CN111548285B - 一类叠加大位阻α-二亚胺配体、镍催化剂及其制备方法和应用 - Google Patents
一类叠加大位阻α-二亚胺配体、镍催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供一类叠加大位阻α‑二亚胺配体、镍催化剂及其制备方法和应用。属于催化剂领域。该配体的结构如式(I)所示。本发明还提供一类叠加大位阻α‑二亚胺配体的制备方法。本发明还提供一种镍催化剂,结构如式(II)所示。本发明还提供一种镍催化剂的制备方法。该类镍催化剂在一定条件下,催化乙烯聚合活性可高达1026.0×106g mol‑1h‑1,且可得到超高分子量,支化度可调的聚乙烯。此外,在110~150℃高温下,该类催化剂仍然具有相当高的催化活性。其中,超高分子量低支化度聚乙烯具有良好的工业应用前景,在一定程度上可考虑作为超高分子量聚乙烯纤维使用。
Description
技术领域
本发明属于催化剂领域,具体涉及一类叠加大位阻α-二亚胺配体、镍催化剂及其制备方法和应用。
背景技术
从1995年以来,由于独特的链行走机理,α-二亚胺镍催化剂(J.Am.Chem.Soc.1995,117,6414)发展到现在已经成为一类非常有用的乙烯聚合催化剂。然而,为了更好地满足工业化的需求,催化剂的催化活性仍有待提高(当前,α-二亚胺镍催化剂催化乙烯聚合最高活性为1.0×108g mol-1h-1,Macromolecules 2000,33,7,2320)。为了提高催化剂的催化活性,同时得到(超)高分子量的聚合物,目前常用手段是调节催化剂的轴向空间位阻,或调控配体的电子效应。
目前α-二亚胺镍催化剂在催化乙烯聚合方面,虽然通过调控配体的空间效应与电子效应,可以得到(超)高分子量(达数百万)的聚合物,但是催化活性仍然有待提高。同时,当前α-二亚胺镍催化剂还难以同时兼具高热稳定性、高活性、高分子量的特性,从而在某种程度上限制了工业化应用。
发明内容
本发明的目的是提供一类叠加大位阻α-二亚胺配体、镍催化剂及其制备方法和应用,该类镍催化剂能够具有兼具高热稳定性、高活性、高分子量的特性。
本发明首先提供一类叠加大位阻α-二亚胺配体,结构如式(I)所示:
式(I)中,R1表示H、C1~C20的烷基或者
R2表示H、CH3、tBu(叔丁基)、Cl、OCH3、CF3、NO2,X表示N,P,CH。
优选的是,所述的一类叠加大位阻α-二亚胺配体,结构式如下:
本发明还提供一类叠加大位阻α-二亚胺配体的制备方法,包括:
步骤一:将通式为(b)的苯胺和通式为(a)的二酮溶于溶剂中,然后加入催化剂,在25~80℃下反应,得到结构式如(c)的单亚胺产物;
步骤二:将结构式如(c)的单亚胺产物和通式为(b)的苯胺溶于溶剂中,然后加入催化剂,将反应混合物回流反应,得到结构如式(I)所示一类叠加大位阻α-二亚胺配体;
优选的是,所述的步骤二中结构式如(c)的单亚胺产物和通式为(b)的苯胺摩尔比为1:1。
本发明还提供一种镍催化剂,结构如式(II)所示:
式(II)中,R1表示H、C1~C20的烷基或者
R2表示H、CH3、tBu(叔丁基)、Cl、OCH3、CF3、NO2,X表示N,P,CH。
优选的是,所述的镍催化剂结构式如下:
本发明还提供一种镍催化剂的制备方法,包括:
将结构如式(I)所示一类叠加大位阻α-二亚胺配体和NiBr2(DME)(DME=1,2-二甲氧基乙烷)溶于二氯甲烷或氯仿溶剂中反应,得到结构如式(II)所示的镍催化剂;
优选的是,所述的结构如式(I)所示一类叠加大位阻α-二亚胺配体和NiBr2(DME)的摩尔比为1:1。
