CN107206370A - 用于烯烃低聚反应的催化剂体系及使用该催化剂体系的烯烃低聚方法 - Google Patents
用于烯烃低聚反应的催化剂体系及使用该催化剂体系的烯烃低聚方法 Download PDFInfo
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- CN107206370A CN107206370A CN201580074915.XA CN201580074915A CN107206370A CN 107206370 A CN107206370 A CN 107206370A CN 201580074915 A CN201580074915 A CN 201580074915A CN 107206370 A CN107206370 A CN 107206370A
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- Prior art keywords
- chromium
- carbon atoms
- group
- oligomerization
- catalyst system
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- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 66
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 51
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title claims abstract description 10
- 239000003426 co-catalyst Substances 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 83
- 150000001875 compounds Chemical class 0.000 claims description 53
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 44
- 229910052804 chromium Inorganic materials 0.000 claims description 41
- 125000005647 linker group Chemical group 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 36
- 239000011651 chromium Substances 0.000 claims description 32
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- 239000004711 α-olefin Substances 0.000 claims description 18
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- 239000005977 Ethylene Substances 0.000 claims description 16
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
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- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
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- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- CNIGXAJYMNFRCZ-UHFFFAOYSA-K butanoate;chromium(3+) Chemical compound [Cr+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O CNIGXAJYMNFRCZ-UHFFFAOYSA-K 0.000 claims description 3
