A kind of thermally stable multifunctional polymerization inhibitor and synthesis method

A technology with multiple functional groups and synthesis methods, which is applied in the field of synthesis of free radical inhibitors, can solve the problems of difficult removal of inhibitors, low efficiency of inhibition, poor thermal stability, etc., to reduce operating costs and operation volume, improve Polymerization inhibition effect, effect of increasing thermal stability

Active Publication Date: 2022-07-12
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, the existing types of polymerization inhibitors still have the following problems in industrial applications: 1) the process operation is limited, and the amount of oxygen added to the reaction system is difficult to control, resulting in lower polymerization inhibition efficiency of some chain transfer type polymerization inhibitors in the anoxic system. Low
2) The thermal stability of the polymerization inhibitor is poor, especially in the high temperature separation process and heavy component recovery process, the thermal decomposition or carbonization deterioration of the polymerization inhibitor will occur, resulting in the loss of the polymerization inhibition effect on the system
3) Industrial production generally removes the polymerization inhibitor through the rectification process, and the low boiling point of the polymerization inhibitor is often brought into the product to affect product quality
Chinese patent application CN1821207A utilizes the combination of nitroxide free radical compound and copper salt inhibitor to improve the inhibitory effect of the inhibitor in the production process of methacrylic acid and its esters, but the stability of the inhibitor is difficult to remove The problem of removing
[0005] In industrial production, the inhibition effect of phenothiazine polymerization inhibitors is better, but because of its better inhibition effect under aerobic conditions, its applicability in the whole process is limited. If different processes use different inhibitors In addition, the thermal stability of the phenothiazine small molecule polymerization inhibitor is poor, and it usually decomposes and carbonizes in the process of high temperature
[0006] It can be seen that there is still a need to develop a new polymerization inhibitor in this field to solve the problems that existing polymerization inhibitors are difficult to be compatible and solve the problems of unsatisfactory inhibition effect, difficult removal of polymerization inhibitor, poor thermal stability, etc.

Method used

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  • A kind of thermally stable multifunctional polymerization inhibitor and synthesis method
  • A kind of thermally stable multifunctional polymerization inhibitor and synthesis method
  • A kind of thermally stable multifunctional polymerization inhibitor and synthesis method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0076] 2-Aminobenzenethiol A-1 (12.52 g, 100.0 mmol) was dissolved in 250 mL of dichloromethane, 2 equivalents of pyridine (15.82 g, 200 mmol) were added to the system, and 1.5 mmol was slowly added to the system while stirring at room temperature. The equivalent of TsCl (28.60 g, 150 mmol) was stirred at room temperature until the substrate was completely reacted. After the reaction of the substrate was completed, saturated copper sulfate solution was added to the system to wash the pyridine, followed by extraction, and the product Ts-protected 2-aminobenzenethiol B-1 was obtained with a yield of 98% (27.34 g). The intermediate B-1 was confirmed by H NMR that the amino hydrogen was halved and the methyl peak was increased.

[0077]

[0078] Add CuCl (10g, 100mmol) and TMEDA (11.6g, 100.0mmol) to a 250mL single-necked flask, add 200mL of acetone to the system and stir at room temperature for 1 hour dark green mixture, trimethylethynylsilicon (4.9g, 50.0 mmol) and B-1 (20 m...

Embodiment 2

[0085] Under a nitrogen atmosphere, the catalyst [Rh(cod)Cl]2 (4.9 mg, 0.01 mmol), the additive AgNTf2 (12 mg, 0.03 mmol) and the ligand dppf (18 mg, 0.03 mmol) were sequentially added to the reaction tube. 50 mL of DCE was added to the reaction flask and stirred at room temperature for 25 minutes. Substrate C-1 (1.0 g 3 mmol) and 4-methylphenylacetylene (0.38 g, 3.3 mmol) were dissolved in another 20 mL of DCE and added to the reaction under argon protection. In the tube, move the reaction tube to a 60°C oil bath and heat until the substrate reacts completely, return the reaction system to room temperature, remove the solvent by rotary evaporation, wash with n-hexane, and recrystallize to obtain the final target product with a yield of 91%. G1.

[0086]

[0087] Take the intermediate product E1 (4.43 g, 10 mmol) in a 250 mL single-neck flask, add 150 mL of acetone to dissolve, then add 5 mL of ammonia water, reflux at 80 ° C for 4 h, after the reaction is completed, the so...

Embodiment 3

[0096] 2-Amino-4 chloro-benzenethiol A-2 (15.9 g, 100.0 mmol) was dissolved in 250 mL of dichloromethane, 2.5 equivalents of pyridine (19.75 g) were added thereto, and the system was slowly added under stirring at room temperature. 1.8 equivalents of TsCl (34.32 g, 180 mmol) were added, and stirring was continued at room temperature until the substrate reacted completely. After the reaction of the substrate was completed, saturated copper sulfate solution was added to the system to wash the pyridine, followed by extraction to obtain the product Ts-protected 2-aminobenzenethiol B-2 with a yield of 98% (30.67 g). The intermediate B-1 was confirmed by H NMR that the amino hydrogen was halved and the methyl peak was increased.

[0097]

[0098] Add CuCl (10g, 100mmol) and TMEDA (11.6g, 100.0mmol) to a 250mL single-necked flask, add 200mL of acetone to the system and stir at room temperature for 1 hour dark green mixture, trimethylethynylsilicon (5.9g, 60.0 mmol) and B-2 (6.26 ...

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Abstract

The invention relates to a thermally stable multifunctional polymerization inhibitor and a synthesis method. The method takes aminobenzenethiol as an original raw material, adopts a coupling reaction to introduce an alkyne group, uses rhodium to catalyze the construction of a phenothiazine skeleton, and uses transesterification to construct a nitrogen oxide Free radical functional groups or phenolic functional groups make the same molecule have two polymerization inhibitory groups at the same time, increase the polymerization inhibitory effect of the polymerization inhibitor, introduce different substituent groups through the benzene ring skeleton, and increase the molecular branching to improve the polymerization inhibitor. Thermal stability, by increasing the molecular weight of the polymerization inhibitor, is beneficial to reduce the entrainment of the polymerization inhibitor during the refining process.

Description

technical field [0001] The invention relates to a method for synthesizing a free radical polymerization inhibitor, in particular to a high-efficiency polymerization inhibitor with good thermal stability and multiple polymerization-inhibiting functional groups. Background technique [0002] The commonly used free radical polymerization inhibitors in industry mainly include: phenols, phenothiazine, nitroxide free radicals, metals, organic amines and other polymerization inhibitors. High-efficiency polymerization inhibitor ZJ-701 belongs to nitroxide free radical type polymerization inhibitor. Since this free radical type polymerization inhibitor has active free radicals, the unpaired oxygen atoms in this molecule can quickly capture the newly formed in the material. It has the characteristics of high polymerization inhibition efficiency, less dosage, and no effect of oxygen on its polymerization inhibition effect. The chain transfer type polymerization inhibitor is reversible...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D279/20C07D417/12C07C57/04C07C51/50C07C69/54C07C67/62
CPCC07D279/20C07D417/12C07C51/50C07C67/62C07C57/04C07C69/54Y02P20/584
Inventor 朱子忠张宏科徐世伟葛飞徐丹
Owner WANHUA CHEM GRP CO LTD
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