本发明还提供上述镍催化剂在催化聚乙烯聚合中的应用。
本发明还提供上述镍催化剂催化聚乙烯的方法,包括:
将反应器与高压气体管线连接,将反应器温度调节至0-150℃,在惰性气氛下,将溶剂和助催化剂加入到反应器中,然后将镍催化剂的二氯甲烷或氯仿溶液注入到反应器中,在搅拌下,通入乙烯并保持在压力为4-40atm,反应1-6min后,得到聚乙烯。
本发明的原理
本发明提供一类叠加大位阻α-二亚胺配体、镍催化剂及其制备方法,本发明的叠加大位阻原理如图1所示,即在N-芳环2,6-位引入双层位阻:第一层位阻在金属中心轴向位置起到位阻作用的同时,在金属中心周围提供足够的空间,便于烯烃配位插入,从而加快链增长,提高聚合活性;第二层位阻在金属中心轴向位置上进一步提供位阻的同时形成关键的空间交错封锁闭合;封锁闭合作用的形成阻碍了烯烃协同置换导致的链转移反应,不仅能够提高聚合物分子量并调控其支化度,还能通过空间交错形成的排斥作用撑开第一层位阻,增加金属中心周围的空间,从而再次提高聚合活性。这一策略核心在于通过双层位阻的巧妙叠加,在保持轴向大位阻的同时形成空间交错封锁效应。
本发明的有益效果
本发明提供一类叠加大位阻α-二亚胺配体、镍催化剂及其制备方法和应用,该类镍催化剂在一定条件下,催化乙烯聚合活性可高达1026.0×106g mol-1h-1,且可得到超高分子量(Mw为3.1~500.4万),支化度可调(支化度为3~32/1000C)的聚乙烯。此外,在110~150℃高温下,该类催化剂仍然具有相当高的催化活性(2.1×106~2.1×107g mol-1h-1)。其中,超高分子量低支化度聚乙烯具有良好的工业应用前景,在一定程度上可考虑作为超高分子量聚乙烯纤维使用。超高分子量聚乙烯纤维在国际上已成为21世纪蓬勃发展的高新技术材料。由超高分子量聚乙烯纤维加工制成的绳索、纺织织物及复合材料被广泛用于国防军工、航空航天、海洋产业、体育器材、医疗卫生、建筑行业等诸多领域,发挥着举足轻重的作用。并且该类催化剂超高的聚合活性可大大降低催化剂生产成本,满足工业生产的潜在要求。
附图说明
图1为本发明的叠加大位阻原理示意图;
图2为本发明实施例4制备得到的α-二亚胺镍催化剂的单晶衍射图;
图3为本发明实施例4制备得到的α-二亚胺镍催化剂的核磁共振氢谱图;
图4为本发明实施例4制备得到的α-二亚胺镍催化剂的质谱图(MALDI-TOF-MS);
图5为本发明实施例6(表5条目15)制备得到的聚合物的核磁共振氢谱图。
具体实施方式
本发明首先提供一类叠加大位阻α-二亚胺配体,结构如式(I)所示:
式(I)中,R1表示H、C1~C20的烷基或者
R2表示H、CH3、tBu(叔丁基)、Cl、OCH3、CF3、NO2,X表示N,P,CH。
优选的是,所述的一类叠加大位阻α-二亚胺配体,结构式如下:
本发明还提供一类叠加大位阻α-二亚胺配体的制备方法,包括:
步骤一:将通式为(b)的苯胺和通式为(a)的二酮溶于溶剂中,所述的通式为(b)的苯胺和通式为(a)的二酮摩尔比为1:N,其中N≥1,N越大,反应时间越短,且可提高产物转化率,优选摩尔比为1:(1-10),更优选为1:5,所述的溶剂优选为甲苯、二甲苯、氯苯、二氯甲烷、氯仿或乙腈,然后加入催化剂,在25~80℃下反应,反应时间优选为6h以上,更优选为12-48h,反应结束后,优选冷却至室温,旋蒸蒸发溶剂直至出现黄色固体,加入过量的甲醇或乙醇析出产品,过滤分离黄色固体,用甲醇或乙醇洗涤三次并在真空下干燥得到结构式如(c)的单亚胺产物;所述的催化剂优选为对甲苯磺酸、甲酸或乙酸,催化剂和通式为(b)的苯胺的摩尔比优选为0.001:1;
