CN101166576B - 用于制备奇数碳原子烯烃的催化剂前体、其制备方法以及所述烯烃的制备方法 - Google Patents

用于制备奇数碳原子烯烃的催化剂前体、其制备方法以及所述烯烃的制备方法 Download PDF

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CN101166576B
CN101166576B CN2006800141268A CN200680014126A CN101166576B CN 101166576 B CN101166576 B CN 101166576B CN 2006800141268 A CN2006800141268 A CN 2006800141268A CN 200680014126 A CN200680014126 A CN 200680014126A CN 101166576 B CN101166576 B CN 101166576B
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M·瑟茨
H·G·阿尔塔
A·A·拉夸巴赫
S·J·帕拉考
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Abstract

本发明涉及一种用于制备奇数烯烃的具有(I)式结构的催化剂前体，其中X和Y是卤素，n是2或3；并且涉及其制备方法和乙烯齐聚的方法。

Description

用于制备奇数碳原子烯烃的催化剂前体、其制备方法以及所述烯烃的制备方法 
本发明涉及一种用于制备奇数烯烃的催化剂前体、其制备方法以及采用该催化剂前体制备奇数烯烃的方法。 
乙烯或者其它烯烃的齐聚过程是现有技术中公知的。例如，已报道了卤化铁与2，6-二亚氨基吡啶的配位化合物可作为乙烯聚合和齐聚的预催化剂，参见Small，B.L.；Brookhart，M.Journal of American Chemical Society1998，120，7143-7144；以及Birtovsek，G.J.P.；Gibson，V.；Kimberley，B.S.；Maddox，P.J.；McTavish，S.J.；Solan，G.A.；White，A.J.P.；Williams，D.J.Chemical Communications(Cambridge)1998，849-850。 
此外，具有奇数碳原子的烯烃，例如1-庚烯、1壬稀、1-十一烯或1-十三烯是用于合成各种化合物的有价值的化学中间体。到目前为止，这样的奇数烯烃主要是从天然产物中分离，或作为生产偶数碳原子烯烃的齐聚物的商业过程中的副产品进行少量生产，例如SHOP过程。 
因此，本发明的目的在于克服现有技术的缺点，并提供一种可用于乙烯齐聚过程来增加奇数碳原子烯的量的催化剂组合物。本发明的另一个目的在于提供一种制备该催化剂组合物的方法： 
Figure DEST_PATH_G22274806150131000D000011
其中X和Y是卤素，n是2或3。 
优选X是氯，Y是氟、氯、溴或碘。 
该目的通过一种用于生产奇数烯烃的具有下式的催化剂前体来实现： 
此外，还提供了一种制备本发明催化剂前体的方法，包括如下步骤： 
(i)将2，6-二乙酰基吡啶与适当取代的苯胺按如下流程反应来制备2，6-二亚氨基吡啶： 
Figure S2006800141268D00021
将步骤(i)获得的2，6-二亚氨基吡啶与卤化铁按如下流程反应： 
Figure S2006800141268D00022
                                          Pr 
步骤(i)和(ii)优选在惰性溶剂中进行，例如甲苯、正丁醇、二氯甲烷或乙醚。 
更优选，铁在卤化铁中的氧化态是+2或+3。 
此外，还提供了一种制备奇数烯烃的方法，包括如下步骤： 
(a)用活化剂活化本发明的催化剂前体；然后 
(b)用步骤(a)中获得的已活化的催化剂前体齐聚合乙烯。 
优选，活化剂是烷基铝、甲基铝氧烷、改性的甲基铝氧烷、硼酸盐或超酸。 
更优选，活化剂是铝化合物，并且铝与铁的比是约50至约10000，优选约200～约3000。 
在一个具体的实施方案中，齐聚反应的温度是约-100℃到约300℃，优选的温度是约-10℃到约100℃。 
齐聚反应可以在惰性溶剂中进行，例如甲苯和/或戊烷。 
最后，乙烯的压力可以优选是约0.1到约60bar，更优选的压力是约0.5 至约10bar。 
令人惊讶地发现，采用本发明的催化剂前体的乙烯齐聚过程能够获得显著高含量的奇数烯烃的烯烃齐聚物。 
此外，根据所选择的特定催化剂前体和特定的反应条件的不同来优化齐聚物中奇数碳原子烯烃与偶数碳原子烯烃的比率。 
本发明主题的附加特征和优点，对于结合附图阅读了以下详细描述和实施例部分的本领域技术人员而言是显而易见的，其中： 
图1是2，6-二-[1-(5-氧-2-甲基苯基亚氨基)-乙基]-吡啶的质谱图； 
图2是2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶的1H和13C NMR谱图； 
图3显示了通过X射线分析2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶的结构； 
图4是[2，6-二-[1-5-(氯-2-甲基苯基亚氨基)-乙基]-吡啶]二氯化亚铁(II)的质谱图； 
本文中还使用了如下缩写： 
FW＝化学式量 
GC＝气相色谱 
GC/MS＝气相色谱质谱联用 
NMR＝核磁共振 
RT＝室温 
MeOH＝甲醇 
EtOH＝乙醇 
THF＝四氢呋喃 
实施例1 
2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶 
在25ml圆底烧瓶中加入3g 2，6-二乙酰基吡啶(FW163.13，18.4mmol)和100ml甲苯。加入几毫克对甲苯磺酸，然后加入7.81g 5-氯-2-甲基苯胺(FW141.60，55.2mmol)后。将反应混合物在迪安-斯托克分水器中加热回流2天，然后冷却到室温。用碳酸氢钠中和后水洗，并通过分液漏斗分离出有机层。 用Na2SO4干燥甲苯溶液并蒸馏除去溶剂。将残余物在乙醇中重结晶得到5.88g(78％收率)淡黄色晶体。将产物进行GC/MS分析： 
MS m/e(％)411(39)，410(36)，409(57)，397(20)，396(70)，395(54)，394(100)，284(13)，244(15)，243(15)，229(16)，166(23)，131(14)，125(32)，89(26)。 
