CN1118479C - 硼苯环结构的烯烃聚合催化剂 - Google Patents

硼苯环结构的烯烃聚合催化剂 Download PDF

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CN1118479C
CN1118479C CN95197369A CN95197369A CN1118479C CN 1118479 C CN1118479 C CN 1118479C CN 95197369 A CN95197369 A CN 95197369A CN 95197369 A CN95197369 A CN 95197369A CN 1118479 C CN1118479 C CN 1118479C
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R·克里什纳莫蒂
S·纳吉
B·P·埃瑟顿
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Abstract

公开了通式(I)的催化剂,其中Q是包含环(II)的配位体,R是氢、N(R′)2、OR′或,每个R′独立地选自C1-C10烷基、C6-C15芳基、C7-C15烷芳基和C7-C15芳烷基,每个X独立地选自氢、卤素、C1-C10烷氧基、C1-C10二烷基氨基、甲基、(III),每个R1独立地选自卤素、C1-C10烷氧基和R′、L是(IV)、(V)、(VI)、(VII)、“n”为0-5,和M是钛、锆、铪。

Description

硼苯环结构的烯烃聚合催化剂
本发明的技术背景
本发明涉及用于乙烯和其它烯烃均聚和共聚的催化剂。更具体地说,本发明涉及含与包含硼苯环结构的配位体成π键的过渡金属催化剂。
至今,聚烯烃主要用传统的齐格勒催化剂体系制备。这些催化剂体系一般都由含过渡金属的化合物和一种或几种有机金属化合物组成。例如,使用齐格勒催化剂例如三氯化钛和氯化二乙基铝,或四氯化钛、三氯化氧钒和三乙基铝的混合物,制备聚乙烯。这些催化剂不贵,但是它们的活性低,因此必须以高浓度使用。结果,有时必须从聚合物中除去催化剂的残留物,这就增加了生产费用。为了克服催化剂残留物的有害影响,必须将中和剂和稳定剂加入聚合物。没有除去的催化剂残留物,使聚合物成黄色或灰色和差的抗紫外线性及低的稳定性。例如,含氯的残留物可以腐蚀聚合物的加工设备。而且,用齐格勒催化剂生产的聚合物有宽的分子量分布,这对某些应用和注塑应用来说是不希望的。在引入α-烯烃共聚单体方面,它们的性能也差。引入共聚单体的差的性质就使得难以控制聚合物的密度。为达到某一密度可能需要大量过剩的共聚单体,而许多较高碳的α-烯烃,例如1-辛烯完全只能以很低的量引入。
自从齐格勒催化剂体系发现以来,虽然进行了相当大的改进,但是现在这些催化剂正被近来发现的茂金属催化剂体系代替。茂金属催化剂通常是由有一个或几个环戊二烯基配位体的过渡金属化合物组成。它们与有机金属化合物如与传统的齐格勒催化剂一起使用的烷基铝一起使用时,活性低,但是它们与作为助催化剂的铝氧烷一起使用时,活性很高。活性通常是这样的高,以致于不需要从聚合物中除去催化剂的残留物。而且,它们生产的聚合物分子量高,且分子量的分布窄。它们引入α-烯烃共聚单体的性能也好。但是,在较高温度下,茂金属催化剂易于产生低分子量的聚合物。这样它们对在约80-约95℃下进行的乙烯气相和浆料聚合有用,但是,它们对在约150-约250℃下在溶液中乙烯的聚合反应通常不能很好地运行。在溶液中乙烯的聚合是希望的,因为允许在分子量和密度宽的范围内,以及使用各种各样的不同共聚单体更灵活的生产聚合物。人们可以生产用于许多不同方面应用的聚合物。例如,高分子量、高密度的聚乙烯(PE)膜用于食品包装的防渗膜,而低密度乙烯共聚物有良好的韧性,和高的抗冲击强度。
                             本发明的概述
我们已经发现了一类以硼苯环结构为基础和含过渡金属的催化剂。本发明的催化剂有非常高的活性,这就意味着它们可以很少的量使用。在将共聚单体引入聚合物方面,它们的性能也很好。在较高的温度下它们具有高的活性,因此,可预期用于溶液中乙烯的聚合反应。最后,本发明范围内的一些催化剂包含叔胺基。令人惊奇地是,虽然许多含胺化合物已知是催化剂的毒物,但是这些催化剂是有效的。
                            优选方案的描述
本发明的催化剂通式为:
Figure C9519736900061
在式中,Q是含硼苯环的配位体。硼苯环的结构为:
