CN105820111B - 一种催化剂的制备方法及其催化制备2,2-联吡啶的方法 - Google Patents
一种催化剂的制备方法及其催化制备2,2-联吡啶的方法 Download PDFInfo
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- C07D—HETEROCYCLIC COMPOUNDS
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
本发明公开了一种催化剂的制备方法，属于催化剂制备及应用领域，该方法包括以下步骤：a)在惰性气体保护下，混合乙酰丙酮、氢氧化钴、苯和/或苯衍生物，然后蒸馏分水，直至回流液中水分含量小于300ppm，得到含有乙酰丙酮钴的溶液A，降温至‑10℃以下备用；b)在惰性气体保护下，将环戊二烯、1，5‑环辛二烯、苯和/或苯衍生物混合降温至‑10℃以下，加入三乙基铝混匀，得到溶液B；c)在0℃以下将溶液B缓慢加入溶液A中，搅拌升温至25℃，反应3~5h，过滤，所得滤液为催化剂1,5‑环辛二烯环戊二烯基钴的苯和/或苯衍生物溶液。本发明还公开了利用该催化剂制备2,2‑联吡啶的方法。
Description
技术领域
本发明属催化剂制备及应用领域，具体涉及一种催化剂的制备方法及其催化制备2,2-联吡啶的方法。
背景技术
2,2-联吡啶是生产除草剂敌草快的必需原料，亦是其它化工原料中间体，广泛应用于农药、医药、香料及染料的合成。同时，它还是一种金属螯合剂，可用于金属显色剂，市场前景良好。
目前，2,2-联吡啶的生产方法主要有卤代吡啶偶联和吡啶脱氢法，两种方法都存在环境污染较大、废水难以治理等问题，生产规模难以扩大。据Synthesis of 2,2 ′‐Bipyridines:Versatile Building Blocks for Sexy Architectures and FunctionalNanomaterials(G R Newkome 等，Eur.J.Org.Chem,2004，235-254) 介绍，采用2-卤代吡啶自身偶联是制备2,2’- 联吡啶的常用方法之一。CN103172559A 及CN103030594A均公开了以廉价的2- 氯吡啶为原料，生产2,2-联吡啶的方法。然而，这些方法通常需要使用大量的重金属锌和较为昂贵的催化剂，生产成本较高，环保性较差。
发明内容
本发明的目的在于提供一种催化剂的制备方法，提供利用该催化剂催化制备2,2-联吡啶的方法则是本发明的另一个目的。
基于上述目的，本发明采用以下技术方案：一种催化剂的制备方法，包括以下步骤：
a) 在惰性气体保护下，混合乙酰丙酮、氢氧化钴、苯和/或苯衍生物，然后升温至共沸点，溶剂开始通过精馏塔蒸发回流，利用苯和/或苯衍生物与水可以形成共沸反应液进行连续蒸馏脱水，凝液在分水器内分水处理，上层苯和/或苯衍生物返回精馏塔，塔顶水和苯、及水共沸物经冷凝再回到分水器中，塔底苯和/或苯衍生物返回到反应体系内继续带水，直至回流夜中水分含量小于300ppm，关闭反应釜到精馏塔连接的气相和液相回流管道，降温得到含有乙酰丙酮钴的溶液A，继续降温至-10℃以下备用；
b) 在惰性气体保护下，将环戊二烯、1，5-环辛二烯、苯和/或苯衍生物混合降温至-10℃以下，加入三乙基铝混匀，得到溶液B，即混合有1,5-环辛二烯和二乙基环戊二烯基铝的苯和/或苯衍生物溶液；
c) 在0℃以下将步骤b)所得的全部溶液B缓慢加入步骤a)所得全部溶液A中，，搅拌升温至25℃，反应3~5h，过滤，所得滤液为催化剂1,5-环辛二烯环戊二烯基钴的苯和/或苯衍生物溶液，1,5-环辛二烯环戊二烯基钴的化学式为CoC5H5(C8H12)。
优选地，按照相同的重量份标准，步骤a)中，各物料的重量份数为：乙酰丙酮12份、苯和/或苯衍生物500份、氢氧化钴11~14份；步骤b)中，各物料的重量份数为：环戊二烯6~9份、1，5-环辛二烯28~30份、苯和/或苯衍生物350份、三乙基铝123~126份。
优选地，所述苯衍生物为甲苯、二甲苯或二者的混合物。
进一步地，步骤b)加入三乙基铝混匀过程中，缓慢加入并控制反应体系的温度在10℃以下。