- GWKHNQIALWXRPA-GECNZSFWSA-N chromium (Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one (E)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one Chemical compound [Cr].CC(C)(C)C(\O)=C/C(=O)C(C)(C)C.CC(C)(C)C(\O)=C/C(=O)C(C)(C)C.CC(C)(C)C(\O)=C\C(=O)C(C)(C)C GWKHNQIALWXRPA-GECNZSFWSA-N 0.000 claims description 3
- WFOOTRPLCMPWIP-UHFFFAOYSA-K chromium(3+) pentanoate Chemical compound [Cr+3].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O WFOOTRPLCMPWIP-UHFFFAOYSA-K 0.000 claims description 3
- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical compound [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 claims description 3
- NMXUZAZJTJAHGK-UHFFFAOYSA-K chromium(3+);dodecanoate Chemical compound [Cr+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O NMXUZAZJTJAHGK-UHFFFAOYSA-K 0.000 claims description 3
- IVKVYYVDZLZGGY-UHFFFAOYSA-K chromium(3+);octadecanoate Chemical compound [Cr+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O IVKVYYVDZLZGGY-UHFFFAOYSA-K 0.000 claims description 3
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 claims description 3
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Classifications
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Abstract
本发明涉及一种用于烯烃低聚反应的催化体系及一种烯烃低聚方法,更具体地,涉及一种用于烯烃低聚反应的催化体系及一种烯烃低聚方法,所述催化体系采用负载于载体上的催化活性组分,仅通过较少量的催化组合物和助催化剂而在烯烃低聚反应中展现出了高的活性,从而更有效地制备α‑烯烃。
Description
相关申请的交叉引用
本申请是基于分别于2015年05月15日和2015年12月23日提交的韩国专利申请第10-2015-0068301号和第10-2015-0185316号,且要求它们的优先权,其公开内容以引用的方式整体并入本文中。
技术领域
本公开内容涉及一种用于烯烃低聚反应的催化剂体系及一种烯烃低聚方法,更具体地,涉及一种用于烯烃低聚反应的催化剂体系及一种烯烃低聚方法,其能够更有效地制备α-烯烃,由于配体化合物负载于载体上,即使采用较少量的催化活性组分和助催化剂,也展现出了在烯烃低聚反应中的高活性。
背景技术
线性α-烯烃被用作清洁剂、润滑剂、增塑剂等,特别是在制备线性低密度聚乙烯(LLDPE)时被用作控制聚合物的密度的共聚单体。
在现有的LLDPE制备方法中,乙烯已与α-烯烃共聚单体(如1-己烯和1-辛烯)共聚,以便在聚合物主链中形成分支,从而控制其密度。
因此,会存在以下问题:在具有高共聚单体含量的LLPDE的制备中共聚单体的成本占了生产成本的一大部分。已有各种各样的尝试来解决所述问题。
此外,由于α-烯烃根据其种类而具有不同的应用领域或市场规模,因此能够同时生产不同烯烃的技术在商业上是非常重要的,并且最近,已开展了关于通过乙烯低聚反应或乙烯聚合反应来特定选择性地制备1-己烯、1-辛烯或聚乙烯的铬催化剂技术的许多研究。
发明内容
[技术问题]
本发明提供了一种用于烯烃低聚反应的催化剂体系,与液相催化剂体系相比,即使采用相对少量的助催化剂,其也展现出了在烯烃低聚反应中高的催化活性和对线性α-烯烃的选择性。
此外,本发明提供了一种采用该催化剂体系的烯烃低聚方法。
[技术方案]
本发明提供了一种用于烯烃低聚反应的催化剂体系,其包含在分子内含有一个以上的由以下化学式1表示的二膦基的配体化合物;铬源;和载体:
[化学式1]
其中,
P为磷原子,以及N为氮原子,
