双核茂金属催化剂的合成、 表征与应用

doi:10.7503/cjcu20180781

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (6): 1324.doi: 10.7503/cjcu20180781

双核茂金属催化剂的合成、表征与应用

邵炉¹, 梁春超¹, 许胜¹(), 米普科¹(), 王婷兰¹, 义建军²

1. 上海先进聚合物材料重点实验室, 超细材料制备与应用教育部重点实验室, 华东理工大学材料科学与工程学院, 化学与分子工程学院, 上海 200237
2. 中国石油, 石油化工研究院, 北京 102206

收稿日期:2018-11-21 出版日期:2019-06-10 发布日期:2019-04-08
作者简介:
联系人简介: 米普科, 男, 教授, 主要从事聚乙烯烃和聚烃材料方面的研究. E-mail: pkmi@ecust.edu.cn; 许胜, 男, 博士, 副教授, 主要从事烯烃聚合方面的研究. E-mail: xusheng@ecust.edu.cn
基金资助:
国家重点研发计划项目(批准号: 2017YFB0306701)、中石油创新基金(批准号: 2017D-007-0501)和国家自然科学基金(批准号: L11362111)资助.

Synthesis of Methylene-bridged Binuclear Metallocene Complexes and Application for Propylene Syndiospecific Polymerization^†

SHAO Lu¹, LIANG Chunchao¹, XU Sheng¹(), MI Puke¹(), WANG Tinglan¹, YI Jianjun²

1. School of Materials Science and Engineering, School of Chemistry and Engineering, Shanghai Key Laboratory of Advance Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, East China University of Science and Technology, Shanghai 200237, China
2. Petrochemical Research Institute, PetroChina, Beijing 102206, China

Received:2018-11-21 Online:2019-06-10 Published:2019-04-08
Supported by:
† Supported by the National Key R&D Program of China(No.2017YFBO306701), the China Petroleum Science and Technology Innovation Fund(No.2017D-5007-0501) and the National Natural Science Foundation of China(No.U1362111).

摘要/Abstract

摘要：

使用桥连配体锂盐与MCl₄络合, 合成了4个不同结构的双核茂金属化合物[μ,μ-(CH₂)₃]{[C(H)·(η⁵-C₅H₄)(η⁵-C₁₃H₈)](MCl₂)}₂[M=Zr or Ti](4, 5)和[μ,μ-(CH₂)₃]{[C(H)(η⁵-C₅H₄)(η⁵-C₉H₆)]·(MCl₂)}₂[M=Zr or Ti](6, 7), 配体和化合物都经过核磁氢谱(¹H NMR)、碳谱(¹³C NMR)、红外光谱(IR)及元素分析等表征, 确认了化学结构. 以甲基铝氧烷(MAO)为助催化剂, 化合物4~7为催化剂催化丙烯聚合, 考察了聚合温度、乙烯压力、铝钛或铝锆比对催化剂活性及聚合物分子量的影响. 结果表明, 多亚甲基桥连双核茂金属是高活性乙烯和丙烯聚合催化剂, 乙烯聚合活性最高达到7.5× 10⁶ g PE/(mol Zr·h)(化合物6), 丙烯聚合活性达 10 × 10⁵ g sPP/(mol Zr·h)(化合物4). 所得间规聚丙烯(sPP)的间规度指数(SI, r) 达到90%. 在同样条件下, 双核化合物的催化活性、聚合物分子量M_w(> 100000)以及分子量分布(MWD>2.5)均比相应的单核化合物高(M_w<70000, MWD≤2), 表明该体系中存在较强的核效应.

关键词: 双核茂金属催化剂, 间规聚丙烯, 核效应

Abstract:

In order to investigate the differences between binuclear metallocene catalysts and mononuclear catalysts for propylene syndiotactic polymerization, binuclear metallocene complexes [μ,μ-(CH₂)₃]·{[C(H)(η⁵-C₅H₄)(η⁵-C₁₃H₈)](MCl₂)}₂[M=Zr or Ti](4, 5), and [μ,μ-(CH₂)₃]·{[C(H)(η⁵-C₅H₄)·(η⁵-C₉H₆)](MCl₂)}₂[M=Zr or Ti](6, 7) were synthesized and characterized by ¹H NMR, ¹³C NMR, mass spectra and elemental analysis. When combined with methylaluminoxane(MAO), these metallocene complexes shown high catalytic activity for the polymerization of ethylene and propylene, the activity of polyethylene(PE) reaches up to 7.5×10⁶ g PE/(mol Zr·h)(complex 6) and 10×10⁵ g sPP/(mol Zr·h)(complex 4) for polypropylene(PP). The syndiotacticity index(SI) of polypropylene(sPP) by complex 4 was more than 90%. It is found that, under the same conditions, binuclear complexes’ catalytic activity, M_w(>100000) and molecular weight distribution(MWD>2.5) are higher than that of corresponding mononuclear metallocene complexes(M_w<70000, MWD≤2), which suggests that there are cooperation effect in binuclear system.