Figure C9519736900062
其中R可以是氢、N(R1)2、OR1或R1,每个R1独立地选自C1-C10烷基、C6-C15芳基、C7-C15烷芳基和C7-C15芳烷基。R基优选为-N(R1)2或苯基,如果R是-N(R1)2,那么-N(R1)2中的R’优选甲基。因为这些催化剂有优良的性质,Q配位体的实例包括:硼-苯环                                硼-萘环                              硼-萘环
Figure C9519736900072
硼-蒽环                                                                  硼-菲环
其中“M”是0-可取代位置的最大数,“m”优选为0,因为这些催化剂很容易制备,每个R1独立地选自卤素,C1-C10的烷氧基,和R1。优选的Q配位体是硼-苯环,硼-萘环和硼-蒽环,因为这些催化剂很容易制备。
在通式中,每个X独立地选自氢、卤素、C1-C10烷氧基、C1-C10二烷基氨基、甲基、
Figure C9519736900082
其中“n”是0-5,优选是0。X基优选是氯或甲基,因为这些催化剂容易制备并具有优良的性质。
同样,通式中的L可以是
Figure C9519736900083
优选L是环戊二烯基,因为这些催化剂最容易制备并具有优良性质。
通常,在催化剂中只使用一个桥键。据认为桥联的配位体改变了围绕催化活性过渡金属的几何形状,和提高了催化活性和其它性质,例如共聚单体的引入性和热稳定性。
通式中的M基可以是钛、锆或铪,但是优选锆,这是因为这些催化剂具有高活性和优良稳定性的最佳组合。
可以使用高达等摩尔量(与M)的碱。使用的路易斯碱通常不优选,因为它倾向于降低催化剂的活性。但是它也倾向于改进催化剂的稳定性,因此包含它是希望的,这取决于所使用它的方法。碱可以是来自催化剂制备所剩余的溶剂,或是为了提高催化剂的性质,单独加入的。可在本发明中使用的碱的实例包括醚类如二乙醚、二丁醚、四氢呋喃和1,2-二甲氧基乙烷、酯类如邻苯二甲酸正丁酯、苯甲酸乙酯和对茴香酸乙酯和膦类如三乙基膦、三丁基膦和三苯基膦。
催化剂Q配位体部分的制备可在文献中找到。例如,参见“硼-苯衍生物21。2,4-戊二烯基硼烷作为新的通往硼环己二烯和硼苯(Boratabenzenes)的关键中间体。〔Li(TMEDA)〕(C5H5BNMe2)的结构”,Gerhard E.Herberich等的论文 有机金属(1993),P2891-2893,本文引入参考。在那篇论文中,2,4-戊二烯基硼烷在N,N,N’,N’-四甲基乙二胺(TMEDA)存在下与四氢呋喃中氨基化锂反应,生成式
Figure C9519736900091
的二甲基氨基硼次苄基锂TMEDA的配合物,同样,参见“9-苯基-9-硼蒽阴离子的反应”,R.Van Veen和F.Bickelhaupt的文章,有机 属化学杂志,(1974),P153-165,这篇文章描述了9-苯基-9-硼蒽基锂的形成。
Figure C9519736900092
其它的Q配位体可以相似的方法或通过其它的方法制备。催化剂可以由Q配位体通过将适当的四价金属化合物的悬浮液加入Q配位体的溶液来制备。这个反应可在-78-50℃的温度发生,但是优选在0℃以下进行。
由于催化剂通常与有机金属助催化剂配合使用,因此优选将催化剂溶于助催化剂也可溶的溶剂中。例如,如果甲基铝氧烷(MAO)或聚甲基铝氧烷(PMAO)是助催化剂,那么甲苯、二甲苯、苯或乙苯可以用作溶剂。其它适宜的助催化剂包括通式为ALR’x(R2)3-x,其中1≤x≤3和R2是氢、卤化物或C1-C20烷基或烷氧基的烷基铝,例如三乙基铝和二氯乙基铝。优选的助催化剂是MAO,因为它产生高活性,而且聚合物有窄的分子量分布。当在聚合反应中使用时,有机金属助催化剂与催化剂的摩尔比一般为0.01∶1-100,000∶1,优选为1∶1-10,000∶1。
为增强催化剂的性质,催化剂可以与含非配位的不活泼阴离子的酸式盐一起使用(参见美国专利5064802号)。酸式盐通常是由附着到硼或铝原子上的松散配位体组成的非亲核化合物,例如四个(五氟苯基)硼酸锂、四个(五氟苯基)铝酸锂,四个(五氟苯基)硼酸苯胺和它们的混合物。当这些化合物与催化剂反应时,生成的阴离子被认为是与金属阳离子的配位。酸式盐与催化剂的摩尔比可为约0.01∶1-约1000∶1,但是优选约1∶1-10∶1。从催化剂和酸式盐制备活性催化剂体系的方法虽没有限制,但是优选在约-78℃-约150℃温度下,在惰性溶剂中混合。如果需要,它们也可在单体存在下混合。酸或盐可以与上述的有机金属助催化剂组合使用。