步骤二:将结构式如(c)的单亚胺产物和通式为(b)的苯胺溶于溶剂中,溶剂优选为甲苯,然后加入催化剂,所述的催化剂优选为对甲苯磺酸一水合物,将反应混合物回流反应,所述的反应温度优选为110℃以上,更优选为120-180℃,反应时间优选为48h以上,更优选为3-4天,反应结束后,冷却至室温,旋蒸蒸发溶剂直至出现黄色固体,加入过量的甲醇或乙醇析出产品,过滤分离黄色固体,用甲醇或乙醇洗涤三次并在真空下干燥得到结构如式(I)所示一类叠加大位阻α-二亚胺配体;所述的结构式如(c)的单亚胺产物、通式为(b)的苯胺和催化剂的摩尔比为优选为1:1:0.001。
本发明还提供一种镍催化剂,结构如式(II)所示:
式(II)中,R1表示H、C1~C20的烷基或者
R2表示H、CH3、tBu(叔丁基)、Cl、OCH3、CF3、NO2,X表示N,P,CH。
优选的是,所述的镍催化剂结构式如下:
本发明还提供一种镍催化剂的制备方法,包括:
将结构如式(I)所示一类叠加大位阻α-二亚胺配体和NiBr2(DME)溶于二氯甲烷或氯仿溶剂中反应,所述的反应温度优选为20~50℃,反应时间为24h以上,更优选为24-48h,然后旋蒸蒸发溶剂,用正己烷或乙醚和二氯甲烷或氯仿重结晶,过滤分离固体,用己烷或乙醚洗涤三次并在真空下干燥得到结构如式(II)所示的镍催化剂;所述的结构如式(I)所示一类叠加大位阻α-二亚胺配体和NiBr2(DME)的摩尔比优选为1:1,所述的溶剂优选为二氯甲烷或氯仿。
本发明还提供上述镍催化剂在催化聚乙烯聚合中的应用。
本发明还提供上述镍催化剂催化聚乙烯的方法,包括:
将反应器优选在90℃下干燥1h以上,然后与高压气体管线连接,将反应器温度调节至0-150℃,优选为30℃,在惰性气氛下,将溶剂和助催化剂加入到反应器中,所述的溶剂优选为甲苯、己烷或氯苯,所述的助催化剂优选为MAO(甲基铝氧烷)、MMAO(改性甲基铝氧烷)、EASC(三氯三乙基络铝)或AlEt2Cl(氯化二乙基铝),然后将镍催化剂先溶于溶剂中,得到催化剂溶液,所述的溶剂优选为二氯甲烷或氯仿,然后通过注射器注入到反应器中,在搅拌下,所述搅拌速度优选为750转以上,通入乙烯并保持在压力为4-40atm,优选8atm,反应1-6min后,优选反应时间为1min,加入大量酸性甲醇(或乙醇)(5%以上的盐酸醇溶液)溶液淬灭聚合反应,过滤聚合物,并在真空烘箱中干燥得到聚乙烯。所述的镍催化剂的浓度优选为0.1-1μmol,优选为0.1-0.25μmol,所述的助催化剂的浓度优选为500μmol。
下面结合具体实施例对本发明做进一步详细的描述,实施例中涉及到的原料均为商购获得。
实施例1 2,6-二(三苯胺基)-4-甲基苯胺的制备
将4-硼酸三苯胺(26.73g,92.45mmol),2,4,6-三甲基苯胺(5.00g,36.98mmol),碳酸钠水溶液(150ml,2M),少量乙醇,四(三苯基膦)钯(4.27g,3.70mmol)的甲苯(150ml)溶液在90℃下搅拌并保持24小时,冷却至室温,旋蒸蒸发溶剂直至出现黄色固体,加入过量的甲醇析出产品,过滤分离黄色固体,用甲醇洗涤三次并在真空下干燥得到黄色固体产物(19.06g,86.8%收率)。
1H NMR(500MHz,298K,DMSO-d6,2.50ppm):δ=7.40-7.28(m,12H,aryl-H),7.11-7.01(m,16H,aryl-H),6.84(s,2H,aryl-H),4.13(s,2H,NH2),2.21(s,3H,CH3).