Key words: Binuclear metallocene catalyst, Syndiotacticity index of polypropylene, Effect of binuclear

中图分类号:

O631
O614.8

TrendMD:

邵炉, 梁春超, 许胜, 米普科, 王婷兰, 义建军. 双核茂金属催化剂的合成、表征与应用. 高等学校化学学报, 2019, 40(6): 1324.

SHAO Lu,LIANG Chunchao,XU Sheng,MI Puke,WANG Tinglan,YI Jianjun. Synthesis of Methylene-bridged Binuclear Metallocene Complexes and Application for Propylene Syndiospecific Polymerization^†. Chem. J. Chinese Universities, 2019, 40(6): 1324.

图/表 12

Fig.1 Structures of complexes C1—C7

Scheme 1 Synthesis of ligands Ⅰand Ⅲ

Scheme 2 Synthesis of complexes 4—7

Fig.2 Structures of mononuclear complexes 8—11

Table 1 Results of ethylene polymerization with complexes 1—11*

Catalyst	Activity/[10⁶g polymer/(molM·h)]	10^-4 M_n	10^-5 M_w	MWD
4(FZr₂)	3.2	8.36	4.88	5.84
8(FZr₁)	2.5	7.32	1.23	1.68
5(FTi₂)	1.7	10.90	5.42	4.97
9(FTi₁)	1.3	5.80	1.09	1.88
6(IZr₂)	7.5	10.00	5.57	5.56
10(IZr₁)	2.1	14.70	2.52	1.71
7(ITi₂)	1.2	13.80	7.51	5.43
11(ITi₁)	0.8	26.40	5.05	1.91

Table 2 Polymerization results of propylene with catalysts 4—11a

Entry	Catalyst	Activity/[10⁵ g polymer/(mol Zr·h)]	10^-4 $M η b$	10^-4 $M w b$	MWD	r(%)
1	4(FZr₂)	10.0		13.0	3.1	90
2	8(FZr₁)	8.0		5.2	1.8	92
3	5(FTi₂)	2.8	16.0			70
4	9(FTi₁)	1.9	12.5			76
5	6(IZr₂)	12.0		10.0	2.9	45
6	10(IZr₁)	8.5		4.5	1.8	56
7	7(ITi₂)	4.5	12.0			30
8	11(ITi₁)	3.2	9.7			40

Table 2 Polymerization results of propylene with catalysts 4—11a

Entry	Catalyst	Activity/[10⁵ g polymer/(mol Zr·h)]	10^-4 $M η b$	10^-4 $M w b$	MWD	r(%)
1	4(FZr₂)	10.0		13.0	3.1	90
2	8(FZr₁)	8.0		5.2	1.8	92
3	5(FTi₂)	2.8	16.0			70
4	9(FTi₁)	1.9	12.5			76
5	6(IZr₂)	12.0		10.0	2.9	45
6	10(IZr₁)	8.5		4.5	1.8	56
7	7(ITi₂)	4.5	12.0			30
8	11(ITi₁)	3.2	9.7			40

Fig.3 13C NMR spectrum of polymer Polymerization conditions: n(Al)/n(Zr)=2000∶1, 25 ℃, 0.3 MPa; solvent: toluene; catalyst: complex 4.

Fig.4 Influence of catalyst concentrstion on polymerization activity and molecular weight Polymerization conditions: n(Al)/n(Zr)=2000, 0.5 h, 60 ℃, 0.4 MPa, V(toluene)=100 mL.

Fig.5 Influence of polymerization temperature on polymerization activity and molecular weight Polymerization conditions: 1×10-5 mol Zr/L, n(Al)/n(Zr)=2000, 0.5 h, 0.4 MPa, V(toluene)=100 mL.

Fig.6 Influence of polymerization temperature on polymer syndiotactic degree Polymerization conditions: 1×10-5 mol Zr/L, n(Al)/n(Zr)=2000, 0.5 h, 0.4 MPa, V(toluene)=100 mL.

Fig.7 Influence of n(MAO)/n(Zr) on polymerization activity and polymer molecular weight Polymerization conditions: 1×10-5 mol Zr/L, 60 ℃, 0.5 h, 0.4 MPa, V(toluene)=100 mL.

Fig.8 Influence of n(MAO)/n(Zr) on polymer syndiotactic degree Polymerization conditions: 1×10-5 mol Zr/L, 60 ℃, 0.5 h, 0.4 MPa, V(toluene)=100 mL.

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双核茂金属催化剂的合成、表征与应用

Synthesis of Methylene-bridged Binuclear Metallocene Complexes and Application for Propylene Syndiospecific Polymerization^†

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Synthesis of Methylene-bridged Binuclear Metallocene Complexes and Application for Propylene Syndiospecific Polymerization†

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双核茂金属催化剂的合成、表征与应用

Synthesis of Methylene-bridged Binuclear Metallocene Complexes and Application for Propylene Syndiospecific Polymerization^†