对苯二甲酰氯的生产工艺及市场分析

介绍了氯化亚砜法、光气法、三氯化磷法、五氯化磷法、酯氯化法和对二甲苯氯化法等几种对苯二甲酰氯工业生产方法,对其优缺点进行了对比。同时从芳纶产业对对苯二甲酰氯的下游市场进行了详细分析。     

光气法合成农药中间体酰氯

酰氯是农药工业的重要中间体。例如:邻氯苯甲酰氯是除虫脲的重要原料;邻甲基苯甲酰氯是灭锈胺的重要原料;1,3-二氯苯甲酰氯是TH 6038的重要原料等。酰氯的生产,通常采用的酰化剂是氯化亚砜、三氯化磷,另外,光气亦可用作酰化剂。我们用上述酰化剂进行了酰氯合成,试验结果表明:用光气法酰氯化具有反应周期短、成本低、三废处理容易、收率高等优点。光气法又可分为加热熔融和溶剂法两种,经试验,溶剂     

对苯二甲酰氯合成

对苯二甲酰氯是重要的化工原料,我们以对苯二甲酸为原料,氯化亚砜为氯化试剂,在催化剂催化下,一步得到对苯二甲酰氯。此法收率很高,产品很好处理,纯度高,比对苯二甲酸和PCl_5和乙酰氯制备方法有更多的优点。     

以固体光气为原料合成邻苯二甲酰氯的工艺研究

以固体光气和邻苯二甲酸为原料,1,2-二氯乙烷作溶剂,DMF为催化剂合成了邻苯二甲酰氯。考察了原料配比、反应温度、溶剂用量、催化剂用量和反应时间对收率的影响。结果表明,当固体光气与邻苯二甲酸摩尔比为1.5∶1,催化剂DMF用量3 mL,反应温度60℃,溶剂1,2-二氯乙烷用量为100 mL,反应时间3.5 h时,合成邻苯二甲酰氯的收率达71.3%,产物纯度为92.4%。利用邻苯二甲酰氯与甲醇的衍生化反应,建立了邻苯二甲酰氯的气相色谱分析方法,并采用外标法对邻苯二甲酰氯进行定量分析,含量为92.4%。     

高效液相色谱法快速测定PC饮用水桶中对叔丁基苯酚、对苯二甲酰氯和间苯二甲酰氯迁移量

建立了一种快速检测聚碳酸酯(PC)桶中对叔丁基苯酚、对苯二甲酰氯和间苯二甲酰氯迁移量的高效液相色谱分析方法。采用ZORBAX SB-C_(18)作为色谱柱,对流动相的组成和洗脱方式、检测波长等参数进行优化。结果表明:以甲醇和水为流动相,梯度洗脱,柱温30℃,可使得对叔丁基苯酚、对苯二甲酰氯和间苯二甲酰氯在10 min内实现分离;在优化条件下,对叔丁基苯酚、对苯二甲酰氯、间苯二甲酰氯在0.1~10.0μg/ml浓度范围内呈良好的线性关系,相关系数为0.999,方法的检出限(LOD,S/N=3)为0.01~0.0.3μg/ml,定量限(LOQ,S/N=10)为0.05~0.1μg/ml。该方法分离效果良好,准确可靠,方便快捷,可用于PC桶中对叔丁基苯酚、对苯二甲酰氯和间苯二甲酰氯的快速检测。     

低色度2,5-呋喃二甲酸异辛酯的合成

采用酰氯法来制备低色度2,5-呋喃二甲酸异辛酯,首先是酰氯的制备,考察了酰化试剂、温度及时间对2,5-呋喃二甲酰氯产率的影响;然后制备2,5-呋喃二甲酸异辛酯,考察了催化剂对直接酯化法制备的2,5-呋喃二甲酸异辛酯色度的影响,温度、时间对酰氯法制备的2,5-呋喃二甲酸异辛酯产率的影响,并对两种方法制备的酯的色度进行了比较。结果表明,在90℃,1.5 h条件下,以固体光气为酰化试剂时,2,5-呋喃二甲酰氯产率最高为91.9%;采用直接酯化法制备的2,5-呋喃二甲酸异辛酯色度均大于500 APAH,而酰氯法制备的2,5-呋喃二甲酸异辛酯的色度为30~40 APAH,且在90℃,1 h条件下,产率最高为98.1%。与直接酯化法相比,酰氯法具有反应温度低、醇用量少、产品色度低等优点,具有良好的工业应用前景。     

超声辐射合成3，3’-偶氮苯二甲酰氯

以3,3’-偶氮苯二甲酸为原料,氯化亚砜为酰基化剂,超声辐射快速合成3,3’-偶氮苯二甲酰氯。较佳工艺条件为：超声功率250W,3,3’-偶氮苯二甲酸1．5g,氯化亚砜30mL,反应温度80℃,反应时间4小时,收率达95．3％。标题化合物结构经红外光谱、核磁共振和元素分析得到确认。     