R1至R4彼此相同或不同,且各自独立地为具有1至20个碳原子的烃基、具有1至20个碳原子的杂烃基或具有1至20个碳原子的烃杂基
(hydrocarboheteryl group),以及
*表示化学式1的基团为单价键合基团。
在这方面,所述配体化合物含有一个以上的由化学式1表示的二膦基,以及所述二膦基可通过连接体L彼此连接。
所述连接体L可为以具有4至10个碳原子的最短的距离连接所述二膦基的连接体,并且所述连接体L可为具有2至20个碳原子的脂肪族连接体、具有3至20个碳原子的脂环族连接体或具有6至20个碳原子的芳香族连接体。
根据一个实施方式,所有的二膦基可与铬形成配位键。
具体地,铬原子与所述配体化合物的摩尔比可优选为1以上。
所述用于烯烃低聚反应的催化剂体系可包含在分子内具有一个以上的由以下化学式2表示的铬配合物基团的有机铬化合物:
[化学式2]
其中,
P为磷原子,N为氮原子,以及Cr为铬原子,
R1至R4彼此相同或不同,且各自独立地为具有1至20个碳原子的烃基、具有1至20个碳原子的杂烃基或具有1至20个碳原子的烃杂基,
Y1至Y3彼此相同或不同,且各自独立地为氢原子、卤素原子、具有1至10个碳原子的烃基、具有1至10个碳原子的杂烃基或具有1至10个碳原子的烃杂基,以及
*表示化学式2的基团为单价键合基团。
根据本发明的另一个实施方式,所述铬源可为选自乙酰丙酮铬(III)、四氢呋喃氯化铬(III)、2-乙基己酸铬(III)、乙酸铬(III)、丁酸铬(III)、戊酸铬(III)、月桂酸铬(III)、三(2,2,6,6-四甲基-3,5-庚二酮酸)铬(III)和硬脂酸铬(III)中的一种以上的化合物。
所述用于烯烃低聚反应的催化剂体系可进一步包含负载于所述载体上的助催化剂。
在这方面,所述助催化剂可为选自三甲基铝、三乙基铝、三异丙基铝、三异丁基铝、倍半乙基氯化铝、二乙基氯化铝、乙基二氯化铝、甲基铝氧烷和改性甲基铝氧烷中的一种以上的化合物。
优选地,相对于1g的所述载体,可以约5mmol/g至约15mmol/g的量负载所述助催化剂。
与此同时,根据本发明的另一个方面,提供了一种烯烃低聚方法,包括在所述催化剂体系的存在下通过进行烯属单体的低聚反应而形成α-烯烃的步骤。
在这方面,所述烯属单体可优选为乙烯。
根据一个实施方式,所述烯属单体的低聚反应可优选在约5℃至约200℃的温度和约1巴至约300巴的压力下进行。
[有益效果]
在本发明的用于烯烃低聚反应的催化剂体系中,催化金属和助催化剂组分均匀地分布在整个载体上,因此,所述催化剂体系,即使以相对较少的量使用,其也可展现出高的活性。
此外,随着固相负载催化剂的使用,会易于将所述催化剂与液相反应物和产物分离,因此,可降低其它异构体的产生。此外,由于固体聚乙烯在所述载体上产生,故可有效防止在反应器的表面上生成积垢。
附图说明
图1分别显示了根据本发明的实施例1和对比实施例1中的乙烯低聚反应后的反应器的内部装置的照片;
图2分别显示了根据本发明的实施例1和对比实施例1中获得的干燥固体产物的照片;以及
图3和图4分别显示了根据本发明的对比实施例2和4中的乙烯低聚反应后的反应器的内部装置和内壁的照片。
具体实施方式
本文中所用的术语仅仅是为了描述特定的实施方式的目的,而不意在限制本发明。单数形式也意在包括复数形式,除非上下文另有明确地指出。还应当理解的是,术语“包括”、“具有”或“具备”,当在本申请文件中使用时,指定了所述特征、整数、步骤、组分或它们的组合的存在,但并不排除一个以上其它特征、整数、步骤、组分或它们的组合的存在或添加。
虽然本发明易于进行各种修改和替代形式,但是其具体实施方式以示例的方式示出,并且将在此详细描述。然而,应当理解,这些并不旨在将本发明限制于所公开的特定形式,而相反,本发明旨在覆盖落入本发明的实质和范围内的所有修改、等同物和替代方案。
如本文中所用的,术语“低聚”是指少量烯烃的聚合。例如,根据待聚合的烯烃的重复数量,低聚统指多聚,包括三聚或四聚。在本发明中,特别地,所述低聚是指由乙烯选择性地制备用作LLDPE的主要共聚单体的1-己烯和/或1-辛烯。
如本文中所用的,除非另有说明,烃基统指烃化合物,例如,烷基、芳基、烯基、炔基、环烷基等,且包括直链和支链形式,以及取代和未取代的形式。
如本文中所用的,烷基芳基是指具有一个以上的烷基作为取代基的芳基,以及芳基烷基是指具有一个以上的芳基作为取代基的烷基。
如本文中所用的,杂原子是指氮、氧、硫或磷,以及杂烃基是指具有一个以上的杂原子的烃基。这样的杂烃基是指具有碳作为官能化结合位点的基团,以及杂基团,如“烃杂基”、“有机杂基”等是指具有杂原子作为官能化结合位点的基团。
下文中,将更加详细地描述本发明。
根据本发明的一个方面的用于烯烃低聚反应的催化剂体系包含:在分子内含有一个以上的由以下化学式1表示的二膦基的配体化合物;
铬源;和
载体:
[化学式1]
其中,
P为磷原子,以及N为氮原子,
