硅钨酸催化合成癸二酸二乙酯

研究了硅钨酸对癸二酸酯化合成癸二酸二乙酯的催化性能 ,得出最佳反应条件 :采用 1 0 .1 g癸二酸与 1 3m L无水乙醇反应 ,1 3m L苯为带水剂 ,以 0 .7g新制的硅钨酸 (或 1 .0 6g存放 48年的硅钨酸 )为催化剂 ,回流反应 3h,酯化率分别达95.81 % (或 93.0 5% )。并研究了几种催化剂的催化能力次序 :Fe Cl3 · 6H2 O≈新制的硅钨酸 >存放 48年的硅钨酸 >浓 H2 SO4 >Al Cl3 >存放 48年的磷钨酸 ,并证实了硅钨酸为该反应的良好催化剂 ,具有催化活性高、化学稳定性好 ,重复使用性能佳、无三废排放的优点。     

铁试剂催化合成二苯甲酮

研究了改用新的铁试剂(CAT)作催化剂后,苯甲酰氯和苯能于低压、160℃以下发生Friedel-Crafts酰化反应合成二苯甲酮的工艺.反应最佳条件:n(苯甲酰氯):n(苯)=1:3,m(铁试剂):m(苯甲酰氯)=0.0285:1,在0.4MPa压力下反应14小时,收率达90%,纯度为99.8%(GC分析).     

联产苯甲酰氯的对苯二甲酰氯合成新工艺

以腐蚀性小、安全性好的三氯甲苯和对苯二甲酸为原料,在酸性催化剂作用下,进行联产苯甲酰氯的对苯二甲酰氯合成新工艺研究。考察了催化剂种类及用量、原料摩尔比、反应时间和反应温度对产品收率的影响,并采用GC-MS、FT-IR、1HNMR等表征手段对产物进行定性和定量分析。单因素试验结果表明:当以Fe Cl3为催化剂,且用量为0.1%(以总投料质量计),三氯甲苯和对苯二甲酸的摩尔比为2.25∶1,反应温度为110℃,反应时间为4 h时,精制产品中对苯二甲酰氯的纯度可达99.2%,收率为67.4%,苯甲酰氯的纯度为98.7%,收率为93.9%。并对Fe Cl3催化三氯甲苯和对苯二甲酸的可能性反应历程进行了探讨。     

提高紫外线吸收剂二苯甲酮收率的研究

以苯甲酰氯和苯为原料在常压下合成二苯甲酮,反应最佳条件为n（苯甲酰氯）:n（苯）＝0.2,n（催化剂）：n(苯甲酰氯）＝1：3,适当调节催化剂三氯化铝的用量,收率达到92％.     

导电涤纶的试制

用碘吸附 -铜离子络合工艺制得比电阻为 8× 10 3～ 1.5× 10 4 Ω· cm的导电涤纶 POY长丝。讨论了诸多因素对纤维比电阻的影响 ,通过实验选定了最佳工艺条件。碘吸附过程的最佳工艺条件为 :I/KI质量比 1.5～ 1.8,碘浓度 2 10 g/L,温度 70～ 80℃ ,时间 80 min;铜离子络合最佳工艺为 :Cu Cl/NH4 Cl质量比 0 .6 ,Cu Cl浓度 2 0～ 4 0 g/L,温度 85～ 95℃ ,时间 4 0 min     

光稳定剂二苯甲酮合成新工艺研究

以苯甲酰氯、三氯化苄和苯为原料合成二苯甲酮,分别研究了反应温度、反应时间、原料配比、催化剂用量、溶剂的用量等条件对合成反应的影响,确定了最佳工艺条件。该方法合成二苯甲酮的最适宜的工艺条件是:反应温度120℃、反应时间12 h、n(苯甲酰氯)∶n(苯)=1∶1.7,n(苯甲酰氯)∶n(三氯化苄)=7.35∶1,催化剂用量为4.25 g(相对于0.588 mol苯甲酰氯),二苯甲酮的收率可达到94.54%以上,产品纯度二苯甲酮99.5%。     

