CN116589613A - 一种单茂钛催化剂的制备方法与在烯烃聚合的应用 - Google Patents
一种单茂钛催化剂的制备方法与在烯烃聚合的应用 Download PDFInfo
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Abstract
本发明提供了一种如式Ⅰ所示的单茂钛催化剂。本发明合成的单茂钛催化剂属于限制几何构型催化剂(CGC),喹啉环的引入使该单茂钛催化剂具有催化活性高、热稳定性好等优点。通过本发明合成的单茂钛催化剂与助催化剂(有机铝化物或有机硼一种或多种)联用,可以高效催化烯烃单体均聚或共聚。
Description
技术领域
本发明属于化工催化剂技术领域,特别涉及一种单茂钛催化剂的制备方法与在烯烃聚合的应用。
背景技术
聚烯烃在工业领域有广泛的应用,如开发新型树脂、橡胶材料和塑料制品等等。
目前茂金属催化剂被证明可高效催化烯烃聚合,且其结构中具有过渡金属独特的单活性位点的特点,从而易于调控聚合物的分子结构得到不同性能的聚烯烃材料。
其中,茂金属催化剂中的一类限制几何构型催化剂(CGC),结构特点为过渡金属一端与环戊二烯或环戊二烯衍生物相连,另一端与杂原子基团相连,两端的基团再由桥基相连,该半夹心结构改善了茂金属催化剂的热稳定性、催化活性、立体选择性,使得茂金属催化剂在烯烃聚合中的应用更加广泛。
因此,开发新型单茂金属催化剂有利于为烯烃聚合工艺和应用提供技术储备。
发明内容
本发明的目的在于提供一种单茂钛催化剂的制备方法与在烯烃聚合的应用。
本发明提供了一种单茂钛催化剂,其中,所述单茂钛催化剂的分子结构式如式Ⅰ所示:
式Ⅰ,
其中,R1为氢,或C1~C10的直链、支链或异构化的烷基,R2为氢,或C1~C10的直链、支链或异构化的烷基;或者,R1为甲基或苯基,R2为甲基或苯基。
本发明还提供了为得到上述单茂钛催化剂的含单茂的桥连配体的制备方法。其中,所述配体的分子结构式如式Ⅱ所示:
式Ⅱ,
其中,R1为氢,或C1~C10的直链、支链或异构化的烷基,R2为氢,或C1~C10的直链、支链或异构化的烷基;或者,R1为甲基或苯基,R2为甲基或苯基。
本发明所述单茂钛催化剂与助催化剂共同组成催化体系,在乙烯均聚、丙烯均聚和乙烯与1-辛烯共聚等烯烃聚合中应用。
本发明提供的单茂钛催化剂属于限制几何构型催化剂,具有良好的热稳定性、催化活性和立体选择性,通过该催化体系得到的烯烃聚合物具有分子量较高和分子量分布窄等优点。
本发明的其他特征和优点将在具体实施方式部分予以说明。
附图说明
为更好理解本发明单茂钛催化剂的制备方法,附图提供了反应流程图。
图1是本发明制备单茂钛催化剂的反应流程图。
实施方式
下面将通过具体实施方式和实施例对本发明进行详细的描述,本发明的特征和优点将完整、清晰地呈现。应当理解的是,所描述具体实施方式和实施例只是列举的本发明的一部分,仅用于解释和说明,而非限制本发明。
本发明提供的单茂钛催化剂的分子结构式如式Ⅰ所示:
式Ⅰ,
其中,R1为氢,或C1~C10的直链、支链或异构化的烷基,R2为氢,或C1~C10的直链、支链或异构化的烷基;或者,R1为甲基或苯基,R2为甲基或苯基。
其中,所述的C1~C10的直链、支链或异构化的烷基可以包括但不限于:甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基。
优选地,R1为甲基,R2为甲基,结构如式Ⅲ所示;或者,R1为苯基,R2为甲基,结构如式Ⅳ所示;或者,R1和R2为苯基,结构如式Ⅴ所示:
式Ⅲ,/>式Ⅳ,/>式Ⅴ。
本发明用于制备单茂钛催化剂的桥连配体的结构如式Ⅱ所示:
式Ⅱ,
其中,R1为氢,或C1~C10的直链、支链或异构化的烷基,R2为氢,或C1~C10的直链、支链或异构化的烷基;或者,R1为甲基或苯基,R2为甲基或苯基。
其中,所述的C1~C10的直链、支链或异构化的烷基可以包括但不限于:甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基。
所述桥连配体的制备方法,其特征在于,组分和配比为:
(1)A组分结构式如式Ⅵ所示,B组分分子结构式如式Ⅶ所示:
式Ⅵ,/>式Ⅶ,
其中,R1为氢,或C1~C10的直链、支链或异构化的烷基,R2为氢,或C1~C10的直链、支链或异构化的烷基;或者,R1为甲基或苯基,R2为甲基或苯基;
