CN115555049A - 一种用于乙烯三聚的催化剂组合物及其应用 - Google Patents
一种用于乙烯三聚的催化剂组合物及其应用 Download PDFInfo
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Abstract
本发明公开了一种用于乙烯三聚的催化剂组合物，由铬化物、1,10‑邻菲咯啉化合物、烷基铝助剂和给电子体组成，各成分的摩尔比为：1:0.1~100:1~1000:1~1000，其中铬化物为异辛酸铬、乙酰丙酮铬或四氢呋喃氯化铬，烷基铝助剂为三乙基铝、甲基铝氧烷（MAO）、三甲基铝或异丁基铝；给电子体为四氯乙烷或六氯乙烷；本发明以1,10‑邻菲咯啉化合物作为配体的乙烯三聚催化剂体系催化乙烯三聚反应时，具有催化剂活性高、1‑己烯选择性高、产物中聚乙烯副产物少，且在产业化中能降低成本等优点。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种用于乙烯三聚的催化剂组合物及其应用。
背景技术
世界α-烯烃生产商主要集中在美、欧、南非和日本等发达国家和地区，2000年总生产能力达2554kt/a，计划和在建装置能力520kt/a。其中1-己烯占α-烯烃总量的20.4%。世界1-己烯市场将货源偏紧、供不应求、价格趋涨。因此，1-己烯、1-辛烯等高碳α烯烃国产化势在必行。1-己烯和1-辛烯等高碳α-烯烃是聚乙烯的重要共聚单体，也是应用广泛的有机化工原料。1-己烯作为重要的有机原料和化学中间体，主要用于生产高端聚乙烯（PE）。目前，我国PE基本上还都是采用1-丁烯作为共聚单体，但是，1-己烯等高碳α-烯烃共聚树脂具有的优异性能是1-丁烯共聚物树脂难以比拟的，1-丁烯共聚物已是走向淘汰的产品。由1-己烯与乙烯共聚生产的线性低密度聚乙烯（LLDPE）及高密度聚乙烯(HDPE)在聚乙烯的机械加工、耐热性、柔韧性和透明性等方面具有明显优势。特别适合于生产包装膜和农用覆盖膜。世界大多数国家已经采用1-己烯和1-辛烯替代1-丁烯生产LLDPE和HDPE。在气相PE生产工艺中，采用凝聚方法还能以最小的投入实现20%以上的生产增长。世界许多厂家利用这种方法来提高生产效益。
当前乙烯三聚制备1-己烯的主流技术为采用金属铬盐、吡咯化合物、烷基铝、卤代烃（主要为氯代烃）组成的四元催化组合物。如中石化的专利CN102558107A和中石油的专利CN03157351.7均采用上述方式实现了1-己烯的高选择性。本发明在金属铬盐、三乙基铝、四氯乙烷或六氯乙烷组分保持不变的基础上，首次使用1,10-邻菲咯啉化合物作为配体，组成催化剂体系。该配体成本低廉，制备的催化剂活性高，1-己烯选择性高，且生成的聚合物极少，有利于长周期运行。
发明内容
为解决上述问题，本发明提供了一种用于乙烯三聚的催化剂组合物，由铬金属盐、1,10-邻菲咯啉化合物、烷基铝和有机氯化物共同组成乙烯三聚组合物，反应产物中1-己烯选择性高，与已公开的催化剂相比（吡咯化合物为配体），副产物聚乙烯含量极少，且具有更高的活性；在产业化中可通过原位聚合进行乙烯三聚反应，不需要预聚。
为实现上述目的，本发明的技术方案为：
一种用于乙烯三聚的催化剂组合物，包括以下组分：
（1）铬化物：异辛酸铬、乙酰丙酮铬或四氢呋喃氯化铬；
（2）配体：1,10-邻菲咯啉化合物，结构式如下：
