CN113527190A - 一种吡啶亚胺配体、基于该配体的吡啶亚胺镍钯配合物及其在催化乙烯聚合反应中的应用 - Google Patents
一种吡啶亚胺配体、基于该配体的吡啶亚胺镍钯配合物及其在催化乙烯聚合反应中的应用 Download PDFInfo
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- -1 Pyridine imine Chemical class 0.000 title claims abstract description 32
- 150000002466 imines Chemical class 0.000 title claims abstract description 28
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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Abstract
Description
技术领域
本发明属于聚烯烃制备技术领域,具体涉及一种吡啶亚胺配体、基于该配体的吡啶亚胺镍钯配合物及其在催化乙烯聚合反应中的应用。
背景技术
聚乙烯(PE)和聚丙烯(PP)等聚烯烃占全球合成聚合物产量的一半以上。在这方面,先进的烯烃聚合催化剂的开发一直是学术界和工业界关注的焦点。由于吡啶亚胺配体是一侧不对称的半开式空间结构,因此吡啶亚胺体系容易发生缔合链转移过程,从而在聚合过程中产生低分子量的烯烃齐聚物。为了解决这个问题,在过去的几十年里,人们开发了许多策略,包括N-芳环上邻位取代基的空间调节,在骨架上引入大位阻取代基,以及电子微扰,但收效甚微。例如,改变吡啶亚胺配体的骨架或在吡啶环的6位引入大的空间位阻取代基都不能提高聚烯烃的分子量。通过利用体积较大的二苯基,可以得到活性较高的Ni(II)和Pd(II)催化剂,然而使用这种体系得到的聚烯烃的分子量仍然很低。
发明内容
本发明针对上述现有技术所存在的问题,提供了一种吡啶亚胺配体、基于该配体的吡啶亚胺镍钯配合物及其在催化乙烯聚合反应中的应用。本发明通过引入二苯并环庚基取代基,从而有效的延缓基于“杂化”苯胺的不对称吡啶亚胺镍体系中的链转移,进而提高所得聚烯烃的分子量。此外,我们发现吡啶亚氨钯催化剂能有效地促进烯烃与丙烯酸酯类的共聚反应,得到高插入比的极性功能化烯烃-丙烯酸酯类共聚物。
本发明吡啶亚胺配体,其结构通式如下式I、II所示:
上述通式中:X1为-CH3、-CH2CH2-、-Bu或-tBu;X2为-O-、-S-或-CH2CH2-;R1为-H、-F、-Cl、-CH3、-OMe或tBu;R2为-H、-CH3或-Ph;R3为-CH3、-CH2CH2-、-Bu、-OMe或-tBu。
所述吡啶亚胺配体是通过包括如下步骤的方法制备获得:
圆底烧瓶中装有ZnCl2、吡啶衍生物和CH3CO2H,加入芳胺,加热回流反应1-10h,冷却至室温后,过滤得到黄色固体,用己烷洗涤;所得固体加入CH2Cl2中,搅拌下加入草酸钾水溶液,0.5-5h后分离,有机层用水洗涤,干燥剂干燥,真空除去溶剂,得到目标产物。
反应路线如下所示:
所述芳胺的结构式为:
本发明还提供了基于该配体的吡啶亚胺镍钯配合物,是由所述吡啶亚胺配体分别与镍、钯化合物所形成的配合物,其结构通式如下式III、IV、V、VI所示:
吡啶亚胺镍配合物
吡啶亚胺钯配合物
所述吡啶亚胺镍配合物是通过包括如下步骤的方法制备获得:
在氮气氛围下,惰性溶剂(如二氯甲烷,氯仿等)中,将所述吡啶亚胺配体与镍化合物按摩尔比1:0.5-2混合,在室温下搅拌反应1-3天,然后再经后处理(减压下蒸发掉大部分液体,加入乙醚,过滤),即获得吡啶亚胺镍配合物;所述镍化合物为DMENiBr2。
所述吡啶亚胺钯配合物是通过包括如下步骤的方法制备获得:
在惰性溶剂(如二氯甲烷,氯仿等)中,将所述吡啶亚胺配体与钯化合物按摩尔比1:0.5-2混合,在室温下搅拌反应1-3天,然后再经后处理(减压下蒸发掉大部分液体,加入乙醚,过滤),即获得吡啶亚胺钯配合物;所述钯化合物为(COD)PdMeCl。
本发明还提供了所述吡啶亚胺镍钯配合物的应用,是作为催化剂催化烯烃的聚合反应,具体包括如下两种催化反应:
(1)将所述吡啶亚胺镍配合物作为催化剂,对烯烃进行催化聚合,获得高分子量聚烯烃;
(2)将所述吡啶亚胺钯配合物作为催化剂,对烯烃与丙烯酸酯类进行催化共聚,获得高插入比的功能化的烯烃-丙烯酸酯类共聚物。
所述烯烃包括乙烯、丙烯或α-烯烃等;所述丙烯酸酯类包括丙烯酸甲酯、丙烯酸乙酯或丙烯酸正丁酯等。
进一步地,在上述两种催化反应体系中,还存在助催化剂,助催化剂优选为氯化二乙基铝(AlEt2Cl)和四(3,5-二(三氟甲基)苯基)硼酸钠(NaBArF)。
进一步地,上述催化反应的温度为20~90℃;烯烃压力为1-10大气压;反应溶剂为二氯甲烷、甲苯、正己烷中的至少一种。
本发明的有益效果体现在:
本发明所得催化剂能够催化烯烃得到高分子量的聚烯烃;除此之外,还能催化烯烃和丙烯酸酯类共聚,得到高插入的烯烃-丙烯酸酯类共聚物。
附图说明
图1为本发明实施例1(I)中所得的吡啶亚胺配体的核磁氢谱图。
图2为本发明实施例1(II)中所得的吡啶亚胺配体的核磁氢谱图。
图3为本发明实施例2(Ni1)中所得的吡啶亚胺镍配合物的质谱图。
图4为本发明实施例2(Ni2)中所得的吡啶亚胺镍配合物的质谱图。
图5为本发明实施例3(Pd1)中所得的吡啶亚胺钯配合物的核磁氢谱图。
图6为本发明实施例3(Pd2)中所得的吡啶亚胺镍配合物的核磁氢谱图。
图7是用本发明吡啶亚胺镍配合物作为催化剂进行乙烯均聚所得聚合物的分子量。
图8是用本发明吡啶亚胺钯配合物作为催化剂将丙烯酸甲酯与乙烯共聚所得共聚物的插入比。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
下述实施例的所有制备过程皆是按标准Schlenk技术进行的。
下述实施例所用试剂如无特殊说明皆从商业来源获得,未经纯化直接使用。
下述实施例核磁共振所用的氘代溶剂在使用前经过干燥和蒸馏。除另有说明外,1H、13C NMR谱由JNM-ECZ600R光谱仪在室温下记录。
下述实施例中,通过(ESI)LCMS-2010A来完成吡啶亚胺配体的质谱分析,通过Atouflex Speed MALDI-TOF MS来完成吡啶亚胺镍(钯)配合物的质谱分析。
下述实施例中,通过凝胶渗透色谱法(GPC),以四氢呋喃溶剂在40℃的条件下来测定由镍和钯配合物获得的聚合物的分子量和分子量分布,并使用聚苯乙烯为标准进行校准。
下述实施例中,DSC通过TA Instruments的DSC Q2000进行。将样品快速加热至150℃并保持5分钟以除去热历史,然后以10K/min的速率冷却至-50℃,最后在氮气流下(50mL/min)以相同的速率再加热至150℃,将最大吸热点作为熔融温度(Tm)。
实施例1:
本实施例制备吡啶亚胺配体,其结构如下:
合成过程为:圆底烧瓶中装有ZnCl2(0.80g,6.0mmol)、2-乙酰吡啶(6.0mmol)和CH3CO2H(20mL),加入芳胺(5.0mmol),加热回流5h;反应结束后冷却至室温,过滤得到黄色固体,用乙醚(3×10mL)洗涤;这种固体被放置在含有CH2Cl2(100ml)的圆底烧瓶中,将20mL草酸钾水溶液(6.0g)加入搅拌后的CH2Cl2溶液中,10min后分离,有机层用水(3×10mL)洗涤,MgSO4干燥,在真空中除去溶剂,即获得目标产物吡啶亚胺配体。制备反应示意图、反应产率、核磁分析、质谱分析如下。
产率:(2.13g,89%).