实施例2 2-{2,6-二(三苯胺基)-4-甲基苯基亚胺基}丁酮的制备
将步骤一中制备的2,6-二(三苯胺基)-4-甲基苯胺(10.00g,16.84mmol),2,3-丁二酮(7.25g,84.21mmol)和对甲苯磺酸(20mg)的甲苯(200mL)溶液在80℃下搅拌并保持24小时,冷却至室温,旋蒸蒸发溶剂直至出现黄色固体,加入过量的甲醇析出产品,过滤分离黄色固体,用甲醇洗涤三次并在真空下干燥得到黄色固体产物(8.87g,79.6%收率)。
1H NMR(500MHz,298K,CDCl3,7.26ppm):δ=7.29-7.23(m,6H,aryl-H),7.22-7.19(m,4H,aryl-H),7.17-7.15(m,2H,aryl-H),7.11-7.06(m,9H,aryl-H),7.04-6.99(m,9H,aryl-H),2.41(s,3H,Ph-Me),2.29(s,3H,O=C-Me),1.47(s,3H,N=C-Me).
实施例3 2,3-二{2,6-二(三苯胺基)-4-甲基苯基亚胺基}丁烷的制备
将步骤二中制备的2-{2,6-二(三苯胺基)-4-甲基苯基亚胺基}丁酮(3.00g,4.53mmol),实施例1制备的2,6-二(三苯胺基)-4-甲基苯胺(2.69g,4.53mmol)和对甲苯磺酸(20mg)的甲苯(200mL)溶液回流3天,120℃加热,然后冷却至室温,旋蒸蒸发溶剂直至出现黄色固体,加入过量的甲醇析出产品,过滤分离黄色固体,用甲醇洗涤三次并在真空下干燥得到黄色固体产物(3.78g,67.4%收率)。
1H NMR(500MHz,298K,CDCl3,7.26ppm):δ=7.17-7.08(m,20H,aryl-H),7.04-6.99(m,8H,aryl-H),6.98-6.93(m,16H,aryl-H),6.92-6.87(m,8H,aryl-H),6.79-6.72(m,8H,aryl-H),2.42(s,6H,Ph-Me),1.37(s,6H,N=C-Me).
实施例4 {2,3-二[2,6-二(三苯胺基)-4-甲基苯基亚胺基]丁烷}二溴化镍的制备
将步骤三中制备的2,3-二{2,6-二(三苯胺基)-4-甲基苯基亚胺基}丁烷(200mg,0.162mmol)和(DME)NiBr2(50.0mg,0.162mmol)(DME=1,2-二甲氧基乙烷)的混合物在20mL二氯甲烷中25℃下搅拌24小时。反应完成后减压蒸发溶剂得到棕色固体,然后过滤并用二氯甲烷/己烷重结晶得到纯化合物,为红棕色固体(208.8mg,88.5%收率)。MALDI-TOF-MS(m/z):1236.6[M-Ni-2Br],1294.5[M-2Br]2+,1373.4[M-Br]+。
实施例4制备得到的α-二亚胺镍催化剂的单晶衍射图如图2所示;核磁共振氢谱图如图3所示,质谱图(MALDI-TOF-MS)如图4所示。
表1为部分通式为(b)的苯胺反应条件和产率
表1
表1中反应物A和反应物B的摩尔比均为1:2.5。
表2为部分式(I)的配体反应条件和产率
表2
表2中通式为(b)的苯胺和通式为(a)的二酮的摩尔比为1:10,结构式如(c)的单亚胺产物和通式为(b)的苯胺摩尔比为1:1。
表3为结构式1-25的催化剂的合成条件和产率
表3
表3中,结构如式(I)所示一类叠加大位阻α-二亚胺配体和NiBr2(DME)的摩尔比为1:1,所述的溶剂为二氯甲烷或氯仿。
实施例5 镍催化剂的应用
