CN110479381B - 一种用于乙烯选择性齐聚的催化剂体系及其制备方法与应用 - Google Patents
一种用于乙烯选择性齐聚的催化剂体系及其制备方法与应用 Download PDFInfo
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- CN110479381B CN110479381B CN201910762738.4A CN201910762738A CN110479381B CN 110479381 B CN110479381 B CN 110479381B CN 201910762738 A CN201910762738 A CN 201910762738A CN 110479381 B CN110479381 B CN 110479381B
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- ethylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
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- 239000005977 Ethylene Substances 0.000 title claims abstract description 38
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003446 ligand Substances 0.000 claims abstract description 33
- 230000000694 effects Effects 0.000 claims abstract description 32
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 19
- 239000012190 activator Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000001639 boron compounds Chemical class 0.000 abstract description 2
- 150000002736 metal compounds Chemical group 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
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- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 5
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
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- 125000001072 heteroaryl group Chemical group 0.000 description 4
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- 125000001424 substituent group Chemical group 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
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- 235000007831 chromium(III) chloride Nutrition 0.000 description 3
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- XIONUQPOXCUMMB-UHFFFAOYSA-N (2-bromophenyl)-diphenylphosphane Chemical compound BrC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XIONUQPOXCUMMB-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- 229940126062 Compound A Drugs 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 2
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- VAEKPJBPSNTBJO-UHFFFAOYSA-N 2-(2-diphenylphosphanylphenyl)aniline Chemical group C1(=CC=CC=C1C1=CC=CC=C1P(C1=CC=CC=C1)C1=CC=CC=C1)N VAEKPJBPSNTBJO-UHFFFAOYSA-N 0.000 description 1
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- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
