CN106166501B - 一种用于烯烃环氧化的催化剂及其制备方法 - Google Patents
一种用于烯烃环氧化的催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于烯烃环氧化的催化剂,其结构为多乙烯多胺基二硫代氨基甲酸盐与过渡金属的螯合物,其制备方法为:在碱性、1~20ºC条件下将多乙烯多胺与二硫化碳混合反应,制得中间产物二硫代氨基甲酸盐(DTC),将DTC投加到过渡金属盐溶液中,得沉淀,为金属的DTC螯合物,即本发明之催化剂。本发明具有如下优点:1、用DTC作为配体,相比传统的多元醇配体合成的金属配合物催化剂不溶于反应液,属于多相催化体系,易于分离;2、用DTC作为配体,相比传统的多元醇配体合成的金属配合物催化剂更稳定;3、用DTC作为配体,相比传统的多元醇配体合成的金属配合物催化剂分子量可调范围更大,易于调变。
Description
技术领域
本发明涉及化工产品催化剂领域,具体说为与二硫代氨基甲酸盐和过渡金属形成的螯合物及其制备方法有关的一种用于烯烃环氧化的催化剂及其制备方法。
背景技术
烯烃环氧化是化学工业中的重要单元反应。低级烯烃的环氧化产物是重要的基本有机化工原料,比如环氧乙烷和环氧丙烷,它们在聚酯和聚醚等工业生产中发挥着举足轻重的作用。高级烯烃的环氧化产物则是精细化工的重要中间体,比如环氧环己烷、环氧辛烷和降冰片烯环氧化物等。乙烯环氧化制环氧乙烷的银催化剂已经成熟;丙烯环氧化制环氧丙烷及其他烯烃环氧化反应则曾通过氯醇法实现,但因强腐蚀、高污染和原子经济性低等缺陷使该方法渐趋淘汰。以丙烯环氧化为例,当前的生产方法为哈尔康法和TS-1催化法,其他烯烃环氧化则主要仍由氯醇法实现。TS-1催化法虽然清洁环保,但存在催化剂制备成本较高和氧化剂过氧化氢成本高等问题使其应用受到一定限制。因此,当前哈尔康法仍是主流。哈尔康法采用有机过氧化物作为氧化剂,以硅烷化Ti/SiO2或钼醇作为催化剂。硅烷化Ti/SiO2催化剂制备过程较为复杂,难以控制,成本较高。钼醇催化剂制备虽较为便利,但由于催化剂溶于反应溶液,体系为均相,所以容易流失且不利于分离。因此,如果能将钼醇型催化剂加以改进,尤其是如果能使其固相化、使催化体系变为多相,则无疑是最具发展前景的催化剂。
虽然已有关于钼与醇胺形成螯合物用作烯烃环氧化催化剂的报道(应用化学,1991, 8(5): 49–51),但其仍不能摆脱催化剂溶于反应溶液、催化体系为均相的缺陷。二硫代氨基甲酸盐(dithiocarbamate,DTC)与金属的络合能力极强,其多种衍生物已被用于无机分析和重金属捕集剂。
发明内容
为了克服上述现有技术中已有钼醇催化剂存在的上述缺陷,本发明提供一种利用过渡金属与DTC形成的螯合物为催化剂,对烯烃环氧化反应具有良好的催化性能,且催化剂不溶于反应溶液,催化体系为多相的用于烯烃环氧化的催化剂及其制备方法。
本发明的目的是这样实现的:
一种烯烃环氧化催化剂的制备方法,包括如下步骤:
(1)、在碱性、1~20 ºC条件下将多乙烯多胺与二硫化碳混合反应,制得中间产物二硫代氨基甲酸盐,即DTC;
(2)、将步骤(1)制备的DTC投加到过渡金属盐溶液中,得沉淀,为钼的DTC螯合物,即本发明之催化剂;
步骤(1)中所述多乙烯多胺为乙二胺、二乙烯三胺、三乙烯四胺和四乙烯五胺中的一种或几种的混合物;
步骤(2)中所述金属为钼、钨、钒、钛、钴、铬、铌、钽中的一种,优选为钼、钨、铌、钽,更优选为钼、钨。
本发明催化剂的中间产物和最终产物结构式分别如下结构式1和结构式2;
中间产物二硫代氨基甲酸盐结构式1
最终产物催化剂结构式2