催化剂和助催化剂可以载持在载体上使用,所述的载体例如硅胶、氧化铝、氧化硅或二氧化钛,但是,因为这些载体都保留在聚合物的污物中,所以它们不优选使用。但是,载体的需要与否取决于所利用的方法。例如,在气相聚合法和浆料聚合反应过程中,为了控制所产生的聚合物的粒径和防止反应器壁的结垢,一般都需要使用载体。为了利用载体,催化剂和促催化剂溶于溶剂,并通过蒸发溶剂的方法,使催化剂和助催化剂沉淀在载体上。助催化剂也可以沉积在载体上,或由载体催化剂独立地引入反应器。
催化剂一但制备,就应当立即使用,尽可能地减少贮存期间可能损失的一些活性。催化剂应当在低温如-100℃-约20℃的温度下贮存。在烯烃单体的聚合反应过程中,催化剂以传统的方式使用。当未饱和单体例如苯乙烯利用本发明的催化剂聚合时,对α-烯烃如丙烯、1-丁烯、1-己烯、1-辛烯和特别是乙烯非常有用。
本发明的催化剂还用于乙烯与未饱和单体如1-丁烯、1-己烯、1-辛烯等混合物的共聚合;乙烯与二烯烃如1,3-丁二烯、1,4-己二烯、1,5-己二烯等混合物的共聚合;和乙烯与未饱和的共聚单体如降冰片烯、亚乙基降冰片烯、乙烯基降冰片烯等的混合物的共聚合。
本发明的催化剂可以用于各种不同的聚合方法。它们可以在液相聚合法(浆料、溶液、悬浮液、体相或它们的组合)、高压流体相或气相聚合法中使用。这些方法可以串联使用,或单独一个方法使用。在聚合反应区中的压力为约1.04×105帕斯卡(15磅/平方英寸)-约3.45×108帕斯卡(50000磅/平方英寸),而温度可为约-100℃-约300℃。催化剂以传统的方式用于烯烃单体如乙烯、丙烯、1-丁烯、1-辛烯、1-己烯、降冰片烯和降冰片二烯的共聚合。
用下述的实例进一步地描述本发明。
                             实施例1
这个实施例描述(B-二甲基氨基硼苯)二氯化环戊二烯基锆的合成,它的通式为:
Figure C9519736900111
其中Cp是环戊二烯基,Me是甲基。
在-78℃,将含0.61g(2.51mmol)二甲基氨基硼次苄基锂四甲基亚乙基二胺的配合物(按上述的G.E.Herberich的有关论文制备)的10ml醚溶液加入含0.56g(2.13mmol)三氯化环戊二烯基锆(购于StremChemicals)的15ml无水醚的悬浮液中。混合物升温到室温后,再搅拌一小时。在真空中除去挥发物后,残留物用30ml己烷洗涤,并用30ml甲苯提取。在减压下蒸发甲苯提取物,得0.23g黑色固体。质子核磁共振光谱表明在产品中存在一些杂质。
                           实施例2
这个实施例描述二氯化环戊二烯基(9-基硼蒽基)锆的合成,它的通式为:
通过在-78℃向含0.47g(1.6mmol)9-基硼蒽的18ml二乙醚溶液加入1.0ml1.6M的正丁基锂的己烷溶液,升温到室温,并继续搅拌二小时制备9-基硼蒽基锂的二乙醚溶液。将溶液冷却到-10℃后,添加0.42g(1.6mmol)的三氯化环戊二烯基锆(StremChemicals)。然后使浴槽达室温后,反应混合物搅拌过夜。在真空下除去挥发物,得到带红褐色的粉末。向这种粉末中加入20ml干燥的甲苯后,过滤该混合物,得到透明的黄-桔色过滤液,并将其浓缩,得到棕色泡沫。这种物质用干燥己烷(20ml)处理后,过滤混合物,得0.26g浅棕褐色固体。产品的质子核磁共振光谱表明,存在一些杂质。
                            实施例3-17
使用实施例1和2的催化剂进行乙烯聚合。(实施例3-13和实施例20使用实施例1制备的催化剂,实施例14-19使用实施例2制备的催化剂。)聚合反应是在1.7升高压釜中于80℃或110℃下进行。干燥无氧甲苯(840ml)加入清洁干燥的无氧反应器。在一些聚合反应中,使用Ethyl有限公司的MAO(10%甲苯)。其它的聚合反应是使用AkzoChemical的PMAO(25%甲苯)进行。在30℃用注射器加入得到表中所示比率的MAO或PMAO的所需要量。反应器加热到所要求的温度后,添加足够的乙烯使反应器的压力达1.04×106帕斯卡(150磅/平方英寸)〔表压〕。使反应器在所要求的温度和压力下达到平衡。通过将0.100g的产品溶于100ml甲苯中制备催化剂溶液。使用得到表中所示的催化剂量所需要的这种溶液量开始聚合反应。为了保持反应器的压力稳定在1.04×106帕斯卡(150磅/平方英寸)〔表压〕,按照产生聚合物所需要的量,使乙烯流入反应器。