2-羟基-2-甲基-1-苯基丙酮的合成

以苯甲醛、镁、2 -溴丙烷、溴等为主要原料 ,经四步反应合成了光敏引发剂 2 -羟基 - 2 -甲基 - 1 -苯基丙酮。在 0°C时 ,将 1 6.5g苯甲醛滴加到由 4g Mg和 2 0 .6g2 -溴丙烷制得的 Grignard试剂中 ,在室温下搅拌 0 .5h,得到 2 0 .5g异丙基苯甲醇。将 2 5g K2 Cr2 O7、1 1 0 m L水和 2 0 m L浓H2 SO4 的混合液加入由 90 m L氯仿、5m L新洁而灭和 35g异丙基苯甲醇组成的混合液中 ,加完后 ,在室温下继续搅拌 2 h,得到 2 9.5g异丙基苯甲酮。在 65～ 75°C,将 32 .5g Br2 和 30 m L四氯化碳滴加到 60 m L CCl4 、1 5m L醋酸和 2 8.5g异丙基苯甲酮中 ,在温度不超过 70°C时搅拌 3h,得到α-溴代异丙基苯甲酮。1 0 gα-溴代异丙基苯甲酮、32 m L质量分数为 1 0 %的 Na OH溶液及 5m L新洁而灭 ,加热回流 3h,得到 6.8g 2 -羟基 - 2 -甲基 - 1 -苯基丙酮。     

紫外线吸收剂二苯甲酮的合成研究

以苯甲酰氯和苯为原料在常压下合成二苯甲酮,反应最佳条件为n(苯甲酰氯):n(苯)=0.2,n(催化剂):n(苯甲酰氯)=1.3,适当调节催化剂三氯化铝的用量,收率达到92%     

三氯化铁低压催化合成二苯酮工艺改进

以三氯化铁为催化剂（催化剂B）,用苯和苯甲酰氯合成二苯酮;以三氧化二铁为助催化剂,可降低反应温度、压力,缩短反应时间,提高产率;考察催化剂B用量、苯甲酰氯加入方式、压力及溶剂用量对反应的影响,表明最优工艺条件为：m（催化剂B）：m（FeCl3）=4：1,苯甲酰氯一次性加入,迅速排气,维持系统压力0．4MPa,反应时间7．5h,二苯酮收率97％。     

离子膜电解工艺指标的制定

分析了离子膜电解工艺指标对运行过程的影响 ,制定出为确保离子膜长期稳定运行的各工艺指标的范围 :进槽盐水为pH >3.0 ,NaClO3<15g L ,Na2 SO4 <7g L ,Ca +Mg <2× 10 - 8,I <5× 10 - 7,SiO2 <1× 10 - 5,Mn <5× 10 - 8,TOC <1× 1- 5,SS <1× 10 - 6 ,Sr>2× 10 - 8,Ba <5× 10 - 8,Fe <1× 10 - 6 ,Al<1× 10 - 7,Ni<1× 10 - 8,F <1× 10 - 6 ;碱液质量分数为 ( 32 .5± 0 .5 ) % ;阳极液质量浓度为 2 2 0～ 2 30g L ;槽温在电流为 12 .5kA时为 ( 85± 2 .5 )℃。     

FeCl_3/ZnCl_2加压催化酰化制备4-氯二苯甲酮工业化技术

研究了在加压和FeCl3/ZnCl2催化下,4-氯苯甲酰氯和苯发生Friedel-Crafts反应制备4-氯二苯甲酮的工艺。157.6 g苯、88.2 g 4-氯苯甲酰氯和1.3 g FeCl3/ZnCl2混合于1 L的高压釜中,在压力为(0.85～1.1)×106Pa、温度为175～185℃的条件下反应8 h,经纯化处理得到4-氯二甲苯酮93.1 g,摩尔收率为86.2%,w(4-氯二苯甲酮)=99.8%(HPLC)。探讨了压力、催化剂和投料比等对收率的影响。经过一次性投料4-氯苯甲酰氯175 kg的生产型中试验证,4-氯二苯甲酮摩尔收率为82.7%。     

Benzoylation of benzene to benzophenone over zeolite catalysts

The liquid phase benzoylation of benzene with benzoyl chloride (BOC) to benzophenone is catalyzed by various zeolites at 353 K. Zeolite H-beta is found to be more active than the other zeolites. The conversion of benzoyl chloride to benzophenone over H-beta increases significantly with increase in the reaction time, temperature, catalyst/BOC (wt/wt) and benzene/BOC (mole) ratios. The yield of benzophenone decreases with increase in SiO₂/Al₂O₃ ratio and isomorphous substitution of Al-by Ga- and Fe-in zeolite H-Al-beta in the following order: Al-> Ga-> Fe-H-beta suggesting that high density of acidic centers along with strong acid sites are required for the reaction.     

Acylation of Benzene over Clay and Mesoporous Si-MCM-41 Supported InCl3, GaCl3 and ZnCl2 Catalysts

Liquid phase acylation of benzene by acyl chloride (e.g., benzoyl chloride, butyryl chloride or phenyl acetyl chloride) over InCl₃, GaCl₃ and ZnCl₂ supported on commercial clays (viz. montmorillonite-K10, montmorillonite-KSF and kaolin) or high silica mesoporous MCM-41 at 80°C has been investigated. The Mont.-K10 and Si-MCM-41 supported InCl₃ and GaCl₃ catalysts showed high activity in the acyation of benzene by benzoyl chloride even in the presence of moisture in the reaction mixture. The redox function of the supported InCl₃, GaCl₃ or ZnCl₂ catalysts seems to play a very important role in the acylation process.     