图1给出了该化合物的质谱图。此外，1H和13C NMR核磁共振谱如下： 
1H NMR(ppm，CDCl3)8.36(d，2H)，7.91(t，1H)，7.19(d，2H)，6.99(d，2H)，6.69(d，2H)，2.32(s，6H)，2.11(s，6H)。 
13C NMR(ppm，CDCl3)167.6，155.1，151.2，132.2，125.4，(Cq)；137.0，131.0，123.3，122.5，119.4，(CH)；16.5，14.7，(CH3)。 
图2给出了1H和13C NMR谱图。 
此外，用二乙醚重结晶后得到用于X射线分析的适宜晶体，并且得到如下晶体数据： 
晶体数据            选择的键长 
单斜晶系            C5-C6＝1.497(2)  C1-C15＝1.500(1) 
空间群P21/c         C6-N2＝1.271(0)  C15-N3＝1.264(2) 
                    N2-C8＝1.425(2)  N3-C17＝1.426(1) 
单位晶包       a＝11.1358(22)
               b＝15.7676(18)
               c＝12.3067(16)
Figure 2006800141268_2
         扭转角 
               β＝95.88(1)°           C6-N2-C8-C14    -81.42(1) 
密度(计算值)   1.268g/cm3               C15-N3-C17-C23  91.47(1) 
图3给出了由该化合物结构获得的结晶数据。 
实施例2 
2，6-二-[1-(5-溴-2-甲基苯基亚氨基)-乙基]-吡啶 
在25ml圆底烧瓶中加入3g 2，6-二乙酰基吡啶(FW163.13，18.4mmol)和100ml甲苯。加入几毫克对甲苯磺酸，然后加入10.27g 5-溴-2-甲基苯胺(FW186.05，55.2mmol)。将反应混合物在迪安-斯托克分水器中加热回流8小时，然后冷却到室温。用碳酸氢钠中和后水洗，并通过分液漏斗分离出有机层。用Na2SO4干燥甲苯溶液并蒸馏除去溶剂。将残余物在甲醇中重结晶得到3.76g(41％收率)淡黄色晶体。将产物进行GC/MS分析： 
停留时间＝918s 
MS m/e(％)501(26)，500(20)，499(51)，497(26)，486(53)，485(26)，484(100)，482(52)，210(16)，171(16)，169(18)，90(24)，89(16)。 
实施例3 
[2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶]二氯化亚铁(II) 
将250ml施兰克试管抽真空并填充氩气，重复三次。加入80ml干燥的正丁醇，将0.501g 2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶(FW410.35，1.2mmol)溶解在其中。加入干燥的二氯化亚铁(II)(FW126.75，0.154g，1.2mmol)，颜色立即从黄色变成蓝色。将反应混合物在室温下搅拌1小时，然后在惰性气氛下过滤沉淀。将残余物用戊烷洗涤，真空干燥得到0.63g(收率96％)。将产物通过质谱表征： 
MS m/e(％)411(34)，410(21)，409(48)，408(18)，396(62)，395(23)，394(100)，296(51)，244(23)，243(19)，229(22)，166(32)，131(17)，125(32)，89(18)。 
图4给出了实施例3的催化剂前体的质谱图。 
实施例4 
[2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶二溴化亚铁(II) 
将250ml施兰克试管抽真空并填充氩气，重复三次。加入80ml干燥的正丁醇，将0.500g 2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶(FW410.35，1.2mmol)溶解在其中。加入干燥的溴化亚铁(II)(FW213.77，0.256g，1.2mmol)，颜色立即从黄色变成蓝色。将反应混合物在室温下搅拌1小时，然后在惰性气氛下过滤沉淀。将残余物用戊烷洗涤，真空干燥得到0.68g(收率90％)。将产物通过质谱表征： 
MS m/e(％)546(20)，411(32)，410(23)，409(46)，396(68)，395(26)，394(100)，244(25)，243(28)，229(34)，209(18)，166(35)，131(27)，125(42)，89(26)，44(31)。 
实施例5 
采用[2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶]二溴化亚铁(II) 作为催化剂前体的齐聚反应 
在装有150ml甲苯的施兰克试管中加入0.068g 2，6-二-[1-(5-氯-2-甲基苯基亚氨基)-乙基]-吡啶溴化亚铁(II)(FW625.99，0.11mmol)。加入共催化剂MAO(11.6ml，Al∶Fe＝500∶1)，将施兰克试管用1bar乙烯加压。常温下反应1小时，活性通过释放压力后的增重来测量。将混合物冷却到0℃，并加水水解。用Na2SO4干燥分离出的有机层，丙进行GC分析。 
最终活性是2480g(PE)/g(Fe)*h-1，奇数碳原子齐聚物的量是19％。 
实施例6 
采用[2，6-二-[1-(5-溴-2-甲基苯基亚氨基)-乙基]-吡啶]二氯化亚铁(II) 作为催化剂前体的齐聚反应 
在装有150ml甲苯的施兰克试管中加入0.0176g 2，6-二-[1-(5-溴-2-甲基苯基亚氨基)-乙基]-吡啶]二氯化亚铁(II)(FW625.99，0.028mmol)。加入共催化剂MAO(4.3ml，Al∶Fe＝750∶1)，将施兰克试管用1bar乙烯加压。在0℃温度下反应1小时，活性通过释放压力后的增重来测量。将混合物加水水解后，用Na2SO4干燥分离出的有机层，并进行GC分析。 
最终活性是2980g(PE)/g(Fe)*h-1，奇数碳原子齐聚物的量是约6％。 
可以看出，在乙烯齐聚过程中采用本发明的催化剂前体能够产生大量的奇碳原子数的齐聚物。 
到目前为止，还没有发现其它催化剂前体从乙烯可产生如此高含量的奇数烯烃。 
在前述说明书、权利要求和/或附图中公开的特征(单独地及其任意组合)都是实现本发明的多样性的材料。 