，其中R1、R2、R3、R4、R5、R6、R7和R8相同或不同，选自氢、烷基、烷氧基、环烷基或卤素；
（3）烷基铝助剂：三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝；
（4）给电子体：四氯乙烷或六氯乙烷。
进一步地，所述铬化物、1,10-邻菲咯啉化合物、烷基铝助剂和给电子体的摩尔比为：1:0.1~100:1~1000:1~1000；优选为1:0.1~10:1~500:1~50；更优选为1: 1~8：1~100:1~10。
上述用于乙烯三聚的催化剂组合物的应用：将用于乙烯三聚的催化剂组合物中各成分分别溶于惰性溶剂中，以均相催化剂形式依次注入或提前混合均匀注入乙烯三聚反应体系中，随后提高乙烯压力，与催化剂充分接触，进行乙烯三聚反应，得到1-己烯。
进一步地，乙烯三聚反应的条件为：温度为30~250℃，压力为0.5~20MPa，时间为0.1~2h；所述惰性溶剂包括苯、甲苯、环己烷、甲基环己烷、正庚烷或正己烷。
进一步地，本发明的用于乙烯三聚的催化剂组合物在催化乙烯三聚反应中的应用具体包括以下步骤：
（1）用于乙烯三聚的催化剂组合物制备：将用于乙烯三聚的催化剂组合物中各成分分别溶于经除水处理的惰性溶剂中制备成铬化物、1,10-邻菲咯啉化合物、烷基铝助剂和给电子体四种溶液备用；
（2）反应前先将反应釜釜体和内衬置于烘箱中120 ℃烘干过夜，安装到反应釜上后密封，抽真空条件下加热至105℃恒温1 h，除去残留的水、氧和含氧杂质，然后温度设置为反应温度，使其自然降温，同时氮气填充，随后抽真空，重复三次，确保空气被置换干净，然后用真空泵抽走氮气，用乙烯填充，重复三次，保证釜体充满乙烯；
（3）在搅拌条件下使用注射器注入步骤（1）制得的烷基铝助剂溶液，待温度稳定至反应温度后，用注射器依次注入铬化物溶液、1,10-邻菲咯啉化合物溶液、给电子体溶液，关闭尾气阀，调节减压阀，待压力升至预定压力值后开始计时，并记录质量流量计数据，反应结束后关闭乙烯气体，反应停止，关闭进气口阀门，卸下反应釜体，浸泡至冰水浴中使反应釜冷却至10℃以下。
开启尾气阀泄压后在搅拌条件下注入一定量5 ml 10%HCl/乙醇溶液，使烷基铝助剂淬灭，随后称取重量记录。取少量液相产物使用GC-MS分析产物。将剩余样品过滤，滤纸提前称量记录质量，随后搅拌桨上的聚合物用勺子刮下来，用溶剂清洗至烧杯里，将所得的聚合物置于真空烘箱中60℃干燥过夜，分别称重，计算获得聚合物的质量。根据MS可标定组分种类，根据GC结果结合液相产物质量和聚合物质量，可计算获得各产物的选择性以及催化剂活性。
本发明与现有技术相比：本发明中1,10-邻菲咯啉化合物中苯环和旁边的两个含氮六元环形成共轭，构成了大π键，三个六元环具有较强的刚性，在配位过程中结构稳定，不易转动，可以较为稳定的和金属中心形成单一活性中心，可以和活性中心发生较好的作用。与金属铬、三乙基铝以及含氯给电子体共同作用，可以更加灵活地调节给单子性能，高效的催化乙烯分子与金属形成七元环，经β脱氢后释放一个1-己烯分子，且与吡咯化合物相比，1,10-邻菲咯啉化合物具有较大的空间位阻，可以有效降低聚合物的生成，有利于长周期运行。
具体实施方式
下面结合具体实施例对本发明进一步说明，但本发明不限于此。
实施例1
