剂主要是以氢氟烃(HFCs)和氢氟烯烃(HFOs)为主要成分的单一或混合产品,气相催化法具有可连续操作和催化剂与产品易于分离等特点,是工业合成氢氟烃和氢氟烯烃的主要方法。介绍了氟氯交换反应、加氢脱氯反应和脱卤化氢反应等常见的气相催化合成氢氟烃和氢氟烯烃的反应类型,概括其反应原理以及影响催化剂活性的主要因素,并综述了气相催化剂在氢氟烃和氢氟烯烃合成中的应用,建议开发高活性的低温、无铬或低铬催化剂。     

2—氯—2—氢六氟丙烷的制备及其与HF的共沸物

介绍了一种2,2－二氯六氟丙烷一元氢解生成2－氯－2－氢六氟丙烷的方法,其过程为：在有效量的负载于三价氧化铬上的钯催化剂及HZ型酸（Z为Cl或F）存在下,于150℃以下的高温下,将2,2－二氯六氟丙烷与氢气反应,生成2－氯－2－氢六氟丙烷,以转化掉的2,2－二氯六氟丙烷计,反应的选择性可达70％以上,还介绍了2－氯－2－氢六氟丙烷与HF形成的共沸物及生成该共沸物的工艺。     

合成有机硅织物后整理助剂用碳官能基硅烷单体的开发

介绍了氨烃基、环氧烃基、巯烃基、羧烃基、羟烃基及氟烃基等碳官能基硅烷单体的合成方法，合成相应的碳官能基改性硅油的工艺路线及其改性硅油在织物中整理中的应用。     

α－（邻甲苯硫基乙酰氧基）烃基膦酸酯的合成

磷试剂α－羟基烃基膦酸酯１与氯乙酰氯反应制得α－（氯代乙酰氧基）烃基膦酸酯２，进而又和邻甲基苯硫酚进行缩合反应，合成了８种新型的α－（邻甲苯硫基乙酰氧基）烃基膦酸酯，收率为８０％～９０％。通过元素分析、ＩＲ及１ＨＮＭＲ确证了化合物的结构。     

α—（邻甲苯硫基乙酰氧基）烃基膦酸酯的合成

磷试剂α－羟基烃基膦酸酯１与氯乙酰氯反应制得α－（氯代乙酰氧基）烃基膦酸酯２，进而又和邻甲基苯硫酚进行缩合反应，合成８种新型的α－（邻甲苯硫基乙酰氧基）烃基膦酸酯，收率为８０％～９０％。通过元素分析，ＩＲ及ＨＮＭＲ确证了化合物的结构。     

国外氢氟氯烃和氢氟烃的开发生产规模及动向

介绍了联合国环境规划署（ＥＰＡ）关于氟氯烃（ＣＦＣ）及其它臭氧破坏物的新规定，国外ＣＦＣＳ的替代物氢氟氯烃（ＨＣＦＣ），氢氟烃（ＨＦＣ）的开发情况，几家大化学公司的ＨＣＦＣ１４１ｂ／１４２ｂ和ＨＦＣＳ，如ＨＦＣ１３４ａ的生产规模及动向。     

氟气中氮气和四氟化碳的快速分析

电解法制得的氟气含有氮气、氟化氢和四氟化碳等杂质。利用氯化钠与氟气反应生成氯气,经NaOH溶液吸收氯气后用普通的气相色谱测定其中四氟化碳含量,操作简单、快速。     

Gas Chromatographic Separation of Halocarbons on Porapak Q Porous Polymer Beads

Abstract

Kováts retention indices can be used to characterize the gas chromatographic behavior of C₁ and C₂ halocarbons on Porapak Q. Within each series of halocarbons the retention index increases with chlorine content, decreases with fluorine and hydrogen content, and is directly proportional to molecular weight and boiling point. Substitution of a fluorine or a bromine atom for a chlorine atom in these compounds results in characteristic changes in the retention index. The heats of adsorption are in the neighborhood of the latent heats of vaporization for the compounds examined.     