Claims (10)

1.用于制备奇数烯烃的具有下式的催化剂前体：
Figure FA20183785200680014126801C00011
其中X是溴且Y是氯，或X是氯且Y是溴；n是2或3。
2.制备权利要求1的催化剂前体的方法，包括如下步骤：
(i)将2，6-二乙酰基吡啶与适当取代的苯胺按如下流程反应来制备2，6-二亚氨基吡啶：
Figure FA20183785200680014126801C00012
(ii)将步骤(i)获得的2，6-二亚氨基吡啶与卤化铁按如下流程反应：
Figure DEST_PATH_IMAGE002
；
其中X是溴且Y是氯或X是氯且Y是溴，n是2或3；卤化铁中的铁的氧化态是+2或+3且步骤(i)和(ii)在惰性溶剂中进行。
3.根据权利要求2的方法，其中惰性溶剂是甲苯、正丁醇、二氯甲烷或乙醚。
4.用于生产奇数烯烃的方法，包括如下步骤： 
(a)用活化剂活化权利要求1所述的催化剂前体；然后
(b)用步骤(a)中获得的已活化的催化剂前体齐聚乙烯，
其中齐聚在惰性溶剂中进行；且齐聚反应的温度是-100到300℃和乙烯的压力是0.1到60巴。
5.根据权利要求4的方法，其中活化剂是烷基铝、甲基铝氧烷、改性的甲基铝氧烷、硼酸盐或超酸。
6.根据权利要求4或5的方法，其中活化剂是铝化合物，并且铝与铁的比是50至10000。
7.根据权利要求6的方法，其中铝与铁的比是200至3000。
8.根据权利要求4的方法，其中齐聚反应的温度是-10℃到100℃。
9.根据权利要求4的方法，其中惰性溶剂是甲苯和/或戊烷。
10.根据权利要求4的方法，其中乙烯的压力是0.5至10bar。 
CN2006800141268A 2005-04-29 2006-04-04 用于制备奇数碳原子烯烃的催化剂前体、其制备方法以及所述烯烃的制备方法 Expired - Fee Related CN101166576B (zh)

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