乙烯齐聚反应在高压不锈钢反应釜中进行。反应前高压反应釜在抽真空条件下加热至100℃恒温1 h，然后将温度设置为80℃，使其自然降温，同时氮气置换数次，然后用乙烯置换数次，保证釜体充满乙烯。随后依次向其中加入溶剂环己烷和催化剂，催化剂中中乙酰丙酮铬：1,10-邻菲咯啉：三乙基铝：六氯乙烷=1: 1:100: 10。控制反应压力为4.5MPa，反应1h后后停止反应，关闭进气口阀门，卸下反应釜体，浸泡至冰水浴中使反应釜冷却至10℃以下。开启尾气阀泄压后在搅拌条件下注入5 mL 10% HCl/乙醇溶液，使烷基铝淬灭，随后称取重量记录。取少量液相产物使用GC-MS分析产物。将剩余样品过滤，滤纸提前称量记录质量，随后搅拌桨上的聚合物用勺子刮下来，用溶剂清洗至烧杯里，将所得的聚合物置于真空烘箱中60℃干燥过夜，分别称重，计算获得聚合物的质量。根据MS可标定组分种类，根据GC结果结合液相产物质量和聚合物质量，可计算获得各产物的选择性以及催化剂活性。数据结果见表1。
实施例2
同实施例1，不同之处在于反应温度为130℃，数据结果见表1。
实施例3
同实施例1，不同之处在于反应压力为6MPa，数据结果见表1。
实施例4
同实施例1，不同之处在于溶剂为庚烷，，数据结果见表1。
实施例5
同实施例1，不同之处在于将乙酰丙酮铬和六氯乙烷的比例改为1:5，数据结果见表1。
对比例1
同实施例1，不同之处在于将1,10-邻菲咯啉改为吡咯，数据结果见表1。
表1 本发明的实施例和对比例反应条件及反应性能汇总表
以上实施例仅为了清楚的说明本发明内容，本发明的实施方式并不限制于此。凡在本发明的精神与原则之内，所做的任何修改、替换、改进等均应包含在本发明的保护范围之内。
Claims (7)
1.一种用于乙烯三聚的催化剂组合物，其特征在于：包括以下组分：
（1）铬化物：异辛酸铬、乙酰丙酮铬或四氢呋喃氯化铬；
（2）配体：1,10-邻菲咯啉化合物，结构式如下：
，其中R1、R2、R3、R4、R5、R6、R7和R8相同或不同，选自氢、烷基、烷氧基、环烷基或卤素；
（3）烷基铝助剂：三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝；
（4）给电子体：四氯乙烷或六氯乙烷。
2.根据权利要求1所述的乙烯三聚催化剂组合物，其特征在于：所述铬化物、1,10-邻菲咯啉化合物、烷基铝助剂和给电子体的摩尔比为：1:0.1~100:1~1000:1~1000。
3.根据权利要求2所述的乙烯三聚催化剂组合物，其特征在于：所述铬化物、1,10-邻菲咯啉化合物、烷基铝助剂和给电子体的摩尔比为1:0.1~10:1~500:1~50。
4.根据权利要求3所述的乙烯三聚催化剂组合物，其特征在于：所述铬化物、1,10-邻菲咯啉化合物、烷基铝助剂和给电子体的摩尔比为1: 1~8：1~100:1~10。
5.一种如权利要求1-4任一项所述用于乙烯三聚的催化剂组合物的应用，其特征在于：将用于乙烯三聚的催化剂组合物中各成分分别溶于惰性溶剂中，以均相催化剂形式依次注入或提前混合均匀注入乙烯三聚反应体系中，随后提高乙烯压力，与催化剂充分接触，进行乙烯三聚反应，得到1-己烯。
6.根据权利要求5所述的应用，其特征在于：乙烯三聚反应的条件为：温度为30~250℃，压力为0.5~20MPa，时间为0.1~2h。
7.根据权利要求5所述的应用，其特征在于：所述惰性溶剂包括苯、甲苯、环己烷、甲基环己烷、正庚烷或正己烷。
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