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Asymmetric alpha-diimine nickel (II) complex for polymerizing ethylene and 1-hexene with o-benzhydryl substituent

A technology of benzhydryl aniline and benzhydryl, which is applied in the field of asymmetric α-diimine nickel complexes, can solve the problems of easy loss of activity and poor stability, and achieve increased instability, high stability, Effect of reducing transfer rate

Inactive Publication Date: 2018-01-30
CHANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the early post-transition metal olefin catalysts have poor stability and tend to lose activity at high temperatures.

Method used

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  • Asymmetric alpha-diimine nickel (II) complex for polymerizing ethylene and 1-hexene with o-benzhydryl substituent
  • Asymmetric alpha-diimine nickel (II) complex for polymerizing ethylene and 1-hexene with o-benzhydryl substituent
  • Asymmetric alpha-diimine nickel (II) complex for polymerizing ethylene and 1-hexene with o-benzhydryl substituent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] (1) Preparation of asymmetric α-diimine ligand:

[0037] Mix 4-methyl-2,6-benzhydrylaniline and excess diacetyl at a molar ratio of 1:1.5, use toluene as solvent, add 0.05 times 4-methyl-2,6-benzhydryl The p-toluenesulfonic acid (TsOH) of the molar amount of base aniline is used as a catalyst, and after reflux reaction overnight at 105° C., the solvent and excess diacetyl are rotary evaporated to obtain a crude product, which is then used in C 2 h 5 Washing with OH gave a yellow solid, ortho-benzhydryl substituted monoketone. The yield was 89%.

[0038] The above-mentioned ortho benzhydryl substituted monoketone and 2,6-diisopropylaniline are mixed in a molar ratio of 1:1.2, and toluene is used as a solvent, and p-toluenesulfonic acid ( TsOH) was used as a catalyst, and after reflux reaction at 105°C for 20 hours, the solvent was removed to obtain a crude product, which was then purified by C 2 h 5 OH / CH 2 Cl 2 The mixed solvent was recrystallized to precipitate ...

Embodiment 2

[0049] (1) Synthesis of the complex: under the protection of nitrogen, add the above-mentioned asymmetric ligand containing 2,6-dimethyl substitution (0.61g, 1.0mmol, the ligand refers to step 1 of Example 1) into a 100mL dry reaction tube (1) method synthesis), then add NiBr 2 (DME) (0.34g, 1.1mmol) and dichloromethane 20mL, stirred and reacted at room temperature for 12 hours, filtered the suspension, removed the solvent from the mother liquor under vacuum, washed the residue three times with ether (3×15mL), and dried in vacuo 0.71 g of brown solid powder was obtained. The yield was 95%.

[0050] Anal. Calcd for (C 45 h 42 Br 2 N 2 Ni): C, 65.17; H, 5.10; N, 3.38. Found: C, 65.49; H, 5.42; N, 3.41. MALDI-TOF-MS(m / z):calcd for C 45 h 42 BrN 2 Ni: 747.1885,found: 747.1255[M-Br] + .

[0051] Its reaction formula is as follows:

[0052]

[0053] (2) Ethylene polymerization: replace the 250mL polymerization bottle with a magnetic stirrer with vacuum-nitrogen circula...

Embodiment 3

[0056] (1) Synthesis of the complex: under the protection of nitrogen, add the above-mentioned asymmetric ligand of aniline (0.58g, 1.0mmol, the ligand is synthesized according to the method of step (1) in Example 1) to a 100mL dry reaction tube, and then Join NiBr 2 (DME) (0.34g, 1.1mmol) and dichloromethane 20mL, stirred and reacted at room temperature for 12 hours, filtered the suspension, removed the solvent from the mother liquor under vacuum, and washed the residue three times with diethyl ether (3×17mL), dried in vacuo 0.66 g of brown solid powder was obtained. The yield was 92%.

[0057] Anal. Calcd for (C 43 h 38 Br 2 N 2 Ni): C, 64.45; H, 4.78; N, 3.50. Found: C, 64.49; H, 4.52; N, 3.45. MALDI-TOF-MS (m / z): calcd for C 43 h 38 BrN 2 Ni: 719.1572,found: 719.1244[M-Br] + .

[0058] Its reaction formula is as follows:

[0059]

[0060] (2) Ethylene polymerization: replace the 250mL polymerization bottle with a magnetic stirrer with vacuum-nitrogen circulat...

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Abstract

The invention discloses an asymmetric alpha-diimine nickel (II) complex for polymerizing ethylene and 1-hexene with an o-benzhydryl substituent. By changing a complex, a coordination environment, a space effect and electronic density of a metal center are changed, the activity of polymerization of ethylene and 1-hexene is finally adjusted, and the microstructure of a copolymer is finally controlled. Under activation of a promoter, namely diethyl aluminum chloride, the complex is relatively good in thermal stability and catalysis activity in catalyzing vinyl polymerization, and in addition, polyethylene high in molecular weight and low in dispersity is prepared. By changing the steric hindrance and the polymerization condition of the complex, the catalysis activity and the molecular weight,the dispersity, the branching coefficient and the thermal performance of the polymer can be effectively operated. The catalyst system can also be applied to catalysis on chain walking polymerizationof long-chain 1-hexene, through variation of the steric hindrance and the polymerization temperature of the complex, the catalysis activity and the properties of the polymer can be very well operated,and in addition, by increasing the steric hindrance of the catalyst, intercalation of 2,1 into 1-hexene is facilitated.

Description

technical field [0001] The invention belongs to the technical field of macromolecules, relates to a class of transition metal catalysts after chain-walking olefin polymerization, in particular to a class of asymmetric α-diimine nickel (II) complexes containing ortho-diphenyl substitutions; it also relates to the Preparation of quasi-complexes and their use in the polymerization of ethylene and 1-hexene. Background technique [0002] Polyolefin is the most consumed synthetic resin, and polyethylene is the most important polyolefin, which greatly improves people's daily life. The development of new olefin polymerization catalysts has played a key role in the synthesis of high-performance polymers. [0003] In the last two decades, chain-walking α-diimine post-transition Ni(II) and Pd(II) olefin polymerization catalysts have attracted extensive attention of scientists. Because these catalysts have unique chain walking properties, the central metal atom has weak electrophilici...

Claims

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Application Information

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IPC IPC(8): C07F15/04C08F210/16C08F210/14C08F4/70
Inventor 李为民李瑞萍王福周田素素陈昶乐郭登峰
Owner CHANGZHOU UNIV
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