R1至R4彼此相同或不同,且各自独立地为具有1至20个碳原子的烃基、具有1至20个碳原子的杂烃基或具有1至20个碳原子的烃杂基,以及
*表示化学式1的基团为单价键合基团。
由于氮原子和磷原子的富电子密度,所述配体化合物在分子内包含二膦基部分,并向铬提供非共享电子对。
与已知的金属环庚烷或金属环壬烷的反应机理相比,由于这些结构特征,可改变整个配体化合物的电子和空间特性,并可改变配体与铬原子之间的键以使得催化剂的结构更加稳定,以及可改变过渡态能(即反应的活化能)以更高活性和选择性地形成α-烯烃。
当通过采用MAO或基于硼酸盐的助催化剂来进行液相反应时,许多现有的基于有机铬的催化剂可被用于高活性和选择性地制备α-烯烃,但当它们与助催化剂一起被负载于载体上时其反应活性显著下降。
然而,根据本发明的一个方面的催化剂体系,即使将其负载于载体(如二氧化硅等)上时,也可被用于高活性和选择性地制备α-烯烃。另外,由于所述催化剂体系处于固相,故易于将所述催化剂与液相反应物和产物分离,因此,可减少因当产物不与催化剂分离时产生的不利影响或副反应而导致的异构体的产生。
照此,所述催化剂体系可易于与反应体系分离,因而减少通过均相液相反应的副反应而生成的副产物,如固体聚乙烯等。
所述烯烃低聚反应可在所述载体内的孔穴中进行,因此,即使形成了固体聚乙烯,也可以防止在均相液相反应时粘附于载体内的固体聚乙烯团块的产生,这可有效防止可能会由残留在反应器中的副产物导致的积垢、管道堵塞等问题。
此外,由于催化活性组分、铬和助催化剂组分负载于相同的载体上,故可容易地发生所述催化剂与所述助催化剂之间的相互作用。因此,尽管以小于液相催化剂的量来使用所述催化剂,但亦可以来高活性地聚合线性α-烯烃。
根据本发明的一个实施方式,所述配体化合物包含两个以上的由化学式1表示的二膦基,其中所述二膦基通过连接体L彼此连接,例如,以下化学式1-1表示:
[化学式1-1]
其中,P为磷原子,
N为氮原子,
R1至R4和R1'至R4'彼此相同或不同,且各自独立地为具有1至20个碳原子的烃基、具有1至20个碳原子的杂烃基或具有1至20个碳原子的烃杂基,以及
L为连接两个以上的二膦基且具有2至30个碳原子的烃基或具有2至30个碳原子的杂烃基。
更具体地,在化学式1和2中,R1至R4和R1'至R4'可为,例如,具有6至20个碳原子的芳基、具有6至20个碳原子的杂芳基或具有6至20个碳原子的芳杂基;或者具有7至20个碳原子的烷基芳基、具有7至20个碳原子的杂烷基芳基、具有7至20个碳原子的烷基杂芳基或具有7至20个碳原子的烷基芳杂基。
所述连接体(L)可为具有各种结构的烃基、杂烃基或烃杂基,且在所述二膦基之间最短距离中的原子数可为2至30个。具体地,所述连接体可为,例如,具有2至20个碳原子的脂肪族连接体、具有2至20个碳原子的杂脂肪族连接体、具有3至20个碳原子的脂环族连接体、具有3至20个碳原子的杂脂环族连接体、具有6至20个碳原子的芳香族连接体或具有6至20个碳原子的杂芳香族连接体,但所述结构没有特别的限制。
如果将选自所述连接体中的两个以上的基团确定为主链,则所述连接体的主链可具有各种结构的取代基。
上述连接体的非限定性实例可包括具有以下结构式的化合物。在以下实例中,为了方便起见,由化学式1表示的二膦基由[A]、[A']或[A”]表示,且各个二膦基可彼此相同或不同。
(i)由2或3个碳原子连接的多个二膦基:
(ii)由4个碳原子连接的多个二膦基:
(iii)由5个碳原子连接的多个二膦基:
所述连接体(L)的更具体的实例可包括第一连接体、第二连接体或第三连接体。
在所述第一连接体中,在二膦基之间的最短距离中的碳原子数可为4,以及所述第一连接体可包括具有1至20个碳原子的脂族连接体、具有3至20个碳原子的脂环族连接体和具有6至20个碳原子的芳香族连接体,并可具有以下结构式:
在所述结构式中,*为与以上所述的由化学式1表示的二膦基相连接的区域,
RR各自独立地为具有1至5个碳原子的烷基,
n可为每个环中的取代数目,且可根据取代数目在1至4的整数范围内变化,以及
连接到一个环上的多个RR可彼此相同或不同。
这种情况下,所述配体化合物可具有,例如,以下结构式:
此外,在所述第二连接体中,在二膦基之间的最短距离中的碳原子数可为5至8,以及所述第二连接体可为具有5至20个碳原子的脂肪族连接体,或为其中具有1至20个碳原子的脂肪族基团与具有6至20个碳原子的芳香族基团相连接的连接体。所述连接体的任何一端可被具有6至20个碳原子的芳基取代或未被取代。
具体地,所述第二连接体可具有以下结构式:
此外,在所述第三连接体中,在二膦基之间的最短距离中的碳原子数可为4至23,以及所述第三连接体可由以下化学式3表示:
[化学式3]
其中,
Q表示由化学式1表示的二膦基,
X为具有1至20个碳原子的亚烷基或具有6至14个碳原子的亚芳基,
