CN113996343A - 一种制备1-辛烯的催化剂组合物 - Google Patents
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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Abstract
本发明公开了一种制备1‑辛烯的催化剂组合物，在金属/配体/烷基铝助催化剂基础上加入第二配体硅氧烷类化合物，与第一配体协同效应，优化催化剂组合物的配位能力，在催化过程中能有效构成双金属中心，提高催化剂的活性，保持1‑辛烯的高选择性，同时进一步降低副产物聚乙烯的生成。协同作用突出，经济效益显著。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种制备1-辛烯的催化剂组合物。
背景技术
1-辛烯作为一种重要的有机单体，在合成高聚物、高性能润滑油和洗涤剂方面有着广阔的应用，以合成聚乙烯为例，以1-辛烯为共聚单体合成的线性低密度聚乙烯（LLDPE）能显著提高其机械性能、光学性能、抗冲击性能和弹性等。1-辛烯和乙烯共聚制备的聚烯烃弹性体（POE）具有优异的力学性能、流变性能和耐紫外光性能，可用于汽车部件，建材，电线电缆，防水卷材、改性剂、医疗器械和儿童玩具等。此外，1-辛烯还能用于合成增塑剂、脂肪酸、洗涤剂和润滑油添加剂等。
目前工业上所使用的1-辛烯主要靠乙烯非选择性齐聚制得，该类工艺生产的α烯烃为C4-C20为主的混合物，产物符合Schulz-Flory分布，在工艺末端要连续精馏才能得到纯净的1-辛烯。而乙烯选择性齐聚可以选择性地生成一到两种α烯烃，生产效率显著提升。目前乙烯二聚制备1-丁烯、三聚制备1-己烯均已实现工业化。Phillips公司和Amoco公司的工艺中1-己烯的选择性普遍高于90%，纯度也高于92%。随后三聚制备1-己烯先后在中石化和中石油两个公司实现国产化，但四聚制备1-辛烯技术仍然被国外垄断。
在乙烯选择性四聚方面，已有相关报道。如中石化的CN102040624B、CN102451759B、CN103100420A、CN105268480B、CN105498840B、CN105562095B、CN105562101B、CN105562102B、CN105562103B、CN105566037B、CN107282128B；中石油的CN103285926A、迈瑞尔公司的CN110801864 A；Sasol公司的US10539517、US10538088、US11629533、US11993396等均公开使用铬化合物/配体/助剂催化剂体系进行乙烯选择性齐聚，产物中1-辛烯选择性可大于70%。但上述技术仍然存在催化剂活性较低和副产物聚烯烃含量高的问题。分析可知，乙烯四聚制备1-辛烯技术的关键在于选择合适的配体提供合适的给电子能力和空间构型，从而有利于1-辛烯的合成。但是当前的主流技术是使用SASOL公司披露的PNP（bis(diarylphosphino)-amine）或者类似衍生物作为配体（US7511183）与有机铬以及MAO形成乙烯四聚催化剂体系。由于单一配体提供的给点力能力受限，达到的效果不是很理想。
发明内容
本发明的目的在于提供一种制备1-辛烯的催化剂组合物，在金属/配体/烷基铝助催化剂基础上加入第二配体硅氧烷类化合物，与第一配体协同效应，优化催化剂组合物的配位能力，在催化过程中能有效构成双金属中心，提高催化剂的活性，保持1-辛烯的高选择性，同时进一步降低副产物聚乙烯的生成。协同作用突出，经济效益显著。
为实现上述目的，本发明采用如下技术方案：
一种乙烯四聚制备1-辛烯的催化剂组合物，含有以下组分的组合物：
（1）铬化物a：为异辛酸铬、乙酰丙酮铬和/或四氢呋喃氯化铬；
（2）第一配体b：PNP（bis(diarylphosphino)-amine）；
（3）烷基铝助催化剂c；
（4）第二配体d：硅氧烷类化合物，包括但不限于环己基甲基二甲氧基硅氧烷、苯基三乙氧基硅氧烷和二苯基二甲氧基硅氧烷；
a、b、c和d的摩尔比为：1:0.1~100:1~1000: 0.5~100。
所述烷基铝助催化剂为甲基铝氧烷、三乙基铝、三甲基铝中的一种。
本发明的有益效果在于：首次使用硅氧烷化合物作为第二配体与第一配PNP体协同作为电子调节组分与金属中心构成催化剂体系用于乙烯四聚反应；催化剂活性明显提高；产物中聚乙烯显著降低；目标产物1-辛烯可保持较高选择性。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
乙烯齐聚反应在300 mL高压反应釜中进行。反应前先将反应釜釜体置于烘箱中120℃烘干过夜，连接到评价体系，密封，抽真空条件下加热至100℃恒温1 h（尾气阀关闭），除去残留的水、氧和含氧杂质。然后将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，确保空气已被置换干净。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。打开尾气阀，在搅拌条件下使用注射器依次注入90 mL环己烷溶剂、一定量甲基铝氧烷(甲基铝氧烷为1.5 mol/L的甲苯溶液)和一定量的配体溶液，待温度稳定至设定温度后，将过渡金属溶液注入反应釜中，随后再用10 mL的环己烷洗注射器，确保全部催化剂组分已注入到反应器中。搅拌3~5min后，关闭尾气阀，调节减压阀，待压力升至设定压力后开始计时，反应一定时间后关闭乙烯气体，记录质量流量计数据，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。开启反应釜后，尽快称量液体和固体总重，在注射器中塞入适量石英棉，取1~2mL液体样品过滤后转移至样品瓶，放至GC-MS上分析产物组分和比例。将剩余样品过滤，滤纸提前称量并记录质量，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，将所有聚合物置于真空烘箱中60oC干燥过夜，分别称重，计算获得纯质量。通过MS可以标定液体产物组成。结合液体和固体总重，固体质量和GC结果可计算各组分选择性，结合催化剂使用量可计算催化剂活性。
实施例1-3和对比例中相关反应条件汇总于表1。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (5)
1.一种制备1-辛烯的催化剂组合物，其特征在于：由以下组分组成：铬化合物、PNP配体、烷基铝、硅氧烷类化合物的摩尔比为：1：0.1~100：1~1000：0.5~100。
2.根据权利要求1所述的组合物，其特征在于：所述的铬化合物为异辛酸铬、乙酰丙酮铬、四氢呋喃氯化铬中的至少一种。
3.根据权利要求1所述的组合物，其特征在于：所述的烷基铝为甲基铝氧烷、三乙基铝、三甲基铝中的一种。
4.根据权利要求1所述的组合物，其特征在于：所述的硅氧烷类化合物为环己基甲基二甲氧基硅烷、苯基三乙氧基硅烷、二苯基二甲氧基硅烷中的一种。
5.一种如权利要求1所述的组合物在乙烯四聚制备1-辛烯中的应用。
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