核磁分析:1H NMR(600MHz,CDCl3)δ8.54(t,J=7.0Hz,1H,Ar-H),8.31(t,J=11.7Hz,1H,Ar-H),7.85–7.78(m,1H,Ar-H),7.48–7.42(m,1H,Ar-H),7.33–7.31(m,2H,Ar-H),7.21–7.05(m,8H,Ar-H),6.95(dt,J=14.4,6.4Hz,2H,Ar-H),6.88(d,J=6.6Hz,2H,Ar-H),6.52–6.43(m,1H,Ar-H),5.25(s,1H,CHAr2),3.63(td,J=13.6,4.4Hz,1H,CH2),3.47–3.39(m,1H,CH2),2.99(ddd,J=17.2,11.2,4.6Hz,1H,CH2),2.56(dt,J=14.3,4.7Hz,1H,CH2),2.30(s,3H,CH3),1.12(s,3H,Py-C(CH3)=N).13C NMR(151MHz,CDCl3)δ168.38(C=N),148.33,144.75,141.58,140.54,140.18,139.51,138.80,136.92,136.09,132.87,132.14,131.94,131.77,131.45,130.96,130.37,129.58,129.39,129.07,128.33,127.78,127.16,126.86,126.79,126.31,126.17,125.47,124.52,121.41,56.63(CHAr2),33.46(CH2),30.72(CH2),21.29(CH3),16.69(Py-C(CH3)=N.
质谱分析:APCI-MS(m/z):calcd for C35H31N2 +:479.2482,Found,479.2459,[M+H]+.
产率:(2.19g,91%).
核磁分析:(2.19g,91%).1H NMR(600MHz,CDCl3)δ8.49(d,J=4.6Hz,1H,Ar-H),8.25(d,J=7.9Hz,1H,Ar-H),7.75(dd,J=12.3,4.6Hz,1H,Ar-H),7.36(d,J=7.9Hz,1H,Ar-H),7.28(dd,J=6.9,5.6Hz,1H,Ar-H),7.19(t,J=7.6Hz,2H,Ar-H),7.12–7.06(m,6H,Ar-H),6.93–6.88(m,3H,Ar-H),6.85(d,J=8.5Hz,3H,Ar-H),5.51(s,1H,CHAr2),2.35(s,3H,CH3),2.32(s,3H,CH3),2.24(s,3H,CH3),1.20(s,3H,Py-C(CH3)=N).13C NMR(151MHz,CDCl3)δ167.77(C=N),156.17,148.33,144.86,141.16,140.53,139.74,136.15,135.47,135.43,134.94,132.67,130.99,129.66,129.57,129.27,129.22,129.19,128.88,128.84,128.74,128.48,127.90,126.40,124.45,51.57(CHAr2),21.19(CH3),21.12(CH3),21.11(CH3),16.78(Py-C(CH3)=N).
质谱分析:APCI-MS(m/z):calcd for C35H33N2 +:481.2638,Found,481.2616,[M+H]+.