(2)配比:摩尔比为n(A)∶n(B)=1∶1。
本发明中单茂钛桥连配体(式Ⅱ)的具体制备步骤为:在氮气保护的环境下,将1份A组分和1份B组分溶于四氢呋喃溶液中,以正丁基锂为催化剂,在-60 ℃至0 ℃下反应12至20小时,产物冷却过滤得到配体。
将上述配体(式Ⅱ)与四氯化钛反应得到单茂钛催化剂,具体制备方法为:在氮气环境里,采用如式Ⅱ的配体1份溶解在石油醚中,缓慢滴加1份溶解在石油醚中的氯化钛,在-60 ℃至-40 ℃反应2-6小时。将反应液减压抽滤,产物溶解于甲苯中重结晶,真空干燥后得到单茂钛催化剂。
本发明中提供了一种单茂钛催化剂的制备方法与在烯烃聚合的应用,该单茂钛催化剂与助催化剂共同组成催化体系。所述的助催化剂为:甲基铝氧烷、乙基铝氧烷、三异丁基铝B(C6F5)3、[PhMe2NH][B(C6F5)4]和[Ph3C][B(C6F5)4]一种或多种联用。茂钛催化剂与助催化剂摩尔比优选为:有机铝化合物中的铝对茂钛化合物的摩尔比为(1~300)∶1;硼化物中的硼对茂钛化合物的摩尔比为10∶1。
本发明还提供乙烯均聚、丙烯均聚和乙烯与1-辛烯共聚三种聚合方法。
聚乙烯制备步骤为:反应釜除氧除水,通入氮气保护,加入含一定量助催化剂的甲苯溶液,通入乙烯气体置换氮气直至饱和,平衡10~30分钟,加入含有一定量的单茂钛甲苯溶液,在总压力为1.0大气压、40~60 ℃聚合0.2~0.5小时,加入乙醇盐酸溶液终止反应,过滤,产物在50~60 ℃真空干燥。
聚丙烯制备步骤为:反应釜除氧除水,通入氮气保护,加入含一定量助催化剂的甲苯溶液,通入丙烯气体置换氮气直至饱和,平衡10~30分钟,加入含有一定量的单茂钛甲苯溶液,在总压力为1.0大气压、40~60 ℃聚合0.5~1小时,加入乙醇盐酸溶液终止反应,过滤,产物在50~60 ℃真空干燥。
乙烯/1-辛烯共聚物制备步骤为:反应釜除氧除水,通入氮气保护,加入含一定量助催化剂的甲苯溶液,再加入一定量的1-辛烯溶液,通入乙烯气体置换氮气直至饱和(乙烯/1-辛烯=3~15 mol),平衡10~30分钟,加入含有一定量的单茂钛甲苯溶液,在总压力为1.0大气压、40~60 ℃聚合0.2~1小时,加入乙醇盐酸溶液终止反应,过滤,产物在50~60 ℃真空干燥。
以下将结合实施例对本发明提供的一种单茂钛催化剂的制备方法与在烯烃聚合的应用进行详细描述。
实施例1:单茂钛桥连配体1a的制备:在氮气保护的环境下,将1 mmol 7-溴喹啉和1 mmol环戊二烯基二甲基氯硅烷溶于20 mL四氢呋喃溶液中,在0.5小时内缓慢滴加含有1mmol正丁基锂5 mL四氢呋喃溶液,在-60 ℃反应12小时。减压抽滤,用乙醚洗涤,得到黄色产物,产率为67%。
实施例2:单茂钛桥连配体1b的制备:在氮气保护的环境下,将1 mmol 7-溴喹啉和1 mmol 1-(氯甲基苯基甲硅烷基)-环戊二烯-(1,3)溶于20 mL四氢呋喃溶液中,在0.5小时内缓慢滴加含有1 mmol正丁基锂5 mL四氢呋喃溶液,在-60 ℃反应15小时。减压抽滤,用乙醚洗涤,得到黄色产物,产率为53%。
实施例3:单茂钛桥连配体1c的制备:在氮气保护的环境下,将1 mmol 7-溴喹啉和1 mmol 环戊二烯基二苯基氯硅烷溶于20 mL四氢呋喃溶液中,在0.5小时内缓慢滴加含有1mmol正丁基锂5 mL四氢呋喃溶液,在-60 ℃反应15小时。减压抽滤,用乙醚洗涤,得到黄色产物,产率为69%。
实施例4:单茂钛催化剂2a的制备:在氮气环境里,将0.5 mmol 1a配体溶解于10mL石油醚中,缓慢滴加10 ml含有0.1 mmol四氯化钛的石油醚溶液,在-60 ℃反应3小时。将反应液减压抽滤,产物溶解于甲苯中重结晶。产物为红棕色粉末,产率43%。结构式如式Ⅲ所示。元素分析:实测值(计算值),C%, 52.39(52.06);H%, 4.17(4.37);N%, 3.90(3.79).
实施例5:单茂钛催化剂2b的制备:在氮气环境里,将0.5 mmol 1b配体溶解于10mL石油醚中,缓慢滴加10 ml含有0.1 mmol四氯化钛的石油醚溶液,在-60 ℃反应3小时。将反应液减压抽滤,产物溶解于甲苯中重结晶。产物为红棕色粉末,产率39%。结构式如式Ⅳ所示。元素分析:实测值(计算值),C%, 58.23(58.49);H%, 4.19(4.21);N%, 3.46(3.25).