熔融法合成邻苯二甲酰氨基酸

以邻苯二甲酸酐为原料,采用熔融法分别和5种氨基酸(甘氨酸、苯丙氨酸、亮氨酸、苏氨酸、天冬氨酸)发生缩合反应得到5种邻苯二甲酰氨基酸,通过~1HNMR和~(13)CNMR对目标化合物的结构进行表征;并以邻苯二甲酰苯丙氨酸的合成为模型反应,探讨了最佳反应条件。结果表明,在n(邻苯二甲酸酐)∶n(苯丙氨酸)为1.5∶1、反应温度为145℃、反应时间为25 min的最佳条件下,邻苯二甲酰苯丙氨酸的收率可达91.5%。在最佳反应条件下,其它4种邻苯二甲酰氨基酸均以较高收率获得。该方法具有操作简单、收率高、反应时间短等优点,可用于邻苯二甲酰氨基酸的简便合成。     

用气相色谱法测定对苯二甲酰氯中的杂质

<正> 对苯二甲酰氯(TPC)是聚对苯二甲酰对苯二胺(芳纶1414)和聚砜酰胺的单体,它是由对苯二酸(TPA)经酰卤化反应制取的。TPC 中杂质的种类和含量与原料TPA 中杂质、TPC 合成情况及纯化方法有关。主要是相应原料酸中杂质酸的酰氯,根据TPA 合成路线的不同,主要有苯甲酰氯(BC)、对甲基苯甲酰氯(PTC)、邻苯二甲酰氯(PC)和间苯二甲酰氯(IPC)等。另外,合成TPC 时,反应不完全或水解产生的对苯二甲酸单酰氯(TPMC)和TPA、氯化氢及合成中产生的其它杂质等等。单酰氯的存在会封闭分子链,得不到高分子量的聚合物,而异构体会影响高聚物链结构。因此,建立TPC 中杂质测定方法对其合成、纯化和稳定地制取高分子量聚合物具有重要意义。酰氯是具有高度反应性的化合物,在空气或色谱     

间苯二甲酰氯在DMAC中的水解行为以及对聚合的影响

芳纶1313聚合的主要工艺之一是由间苯二甲酰氯和间苯二胺在DMAC中缩聚。实验发现,其聚合单体间苯二甲酰氯容易水解为间酰氯苯甲酸或间苯二甲酸,温度越高,则水解行为越快。研究表明,这两种水解产物和原料间苯二甲酰氯中可能存在的含氯间苯二甲酰氯对芳纶1313聚合的相对分子的质量和分布有很大的影响。     

邻苯二甲酸酯Gemini表面活性剂的合成及性能

采用N,N-二甲基乙醇胺与邻苯二甲酰氯反应得到二(二甲基胺基乙基)邻苯二甲酸酯(Ⅰ),然后Ⅰ再与正溴代十六烷反应,经处理后得到邻苯二甲酸酯基Gemini表面活性剂SHZ16,收率83%(以邻苯二甲酰氯计)。用两相滴定法分析其质量分数为99.2%。采用电导法测定了其CMC值为2.02×10-5mol/L,采用滴体积法测定了γCMC为41.87 mN/m,并考察了其增溶性、黏度、乳化性能和泡沫性质,该性能优于传统表面活性剂十二烷基硫酸钠(SDS)。     

邻苯二甲酸酯Gemini表面活性剂的合成及性能研究

研究采用N,N-二甲基乙醇胺与邻苯二甲酰氯反应得到二（二甲基胺基乙基）邻苯二甲酸酯（I）,然后（I）再与正溴代十六烷反应,经处理后得到邻苯二甲酸酯基Gemini表面活性剂SHZ16,收率83%（以邻苯二甲酰氯计）。用两相滴定法分析其纯度为99.2%。采用电导法测定了其CMC值为2.02×10-5mol/L,采用滴体积法测定了CMC为41.87mN/m, 并研究了其増溶性、粘度、乳化性能和泡沫性质,其性能优于传统表面活性剂十二烷基硫酸钠（SDS）。     

A new method of synthesis of alkyl-glycidyl esters of dicarboxylic acids in high yields

A series of new alkyl-glycidyl esters of dicarboxylic acids which could be used as PVC plasticizers were synthesized. The method adopted is a new synthetic process which can be carried out in two stages. During the first stage, the carboxylic acid anhydride reacts with the salt of the alcohol, and the sodium salt produced reacts with epichlorhydrin in the presence of a catalyst to yield an alkyl-glycidyl ester. The specific reactions give pure products in high yields. The reaction of phthalic acid bisodium salt with epichlorhydrin, as well as the reaction of phthaloyl chloride with glycidol, gave diglycidyl phthalate in 36% and 22% yields, respectively.     