实施例2:
本实施例制备吡啶亚胺镍配合物,其结构如下:
合成过程为:将1mmol的吡啶亚胺配体与DMENiBr2(308.62mg,1mmol)溶解在20mL二氯甲烷中,在室温下搅拌过夜;在搅拌过程中,溶液的颜色加深。反应结束后,在减压条件下蒸发掉大部分的二氯甲烷,将溶液浓缩至2mL,加乙醚得到棕色固体粉末,用乙醚洗涤固体,真空高中保存。本实施例制备的吡啶亚胺镍配合物的产率、质谱分析如下:
产率(Ni1):(0.63g,91%)
质谱分析(Ni1):MALDI-TOF MS(m/z):calcd for C35H30BrN2Ni:615.0946,Found,615.0945,[M-Br]+
产率(Ni2):(64mg,91%).
质谱分析(Ni2):MALDI-TOF MS(m/z):calcd for C35H32BrN2Ni:617.1102,Found,617.1095,[M-Br]+
实施例3:
本实施例制备吡啶亚胺钯配合物,其结构如下:
合成过程为:将1mmol的吡啶亚胺配体与(COD)PdMeCl(265mg,1mmol)溶解在20mL二氯甲烷中,在室温下搅拌反应3天;在搅拌过程中,溶液的颜色加深。反应结束后,在减压条件下蒸发掉大部分的二氯甲烷,将溶液浓缩至2mL,用20ml乙醚将产物沉出,用3×5ml乙醚洗涤。然后在室温下减压干燥约5小时,得到纯化合物为黄色固体备用。本实施例制备的吡啶亚胺钯配合物的产率、核磁分析、质谱分析如下:
产率(Pd1):(0.57g,89%)
核磁分析(Pd1):1H NMR(600MHz,CDCl3)δ9.51,9.30(d,J=4.7Hz,1H,Ar-H),8.76,8.01–7.33(m,5H,Ar-H),7.33–7.03(m,9H,Ar-H),7.03–6.75(m,3H,Ar-H),6.39,6.12(t,J=7.6Hz,1H,Ar-H),6.36,6.06(s,1H,CHAr2),3.45(td,J=14.0,4.5Hz,1H,CH2CH2),3.35(dt,J=17.6,3.7Hz,1H,CH2CH2),2.99(ddd,J=18.0,14.3,4.6Hz,1H,CH2CH2),2.43(dt,J=13.7,4.2Hz,1H,CH2CH2),2.30,2.24(s,3H,Ar-CH3),1.05,0.84(s,3H,Pd-CH3)0.92,0.89(s,3H,N=C-CH3).13C NMR(151MHz,CDCl3)δ175.94(C=N),152.83,149.25,141.49,140.93,139.62,138.84,138.72,138.28,137.10,135.96,134.38,134.29,132.57,131.95,131.74,130.96,130.26,129.55,128.98,128.33,127.88,127.36,127.28,127.00,126.79,125.24,124.59,55.64(CHAr2),33.48(CH2-CH2),30.10(CH2-CH2),21.41(Ar-CH3),17.86(N=C-CH3),0.93(Pd-CH3).Elemental analysis:calc.for C36H33N2ClPd:C,68.04;H,5.23;N,4.41.Found:C,68.17;H,5.27;N,4.36.
质谱分析(Pd1):MALDI-TOF MS(m/z):calcd for C35H30N2Pd:584.1444,Found,584.1450,[M-Cl-CH3]+.
产率(Pd2):(293mg,92%).
核磁分析(Pd2):1H NMR(400MHz,Chloroform-d)δ9.49,9.25(d,J=4.3Hz,1H,Ar-H),8.05–7.52(m,3H,Ar-H),7.39–6.98(m,9H,Ar-H),6.96–6.69(m,6H,Ar-H),6.61,6.48(s,1H,CHAr2),2.34,2.33,2.29,2.18(s,9H,Ar-CH3),1.17,0.85(s,3H,Pd-CH3),0.96,0.94(s,3H,N=C-CH3).13C NMR(101MHz,CDCl3)δ175.15(C=N),152.65,149.34,140.02,139.09,138.76,138.57,138.32,137.41,136.87,136.06,135.87,134.32,130.30,129.76,129.59,129.57,129.53,129.05,128.97,128.49,128.02,127.38,124.17,51.73(CHAr2),21.40(Ar-CH3),21.16(Ar-CH3),21.07(Ar-CH3),17.90(N=C-CH3),1.73(Pd-CH3).Elemental analysis:calc.for C36H35ClN2Pd:C,67.82;H,5.53;N,4.39.Found:C,67.79;H,5.48;N,4.35.
