Unlock instant, AI-driven research and patent intelligence for your innovation.

Snn ligand based on quinoline skeleton, its iron complex and preparation method and application

A compound and alkyl technology, applied in the field of SNN ligands, can solve the problems that the polymer molecular weight and its distribution are not given, and cannot catalyze the polymerization of 1-hexene, and achieve excellent catalytic activity and high monomer insertion rate.

Active Publication Date: 2022-08-09
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
View PDF6 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Frédéric Peruch et al. briefly reported the small sterically hindered 2,6-(2,6-dimethylphenyl)diimide pyridine iron complex catalyzed the copolymerization of ethylene and 1-hexene, in which the insertion rate of 1-hexene About 3.5%, the author did not give the molecular weight of the polymer and its distribution. In addition, this complex cannot catalyze the polymerization of 1-hexene (F.Peruch et al.C.R.Chimie 2002,5,43.)

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Snn ligand based on quinoline skeleton, its iron complex and preparation method and application
  • Snn ligand based on quinoline skeleton, its iron complex and preparation method and application
  • Snn ligand based on quinoline skeleton, its iron complex and preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0234] Example 1: Preparation of SNN ligands

[0235]

[0236] Compound 2a: add 2-acetyl-8-bromoquinoline (0.50g, 2mmol), 2,6-dimethylaniline (0.24g, 2mmol), p-toluenesulfonic acid to the three-necked flask of 100mL Monohydrate (19 mg, 0.1 mmol), and 35 mL of solvent toluene were installed in a reflux device, and the reaction was heated and refluxed for 48 h. It was cooled to room temperature, concentrated in vacuo, and purified by flash column chromatography (ethyl acetate:petroleum ether=1:200) to obtain a yellow solid (0.65 g, 92%). 1 H NMR(400MHz, CDCl3)δ8.61(d,J=8.8Hz,1H),8.23(d,J=8.8Hz,1H),8.09(dd,J=7.6Hz,1H),7.84(dd,J =8.0Hz,1H),7.45(t,J=8.0Hz,1H),7.10(d,J=7.6Hz,2H),6.98(t,J=7.6Hz,1H),2.41(s,3H), 2.07(s,6H). 13 C NMR (101MHz, CDCl3) δ167.55, 156.48, 136.63, 133.15, 136.76, 129.99, 127.89, 127.80, 127.37, 125.87, 125.15, 123.12, 119.37, 17.95, 16.29.

[0237]

[0238] Compound 2b: The synthesis of this compound is the same as that of 2a, and the yield of 2b is ...

Embodiment 2

[0265] Example 2: Preparation of SNN-type iron complex

[0266]

[0267] ( iPr SNN iPr )FeCl 2 (Complex 4a): Ligand 3a (0.1214 g, 0.3 mmol) was slowly added to FeCl in an Ar glove box 2 (0.0317 g, 0.25 mmol) in a clear solution of THF (10 mL), a dark green solid precipitated immediately. The reaction was stirred at room temperature for 10 h, filtered, washed with n-hexane, and dried in vacuo to obtain a green solid (111.6 mg, 84%). Elemental analysis calculated value C 26 H 32 Cl 2 FeN 2 S: C, 58.77; H, 6.07; N, 5.27. Measured: C, 58.26; H, 6.35; N, 5.31.

[0268]

[0269] ( Et SNN iPr )FeCl 2 (Complex 4b): The synthesis of this complex is the same as that of 4a, and the yield of 4b is 71%. Elemental analysis calculated value C 25 H 30 Cl 2 FeN 2 S: C, 58.04; H, 5.85; N, 5.42. Measured: C, 57.63; H, 5.85; N, 5.50.

[0270]

[0271] ( tBu SNN iPr )FeCl 2 (Complex 4c): The synthesis of this complex is the same as that of 4a, and the yield of 4c is 89...

Embodiment 3

[0290] Example 3: Experiment of the catalytic activity of the complex to ethylene polymerization

[0291] (Table 1, item 1) Under the ethylene atmosphere of 300 psi, the freshly dried autoclave was assembled, and the ethylene gas was replaced three times. The autoclave was placed in an oil bath, the temperature of the oil bath was controlled to 120°C, and the oil was vacuum-dried with an oil pump for 2 hours. Lower the temperature of the oil bath to 20°C, and after the kettle body also reaches the predetermined temperature, add 100 mL of solvent toluene under the flow of ethylene, and stir for 10 minutes to make the solution reach the predetermined temperature and saturate ethylene in toluene. A certain amount of cocatalyst (MMAO, 600eq) was added and stirred for 2 minutes. The catalyst complex 4a solution was added, while the ethylene gas pressure was adjusted to 300 psi, the timer was started, and the reaction was carried out for 15 minutes. After the polymerization, the e...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

PropertyMeasurementUnit
molecular weight distributionaaaaaaaaaa
Login to View More

Abstract

The present invention disclosed a SNN ligand, its iron compounds and preparation methods and applications based on a pyrodoline skeleton.The present invention provides a SNN ligand based on a pyrine -based skeleton shown in the type i. Its iron compounds have a polymerization response to an olefin compounds. It has excellent catalytic activity.The shape is wax or oily polyolefin product.And the above catalytic reactions mainly generate the main chains containing unsaturated keys when the substrate is ethylene and non -co -crickets, and there are fewer branches of branches.

Description

technical field [0001] The invention belongs to the field of olefin polymerization, and in particular relates to a quinoline skeleton-based SNN ligand, an iron complex thereof, a preparation method and application thereof. Background technique [0002] Ziegler-Natta catalysts discovered in the 1950s (K. Ziegler et al. Angew. Chem. 1995, 67, 424; K. Ziegler et al. Angew. Chem. 1995, 67, 541; N. Kashiwa et al. USP 3642746, 1968), It is widely used in industry to produce high density polyethylene (HDPE), linear low density polyethylene (LLDPE), syndiotactic polypropylene (i-PP). Ziegler-Natta catalysts are heterogeneous and have multiple active sites, and currently, the structure and properties of polymers cannot be well controlled by adjusting the catalyst structure. The metallocene catalysts discovered in the 1980s solved this problem better, allowing people to obtain polymers with specific structures by changing the structure of the catalyst as needed (W.Kaminsky et al.Adv....

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07D215/36C07F15/02C08F110/02C08F210/18C08F236/20C08F4/70
CPCC07D215/36C07F15/025C08F110/02C08F210/18C08F4/7045C08F2500/03C08F2500/02C08F236/20Y02P20/52
Inventor 黄正侯文君张丹刘桂霞
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI