CN113880879B - 一种芴二膦类化合物的合成及其在乙烯齐聚中的应用 - Google Patents
一种芴二膦类化合物的合成及其在乙烯齐聚中的应用 Download PDFInfo
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- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
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Abstract
本发明属于乙烯四聚反应技术领域,具体涉及一种芴二膦类化合物的合成及其在乙烯齐聚中的应用。具体芴二膦类化合物为或芴二膦类化合物作为乙烯四聚催化剂的配体,在催化过程中能有效构成双金属中心提高1‑辛烯的选择性,同时可有效抑制聚乙烯副产物的生成。其作为催化剂组分在催化乙烯齐聚时,具有催化剂活性高、产物中1‑辛烯选择性高、聚乙烯副产物少等优点。
Description
技术领域
本发明属于乙烯四聚反应技术领域,具体涉及一种芴二膦类化合物的合成及其在乙烯齐聚中的应用。
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。
然而,目前工业上所使用的1-辛烯仍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,因而在工艺末端需连续精馏才能要得到纯净的1-辛烯,需消耗大量的能量。乙烯选择性齐聚是与非选择性齐聚相反的一种制备α烯烃的工艺,该类工艺选择性地生成一到两种α烯烃,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。其中由Phillips公司、Amoco公司和日本出光公司各自发展出独立工艺,成功在世界范围内推广,其中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,打破了国外的技术垄断。但截至目前四聚制备1-辛烯技术仍然被国外掌握。
在乙烯选择性四聚方面,已有大量的专利。如中石化申请的专利CN102040624B、CN102451759B、CN103100420A、CN105268480B、CN105498840B、CN105562095B、CN105562101B、CN105562102B、CN105562103B、CN105566037B、CN107282128B;中石油的CN103285926 A、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%。
根据大量披露的专利或报道,现有技术仍然存在副产物聚烯烃含量高的问题,导致乙烯四聚难以实现连续生产。
从上述分析可知,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。现有专利中使用的配体大部分为PNP型结构,合成过程较为复杂,极易吸水造成失活,且容易导致聚合物的行程,不利于长周期运行。
发明内容
本发明的目的在于提供一种芴二膦类化合物的合成方法及其在乙烯四聚中的应用,本发明要求保护的上述芴二膦类化合物作为乙烯四聚催化剂的配体,在催化过程中能有效构成双金属中心提高1-辛烯的选择性,同时可有效抑制聚乙烯副产物的生成。该催化剂催化乙烯齐聚时,具有催化剂活性高、产物中1-辛烯选择性高、聚乙烯副产物少等优点。
为实现上述目的,本发明采用如下技术方案:
所述芴二膦类化合物,具体为式(I)和(II)所示的配体化合物中的任意一种:
式(I)的合成方法分为两步,其中步骤一:通过碱夺取芴上的活泼氢与多聚甲醛发生亲核反应,接着水解得到芴二醇类化合物;步骤二:在三乙胺碱的作用下,芴二醇和二苯基氯化膦发生盐消除反应脱出氯化氢,最后得到目标产物芴二氧膦类化合物;
式(II)的合成方法分为两步,其中步骤一:通过碱夺取芴上的活泼氢与多聚甲醛发生亲核反应,接着水解得到芴二醇类化合物,接着将芴二醇溴代然后和多硫化钠反应得到芴二硫醇;步骤二:在三乙胺碱的作用下,芴二硫醇和二苯基氯化膦发生盐消除反应脱出氯化氢,最后得到目标产物芴二硫膦类化合物。
进一步地,所述芴二膦类化合物在乙烯四聚催化剂中的应用,其中该乙烯四聚催化剂还包括过渡金属化合物以及烷基铝助催化剂。
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;
所述过渡金属化合物选自铬化合物、钼化合物、铁化合物、钛化合物、锆化合物和镍化合物中的至少一种,优选为乙酰丙酮铬、异辛酸铬、三(四氢呋喃)三氯化铬或二(四氢呋喃)二氯化铬中的至少一种;
所述烷基铝助催化剂与乙烯四聚催化剂中金属的摩尔比100:1~1000:1;
所述芴二膦类化合物与乙烯四聚催化剂中金属的摩尔比0.01:1~100:1;优选为0.1:1~10:1;
所述乙烯四聚催化剂进行烯齐聚反应,优选在有机溶剂,更优选在烷烃溶剂中进行乙烯齐聚反应;
进一步地,在所述乙烯齐聚反应中,反应温度为0-200℃,优选为30-100℃;乙烯压力为0.1-20.0MPa,优选为0.5-6.0MPa;反应时间0.5~4h;
进一步地,所述乙烯四聚催化剂进行乙烯三聚和/或四聚反应,优选在有机溶剂、更优选在烷烃中进行乙烯三聚和/或四聚反应。
具体地,所述乙烯四聚催化剂的使用方法,包括以下步骤:
(1)反应前先将反应釜釜体和内衬置于烘箱中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1h(尾气阀关闭),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。
(2)打开尾气阀,在搅拌条件下使用注射器依次注入环己烷溶剂和一定量烷基铝助催化剂,待温度稳定至反应温度后,用注射器注入过渡金属化合物和芴二膦类化合物,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,加入烷基铝助剂,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。
(3)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60℃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。
本发明的显著优点在于:
(1)首次使用芴二膦类化合物作为四聚催化剂的配体与金属中心构成催化剂体系用于乙烯选择性齐聚反应;
(2)产物中1-辛烯选择性高;
(3)产物中聚乙烯含量极少。
附图说明
图1实施例1芴二氧膦配体(目标产物I)的核磁氢谱;
图2实施例1芴二氧膦配体(目标产物I)的核磁磷谱。
具体实施方式
为进一步公开而不是限制本发明,以下结合实例对本发明作进一步的详细说明。
实施例1芴二氧膦配体的制备
9,9-双((二苯基膦基)甲基)芴的合成:
步骤一:
在500mL 2L的三口烧瓶上,装置机械搅拌器、滴液漏斗和导气管。在氮气保护下,采用冰盐浴冷却,向瓶中依次加入100mLDMSO、16.0g多聚甲醛、3.4g乙醇钠、12mL乙醇,开动机械搅拌,冷却反应物料至0℃以下。在30s内迅速加入溶有32.0g芴的100mLDMSO溶液,使反应温度保持12~14℃,反应3min后用3mL浓盐酸终止反应;加入蒸馏水稀释,20min后停止搅拌,进行抽滤,得到固体粗产品,先用乙醇重结晶,再用甲苯重结晶,去除溶剂晾干后得到白色固体9,9-(二甲醇)芴,产率88%。
步骤二:
在100mL圆底烧瓶中依次加入2.26g的9,9-(二甲醇)芴、、5.0mL三乙胺和50mL四氢呋喃溶剂;将混合物冷却至-78℃。在-78℃下滴加8.0mL新蒸馏的二苯基氯化磷溶液,将混合物搅拌3小时,使其达到室温。然后滤出三乙基氯化铵。真空除去挥发物,固体用50mL乙醚洗涤,得到无色粉末,为目标产物9,9-双((二苯基膦基)甲基)芴,产率83%。
实施例2芴二硫膦配体的合成:
步骤一:
在500mL 2L的三口烧瓶上,装置机械搅拌器、滴液漏斗和导气管。在氮气保护下,采用冰盐浴冷却,向瓶中依次加入100mLDMSO、16.0g多聚甲醛、3.4g乙醇钠、12mL乙醇,开动机械搅拌冷却反应物料至0℃以下。在30s内迅速加入溶有32.0g芴的100mL DMSO溶液,使反应温度保持12~14℃,反应3min后用3mL浓盐酸终止反应;加入蒸馏水稀释,20min后停止搅拌,进行抽滤,得到固体粗产品,先用乙醇重结晶,再用甲苯重结晶,去除溶剂晾干后得到白色固体,产率88%。然后将得到的芴二醇溶于50mL甲苯中,向其中加入5mL HBr,室温搅拌反应2h后,再向其中加入2.8g硫氢化钠反应12h。抽干溶剂,使用3x50mL无水乙醚萃取,浓缩、重结晶得到白色晶体9,9-(二甲硫醇)芴,产率87%。
步骤二:
在100mL圆底烧瓶中依次加入2.58g的9,9-(二甲硫醇)芴、5.0mL三乙胺和50mL四氢呋喃溶剂;将混合物冷却至-78℃。在-78℃下滴加8.0mL新蒸馏的二苯基氯化磷溶液,将混合物搅拌5小时,使其达到室温。然后滤出三乙基氯化铵。真空除去挥发物,固体用2x50mL乙醚洗涤,得到白色粉末,为目标产物9,9-双((二苯基硫膦基)甲基)芴,产率76%。
应用例
乙烯齐聚反应在300mL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1h(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90mL环己烷溶剂、一定量甲基铝氧烷(甲基铝氧烷为1.5mol/L的甲苯溶液)和一定量的配体溶液(本发明芴二膦类化合物),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10mL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60℃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。应用例1~4和对比例中相关反应条件汇总于表1。
表1实施例反应条件汇总表
表2本发明应用例和对比例乙烯齐聚活性和产物分布。
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 (9)
1.芴二硫膦配体化合物在催化乙烯四聚制备1-辛烯中的应用,其特征在于:所述芴二硫膦配体化合物的结构式为:
。
2.如权利要求1所述的应用,其特征在于:其合成方法分为两步,其中步骤一:通过碱夺取芴上的活泼氢与多聚甲醛发生亲核反应,接着水解得到芴二醇类化合物,接着将芴二醇溴代然后和硫氢化钠反应得到芴二硫醇;步骤二:在三乙胺的作用下,芴二硫醇和二苯基氯化膦发生盐消除反应脱出氯化氢,最后得到目标产物芴二硫膦配体化合物。
3.如权利要求1所述的应用,其特征在于:乙烯四聚催化剂组分中还包括过渡金属化合物以及烷基铝助催化剂。
4.根据权利要求3所述的应用,其特征在于: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。
5.根据权利要求3所述的应用,其特征在于:所述过渡金属化合物选自铬化合物、钼化合物、铁化合物、钛化合物、锆化合物和镍化合物中的至少一种。
6.根据权利要求3所述的应用,其特征在于:所述烷基铝助催化剂与乙烯四聚催化剂组分中金属的摩尔比100:1~1000:1。
7.根据权利要求3所述的应用,其特征在于:所述芴二硫膦配体化合物与乙烯四聚催化剂组分中金属的摩尔比0.01:1~100:1。
8.根据权利要求3所述的应用,其特征在于:所述乙烯四聚催化剂在有机溶剂进行乙烯齐聚反应,反应温度为0-200℃。
9.根据权利要求8所述的应用,其特征在于:乙烯齐聚反应中乙烯压力为0.1-20.0MPa,反应时间0.5~4h。
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