氯乙酰氯和苯甲酰氯联产工艺的研究

研究了三氯甲苯和氯乙酸在催化剂存在下反应生成氯乙酰氯和苯甲酰氯的工艺条件。７０－０ ｇ氯乙酸和０－６ ｇ ＺｎＯ／ＳｎＣｌ２ 混合加热到１２０ ℃,在２～３ ｈ 内滴加１６０－０ ｇ 三氯甲苯,常压蒸馏反应混合物得到８１－０ ｇ 氯乙酰氯,纯度为９９％ ;然后减压蒸馏得到１００－０ ｇ 苯甲酰氯,纯度为９８％ ,收率＞９０％ 。     

光氯化法制造邻氰基氯苄中试工艺研究

研究了邻氰基甲苯用光氯化法制备邻氰基氯苄的中试工艺。把160 kg的邻氰基甲苯投入到300 L的搪瓷反应釜中,把3只100 W白炽灯的光照引入到邻氰基甲苯液体中,在130~155℃下以9~10 kg/h速度通入干燥的氯气,通氯约40 kg停止反应,冷却氯化液,用离心机分离析出的晶体,母液再投入到反应釜中,重复上述操作,通氯质量分别为16 kg、11 kg和6 kg,把所得的邻氰基氯苄合并,用乙醇重结晶,干燥,共得到产物168 kg,总收率81.3%,w(邻氰基氯苄)=99.2%。     

Anionic synthesis and characterization of ω-formyl-functionalized polystyrenes

ω-Formyl-functionalized polystyrenes can be synthesized in quantitative yield by reacting poly(styryl)lithium (M _n = 2 × 10³?8 × 10³ g/mol) in benzene with a 0.1?0.4 molar excess of 4-morpholinecarboxaldehyde followed by methanol termination and precipitation into methanol. Narrow molecular weight distribution ω-formyl-functionalized polystyrenes were characterized by hydroxylamine end-group titration, thin layer chromatography and both ¹H and ¹³C NMR spectroscopy. The mechanism of the functionalization was studied by trapping the tetrahedral α-amino alkoxide intermediate with diphenylphosphinic chloride.     

Alkylation of benzene with propylene catalyzed by FeCl3-Chloropyridine ionic liquid

Alkylation of benzene with propylene was carried out with FeCl₃-chloro-butyl-pyridine (FeCl₃-[bpc]) ionic liquid as catalyst to obtain cumene. Significant improvements in propylene conversion and cumene selectivity under mild reaction conditions were attained by modification of the catalyst with HCl. Under 20°C, 0.1 MPa, reaction time 5 min, mole ratio of benzene to propylene 10:1 and mass ratio of FeCl₃-[bpc] to benzene 1:100, conversion of propylene can increase from 83.60% to 100.00% and selectivity of cumene can increase from 90.86% to 98.47%. If reaction is carried out in following two stages, the result will be very good. At the initial stage of the reaction, alkylation is the main reaction and a higher conversion of propylene is obtained at a lower temperature. At the later stage of the reaction, transalkylation is the main reaction and selectivity to cumene can be increased by appropriately raising the reaction temperature. Translated from Petrochemical Technology, 2006, 35(9): 819–823 [译自: 石油化工]     

Sorption of benzene by poly(ethylene oxide)

The activity of benzene in poly(ethylene oxide), PEO, has been determined over the concentration range 0.3 to ～35 wt% benzene using the piezoelectric sorption method. The temperature range was 64° to 97°C and the molecular weights of polymer samples were 1.0 × 10⁵, 6.0 × 10⁵, and 5.0 × 10₆ g/g mol. The Flory-Huggins interaction parameters, χ, determined in this work agree within experimental error with χ values determined by gas chromatography and by vapour pressure measurement. The values of χ extrapolated to zero solvent concentration, χ^∞, have a minimum and negative value in the vicinity of 85°C for the sample of molecular weight 1.0 × 10⁵, 84°C for the sample of molecular weight 6.0 × 10⁵, and 77°C for the sample of molecular weight 5.0 × 10⁶. In the vicinity of 65°C, χ^∞ is negative for each molecular weight of polymer and increases to positive values with an increase in temperature. For all samples studied, the χ^∞ parameters reach constant values (0.22 to 0.30) at temperatures higher than 90°C.