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- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
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- GYVCVTQHUUFHPO-UHFFFAOYSA-N [Cr]C1=CC=CC=C1 Chemical compound [Cr]C1=CC=CC=C1 GYVCVTQHUUFHPO-UHFFFAOYSA-N 0.000 description 1
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- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RFSMBYZNFSGFAA-UHFFFAOYSA-N azane;triphenylborane Chemical compound N.C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 RFSMBYZNFSGFAA-UHFFFAOYSA-N 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 description 1
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
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- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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Abstract
Description
技术领域
本发明涉及乙烯选择性齐聚的催化剂体系,以及通过使用该催化剂体系使乙烯四聚从而制备1-辛烯的方法。
背景技术
1-辛烯(其是用于制备线性低密度聚乙烯的单体或共聚单体)是广泛用于聚合工艺中的重要商业原料,并且被用作特定的药物。癸烯-1、辛烯-1和己烯-1等高级线性α-烯烃是通过乙烯齐聚反应而得到的。但是在常规的乙烯齐聚技术中,产物中一般会含有多种高级α-烯烃,符合Schulz-Flory分布或Poisson分布。如美国专利US 6184428公开了一种镍系催化剂,其包含作为螯合配体的2-二苯基磷苯甲酸、作为镍前体的NiCl2·6H2O、以及作为催化活化剂的四苯硼酸钠。该专利文献中还披露,在使用该镍系催化剂的乙烯齐聚反应中,1-辛烯的选择性为19%。SHOP工艺(US 3676523、US 3635937)使用相似的催化体系,齐聚产物中1-辛烯的含量占11%。其它典型的乙烯齐聚工艺,如海湾石油公司的Chevron工艺(DE1443927)、乙基公司(BP/Amoco,US3906053)的乙烯齐聚工艺中,1-辛烯的含量一般为13~25%。
最近报道的乙烯四聚三元催化剂体系可以高选择性合成1-辛烯(WO 2004/056478A1),其目的产物中1-辛烯的含量达到60%。专利文献WO04/056479、US20090118117、US7906681、US7829749、US7511183、US7381857、US7297832公开了通过使用铬系催化剂使乙烯四聚来制备1-辛烯的方法,其中所述的铬系催化剂含有具有磷和氮作为杂原子的杂原子配体,如(苯基)2PN(异丙基)P(苯基)2等。专利CN101720253、CN101606605、CN101600722、CN101351424、CN101291734、CN1993180A、CN1741850A和CN1741849A等都公开了烯烃四聚的方法,所述的催化体系都包括杂原子配体、过渡金属化合物及助催化剂,其它所述的助催化剂主要为烷基铝、烷基铝氧烷及硼化合物等。在上述乙烯四聚技术中公开了可通过使用铬系催化剂使乙烯四聚来制备选择性超过70%的1-辛烯,其中所述铬系催化剂含有具有磷和氮作为杂原子的杂原子配体。
迄今为止在科学和专利文献中公开的乙烯四聚催化剂及方法通常具有一种或多种下列缺陷:①产物1-辛烯选择性偏低;②低聚物生成量高,导致反应器堵塞,影响装置连续长周期运行;③催化剂活性差、助催化剂成本高;④反应条件苛刻、需要高压,导致投入、维护和能源成本高;⑤对助催化剂质量的变化敏感。
发明内容
本发明的目的之一是提供一种用于乙烯选择性齐聚的催化剂体系,以解决现有技术乙烯齐聚反应中催化剂活性仍较低,1-辛烯选择性不高的技术问题。
为了达到上述目的,本发明提供了一种用于乙烯选择性齐聚的催化剂体系,其特征在于,包括四种组分:配体A,过渡金属化合物B,活化剂C,活性促进剂D;
所述配体A,其结构式为
其中,R1和R2独立地选自C1~C8烷基、C3~C8环烷基、苯基、取代的苯基、1-萘基、2-萘基、杂芳基、苄基等对反应无不利影响的基团;所述的取代的苯基上的取代基为C1~C8烷基、C3~C8环烷基、苯基、烷氧基以及卤素等对反应无不利影响的基团,取代基数量为1~5;所述的杂芳基为呋喃基、噻吩基或吡啶基;R1、R2可以相同,也可不同;R1、R2可并为C3~C8脂肪环或芳香环;
X1、X2独立地选自H、C1~C8烷基、C3~C8环烷基、苯基、取代的苯基、1-萘基、2-萘基、杂芳基、苄基、卤素等对反应无不利影响的基团;所述的取代的苯基上的取代基为C1~C8烷基、C3~C8环烷基、苯基、烷氧基以及卤素等对反应无不利影响的基团,取代基数量为1~5;所述的杂芳基为呋喃基、噻吩基或吡啶基等;m=0~3,n=0~3;当m≥2时,两个相邻的X1可并为C3~C8脂肪环或芳香环;当n≥2时,两个相邻的X2可并为C3~C8脂肪环或芳香环;X1、X2可以相同,也可不同;