Effect of the Acidity of the Groups of Functionalized Silicas on the Direct Synthesis of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

Three catalysts consisting of palladium supported on functionalized silica with different acid groups (namely aryl sulfonic, alkyl phosphonic and alkyl carboxylic groups) were prepared and tested in the direct synthesis of hydrogen peroxide in neutral methanol medium at an overall pressure of 5.0 MPa. These catalysts can produce hydrogen peroxide. In addition, the activity results indicated correlations among the acid strength of the acidic group on the supports, the proportion of high binding energy palladium species and the selectivity for hydrogen peroxide.     

Mapping the fluorophilicity of a hydrophobic pocket: synthesis and biological evaluation of tricyclic thrombin inhibitors directing fluorinated alkyl groups into the p pocket

In the completion of our fluorine scan of tricyclic inhibitors to map the fluorophilicity/fluorophobicity of the thrombin active site, a series of 11 new ligands featuring alkyl, alkenyl, and fluoroalkyl groups was prepared to explore fluorine effects on binding into the hydrophobic proximal (P) pocket, lined by Tyr 60A and Trp 60D, His 57, and Leu 99. The synthesis of the tricyclic scaffolds was based on the 1,3-dipolar cycloaddition of azomethine ylides, derived from L-proline and 4-bromobenzaldehyde, with N-(4-fluorobenzyl)maleimide. Introduction of alkyl, alkenyl, and partially fluorinated alkyl residues was achieved upon substitution of a sulfonyl group by mixed Mg/Zn organometallics followed by oxidation/deoxyfluorination, as well as oxidation/reduction/deoxyfluorination sequences. In contrast, the incorporation of perfluoroalkyl groups required a stereoselective nucleophilic addition reaction at the "upper" carbonyl group of the tricycles, thereby yielding scaffolds with an additional OH, F, or OMe group, respectively. All newly prepared inhibitors showed potent biological activity, with inhibitory constants (K(i) values) in the range of 0.008-0.163 microM. The X-ray crystal structure of a protein-ligand complex revealed the exact positioning of a difluoromethyl substituent in the tight P pocket. Fluorophilic characteristics are attributed to this hydrophobic pocket, although the potency of the inhibitors was found to be modulated by steric rather than electronic factors.     

Effect of Partially Fluorinated N‐Alkyl‐Substituted Piperidine‐2‐carboxamides on Pharmacologically Relevant Properties

The modulation of pharmacologically relevant properties of N‐alkyl‐piperidine‐2‐carboxamides was studied by selective introduction of 1–3 fluorine atoms into the n‐propyl and n‐butyl side chains of the local anesthetics ropivacaine and levobupivacaine. The basicity modulation by nearby fluorine substituents is essentially additive and exhibits an exponential attenuation as a function of topological distance between fluorine and the basic center. The intrinsic lipophilicity of the neutral piperidine derivatives displays the characteristic response noted for partially fluorinated alkyl groups attached to neutral heteroaryl systems. However, basicity decrease by nearby fluorine substituents affects lipophilicities at neutral pH, so that all partially fluorinated derivatives are of similar or higher lipophilicity than their non‐fluorinated parents. Aqueous solubilities were found to correlate inversely with lipophilicity with a significant contribution from crystal packing energies, as indicated by variations in melting point temperatures. All fluorinated derivatives were found to be somewhat more readily oxidized in human liver microsomes, the rates of degradation correlating with increasing lipophilicity. Because the piperidine‐2‐carboxamide core is chiral, pairs with enantiomeric N‐alkyl groups are diastereomeric. While little response to such stereoisomerism was observed for basicity or lipophilicity, more pronounced variations were observed for melting point temperatures and oxidative degradation.     

Molar group contributions to the heat of combustion

Experimental results for the gross heat of combustion of over 140 commercial and developmental polymers and small molecules of known chemical structure were used to derive additive molar group contributions to the heat of combustion. The materials examined contained carbon, hydrogen, oxygen, nitrogen, phosphorus, sulphur, chlorine, fluorine and silicon in linear, branched and cyclic structures. Values for the molar group contributions were summed and divided by the molecular weight of the molecule or polymer repeat unit to yield the gross heat of combustion as determined by oxygen bomb calorimetry. This new method provides an accurate single step method for calculating the heat of combustion. The average relative error of the calculated gross heats of combustion is 2.8%. Published in 2002 by John Wiley & Sons, Ltd.     