Linear polythioesters,XXIII. Products of interfacial polycondensation of 4,4′-dimercaptobiphenyl with acid dichlorides

New polythioesters were obtained by interfacial polycondensation of 4,4′-dimercaptobiphenyl with selected aliphatic and isomeric phthaloyl dichlorides. To determine the optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield were studied: type of organic phase, concentration of hydrogen chloride acceptor, type of catalyst, reaction temperature and rate of acid dichloride addition. A thorough examination was carried out only for the polycondensation of dithiol with isophthaloyl dichloride chosen as a model system. The structures of polythioesters were determined by elemental analysis, X-ray and infrared spectra. The temperature of initial decomposition, the percentage of its mass loss, and temperature of the fastest decomposition process were determined from curves of differential and thermogravimetric analysis. Some physicochemical, mechanical and electrical properties were determined. The molecular weights were not measured because of the low solubility of the obtained polythioesters.     

Electroreduction of (1<Emphasis Type="Italic">S,2S</Emphasis>)-2-amino-1-(4-nitrophenyl)-propane-1,3-diol derivatives. Behaviour of electrogenerated species and applications to organic synthesis

Hydroxylamines electrogenerated from (1S,2S)-2-amino-1-(4-nitrophenyl)-propane-1,3-diol derivatives (derivatives of p-nitrophenylserinol) are unstable in methanol–acetate buffer and practically stable in acetonitrile–aqueous acetate buffer. This latter medium was used to carry out subsequent reactions in situ involving the triacetylated p-hydroxylaminophenylserinol and various reagents. An azoxy compound was the major product isolated after reaction with maleic or phthalic anhydrides. In contrast, a benzoxazine dione was normally obtained with phthaloyl dichloride and a N-sulphonylated hydroxylamine was produced with p-toluenesulphonyl chloride.     

Linear polyesters. Products of interfacial polycondensation of bis(4-hydroxyphenyl) ether with isomeric phthaloyl chlorides

New polyesters were obtained by interfacial polycondensation of bis(4-hydroxyphenyl) ether with phthaloyl, isophthaloyl, and terephthaloyl chlorides. The initial reaction conditions were as follows: the aqueous to organic phase ratio 1 : 1, reaction temperature 25°C, the rate of chloride addition about 10 min, and molar ratio of the reagents diol/acid dichloride 1 : 1.1, benzene-hexane as an organic phase. To determine the optimal conditions for interfacial polycondensation, the influence of the following factors on yield and value of reduced viscosity were studied: organic phase, excess of sodium hydroxide as an acceptor of HCl, contribution of benzyltriethylammonium chloride as a catalyst, and contribution of an emulsifier, Mersolan. The structure of all polyesters was determined by elemental analysis and infrared spectra. Initial decomposition and initial intensive decomposition temperature were defined by the curves of thermogravimetric analysis. Some mechanical and electrical properties of isophthaloyl polyester, only partly soluble in organic solvents, were determined.     

亚硫酰氯法合成2氯代苯并噻唑

采用２ 巯基苯并噻唑和亚硫酰氯为原料合成２ 氯代苯并噻唑,反应的最佳配比为：２ 氯代苯并噻唑∶亚硫酰氯（ｍｏｌ／ｍｏｌ） ＝ １∶１ ．０５ , 最佳反应温度为１１５ ℃, 催化剂用量为２ 巯基苯并噻唑用量的８ ‰,２ 氯代苯并噻唑的收率为９６－７ ％ , 较文献值高约８ ％ , 纯度≥９８ ％ 。     

Linear polythioesters. XXII. Products of interfacial polycondensation of bis(4-mercaptomethylphenyl)sulfide with some aliphatic and isomeric phthaloyl dichlorides

New polythioesters were obtained by interfacial polycondensation of bis(4-mercaptomethylphenyl) sulfide with some aliphatic and isomeric phthaloyl dichlorides. To determine optimal conditions for polycondensation, the polythioester from bis(4-mercaptomethylphenyl) sulfide and sebacoyl dichloride was chosen as a model system. The influence of some factors on the reduced viscosity and the yield were studied. Polythioesters from aliphatic and isomeric phthaloyl dichlorides were prepared under the same optimal conditions as those established for the reaction of the dithiol with sebacoyl dichloride. The structure of all polythioesters was determined by elementary, infrared spectra, and X-ray analysis. Initial decomposition temperature and maximum rate of decomposition temperature were defined from the curves of thermogravimetric analysis. Some physicochemical, mechanical, and electrical properties have been determined. © 1994 John Wiley & Sons, Inc.     

三氯乙酰氯的合成

本文对三氯乙酰氯的各种合成路线进行了分析对比，并对以氯油为起始原料经硝酸氧化和氯化亚砜酰氯化合成三氯乙酰氯的方法进行了深入研究，指出了提高产品收率的关键。研究确定的合成方法具有原料便宜易行，工艺简单易行，而且产品收率较高的优点，适合工业化生产。