所述的过渡金属化合物B为IVB~VIII族的金属化合物;
所述的活化剂C为含有IIIA族金属的化合物;
所述的活性促进剂D为具有以下通式F-R3[R4 bX(3-b)]的一类化合物,其中:F为醛基、酰基或羟基,R3是一个二价的C1~C10的脂肪基或者芳香基,其与官能团F中的氧原子相连,R4是氢、未取代的或者卤素取代的C1~C6烷基、环烷基或芳香基,b是0、1或2,X是F、Cl或Br。
优选地,所述的C1~C8烷基为甲基、乙基、正丙基、异丙基、正丁基、叔丁基等;所述的C3~C8环烷基为环丙基、环丁基、环戊基、环己基等;所述的烷氧基为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基等。
优选地,所述配体A为配体化合物1~3中的任意一种,其结构式为:
优选地,所述过渡金属化合物B为铬化合物。
更优选地,从易于溶解和易于操作的角度考虑,所述铬化合物为醋酸铬、异辛酸铬、正辛酸铬、乙酰丙酮铬、二异戊二烯铬、二苯铬、CrCl3(THF)3、CrCl2(THF)2、(苯基)三羰基铬和六羰基铬的任意一种或多种。
进一步地,所述铬化合物为CrCl3(THF)3、乙酰丙酮铬和CrCl2(THF)2的任意一种或多种。
优选地,所述活化剂C为有机铝化合物和/或有机硼化合物。
更优选地,所述有机铝化合物为LiAlH4或AlR3,其中R均独立地为具有1至12个碳原子的烷基、含氧烷基或卤化物。
更优选地,所述有机铝化合物为三甲基铝(TMA)、三乙基铝(TEA)、三异丁基铝(TIBA)、三正辛基铝、二氯化甲基铝、二氯化乙基铝、氯化二甲基铝、氯化二乙基铝、异丙醇铝、倍半氯化乙基铝、倍半氯化甲基铝和铝氧烷及其衍生物中的任意一种或多种。
进一步地,所述铝氧烷为线性铝氧烷、环状铝氧烷和笼状铝氧烷中的任意一种或多种。铝氧烷是本领域中公知的低聚化合物,其可通过将烷基铝化合物(如三甲基铝)与水混合来制备。
更优选地,所述有机铝化合物为铝氧烷及其衍生物。
更优选地,所述有机硼化合物为环硼氧烷、NaBH4、三乙基硼烷、三苯基硼烷、三苯基硼烷氨络合物、硼酸三丁酯、硼酸三异丙酯、三(五氟苯基)硼烷、三苯甲基四(五氟苯基)硼酸盐、二甲基苯基铵四(五氟苯基)硼酸盐、二乙基苯基铵四(五氟苯基)硼酸盐、甲基二苯基铵四(五氟苯基)硼酸盐、乙基二苯基铵四(五氟苯基)硼酸盐中的任意一种或多种。
优选地,所述活性促进剂D为Cl3CCH2OH、Cl2CHCH2OH、ClCH2CH2OH、F3CCH2OH、Cl3CC(CH3)2(OH)、Cl3CCOCl、Cl2CHCOCl和ClCH2COCl中的任意一种或多种。
更优选地,所述活性促进剂D为Cl3CCH2OH、F3CCH2OH和Cl3CCOCl中的任意一种或多种。
优选地,所述配体A、过渡金属化合物B、活化剂C、活性促进剂D的摩尔比为1:(0.5~100):(1~5000):(0.1~100)。
更优选地,所述配体A、过渡金属化合物B、活化剂C、活性促进剂的摩尔比为1:(0.5~50):(1~1000):(0.1~10)。
进一步地,所述配体A、过渡金属化合物B、活化剂C、活性促进剂的摩尔比为1:(0.5~10):(1~300):(0.2~5)。
本发明还提供了上述催化剂体系的制备方法,其特征在于,包括:将配体A、过渡金属化合物B、活化剂C、活性促进剂D预先混合或直接加入到反应体系中进行原位合成。
本发明的还提供了一种乙烯齐聚制1-辛烯的方法,其特征在于,采用上述催化剂体系,在惰性溶剂中经乙烯齐聚反应制得。
优选地,所述惰性溶剂为烷烃、芳烃、或环烷烃中的任意一种或多种。
优选地,所述惰性溶剂包括苯、甲苯、二甲苯、异丙苯、正庚烷、正己烷、甲基环己烷和环己烷的任意一种或多种。
优选地,所述惰性溶剂为甲基环己烷。
优选地,所述乙烯齐聚反应的温度为0~200℃,压力为0.1~50MPa。
更优选地,所述乙烯齐聚反应的温度为50~150℃,压力为1.0~10MPa。
优选地,以过渡金属化合物B计,所述反应体系中催化剂的浓度为0.01~1000μmol金属/L。
更优选地,所述反应体系中催化剂的浓度为0.1~10μmol金属/L。
相对于现有技术,本发明所述的用于乙烯选择性齐聚的催化剂体系具有以下优势:
(1)催化剂体系催化活性高,以金属铬计可达127.5Kg/g-Cr;
(2)目的产物1-己烯和1-辛烯的总选择性高,1-丁烯及1-C10+质量百分含量较低,其中产物中C6~C8线性α-烯烃的质量百分含量>80%;
(3)固体低聚物含量较低,可以低至3%(wt)。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
高分辨质谱由APEXII型FT-ICR质谱仪测定,以ESI(电喷雾电离)或MALDI(基质辅助激光解吸附电离)为离子源;
元素分析由Elementar Vario EL元素分析仪测定;
气相色谱分析采用Agilent 7890A气相色谱仪进行。
以下结合具体实例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
配体化合物1的制备