R5至R14彼此相同或不同,且各自独立地为具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至14个碳原子的芳基、具有7至18个碳原子的烷基芳基、具有7至18个碳原子的芳基烷基或具有7至18个碳原子的烷氧基芳基。
在此情况下,所述配体化合物的代表性实例可具有以下结构式:
由于所述连接体(L)的上述结构,可进一步改善负载催化剂的活性,且所述催化剂可在对线性α-烯烃的选择性方面是有利的。
根据本发明的一个实施方式,属于配体化合物中所包含的两个以上的二膦基的一个以上的二膦基的非共享电子对与铬原子配位,从而成为有机铬化合物的形式。
优选所有的二膦基与铬形成配位键,为此,铬原子与所述配体化合物的摩尔比可为1以上,且优选约1至约2。
例如,所述用于烯烃低聚反应的催化剂体系可包含在分子内具有一个以上的由以下化学式2表示的铬配合物基团的有机铬化合物:
[化学式2]
其中,
P为磷原子,N为氮原子,以及Cr为铬原子,
R1至R4彼此相同或不同,且各自独立地为具有1至20个碳原子的烃基、具有1至20个碳原子的杂烃基或具有1至20个碳原子的烃杂基,
Y1至Y3彼此相同或不同,且各自独立地为氢原子、卤素原子、具有1至10个碳原子的烃基或具有1至10个碳原子的杂烃基或具有1至10个碳原子的烃杂基,以及
*表示化学式2的基团为单价键合基团。
即,所述二膦基的磷原子与铬原子配位,从而成为有机铬化合物的形式。一分子的所述有机铬化合物可具有至少一个,优选两个以上的用于烯烃低聚反应的催化活性位点。
因此,可进一步改善对线性α-烯烃的催化活性和选择性,且可改善负载效率,以及可减少在反应或分离期间催化剂组分与载体的分离。
在这个观点中,所述连接体(L)可更优选地包括相对柔韧的脂肪族连接体,以增强各个二膦基的束缚及其作为活性位点的功能。例如,当所述连接体仅由脂环族或芳香族连接体而非脂肪族连接体组成时,刚性键极大地限制了相互作用,结果,可极大地降低催化活性,且还可降低对线性α-烯烃的选择性。
此外,基于与铬原子配位的配体化合物的重量,相对于100重量份的载体,可以约0.5至约20重量份,优选约1至约15重量份,以及更优选约1至约10重量份的量来包含所述配体化合物。
根据本发明的一个实施方式,铬原子与所述配体化合物的摩尔比可以为1以上,优选1:1至10:1,以及更优选1:1至5:1。
所述载体具有足以负载催化组分的比表面积,并且可采用内部具有大量孔穴的常规载体来促进所述烯烃低聚反应。
即,负载催化剂通常采用的金属或非金属、盐或其氧化物可被用作所述载体而没有特别的限制,其具体实例可包括二氧化硅、氧化铝、二氧化硅-氧化铝、二氧化硅-氧化镁等,但本发明并不限于此。所述载体可为在高温下干燥的载体,且所述载体可通常包括金属氧化物、碳酸盐、硫酸盐或硝酸盐,如氧化钠、碳酸钾、硫酸钡、硝酸镁等。
优选所述载体的表面上的羟基的数目尽可能地少。实际上,除去所有的羟基是困难的。重要的是可通过在制备所述载体期间调节干燥条件来控制羟基的数目。例如,相对于所述载体的重量,所述羟基可为约10mmol/g以下,优选约1mmol/g以下,以及更优选约0.5mmol/g以下。为了防止由于干燥后残留的痕量羟基的副反应,可采用选择性除去羟基,同时保留具有高负载反应性的硅氧烷基团的载体。
在所述催化剂体系中,铬的来源可为有机或无机铬化合物,其中铬的氧化态为0至6。例如,所述铬的来源可为铬金属或任何有机或无机基团与铬结合的化合物。在这里,所述有机基团可为各自具有1至20个碳原子的烷基、烷氧基、酯、酮、酰胺基或羧酸根基团,以及所述无机基团可为卤化物、硫酸根、氧化物等。
所述铬源的具体实例可为选自乙酰丙酮铬(III)、四氢呋喃氯化铬(III)、2-乙基己酸铬(III)、乙酸铬(III)、丁酸铬(III)、戊酸铬(III)、月桂酸铬(III)、三(2,2,6,6-四甲基-3,5-庚二酮酸)铬(III)和硬脂酸铬(III)中的一种以上的化合物。
根据本发明的另一个实施方式,以上所述的催化剂体系可进一步包括负载于所述载体上的助催化剂。
优选地,所述助催化剂可为含有第13族金属的有机金属化合物,且所述助催化剂没有特别的限制,只要其可通常用于在过渡金属化合物的催化剂存在下的烯烃聚合反应中即可。
例如,所述助催化剂可为选自由以下化学式4至6表示的化合物中的一种以上的化合物:
[化学式4]
-[Al(Rx)-O]c-
其中,Al为铝,
Rx彼此相同或不同,且各自独立地为卤素基团、具有1至20个碳原子的烃基、具有1至20个碳原子的卤素取代的烃基,以及c为2以上的整数,
[化学式5]
D(Ry)3
其中,D为铝或硼,Ry为具有1至20个碳原子的烃基或具有1至20个碳原子的卤素取代的烃基,
[化学式6]
[L-H]+[Q(E)4]-