式中R1、R2 、R3为另一个结构类似但链长相同或不同的二硫代氨基甲酸盐分子,包括二乙烯三胺基与三乙烯四胺基;M为金属。
积极有益效果:1、用二硫代氨基甲酸盐作为配体,相比传统的多元醇配体合成的金属配合物催化剂不溶于反应液,属于多相催化体系,易于分离;2、用二硫代氨基甲酸盐作为配体,相比传统的多元醇配体合成的金属配合物催化剂更稳定;3、用二硫代氨基甲酸盐作为配体,相比传统的多元醇配体合成的金属配合物催化剂分子量可调范围更大,易于调变。
具体实施方式
下面结合实施例对本发明做进一步的说明:
实施例1-8
(1)、催化剂制备分两步。
在100 mL三口烧瓶中加入一定质量的乙二胺或二乙烯三胺或三乙烯四胺或四乙烯五胺中的一种、2 g氢氧化钠、2.3 g二硫化碳和40 mL水,20 ºC条件下搅拌4 h,过滤溶剂,得黄色沉淀,干燥,得产品二硫代乙二氨基甲酸钠,记为DTC;
将上述DTC1投入到20 mL、含一定质量的二(乙酰丙酮)氧化钼或钨酸钠水溶液中,搅拌反应2 h,过滤、干燥,得沉淀,记为催化剂Cat。
(2)、催化反应评价过程如下。在100 mL玻璃反应器中,加入17 mL环己烯、27 mL浓度为70%的异丙苯过氧化氢(CHP)溶液(异丙苯作溶剂)、6 mL内标物正辛烷,升温至60 oC时加入0.1 g催化剂,搅拌反应2 h。CHP含量用标准的碘量法测定,产物环氧环己烷(CHO)的含量用色谱仪分析,配毛细管柱(HP-1)和FID检测器。CHP的转化率和对CHO的选择性定义如下:
X CHP = 100% × ([CHP]0 – [CHP])/ [CHP]0
S CHO = 100% × [CHO]/( [CHP]0 – [CHP])
其中,[CHP]0和[CHP]分别代表反应初始和结束时的CHP量,[CHO]代表生成CHO的量;所有量均以摩尔(mol)计。
采用本发明部分条件和对烯烃环氧化催化效果见下表:
注:1、Cat1~8指的是实施例1~8所对应的催化剂;
2、酮钼指的是上文中的二(乙酰丙酮)氧化钼。
本发明具有如下优点:1、用二硫代氨基甲酸盐作为配体,相比传统的多元醇配体合成的金属配合物催化剂不溶于反应液,属于多相催化体系,易于分离;2、用二硫代氨基甲酸盐作为配体,相比传统的多元醇配体合成的金属配合物催化剂更稳定;3、用二硫代氨基甲酸盐作为配体,相比传统的多元醇配体合成的金属配合物催化剂分子量可调范围更大,易于调变。
以上实施案例仅用于说明本发明的优选实施方式,但本发明并不限于上述实施方式,在所述领域普通技术人员所具备的知识范围内,本发明的精神和原则之内所作的任何修改、等同替代及改进等,均应视为本申请的保护范围。
Claims (1)
1.一种催化剂在烯烃环氧化反应中的应用,其特征在于,所述的催化剂的制备过程如下:在100 mL三口烧瓶中加入一定质量的乙二胺或二乙烯三胺或三乙烯四胺或四乙烯五胺中的一种、2g氢氧化钠、2.3g二硫化碳和40mL水,20oC条件下搅拌4h,过滤溶剂,得黄色沉淀,干燥,得产品二硫代乙二氨基甲酸钠,记为DTC;将上述DTC投入到20mL、含一定质量的二(乙酰丙酮)氧化钼或钨酸钠水溶液中,搅拌反应2h,过滤、干燥,得沉淀,记为催化剂Cat;
所述烯烃环氧化反应过程如下:在100 mL玻璃反应器中,加入17mL环己烯、27mL浓度为70%的异丙苯过氧化氢溶液以及6mL内标物正辛烷,升温至60oC时加入0.1g上述催化剂Cat,搅拌反应2h;所述异丙苯过氧化氢溶液中异丙苯作为溶剂。
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