Group contribution methods for coal-derived liquids: hydrogen solubilities using a UNIFAC approach

The solubility of hydrogen in a Wilsonville ITSL coal derived liquid was estimated using the UNIFAC group contribution method. Functional group concentrations estimated from analytical data were combined with literature values of group contribution parameters to provide reasonable estimates of hydrogen solubility. A sensitivity analysis indicated that the most significant structural features in determining hydrogen solubility were aromatic ring size, the length of alkyl substituents and the concentration of aromatic hydroxyl groups.     

离子色谱法测定废旧锂电池湿法浸出液中氟和氯

建立了离子色谱法同时测定废旧锂电池湿法浸出液中氟和氯含量的方法。以高沸点硫酸为蒸馏介质,在160~180 ℃下以水蒸气蒸馏法分离富集浸出液中氟化物和氯化物并被氢氧化钠吸收液吸收,可消除浸出液中有机物及大量共存金属离子对测定的干扰。吸收液经0.22 μm微孔滤膜过滤,并用4.5 mmol/L 碳酸钠-1.0 mmol/L 碳酸氢钠混合溶液淋洗,高容量AS23型阴离子分析柱分离,电导检测器对其检测。实验表明,氟和氯离子质量浓度在0.1~10.0 mg/L与其对应的峰面积呈良好的线性关系,线性相关系数分别为0.999 8和0.999 6。方法用于废旧锂电池湿法浸出液中氟和氯的测定,加标回收率分别为95.47%和96.29%,相对标准偏差（RSD, n=10）分别为2.9%和3.7%,结果满意。     

Preparation and characterization of silylated graphite oxide

Graphite oxide was silylated by various alkylchlorosilanes in the presence of butylamine and toluene, and new intercalation compounds were obtained. The silylating reagents with two or three chlorine atoms at silicon in them reacted with graphite oxide, while no reaction occurred when silylating reagents with only one chlorine atom was used. The silylating reagent mainly reacted with hydroxyl group of graphite oxide, forming Si-O bonding. The role of butylamine was not only exfoliating graphite oxide layer but also scavenging HCl molecule which caused the decomposition of silylated graphite oxide. The silicon content was almost constant ≈0.6 mol/graphite oxide for the samples silylated by alkyltrichlorosilane with shorter alkyl chain lengths. It increased with the increase of alkyl chain length and reached 1.7 mol/graphite oxide. The higher silicon content could be ascribed to further silylation on hydroxyl groups formed at silicon atoms of silylating reagent bonded to graphite oxide, bridging two silylating reagents.     

Bis(thien-2-yl)-2,1,3-benzothiadiazole-diketopyrrolopyrrole-based acceptor–acceptor conjugated polymers: Design,synthesis, and the synergistic effect of the substituent on their solar cell properties

Three acceptor–acceptor conjugated copolymers ( TBT-DPP , FTBT-DPP , and HFTBT-DPP ) with different substituent groups have been synthesized with palladium-catalyzed Stille coupling condensation polymerization assisted with microwave. Polymer solar cells (PSCs) based on these copolymers as the electron donors and PC71BM as the acceptor have been fabricated. The synergistic effect of the substituent between two fluorine atoms and hexyl alkyl chains in bis(thien-2-yl)-2,1,3-benzothiadiazole fragment on their solar cell properties has been investigated. Both the fluorine atoms and the synergistic effect can improve the solubility of the polymers effectively while the excellent thermal stability properties are still retained. Two fluorine atoms (polymer FTBT-DPP ) increased the power conversion efficiency of the PSCs twice compared with TBT-DPP (without substituent). The synergistic effect (polymer HFTBT-DPP ) decreased that seriously to zero. Density function theory calculations showed that the conjugation level of the polymer backbone is one of key factors. It demonstrates that the synergistic effect of fluorine atoms and alkyl chains in the same fragment does not always work well in improving the PSCs performance.