利用上述1,5-环辛二烯环戊二烯基钴催化剂制备2,2-联吡啶的方法，将催化剂1,5-环辛二烯环戊二烯基钴的苯和/或苯衍生物溶液与2-氰基吡啶混合，升温至100℃后，通入乙炔于120~200℃反应2h得2,2-联吡啶溶液，将2,2-联吡啶反应液蒸馏分离出粗品后，精制得到无色或者浅粉红色的2,2-联吡啶结晶体。
进一步地，催化剂1,5-环辛二烯环戊二烯基钴的苯和/或苯衍生物溶液与2-氰基吡啶的重量份数比为1︰（1~6）。
本发明在制备含有乙酰丙酮钴的溶液A、制备溶液B（混合有催化剂1,5-环辛二烯和二乙基环戊二烯基铝的苯和/或苯衍生物溶液）以及制备的过程采用同一种溶剂（苯和/或苯衍生物）；催化剂的制备过程不需要结晶蒸馏等提纯工序，无需单独把催化剂分离出来，可以直接用于制备2,2-联吡啶的合成反应，可以省去不同溶剂的回收过程，减少催化剂的损失，并能保证在制备2,2-联吡啶时1,5-环辛二烯环戊二烯基钴保持良好的催化活性，降低了催化剂的制备难度和成本，大大提高了生产安全，适用于工业化大规模制备2,2-联吡啶。
本发明将2-氰基吡啶与乙炔环合制备2,2-联吡啶，原子利用率高，有利于降低经济成本，反应过程为无水反应过程，2-氰基吡啶与乙炔过程没有废水生成，绿色环保。
具体实施方式
下面结合实施例对本发明进行详细说明。
实施例1
一种含有催化剂的制备方法，包括以下步骤：
a) 在反应釜中通入氮气保护，强力搅拌加入12份乙酰丙酮、500份甲苯，控制反应体系的温度在10℃以下，缓慢加入11份氢氧化钴，升温至溶剂开始通过精馏塔蒸发回流，利用苯和/或苯衍生物与水可以形成共沸反应液进行连续蒸发脱水，凝液在分水器内分水处理，上层苯和/或苯衍生物返回精馏塔，塔顶水和苯、及水共沸物经冷凝再回到分水器中，塔底苯和/或苯衍生物返回到反应体系内继续带水，直至回流夜中水分含量小于300ppm，关闭反应釜到精馏塔连接的气相和液相回流管道，降温得到含有乙酰丙酮钴的溶液A，继续降温至-10℃以下备用；
b) 在氮气保护下，将6份环戊二烯、30份1,5-环辛二烯、350份甲苯搅拌降温至-10℃以下，搅拌加入123份三乙基铝，得到溶液B，即混合有1,5-环辛二烯和二乙基环戊二烯基铝的甲苯溶液；
c) 在0℃以下将溶液B缓慢加入溶液A中，搅拌升温至25℃，反应3h，过滤，所得滤液即为催化剂1,5-环辛二烯环戊二烯基钴（CoC5H5(C8H12)）的甲苯溶液。
将200份含有CoC5H5(C8H12)的甲苯溶液与225份2-氰基吡啶混合，升温至100℃后，通入乙炔并控制反应温度为120~200℃，反应2h后得2,2-联吡啶溶液，所得溶液中2-氰基吡啶的转化率达到94.5%。
实施例2
一种含有催化剂的制备方法，包括以下步骤：
a) 在反应釜中通入氮气保护，强力搅拌加入12份乙酰丙酮、500份二甲苯，控制反应体系的温度在10℃以下，缓慢加入12份氢氧化钴，升温到溶剂开始通过精馏塔蒸发回流，利用苯和/或苯衍生物与水可以形成共沸反应液进行连续蒸发脱水，凝液在分水器内分水处理，上层苯和/或苯衍生物返回精馏塔，塔顶水和苯、及水共沸物经冷凝再回到分水器中，塔底苯和/或苯衍生物返回到反应体系内继续带水，直至回流夜中水分含量小于300ppm，关闭反应釜到精馏塔连接的气相和液相回流管道，降温得到含有乙酰丙酮钴的溶液A，继续降温至-10℃以下备用；
b) 在氮气保护下，将7份环戊二烯、29份1,5-环辛二烯、350份二甲苯搅拌降温至-10℃以下，搅拌加入125份三乙基铝，得到溶液B，即混合有1,5-环辛二烯和二乙基环戊二烯基铝的二甲苯溶液；
c) 在0℃以下将溶液B缓慢加入溶液A中，搅拌升温至25℃，反应4h，过滤，所得滤液即为含有催化剂1,5-环辛二烯环戊二烯基钴（CoC5H5(C8H12)）的二甲苯溶液。
将200份含有CoC5H5(C8H12)的二甲苯溶液与245份2-氰基吡啶混合，升温至100℃后，通入乙炔并控制反应温度为120~200℃，反应2h后得2,2-联吡啶溶液，所得溶液中2-氰基吡啶的转化率达到94%。
实施例3
一种含有催化剂的制备方法，包括以下步骤：