在一小时(如果活性很高小于一小时)的结尾,停止乙烯流入反应器,反应器迅速冷却到室温。打开反应器后,从甲苯中滤出聚合物。产品在真空炉中干燥过夜。下表给出了反应条件和聚合反应的结果。
实施例  反应器温度(℃)  时间(分) H2数量(mmoles)     共聚单体 共聚单体(ml)   催化剂(mmoles)     Al/Zr(原子比) 助催化剂
    3     80   60     0     无     0  9.00E-03     1430  PMAO
    4     80   60     0     无     0  4.50E-03     2870  PMAO
    5     80   60     180     无     0  4.50E-03     2870  PMAO
    6     80   60     0     丁烯-1     20  4.50E-03     2870  PMAO
    7     110   60     0     无     0  4.50E-03     2870  PMAO
    8     110   60     0     无     0  4.50E-03     2870  MAO
    9     110   30     30     无     0  4.50E-03     2870  MAO
    10     110   60     0     丁烯-1     20  4.50E-03     2870  MAO
    11     110   60     90     丁烯-1     20  4.50E-03     2870  MAO
    12     110   30     90     己烯-1     20  4.50E-03     2870  MAO
    13     110   60     0     辛烯-1     20  4.50E-03     2870  MAO
    14     80   30     30     丁烯-1     17  4.79E-03     1570  MAO
    15     80   15     30     丁烯-1     17  4.79E-03     1570  MAO
    16     80   30     30     丁烯-1     17  4.79E-03     1570  MAO
    17     80   30     30     丁烯-1     17  4.79E-03     2190  MAO
    18     110   10     0     丁烯-1     17  4.79E-03     2190  MAO
    19     110   30     0     丁烯-1     17  2.87E-03     2190  MAO
    20     80   60     0     5-乙烯基-2-降冰片烯     30  3.00E-03     4500  MAO
实施例  wt.PE(g) 催化剂生产率(kg/g/hr)     MI2(dg/min)   WI20(dg/min)   WFR  密度(g/ml)    Mw/Mn
    3   77.1     93.9     0.17     2.37  13.9  0.9574    2.00
    4   81.3     198.1     0.14     2.57  18.0  0.9587    1.75
    5   92.5     225.4     10.28     333  32.4  0.9720    -
    6   71.7     174.7     1.11     24.92  22.5  0.9323    -
    7   70.4     171.5     1.10     22.64  20.6  0.9616    1.70
    8   80.1     195.2     1.50     35.81  23.9  0.9637    1.84
    9   105.0     511.7     18.40     539  29.3  0.9714    4.194