2′-二苯基膦基-2-胺基-1,1′-联苯的合成:在装有磁力搅拌子的干燥洁净的100mL封管中加入(2-溴苯基)-二苯基膦(1.2g,3.5mmol,分析纯,购自阿拉丁试剂公司)、2-氨基苯硼酸(480mg,3.5mmol,分析纯,购自阿拉丁试剂)、[1,1′-双(二苯基膦基)二茂铁]二氯化钯(143mg,0.18mmol,分析纯,购自阿拉丁试剂)、无水磷酸钾(2.3g,11.5mmol,分析纯,购自阿拉丁试剂)。将封管转移至氩气氛围的手套箱中,加入30mL无水1,4-二氧六环(分析纯,购自阿拉丁试剂),将封管用旋塞封好后取出,油浴加热100-105℃反应16小时。停止加热,冷却至室温后,加入20mL水淬灭反应,以乙酸乙酯(分析纯,购自阿拉丁试剂)(20mL×3)萃取水相,有机相以饱和食盐水洗涤一次,无水硫酸钠干燥。抽滤除去干燥剂,滤液用旋转蒸发仪脱除溶剂,残余物经硅胶柱层析(石油醚/乙酸乙酯=5∶1)得到1.1g白色固体27a,收率86%,熔点:103~105℃。
2′-二苯基膦基-N-(吡啶-2-甲基)-2′-氨基-1,1′-联苯(配体1):在装有磁力搅拌子的干燥洁净的50mL Schlenk瓶中加入13(706mg,2.0mmol),NaBH(OAc)3(851mg,4.0mmol),置换成氮气氛围后,加入15mL 1,2-二氯乙烷,搅拌充分溶解后再加入吡啶-2-甲醛(257mg,2.4mmol)。室温搅拌反应4h,TLC监测反应。慢慢加入10mL饱和碳酸氢钠水溶液淬灭反应,水相用乙酸乙酯萃取(10mL×3),合并有机相,无水硫酸镁干燥。抽滤除去干燥剂,滤液用旋转蒸发仪脱除溶剂,残余物经硅胶柱层析(石油醚∶乙酸乙酯=2∶1)得到809mg白色固体1,两步收率78%,熔点:54~56℃。配体化合物分子式为C30H25N2P,分子量444。
配体化合物2的制备
除了将(2-溴苯基)-二苯基膦替换为(2-溴苯基)-二(3-甲氧基苯基)膦(1.4g,3.5mmol,分析纯,购自阿拉丁试剂公司),其它同配体化合物1的制备,得到白色固体,两步收率74%,熔点:60~62℃。配体化合物分子式为C32H30O2N2P,分子量505。
实施例1
本实施例提供了一种用于乙烯选择性齐聚制1-辛烯的催化剂体系,包括四种组分:配体A,过渡金属化合物B,活化剂C,活性促进剂D;
所述配体A为2,5-二(2-二苯基膦-苯基)苯胺(配体化合物1),过渡金属化合物B为CrCl3(THF)3,活化剂C为甲基铝氧烷(MAO),活性促进剂D为Cl3CCOCl;
将上述催化剂体系用于乙烯齐聚制1-辛烯,具体步骤如下:
步骤1:将100mL环己烷、MAO(Al:5.0mmol)加入到300mL的经氮气置换的不锈钢反应器中,随后加热至50℃;
步骤2:在氮气气氛的手套箱内,将处于20mL甲苯中的CrCl3(THF)33.7mg(0.010mmol)加入50mL的烧瓶中,随后加入4.4mg(0.010mmol)2-二苯基膦基-N-(吡啶-2-甲基)-2-氨基-1,1-联苯(配体化合物1),在室温下搅拌该混合物5min,然后再加入2mg(0.010mmol)Cl3CCOCl,搅拌5分钟,然后将其加入到步骤1中的不锈钢反应器中;
步骤3:在30MPa的压力下将乙烯供入反应器中,然后以300rpm的搅拌速度进行搅拌,30min后,停止供入乙烯和搅拌,并将反应器冷却至低于10℃的温度,随后将混合有10%(v/v)的盐酸的乙醇加入到存在于反应器内的液体中,过滤、分离,所得各类产物质量及比例,催化剂活性(催化剂活性指总聚合产物的质量相对于过渡金属化合物B中金属质量的比值)如表1所示。
实施例2
本实施例与实施例1的不同之处在于配体A为配体化合物2(C30H25N2P),加入量为4.7mg(0.010mmol)。所得各类产物质量及比例,催化剂活性如表1所示。
实施例3
本实施例与实施例1的不同之处在于过渡金属化合物B为Cr(C5H7O2)3(乙酰丙酮铬(III)),加入量为3.5mg(0.010mmol)。所得各类产物质量及比例,催化剂活性如表1所示。
实施例4
本实施例与实施例1的不同之处在于活化剂C为MMAO,加入量为5.0mmol。所得各类产物质量及比例,催化剂活性如表1所示。
实施例5
本实施例与实施例1的不同之处在于活性促进剂D为Cl3CCH2OH,加入量为3.0mg(0.02mmol)。所得各类产物质量及比例,催化剂活性如表1所示。
对比实施例1
本实施例与实施例1的不同之处在于配体化合物A为PNP型配体P(Ph)2N(i-C3H7)P(Ph)2,加入量为4.3mg(0.010mmol)。所得各类产物质量及比例,催化剂活性如表1所示。
对比实施例2
本实施例与实施例1的不同之处在于不加活性促进剂D,且配体化合物A为PCCP型配体P(Ph)2CHCHP(Ph)2,加入量为4.0mg(0.010mmol)。所得各类产物质量及比例,催化剂活性如表1所示。
表1本发明实施例中各类产物质量及比例,催化剂活性
由实验数据可得,本发明的催化剂体系用于乙烯齐聚时,具有较高的四聚制1-辛烯的选择性,较低的固体低聚物生成量,突出的齐聚活性,在乙烯齐聚制1-辛烯技术领域具有较明确的应用前景。
Claims (3)
2.如权利要求1所述用于乙烯选择性齐聚的催化剂,其特征在于,所述配体A、过渡金属化合物B、活化剂C、活性促进剂D的摩尔比为1:(0 .5~100):(1~5000):( 0 .1~100)。
3.一种乙烯齐聚制1-辛烯的方法,其特征在于,采用权利要求1~2任一项所述催化剂,在惰性溶剂中经乙烯齐聚反应制得,所述惰性溶剂为苯、甲苯、二甲苯、异丙苯、正庚烷、正己烷、甲基环己烷和环己烷中的任意一种或多种;所述乙烯齐聚反应的温度为0~200℃,压力为0 .1~50MPa;以过渡金属化合物B计,所述反应体系中催化剂的浓度为0.01mmol金属/L。
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