实施例6:单茂钛催化剂2c的制备:在氮气环境里,将0.5 mmol 1c配体溶解于10mL石油醚中,缓慢滴加10 ml含有0.1 mmol四氯化钛的石油醚溶液,在-60 ℃反应3小时。将反应液减压抽滤,产物溶解于甲苯中重结晶。产物为红棕色粉末,产率47%。结构式如式Ⅴ所示。元素分析:实测值(计算值),C%, 64.51(64.30);H%, 3.79(4.09);N%, 2.90(2.84).
实施例7:聚乙烯的制备:反应釜除氧除水,通入氮气保护,加入20 mL含一定量助催化剂的甲苯溶液(如助催化剂为甲基铝氧烷,摩尔比Al/Ti=100),通入乙烯气体置换氮气直至饱和,平衡10 ~20分钟,加入20 mL含有0.4 μmmol单茂钛催化剂(2a、2b或2c)的甲苯溶液,在总压力为1.0大气压、60 ℃聚合0.2小时,加入乙醇盐酸溶液终止反应,过滤,产物在60 ℃真空干燥。表1记录了本实施例的相关聚合数据。
实施例8:聚丙烯的制备:反应釜除氧除水,通入氮气保护,加入20 mL含一定量助催化剂的甲苯溶液(如助催化剂为甲基铝氧烷,Al/Ti=100),通入丙烯气体置换氮气直至饱和,平衡10 ~15分钟,加入20 mL含有0.4 μmmol单茂钛催化剂(2a、2b或2c)的甲苯溶液,在总压力为1.0大气压、60 ℃聚合0.5小时,加入乙醇盐酸溶液终止反应,过滤,产物在60 ℃真空干燥。表1记录了本实施例的相关聚合数据。
实施例9:乙烯/1-辛烯共聚物的制备:反应釜除氧除水,通入氮气保护,加入20 mL含一定量助催化剂的甲苯溶液(如助催化剂为甲基铝氧烷,Al/Ti=100~300),再加入5 mL1-辛烯溶液,通入乙烯气体置换氮气直至饱和,平衡10 ~20分钟,加入20 mL含有0.4 μmmol单茂钛催化剂(2a、2b或2c)的甲苯溶液,在总压力为1.0大气压、60 ℃聚合0.2小时,加入乙醇盐酸溶液终止反应,过滤,产物在60 ℃真空干燥。表1记录了实施例7~9的相关聚合数据。
表1 实施例7~9的聚合数据。
注:聚合物分子量和分子量分布均由GPC测得,标样为聚苯乙烯。
本发明公开了一种烯烃聚合的单茂钛催化剂,所述的催化剂可高效催化烯烃聚合,如乙烯均聚、丙烯均聚、乙烯/1-辛烯共聚,该催化剂在工业大规模生产烯烃聚合物中有较好的应用前景。
Claims (8)
1.一种用于烯烃聚合的单茂钛催化剂,其特征在于,其分子结构式如式Ⅰ所示:
式Ⅰ,
其中,R1为氢,或C1~C10的直链、支链或异构化的烷基,R2为氢,或C1~C10的直链、支链或异构化的烷基;或者,R1为甲基或苯基,R2为甲基或苯基。
2.一种用于烯烃聚合的单茂钛催化剂的制备方法,其特征在于,得到以下式Ⅱ所示结构含单茂的桥连配体:
式Ⅱ,
其中,R1为氢,或C1~C10的直链、支链或异构化的烷基,R2为氢,或C1~C10的直链、支链或异构化的烷基;或者,R1为甲基或苯基,R2为甲基或苯基。
3.制备如权利要求书1所述催化剂的方法,其特征在于,其步骤和条件如下:在氮气环境里,采用如权利要求书2所述的配体溶解在石油醚中,在-60 ℃至-40 ℃加入四氯化钛(TiCl4),反应2-6小时,减压抽滤,将产物重结晶,真空干燥后得到单茂钛催化剂。
4.如权利要求书3所述的制备方法,配体和TiCl4的摩尔比为1∶1。
5.根据权利要求书1所述的单茂钛催化剂在烯烃聚合的应用,其特征在于,与有机铝化物或有机硼一种或多种联用,助催化剂组分和配比为:有机铝化合物中的铝对茂钛化合物的摩尔比为(1~300)∶1;硼化物中的硼对茂钛化合物的摩尔比为10∶1。
6.根据权利要求书5所述的有机铝化物为甲基铝氧烷、乙基铝氧烷和三异丁基铝。
7.根据权利要求书5所述的有机硼化物为B(C6F5)3、[PhMe2NH][B(C6F5)4]和[Ph3C][B(C6F5)4]。
8.根据权利要求书1所述的单钛茂催化剂,其特征在于,其在有机溶剂中催化烯烃进行均聚或共聚反应。
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