首先将与高压气体管线连接的350mL玻璃压力反应器在90℃下真空干燥至少1小时。然后将反应器调节至30℃,在惰性气氛下将98mL甲苯和500μmol的MAO加入到反应器中,然后将1μmol的表4所示的Ni催化剂溶解在2mL二氯甲烷(或氯仿)中通过注射器注入到聚合体系中。在快速搅拌下(750转以上),通入乙烯并保持在8atm。3分钟后,排空压力反应器,加入大量酸性甲醇(或乙醇)(5%以上的盐酸醇溶液)溶液淬灭聚合反应,过滤聚合物,并在真空烘箱中干燥至恒重。不同镍催化剂对乙烯聚合的影响如表4所示。
表4.不同镍催化剂(改变取代基R1、R2、X)对乙烯聚合的影响
所有数据至少是基于两条平行试验得出的结果(除非另有说明)。活性:以106gmol-1h-1为单位。Mw、Mw/Mn:分别为重均分子量、聚合物分散性指数,150℃下,在1,2,4-三氯苯中通过GPC测定,相对于聚苯乙烯标准物。支化度=每1000个碳,支化的个数,由核磁共振氢谱测定。
表4的数据说明:当控制催化剂取代基R1、X不变,改变取代基R2时,在同等的聚合条件下(时间、温度、压力、助催化剂浓度一致),R2如果为供电子基团(CH3、tBu、OCH3)相比于其为吸电子基团(Cl、CF3、NO3)拥有更高的活性和分子量,但是支化度类似。同样,当控制催化剂取代基R1、R2不变,改变取代基X时,在同等的聚合条件下(时间、温度、压力、助催化剂浓度一致),X是N时,具有最高的分子量和活性。当控制催化剂取代基R2、X不变,改变取代基R1时,在同等的聚合条件下(时间、温度、压力、助催化剂浓度一致),R1为CH3时,得到最高的活性,时,聚合物得到最高的分子量。
实施例6 镍催化剂的应用
首先将与高压气体管线连接的350mL玻璃压力反应器或高压反应器在90℃下真空干燥至少1小时。然后将反应器调节至对应温度,在惰性气氛下将98mL甲苯和500μmol的MAO或MMAO加入到反应器中,然后将Ni催化剂(R1=CH3,R2=CH3,X=N)溶解在2mL二氯甲烷(或氯仿)中通过注射器注入到聚合体系中。在快速搅拌下(750转以上),通入乙烯并保持在对应压力。1~6分钟后,排空压力反应器,加入大量酸性甲醇(或乙醇)(5%以上的盐酸醇溶液)溶液淬灭聚合反应,过滤聚合物,并在真空烘箱中干燥至恒重。不同反应条件对α-二亚胺镍催化剂催化乙烯聚合的影响如表5所示。
表5.不同反应条件对α-二亚胺镍催化剂催化乙烯聚合的影响
注:条目1~10和20:助催化剂MMAO(500μmol),条目11~19:助催化剂MAO(500μmol).条目1~18和20:溶剂为甲苯,条目19:溶剂为对二甲苯。
所有数据至少是基于两条平行试验得出的结果(除非另有说明)。活性以106g mol-1h-1为单位。Mw、Mw/Mn:分别为重均分子量、聚合物分散性指数,150℃下,在1,2,4-三氯苯中通过GPC测定,相对于聚苯乙烯标准物。支化度=每1000个碳,支化的个数,由核磁共振氢谱测定。其中表5中条目15得到的聚合物的核磁共振氢谱图如图5所示。
表5数据说明:当保持时间不变(1min)、温度不变(30℃)、催化剂添加量不变(0.25μmol),随着乙烯压力的提升,活性先增加后下降而聚合物分子量逐渐变大;当保持压力不变(8atm)、温度不变(30℃)、催化剂添加量不变(0.10μmol),活性随着时间的变大而逐渐变小,聚合物分子量随着时间的变大而逐渐变大;当保持压力不变(8atm)、时间不变(3min)、催化剂添加量不变(1.00μmol),聚合物的分子量随着温度的升高先增加再减小,活性随着温度的升高逐渐减小;当保持时间不变(1min)、温度不变(30℃)、压力不变(8atm),随着催化剂添加量的减小,催化活性和分子量逐渐增大。在极低的催化剂添加量(0.10μmol),压力(32atm),温度(30℃)条件下,催化活性达到惊人的1026.0×106g mol-1h-1,且分子量Mw达到419.5万。