质谱分析(Pd2):MALDI-TOF MS(m/z):calcd for C35H32ClN2Pd:621.1289,Found,621.1294,[M-CH3]+
实施例4:
用实施例2制备的吡啶亚胺镍配合物作为催化剂进行乙烯均聚的一般方法:首先在真空90℃下干燥一台连接高压气体管路的300mL不锈钢压力反应器,干燥时间至少为1h;然后将反应器调整到所需的聚合温度。在氮气气氛下向反应器中加入20mL甲苯和所需量的MAO(本实施例中的MAO加入量为1000μmol),然后通过注射器将含所需吡啶亚胺镍催化剂的2mL二氯甲烷溶液注入聚合体系(本实施例中催化剂加入量为2μmol)中。在快速搅拌后,将压力反应器放空,将聚合物在真空下干燥过夜。测得聚合物的分子量如图7所示,通过聚合数据可以看出,含有二苯并环庚基取代基的吡啶亚胺配合物Ni1所得聚合物的分子量,比Ni2要高得多。因此,二苯并环庚基取代基在吡啶亚氨镍体系中具有延缓链转移的能力,能够提高所得聚合物的分子量。
实施例5:
用实施例3制备的吡啶亚胺钯配合物作为催化剂将丙烯酸甲酯与乙烯共聚的一般方法为:首先在真空90℃下干燥一台连接高压气体管路的300mL不锈钢压力反应器,干燥时间至少为1h;然后将反应器调整到所需的聚合温度(本实验实施温度为40℃。在氮气气氛下向反应器中加入20mL的二氯甲烷与极性单体的混合溶液和所需量的NaBArF(本实施例中的NaBArF加入量为0.04mmol,极性单体为1mol/L),然后通过注射器将含所需吡啶亚胺钯催化剂的二氯甲烷溶液注入聚合体系(本实施例中催化剂加入量为0.02mmol)中。在快速搅拌后,将压力反应器放空,将聚合物在真空下干燥过夜。所得共聚物的插入比如图8所示,吡啶亚氨钯催化剂能有效地促进乙烯与丙烯酸甲酯(MA)的共聚反应,得到高插入比的极性功能化乙烯-MA共聚物。
Claims (9)
3.一种权利要求2所述吡啶亚胺镍钯配合物的应用,其特征在于:
所述吡啶亚胺镍钯配合物作为催化剂催化烯烃的聚合反应。
4.根据权利要求3所述的应用,其特征在于:
将所述吡啶亚胺镍配合物作为催化剂,对烯烃进行催化聚合,获得高分子量聚烯烃。
5.根据权利要求4所述的应用,其特征在于:
所述烯烃包括乙烯、丙烯或α-烯烃。
6.根据权利要求4所述的应用,其特征在于:
在催化反应体系中,还存在助催化剂,助催化剂为氯化二乙基铝、四(3,5-二(三氟甲基)苯基)硼酸钠。
7.根据权利要求3所述的应用,其特征在于:
将所述吡啶亚胺钯配合物作为催化剂,对烯烃与丙烯酸酯类进行催化共聚,获得高插入比的功能化的烯烃-丙烯酸酯类共聚物。
8.根据权利要求7所述的应用,其特征在于:
所述烯烃包括乙烯、丙烯或α-烯烃;所述丙烯酸酯类包括丙烯酸甲酯、丙烯酸乙酯或丙烯酸正丁酯。
9.根据权利要求7所述的应用,其特征在于:
在催化反应体系中,还存在助催化剂,助催化剂为氯化二乙基铝、四(3,5-二(三氟甲基)苯基)硼酸钠。
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