a) 在反应釜中通入氮气保护，强力搅拌加入12份乙酰丙酮、500份苯，控制反应体系的温度在10℃以下，缓慢加入13份氢氧化钴，升温到溶剂开始通过精馏塔蒸发回流，利用苯和/或苯衍生物与水可以形成共沸反应液进行连续蒸发脱水，凝液在分水器内分水处理，上层苯和/或苯衍生物返回精馏塔，塔顶水和苯、及水共沸物经冷凝再回到分水器中，塔底苯和/或苯衍生物返回到反应体系内继续带水，直至回流夜中水分含量小于300ppm，关闭反应釜到精馏塔连接的气相和液相回流管道，降温得到含有乙酰丙酮钴的溶液A，继续降温至-10℃以下备用；
b) 在氮气保护下，将8份环戊二烯、28份1,5-环辛二烯、350份甲苯搅拌降温至-10℃以下，搅拌加入136份三乙基铝，得到溶液B，即混合有1,5-环辛二烯和二乙基环戊二烯基铝的苯溶液；
c) 在0℃以下将溶液B缓慢加入溶液A中，搅拌升温至25℃，反应5h，过滤，所得滤液即为含有催化剂1,5-环辛二烯环戊二烯基钴（CoC5H5(C8H12)）的苯溶液。
将200份含有CoC5H5(C8H12)的苯溶液与265份2-氰基吡啶混合，升温至100℃后，通入乙炔并控制反应温度为120~200℃，反应2h后得2,2-联吡啶溶液，所得溶液中2-氰基吡啶的转化率达到96%。
实施例4
一种含有催化剂的制备方法，包括以下步骤：
a) 在反应釜中通入氮气保护，强力搅拌加入12份乙酰丙酮、500份甲苯，控制反应体系的温度在10℃以下，缓慢加入14份氢氧化钴，升温到溶剂开始通过精馏塔蒸发回流，利用苯和/或苯衍生物与水可以形成共沸反应液进行连续蒸发脱水，凝液在分水器内分水处理，上层苯和/或苯衍生物返回精馏塔，塔顶水和苯、及水共沸物经冷凝再回到分水器中，塔底苯和/或苯衍生物返回到反应体系内继续带水，直至回流夜中水分含量小于300ppm，关闭反应釜到精馏塔连接的气相和液相回流管道，降温得到含有乙酰丙酮钴的溶液A，继续降温至-10℃以下备用；
b) 在氮气保护下，将9份环戊二烯、30份1,5-环辛二烯、350份甲苯搅拌降温至-10℃以下，搅拌加入125份三乙基铝，得到溶液B，即混合有1,5-环辛二烯和二乙基环戊二烯基铝的甲苯溶液；
c) 在0℃以下将溶液B缓慢加入溶液A中，搅拌升温至25℃，反应4h，过滤，所得滤液即为含有催化剂1,5-环辛二烯环戊二烯基钴（CoC5H5(C8H12)）的甲苯溶液。
将200份含有CoC5H5(C8H12)的甲苯溶液与245份2-氰基吡啶混合，升温至100℃后，通入乙炔并控制反应温度为120~200℃，反应2h后得2,2-联吡啶溶液，所得溶液中2-氰基吡啶的转化率达到95%。
Claims (4)
1.利用催化剂制备2,2-联吡啶的方法，其特征在于，将催化剂1,5-环辛二烯环戊二烯基钴的苯和/或苯衍生物溶液与2-氰基吡啶混合，升温至100℃后，通入乙炔于120~200℃反应2h,得2,2-联吡啶溶液；所述催化剂的制备方法包括以下步骤：
a) 在惰性气体保护下，混合乙酰丙酮、氢氧化钴、苯和/或苯衍生物，所述苯衍生物为甲苯、二甲苯或二者的混合物，然后蒸馏分水，直至回流液中水分含量小于300ppm，得到含有乙酰丙酮钴的溶液A，降温至-10℃以下备用；
b) 在惰性气体保护下，将环戊二烯、1，5-环辛二烯、苯和/或苯衍生物混合降温至-10℃以下，加入三乙基铝混匀，得到溶液B；
c) 在0℃以下将步骤b)所得溶液B缓慢加入步骤a)所得溶液A中，搅拌升温至25℃，反应3~5h，过滤，所得滤液为催化剂1,5-环辛二烯环戊二烯基钴的苯和/或苯衍生物溶液。
2.根据权利要求1所述的利用催化剂制备2,2-联吡啶的方法，其特征在于，步骤a)中，各物料的重量份数为：乙酰丙酮12份、苯和/或苯衍生物500份、氢氧化钴11~14份；步骤b)中，各物料的重量份数为：环戊二烯6~9份、1，5-环辛二烯28~30份、苯和/或苯衍生物350份、三乙基铝123~126份。
3.根据权利要求1所述的利用催化剂制备2,2-联吡啶的方法，其特征在于，步骤b)中加入三乙基铝过程中，控制反应体系的温度在10℃以下。
4.根据权利要求3所述的利用催化剂制备2,2-联吡啶的方法，其特征在于，催化剂1,5-环辛二烯环戊二烯基钴的苯和/或苯衍生物溶液与2-氰基吡啶的重量份数比为1︰（1~6）。
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