其中,L为中性路易斯碱,[L-H]+为布朗斯台德酸,Q为+3氧化态的硼或铝,E各自独立地为其中一个以上的氢原子被卤素、具有1至20个碳原子的烃基、烷氧基官能团或苯氧基官能团取代或未被取代的具有6至20个碳原子的芳基或具有1至20个碳原子的烷基。
根据一个实施方式,由化学式4表示的化合物可包括烷基铝氧烷,如甲基铝氧烷、乙基铝氧烷、异丁基铝氧烷、丁基铝氧烷等。
根据一个实施方式,由化学式5表示的化合物可为三甲基铝、三乙基铝、三异丁基铝、三丙基铝、三丁基铝、二甲基氯化铝、二甲基异丁基铝、二甲基乙基铝、二乙基氯化铝、三异丙基铝、三仲丁基铝、三环戊基铝、三戊基铝、三异戊基铝、三己基铝、乙基二甲基铝、甲基二乙基铝、三苯基铝、三对甲苯基铝、二甲基甲氧基铝、二甲基乙氧基铝、三甲基硼、三乙基硼、三异丁基硼、三丙基硼、三丁基硼等。
根据一个实施方式,由化学式6表示的化合物可为三乙基铵四苯基硼、三丁基铵四苯基硼、三甲基铵四苯基硼、三丙基铵四苯基硼、三甲基铵四(对甲苯基)硼、三丙基铵四(对甲苯基)硼、三乙基铵四(邻,对二甲苯基)硼、三甲基铵四(邻,对二甲苯基)硼、三丁基铵四(对三氟甲基苯基)硼、三甲基铵四(对三氟甲基苯基)硼、三丁基铵四(五氟苯基)硼、N,N-二乙基苯胺四苯基硼、N,N-二乙基苯胺四苯基硼、N,N-二乙基苯胺四(五氟苯基)硼、二乙基铵四(五氟苯基)硼、三苯基膦四苯基硼、三甲基膦四苯基硼、三乙基铵四苯基铝、三丁基铵四苯基铝、三甲基铵四苯基铝、三丙基铵四苯基铝、三甲基铵四(对甲苯基)铝、三丙基铵四(对甲苯基)铝、三乙基铵四(邻,对二甲苯基)铝、三丁基铵四(对三氟甲基苯基)铝、三甲基铵四(对三氟甲基苯基)铝、三丁基铵四(五氟苯基)铝、N,N-二乙基苯胺四苯基铝、N,N-二乙基苯胺四苯基铝、N,N-二乙基苯胺四(五氟苯基)铝、二乙基铵四(五氟苯基)铝、三苯基膦四苯基铝、三甲基膦四苯基铝、三苯基碳鎓四苯基硼、三苯基碳鎓四苯基铝、三苯基碳鎓四(对三氟甲基苯基)硼、三苯基碳鎓四(五氟苯基)硼等。
此外,所述助催化剂的非限定性实例可包括有机铝化合物、有机硼化合物、有机镁化合物、有机锌化合物、有机锂化合物或它们混合物。根据一个实施方式,所述助催化剂可优选为有机铝化合物,且更优选为选自三甲基铝、三乙基铝、三异丙基铝、三异丁基铝,倍半乙基氯化铝、二乙基氯化铝、乙基二氯化铝、甲基铝氧烷和改性甲基铝氧烷中的一种以上的化合物。
当所述配体化合物与所述助催化剂都负载于所述载体上时,各组分的含量没有限制。不过,所述配体化合物与所述助催化剂的摩尔比可为约1:5至约1:1,000,以及优选约1:10至约1:250。
此外,基于100重量份的所述载体,可以约1至约1,000重量份,优选约10至约100重量份,以及更优选约40至约150重量份的量分别包含所述助催化剂。
作为负载形式,与铬原子配位的配体化合物和助催化剂可均匀地负载于一种载体上,或可分别负载于不同的载体上。
此外,负载的方法没有特别的限制,可先负载所述助催化剂,然后再负载与铬原子配位的配体化合物。在此情况下,最终待负载的助催化剂的量被分为两部分,然后被负载。
所述助催化剂和所述配体化合物的负载可在约20℃至约120℃的温度范围内进行约1小时至约20小时。
详细地,所述负载可包括以下步骤:通过使所述助催化剂与所述载体接触而将所述助催化剂负载于所述载体的内部和表面上;以及将含有所述配体化合物和所述铬源的混合物加入并负载到负载有所述助催化剂的载体上。
此外,在负载所述助催化剂的步骤中,可在进料所述助催化剂时将助催化剂进料分份并在不同温度下进料一次或多次,并且各个进料温度可在逐渐降低的温度条件下,例如,在约-50℃至约150℃下,从初始进料温度逐渐降低。
与此同时,根据本发明的另一个方面,提供了一种烯烃低聚方法,包括在以上所述催化剂体系的存在下通过进行烯属单体的低聚反应而形成α-烯烃的步骤。
在这方面,所述烯属单体可优选为乙烯。
一般而言,烯烃低聚反应可通过采用常规设备和接触技术来进行。非限定性的例子,常规烯烃低聚反应可通过在无活性溶剂的存在或不存在的情况下进行的均相液相反应,通过一部分催化剂体系或全部的催化剂不溶的淤浆反应,通过产物α-烯烃或聚乙烯作为主要介质的本体相反应,或者通过气相反应来进行。
然而,在均相液相反应中,作为副产物的固体聚乙烯的产生不可避免,且该固体聚乙烯异相地残留于反应体系的液体中,从而降低了低聚反应的效率,降低了对线性α-烯烃的选择性,以及产生诸如积垢等的不利影响。
不过,在本发明中,采用固体负载催化剂以在所述负载催化剂的内部孔穴中进行低聚反应,因此,所述催化剂具有非常高的稳定性,并且即使生成了固体聚乙烯也可维持低聚反应的形态。
此外,包含于所述配体化合物中的一个以上的二膦基强烈地束缚于载体上,从而减少催化活性组分的浸出。因此,如上所述,可提高反应效率,以及可降低杂质的含量。
所述烯烃低聚反应可在惰性溶剂的存在下进行。所述惰性溶剂的非限定性实例可包括苯、甲苯、二甲苯、枯烯、氯苯、二氯苯、庚烷、环己烷、甲基环己烷、甲基环戊烷、正己烷、1-己烯、1-辛烯等。