实施例7 镍催化剂的应用
首先将与高压气体管线连接的350mL玻璃压力反应器在90℃下真空干燥至少1小时。然后将反应器调节至30℃,在惰性气氛下将98mL溶剂(甲苯、己烷、氯苯)和250~2000当量的助催化剂(MAO、MMAO、EASC、AlEt2Cl)加入到反应器中,然后将0.25μmol的Ni催化剂(R1=CH3,R2=CH3,X=N)溶解在2mL二氯甲烷(或氯仿)中通过注射器注入到聚合体系中。在快速搅拌下(750转以上),通入乙烯并保持在8atm。1分钟后,排空压力反应器,加入大量酸性甲醇(或乙醇)(5%以上的盐酸醇溶液)溶液淬灭聚合反应,过滤聚合物,并在真空烘箱中干燥至恒重。不同助催化剂与溶剂对α-二亚胺镍催化剂催化乙烯聚合的影响如表6所示。
表6.不同助催化剂与溶剂对α-二亚胺镍催化剂催化乙烯聚合的影响
反应条件:镍催化剂(0.25μmol,R1=CH3,R2=CH3,X=N),溶剂/二氯甲烷或氯仿(98mL/2mL),乙烯压力(8bar),聚合时间(1min),聚合温度(30℃)所有数据至少是基于两条平行试验得出的结果(除非另有说明)。Al/Ni:助催化剂与镍催化剂的摩尔比值。活性以106g mol-1h-1为单位。Mw、Mw/Mn:分别为重均分子量、聚合物分散性指数,150℃下,在1,2,4-三氯苯中通过GPC测定,相对于聚苯乙烯标准物。支化度=每1000个碳,支化的个数,由核磁共振氢谱测定。
表6数据说明:控制镍催化剂不变(0.25μmol,R1=CH3,R2=CH3,X=N),聚合条件一致(时间、温度、压力):当聚合溶剂为甲苯、助催化剂为MAO、MMAO、EASC、AlEt2Cl时,随着Al/Ni比值增大,聚合物活性先增大后减小,比值为500时活性最大,分子量随着Al/Ni比值增大,先减小后增加,支化度基本不变;其中当助催化剂为MMAO时,相对来说活性最高,当助催化剂为MAO时,分子量最高;当保持助催化剂为MMAO不变时,在不同的溶剂下(甲苯、己烷、氯苯),数据显示,使用甲苯的活性与分子量均占优势。
Claims (10)
4.根据权利要求3所述的一类叠加大位阻α-二亚胺配体的制备方法,其特征在于,所述的步骤二中结构式如(c)的单亚胺产物和通式为(b)的苯胺摩尔比为1:1。
8.根据权利要求7所述的一种镍催化剂的制备方法,其特征在于,所述的结构如式(I)所示一类叠加大位阻α-二亚胺配体和NiBr2(DME)的摩尔比为1:1。
9.权利要求5所述的一种镍催化剂在催化乙烯聚合中的应用。
10.根据权利要求9所述的一种镍催化剂在催化聚乙烯聚合中的应用,其特征在于,上述镍催化剂催化聚乙烯的方法,包括:
将反应器与高压气体管线连接,将反应器温度调节至0-150℃,在惰性气氛下,将溶剂和助催化剂加入到反应器中,然后将镍催化剂的二氯甲烷或氯仿溶液注入到反应器中,在搅拌下,通入乙烯并保持在压力为4-40atm,反应1-6min后,得到聚乙烯;
所述的助催化剂优选为甲基铝氧烷、改性甲基铝氧烷、三氯三乙基络铝或氯化二乙基铝。
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