CN116174040A - 一种乙烯三聚催化剂组合物及其应用 - Google Patents
一种乙烯三聚催化剂组合物及其应用 Download PDFInfo
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- 239000005977 Ethylene Substances 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 34
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
本发明公开了一种乙烯三聚催化剂组合物及其应用，所述乙烯三聚催化剂组合物由铬化物、吡啶化合物、烷基铝助剂和给电子体组成，本发明首次在乙烯三聚催化剂体系中使用吡啶化合物作为配体，即本发明由铬金属盐、吡啶化合物、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（吡咯及其衍生物为配体），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。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种乙烯三聚催化剂组合物及其应用。
背景技术
以线性α-烯烃与乙烯共聚合成的线性低密度聚乙烯（LLDPE）具有优异的抗撕裂性、抗冲击强度，且使用也寿命也大大提高，故该类树脂也被广泛应用在包装膜、温室膜和地膜方面。在共聚单体方面，1-己烯或1-辛烯与乙烯共聚合成的LLDPE的性能远远优于1-丁烯与乙烯共聚合成的LLDPE，因而，研发人员对长链的线性α烯烃的制备进行了广泛研究。在众多制备线性α烯烃的技术中，以铬系催化剂应用最为广泛。又以Phillips公司（US5856257）最为突出，该公司以铬盐、含氮配体、2种助催化剂组成的四组分催化体系在乙烯选择性齐聚反应中表现出优异的性能，其中1-己烯的选择性可达90%以上，该公司以此催化剂为基础成功实现了工业化。随后，各大公司对乙烯选择性齐聚进行了大量的研究并取得不错，国内以中石油、中石化最为突出，中石油自主研发的催化体系在大庆石化和独山子石化分别建成了5kt/a和2wt/a的1-己烯生产装置，中石化自主研发的催化体系在燕山石化建成5wt/a的1-己烯生产装置。
1999年，Phillips申请专利US5856257采用铬系催化剂催化乙烯发生选择性三聚反应生成选择性高达95%的1-己烯，该装置工艺是目前世界上最先进的1-己烯工艺技术。中石化在专利CN103787935B披露了一种无毒或毒性很小的硫氮杂原子配体的合成方法，该方法采用R1SR2X与氨在碱性条件下反应得到（R1SR2)2NH，以该配体制得的三氯化铬（二（2-苯硫基-乙基）-胺）为催化剂催化乙烯三聚反应，1-己烯的选择性高达99.8%
中石油专利CN108686706B保护了一种脱氢吡啶轮烯型配体，1-己烯选择性为97.65%。天津科技大学在专利CN107597191A公开了一种用于乙烯三聚制备1-己烯的催化剂，其中的含P化合物是具有联苯或联萘骨架的双膦配体。该催化剂用于乙烯三聚制备1-己烯的选择性接近100%，避免了后续的分离过程，降低了工业成本。
由此可见，在乙烯选择性三聚催化体系中，人们把注意力集中在合成新的配体上，以期获得更高的1-己烯选择性，同时降低副产物的选择性。
发明内容
现有技术仍然存在催化剂活性低、原料成本高、1-己烯的选择性低、聚合过程中会生成少量聚合物，影响装置连续运行的问题，为解决上述问题，本发明提供了一种乙烯三聚催化剂组合物及其应用，在金属铬盐、烷基铝、有机氯组分保持不变的基础上，使用吡啶化合物作为配体，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。
为实现上述目的，本发明的技术方案为：
一种乙烯三聚催化剂组合物，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）吡啶化合物：结构式如下：
（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、吡啶化合物、烷基铝助剂、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。
上述乙烯三聚催化剂组合物的应用：将乙烯三聚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，本发明的乙烯三聚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）乙烯三聚催化剂组合物制备：将乙烯三聚催化剂组合物中各成分分别溶于经除水处理的惰性溶剂制备成铬化物溶液、吡啶化合物溶液、烷基铝助剂溶液、给电子体溶液备用；
（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、吡啶化合物溶液、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：
（1）本发明首次在乙烯三聚催化剂体系中使用吡啶化合物作为配体，即本发明由铬金属盐、吡啶化合物、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。
（2）本发明中吡啶环上通过连接不同的基团，与金属铬、三乙基铝以及含氯给电子体共同作用，可以灵活调节其给电子性能和空间结构，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，且与吡咯相比，含有不同基团的吡啶化合物具有与之更大的空间构型，因此在乙烯三聚催化剂中与金属配位后具有合适的空间位阻，可以有效降低聚合物的生成。
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。高压釜抽真空条件下加热至100℃恒温1 h，除去残留的水、氧和含氧杂质。然后将温度设置为90 ℃，使其自然降温，同时用氮气置换数次。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：吡啶化合物：三乙基铝：六氯乙烷=1: 1:100: 10），其中吡啶化合物1中R1=R3=R5=Cl，R2=R4=H。控制反应压力为3MPa，反应1h后后停止反应，关闭进气口阀门，迅速降温至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120℃，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，不同之处在于将乙酰丙酮铬和吡啶化合物比例改为1:5，数据结果见表1。
实施例5
同实施例1，不同之处在于吡啶化合物2中R1=R5=CH3，R2=R3=R4=H，数据结果见表1。
对比例1
同实施例1，不同之处在于将吡啶化合物1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)
1.一种乙烯三聚催化剂组合物，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）吡啶化合物：结构式如下：
（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、吡啶化合物、烷基铝助剂、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、吡啶化合物、烷基铝助剂、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、吡啶化合物、烷基铝助剂、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任一项所述乙烯三聚催化剂组合物的应用，其特征在于：将乙烯三聚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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