所述烯烃低聚反应可在约0℃至约200℃、或约0℃至约150℃、或约30℃至约100℃、或约50℃至约100℃的温度下进行。此外,所述反应可在约1巴至约300巴或2巴至约150巴的压力下进行。
下文中,将参照本发明的具体实施例来更加详细地解释本发明的作用和效果。然而,这些实施例仅仅是对本发明的说明,且不能由此确定本发明的范围。
<实施例>
载体的制备
将二氧化硅(SP952X,格雷斯-戴维森公司(Grace Davison))在200℃下真空干燥12小时以制备载体,在氩气氛下将其储存在手套箱中。
催化剂体系的制备
[实施例1]
的制备
在氩气氛下,用烧瓶将5mmol的3-(氨基甲基)3,5,5-三甲基环己胺和三乙胺(4至10胺当量)溶于80ml的二氯甲烷中。
在将烧瓶浸入水浴中时,缓慢加入氯化二甲苯基膦(相对于胺,4当量),并将混合物搅拌过夜。
在真空下除去溶剂,然后加入THF,随后充分搅拌,并采用无空气的玻璃过滤器除去三乙铵盐酸盐。从滤液中除去溶剂,以获得由上述结构式表示的配体化合物。
除了该配体化合物之外,还制备了三价乙酸铬(146.7mg,0.42mmol)作为铬源,并以铬:配体化合物的摩尔比为2:1置于烧瓶中。向其中加入65ml的甲苯,搅拌,以制得11mM的有机铬配合物。
在40℃下将7g的如此制得的载体置于玻璃反应器中,向甲苯溶液中加入77mmol的含铝的甲基铝氧烷(MAO)溶液,随后进行负载。
向其中加入如此制得的有机铬配合物,并通过搅拌反应2小时。停止搅拌后,除去滤液。
将所得物用足量的甲苯洗涤,向其中加入100ml的己烷,随后搅拌。将如此制得的浆料溶液转移至氩气吹扫过的烧瓶中,除去滤液,随后真空干燥。最终,获得了固体粉末形式的负载催化剂。
[制备实施例2]
的制备
除了采用2,6-二乙基苯胺来代替3-(氨基甲基)3,5,5-三甲基环己胺,以及仅使用0.35mmol的铬源以使得配体化合物与铬原子的摩尔比为1:1之外,以与制备实施例1相同的方式制得了负载催化剂。
[制备实施例3]
的制备
除了采用对甲苯胺来代替3-(氨基甲基)3,5,5-三甲基环己胺,以及仅使用0.35mmol的铬源以使得配体化合物与铬原子的摩尔比为1:1之外,以与制备实施例1相同的方式制得了负载催化剂。
乙烯低聚物的制备
[实施例1至3]
在由金属合金制成的600ml反应器中进行低聚反应,所述反应器配置有机械搅拌器,温度可控,且可在高压下操作。
在干燥箱中称取30mg的制备实施例1至3中制得的负载催化剂,并各自放入50ml玻璃瓶中。将该瓶用橡胶隔膜密封,从干燥箱中取出,并准备注入反应器中。
将400ml的含有1.0mmol的三乙基铝的己烷和制得的负载催化剂在不接触空气的情况下进料至反应器中,并在80℃和30巴的压力下连续供应气相乙烯单体以进行低聚反应1小时。
此后,停止搅拌,以及通过脱气除去未反应的乙烯来终止反应。
取少量反应器中的液体部分并用水淬灭,利用PTFE注射器过滤器过滤有机层,之后进行GC分析。
向剩余的反应液中加入409ml的乙醇/HCl(10体积%),搅拌并过滤混合物以获得聚合物。将所述聚合物在60℃真空烘箱中干燥12小时或更久,然后称重。
[对比实施例1至3]
除了制备实施例1至3中制得的各有机铬化合物不被负载于载体上,而用作液相催化剂以进行均相液相反应之外,以在与实施例1相同的助催化剂组成和反应条件下进行反应。
结果总结在下表1中。
[表1]
参照表1,尽管在相同条件下以相同的比例使用有机铬化合物和助催化剂,但负载催化剂体系即使采用相对少量的助催化剂,也显示出非常高的催化活性和对线性α-烯烃的高的选择性。
这些结果似乎归因于负载于单一载体上的助催化剂与催化活性组分(配体化合物-铬配合物)之间的短的距离,且还归因于铬和助催化剂在载体内部和外部的均匀分布。
此外,与实施例相比,对比实施例显示出非常低的催化活性。这些结果似乎归因于仅使用220当量的助催化剂,但是在液相催化剂体系的情况下,为了确保活性,相对于铬的摩尔数,应当采用600当量以上,优选900至1500当量的助催化剂(基于铝的当量)。
图1分别显示了根据本发明的实施例1和对比实施例1中的乙烯低聚反应后的反应器的内部装置的照片。
图3和图4分别显示了根据本发明的对比实施例2和4中的乙烯低聚反应后的反应器的内部装置和内壁的照片。
参照上述附图,在对比实施例中,固体产物,即固体聚乙烯粘附于反应器的内部装置和内壁,导致生成严重的积垢。与此相反,在实施例中,即使在乙烯低聚反应之后,所述反应器的内部装置和内壁也保持了清洁。这些结果似乎归因于负载催化剂对乙烯低聚物的高选择性以及有效防止了积垢,积垢被防止是因为尽管固体聚乙烯部分地产生,但其仅存在于所述载体的内部。
图2分别显示了根据本发明的实施例1和对比实施例1中获得的干燥固体产物的照片。