    10   96.5     235.1     7.92     152  19.2  0.9448    -
    11   110.0     536.1     41.94     1202  28.7  0.9521    -
    12   138.9     676.9     16.27     588  36.1  0.9584    4.85
    13   65.0     158.4     9.29     185  19.9  0.9515    -
    14   31.8     145.7     549     -  -  -    -
    15   34.5     316.1     <0.01     2.89  -  -    -
    16   44.5     203.8     106     -  -  -    -
    17   83.6     383.0     25.8     588  22.8  -    -
    18   66.1     908.4     <0.01     49.1  -  -    -
    19   33.2     253.5     <0.01     31.9  -  -    -
    20   49.1     179.4     0.07     1.18  17.1  0.9415    -
根据ASTM D-1238,条件E和F测量聚合物的熔体指数。MI2是用2.16kg重量(条件E)测定的熔体指数。MI20是用21.6kg重量(条件F)测量的熔体指数。MFR是MI20与MI2的比。按照ASTMD-1505测量聚合物密度。聚合物的分子量的分布使用Waters 150C凝胶渗透色谱仪,在135℃用1,2,4-三氯代苯作溶剂测量。使用重均分子量(Mw)和Mw与Mn(数均分子量)的比表征分子量的分布。表示出了在80℃时高活性,在110℃时活性几乎没有下降(实施例9与实施例2比较)。
催化剂有优良的共聚单体引入特性。在实施例6和10中记录的异常高的丁烯-1引入产生了较低密度的聚合物。此时,催化剂易于引入通常难以共聚的共聚单体。这是以实施例20中乙烯与5-乙烯基-2-降冰片烯的共聚反应为例。在实施例3中,表明分子量分布的重均分子量与数均分子量的比测量为2.00。Mw/Mn为2.00表明很窄的分子量分布。

Claims (14)

1.一种通式所示的催化剂
Figure C9519736900021
其中Q是含环的配位体,所述的环是
Figure C9519736900022
R选自由氢,N(R′)2、OR′和R′组成的组,每个R′独立地选自由C1-C10烷基、C6-C15芳基、C7-C15烷芳基和C7-C15芳烷基组成的组,每个X独立地选自氢、卤素、C1-C10烷氧基、C1-C10二烷基氨基、甲基
Figure C9519736900024
每个R1独立地选自由卤素、C1-C10烷氧基和R′组成的组,L是
Figure C9519736900025
  “n”为0-5和M选自由钛、锆和铪组成的组。
2.按权利要求1的催化剂,其中M是锆。
3.按权利要求1的催化剂,其中每个X是氯。
4.按权利要求1的催化剂,其中每个X是甲基。
5.按权利要求1的催化剂,其中L是环戊二烯基。
6.按权利要求1的催化剂,其中Q是和R是-N(R1)2或苯基。
7.按权利要求6的催化剂,其中Q是
8.按权利要求1的催化剂,其中Q是
Figure C9519736900033
其中“m”为0-7。
9.按权利要求1的催化剂,其中Q是
其中“m”为0-9。
10.按权利要求1的催化剂,每摩尔上述催化剂与0.01-100,000摩尔的有机金属助催化剂组合使用。
11.按权利要求10的催化剂,其中上述的有机金属助催化剂是甲基铝氧烷或聚甲基铝氧烷。
12.按权利要求1的催化剂,每摩尔上述催化剂与0.01-1000mol的含非配位不活泼的阴离子的酸式盐组合使用。
13.按权利要求12的催化剂,其中上述酸式盐选自由四个(五氟苯基)硼酸锂、四个(五氟苯基)铝酸锂、四个(五氟苯基)硼酸苯胺和它们的混合物组成的组。
14.α-烯烃的一种聚合方法,包括在权利要求1的催化剂存在下,加热上述的α-烯烃。
CN95197369A 1995-01-17 1995-12-20 硼苯环结构的烯烃聚合催化剂 Expired - Fee Related CN1118479C (zh)

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