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Metallocene compound and olefin polymerization catalyst as well as application thereof

A metallocene compound, olefin polymerization technology, applied to olefin polymerization catalyst, the application field of olefin polymerization catalyst in the preparation of ethylene-1-octene copolymer, can solve the problem of less copolymerization ability and the like, and achieve excellent copolymerization catalytic ability , high catalytic activity, good catalytic activity effect

Active Publication Date: 2018-11-23
SHANGHAI BILOR NEW MATERIALS TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] On the other hand, studies have found that conventional Cp 2 MCl 2 Metallocene catalysts of this type seldom exhibit sufficient copolymerization ability. Traditional metallocene catalysts cannot catalyze the copolymerization of ethylene and α-olefins under general conditions. copolymerization

Method used

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  • Metallocene compound and olefin polymerization catalyst as well as application thereof
  • Metallocene compound and olefin polymerization catalyst as well as application thereof
  • Metallocene compound and olefin polymerization catalyst as well as application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] The present embodiment provides a kind of metallocene compound of bifunctional restriction configuration, and the molecular formula of this complex C3 is: [η 5 -(allyl-C 5 h 4 )][η 5 -(PhC(CH 3 ) 2 C 5 h 3 )]TiCl 2 .

[0034] The synthetic route of complex C3 is as follows:

[0035]

[0036] The specific preparation process of complex C3 is:

[0037] Under the protection of argon, add 6,6-dimethylfulvene (7.32g, 50mmol) in 30mL tetrahydrofuran solution dropwise to phenyl lithium (4.21g, 50mmol) in 100mL tetrahydrofuran solution at -20°C, the dropwise addition was completed Then slowly rise to room temperature and continue to stir for 8h to obtain [Ph C (CH 3 ) 2 C 5 h 3 ] Li solution.

[0038] Under anhydrous and oxygen-free conditions, [Ph C(CH 3 ) 2 C 5 h 3 ]Li (10mmol) in 50mL tetrahydrofuran solution was slowly added dropwise to (Allyl-Cp)TiCl 3 (10mmol) in 25mL tetrahydrofuran solution, the reaction solution gradually turned red, slowly rose t...

Embodiment 2

[0040] The present embodiment provides a kind of metallocene compound of bifunctional restriction configuration, and the molecular formula of this complex C5 is: [η 5 -(allyl-C 5 h 4 )][η 5 -(1-allyl-3-PhC(CH 3 ) 2 -C 5 h 3 )]TiCl 2 .

[0041] The synthetic route of complex C5 is as follows:

[0042]

[0043] The synthesis operation is similar to the synthesis of C3, replacing 6,6-dimethylfulvene with allyl-6,6-dimethylfulvene. After recrystallization, 2.55 g of complex C5 was obtained as a red solid, with a yield of 57%. 1 H NMR (400MHz, CDCl 3 )δ7.37–7.23(m,5H,Ph-H),6.56–6.53(m,2H,Cp-H),6.12(dd,J=4.9,2.2Hz,1H,Cp-H),6.05(dd ,J=4.9,2.2Hz,1H,Cp-H),5.98(t,J=2.7Hz,1H,Cp-H),5.96(dd,J=5.7,2.7Hz,1H,Cp-H),5.94 –5.89(m,1H,=CH),5.89–5.86(m,1H,=CH),5.85–5.83(m,1H,Cp-H),5.08–5.06(m,2H,=CH 2 ),5.03–4.98(m,2H,=CH 2 ), 3.56–3.46 (m,2H,Cp-CH 2 ), 3.41 (dd, J=16.4, 6.4Hz, 1H, Cp-CH 2 ), 3.26 (dd, J=16.4, 6.4Hz, 1H, Cp-CH 2 ),1.69(s,3H,-CH 3 ),1.68(s,3H,-CH 3 ). 13 C NMR...

Embodiment 3

[0045] The present embodiment provides a kind of metallocene compound of bifunctional restriction configuration, and the molecular formula of this complex rac / meso-C6 is: [η 5 -[η 5 -(1-allyl-3-PhC(CH 3 ) 2 -C 5 h 3 )] 2 TiCl 2 .

[0046] The synthetic route of complex rac / meso-C6 is as follows:

[0047]

[0048] The synthesis of rac / meso-C6 is similar to C5, using TiCl 4 2THF instead of (Allyl-Cp)TiCl 3 , 2.01 g of red solid was obtained after column chromatography, yield 71%. The resultant was subjected to column chromatography and recrystallized from toluene to obtain 1.03 g of red crystal rac-C6 with a yield of 36.4%. After filtration, the filtrate was recrystallized by adding n-hexane to obtain 0.81 g of meso-C6 with a yield of 28.6%.

[0049] rac-C6: 1 H NMR (400MHz, CDCl 3 )δ7.30–7.17(m,10H,Ph-H),6.66(t,J=2.6Hz,2H,Cp-H),6.01(t,J=2.6Hz,2H,Cp-H),5.97– 5.87(m,2H,=CH),5.05–4.93(m,4H,=CH 2 ), 4.96(t, J=2.6Hz, 2H, Cp-H), 3.59(dd, J=16.4, 6.4Hz, 2H, Cp-CH 2 )...

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Abstract

The invention provides a metallocene compound. The metallocene compound has the following structural formula: the formula is shown in the description, M is Ti or Zr; R3 is selected from any one of H,allyl and 2-butenyl; one of R4 and R5 is allyl or 2-butenyl, the other one is H or (the formula is shown in the description); R1 and R2 are separately independently selected from any one of H, methyl,ethyl, n-propyl, n-butyl, n-amyl and n-hexyl; and Ph is phenyl or 3,5-dialkyl substituted phenyl, and the alkyl is C1 to C6 chain alkyl. The large steric hindrance aryl group in the metallocene compound limits the relative rotation of cyclopentadienyl loops without influencing the insertion of alpha-olefin, so that the catalytic activity is good, the copolymerization catalytic capability is moreexcellent, the metallocene compound not only reserves the activity of the mono-center catalyst, but also can easily control a space effect and electronic effect of two cyclopentadienyl loops so as tofurther regulate and control the molecular weight and distribution of the molecular weight of the polymerization product, and can catalytically produce an olefin homopolymer with high molecular weightand wide molecular weight distribution as well as an olefin copolymer.

Description

technical field [0001] The present invention relates to the technical field of olefin polymerization reaction catalysts, in particular to a metallocene compound, an olefin polymerization catalyst having the metallocene compound, and the application of the olefin polymerization catalyst in the preparation of ethylene-1-octene copolymer . Background technique [0002] As the core of the polyolefin production industry, polyolefin catalysts have been widely concerned by academic and industrial circles at home and abroad. [0003] As we all know, metallocenes, especially group IV metallocenes, have attracted great attention from researchers in the field of polyolefins because of their excellent catalytic properties. and electronic effects can be tuned in a wide range, resulting in catalysts with unique steric and electronic properties. [0004] At present, the introduction of functional groups on cyclocene ligands is the key to promoting the industrialization of metallocene cat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F4/6592C08F210/16C08F210/14C08F110/02
CPCC08F10/00C08F110/02C08F210/16C08F2420/03C08F4/65925C08F210/14
Inventor 沈颖夏紫薇李沐豪刘静刘世钰许胜周雨刘强林楚慧封晓晓窦清玉黄相丞吕中文
Owner SHANGHAI BILOR NEW MATERIALS TECH