参照图2,在进行液相反应的对比实施例中,固体产物的形态太不均匀而不能被利用,且团聚的颗粒也不会被分解。与此相反,在实施例中,以均匀的粉末获得了产物,因此,预期其可用性将高于对比实施例的产物。
Claims (14)
1.一种用于烯烃低聚反应的催化剂体系,其包含:在分子内含有一个以上的由以下化学式1表示的二膦基的配体化合物;
铬源;和
载体:
[化学式1]
其中,
P为磷原子,以及N为氮原子,
R1至R4彼此相同或不同,且各自独立地为具有1至20个碳原子的烃基、具有1至20个碳原子的杂烃基或具有1至20个碳原子的烃杂基,以及
*表示化学式1的基团为单价键合基团。
2.如权利要求1所述的用于烯烃低聚反应的催化剂体系,其中,所述配体化合物含有两个以上的由化学式1表示的二膦基,以及
所述二膦基通过连接体L彼此连接。
3.如权利要求2所述的用于烯烃低聚反应的催化剂体系,其中,所述连接体L为以具有4至10个碳原子的最短距离连接所述二膦基的连接体,并且所述连接体L为具有2至20个碳原子的脂肪族连接体、具有3至20个碳原子的脂环族连接体或具有6至20个碳原子的芳香族连接体。
4.如权利要求2所述的用于烯烃低聚反应的催化剂体系,其中,所有的二膦基与铬形成配位键。
5.如权利要求1所述的用于烯烃低聚反应的催化剂体系,其中,所述铬原子与所述配体化合物的摩尔比为1以上。
6.如权利要求1所述的用于烯烃低聚反应的催化剂体系,其包含在分子内具有一个以上的由以下化学式2表示的铬配合物基团的有机铬化合物:
[化学式2]
其中,
P为磷原子,N为氮原子,以及Cr为铬原子,
R1至R4彼此相同或不同,且各自独立地为具有1至20个碳原子的烃基、具有1至20个碳原子的杂烃基或具有1至20个碳原子的烃杂基,
Y1至Y3彼此相同或不同,且各自独立地为氢原子、卤素原子、具有1至10个碳原子的烃基、具有1至10个碳原子的杂烃基或具有1至10个碳原子的烃杂基,以及
*表示化学式2的基团为单价键合基团。
7.如权利要求1所述的用于烯烃低聚反应的催化剂体系,其中,所述铬源为选自乙酰丙酮铬(III)、四氢呋喃氯化铬(III)、2-乙基己酸铬(III)、乙酸铬(III)、丁酸铬(III)、戊酸铬(III)、月桂酸铬(III)、三(2,2,6,6-四甲基-3,5-庚二酮酸)铬(III)和硬脂酸铬(III)中的一种或多种化合物。
8.如权利要求1所述的用于烯烃低聚反应的催化剂体系,其进一步包含负载于所述载体上的助催化剂。
9.如权利要求8所述的用于烯烃低聚反应的催化剂体系,其中,所述助催化剂为选自三甲基铝、三乙基铝、三异丙基铝、三异丁基铝、倍半乙基氯化铝、二乙基氯化铝、乙基二氯化铝、甲基铝氧烷和改性甲基铝氧烷中的一种或多种化合物。
10.如权利要求8所述的用于烯烃低聚反应的催化剂体系,其中,相对于1g的所述载体,以5mmol/g至15mmol/g的量负载所述助催化剂。
11.一种烯烃低聚方法,包括在权利要求1至10中任一项所述的催化剂体系的存在下通过进行烯属单体的低聚反应而形成α-烯烃的步骤。
12.如权利要求11所述的烯烃低聚方法,其中,所述方法为用于乙烯低聚的方法。
13.如权利要求11所述的烯烃低聚方法,其中,所述烯属单体的低聚反应在5℃至200℃的温度下进行。
14.如权利要求11所述的烯烃低聚方法,其中,所述烯属单体的低聚反应在1巴至300巴的压力下进行。
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JP6490226B2 (ja) | 2019-03-27 |
CN107428862B (zh) | 2020-11-06 |
KR20160134455A (ko) | 2016-11-23 |
EP3260475B1 (en) | 2020-01-01 |
JP2018503509A (ja) | 2018-02-08 |
EP3225637B1 (en) | 2020-02-05 |
KR101937993B1 (ko) | 2019-01-11 |
JP2018505948A (ja) | 2018-03-01 |
EP3260475A4 (en) | 2018-12-05 |
CN107567465B (zh) | 2020-09-22 |
EP3225637A4 (en) | 2018-09-12 |
JP6503472B2 (ja) | 2019-04-17 |
KR101768194B1 (ko) | 2017-08-16 |
US20180094085A1 (en) | 2018-04-05 |
JP2018508355A (ja) | 2018-03-29 |
CN107206370B (zh) | 2019-12-10 |
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