CN117229433A - Cyclic peroxide initiator containing hindered amine phlegmatizer and synthesis method and application thereof - Google Patents

Cyclic peroxide initiator containing hindered amine phlegmatizer and synthesis method and application thereof Download PDF

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CN117229433A
CN117229433A CN202211667599.5A CN202211667599A CN117229433A CN 117229433 A CN117229433 A CN 117229433A CN 202211667599 A CN202211667599 A CN 202211667599A CN 117229433 A CN117229433 A CN 117229433A
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hindered amine
reaction
cyclic peroxide
phlegmatizer
cyclic
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任国辉
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Abstract

The invention belongs to the technical field of organic synthesis and fine chemical engineering, and particularly relates to a cyclic peroxide initiator containing a hindered amine phlegmatizer, and a synthesis method and application thereof. The initiator comprises cyclic peroxide and a hindered amine phlegmatizer, wherein the hindered amine phlegmatizer accounts for 10-80% of the weight of the cyclic peroxide. The preparation method of the initiator comprises the following steps: the ketone compound and hydrogen peroxide aqueous solution are used as raw materials, and the cyclic peroxide is obtained through peroxidation under the catalysis of acid, and a hindered amine desensitizer is added during or after the reaction. The process is safe and reliable, and can obtain the target product with high yield and high purity; the invention has mild reaction condition and simple process, and the product does not need to be purified; the process is environment-friendly, and is suitable for amplification and industrial production.

Description

Cyclic peroxide initiator containing hindered amine phlegmatizer and synthesis method and application thereof
Technical Field
The invention belongs to the technical field of organic synthesis and fine chemical engineering, and particularly relates to a cyclic peroxide initiator containing a hindered amine phlegmatizer, and a synthesis method and application thereof.
Background
The cyclic peroxide is a cyclic compound with a peroxy chain, namely-O-, and can be used as a free radical initiator and participate in oxidation reaction due to the existence of peroxy bonds and higher oxygen element content in a molecular structure, so that the cyclic peroxide can be used for various aspects of organic synthesis, new material processing and manufacturing, fuel oil performance improvement and the like, is an emerging important chemical product, and has wide application fields.
The compounds are typically of a structure type having 2 peroxide structural units from the smallest six-membered ring and 3 peroxide structural units from the nine-membered ring, and the larger ring, i.e. the compound having more peroxide structural units, is quite rare. The structural type with nine rings, i.e. 3 peroxide building blocks, has the following structural features:
r represents the same or different aliphatic alkyl or aromatic substituent groups.
The method reported in the literature for synthesizing the compound is single, the method for synthesizing the compound is reported for the first time in N.A. Milas in 1959, and related patent US3003000 is filed in 1961. The technical process developed by Milas is complex in operation, peroxide monomer is mainly obtained, the cyclic product is separated only in the form of impurities,
the yield is very low, and thus industrial mass production cannot be realized.
In 2004, WO2004/076405 by german dezasie corporation reports a process method for synthesizing acetic acid under the condition of using nitric acid as a solvent, such as isododecane, and the like, the reaction efficiency of the method is low, the components of the product are complex, the purification is required, the process is complex, the produced nitric acid-acetic acid mixture cannot be effectively utilized, and the process safety cannot be ensured.
WO2015/135865 filed by the company of akunobel in 2015 also examines the fact that various solvents such as isododecane are used as reaction solvents for synthesis, and the defects that the components of the product are complex and need to be separated and purified exist, so that the complex and the addition of the product are not facilitated, and the safety guarantee level of the process is low.
Disclosure of Invention
In order to solve the technical problems, the invention provides a cyclic peroxide initiator containing a hindered amine phlegmatizer, a synthesis method and application thereof, and the phlegmatizer is added into a reaction system or a reaction product to reduce the safety risk of a peroxide product and reduce the safety risk in production.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in one aspect the present invention provides a cyclic peroxide initiator comprising a sterically hindered amine phlegmatiser, said initiator comprising a cyclic peroxide and a sterically hindered amine phlegmatiser, said sterically hindered amine phlegmatiser being present in an amount of from 10% to 80%, preferably from 30% to 60% by weight of the cyclic peroxide.
In the above technical scheme, further, the cyclic peroxide is a six-membered ring containing 2 peroxy groups in formula (i) or a nine-membered ring containing 3 peroxy groups in formula (ii):
r represents the same or different aliphatic alkyl or aromatic substituent groups.
In the above technical scheme, further, the hindered amine phlegmatizer is a hydrocarbon containing a hindered amine compound, and the structure of the hindered amine compound is shown in formula (iii) or formula (iv):
wherein R is 1 Represents various aliphatic alkyl groups of the same or different length, preferably C 5 ~C 10 An alkyl group;
the hydrocarbon comprises straight-chain alkane with a certain carbon chain length or isomer thereof, preferably C 8 ~C 18 Alkanes or isomers thereof, more preferably C 10 ~C 18 An alkane or isomer thereof;
in the hindered amine phlegmatizer, the content of the hindered amine compound is 0.5-20% of the weight of hydrocarbon, and is preferably 0.5-5%.
In the above technical scheme, further, the cyclic peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane or 3,6, 9-bis (triethyl) -1,4, 7-triperoxonane.
In another aspect, the present invention provides a method for synthesizing the cyclic peroxide initiator containing the hindered amine phlegmatizer, comprising the steps of: adding a ketone compound into a reactor, adding a hydrocarbon desensitizer containing a hindered amine compound, adding an acid catalyst, controlling the temperature of a reaction system, then adding a hydrogen peroxide aqueous solution, controlling the temperature of the reaction system, standing the reaction mixture for layering after the heat preservation reaction is finished, and collecting an oil phase to obtain the cyclic peroxide containing the hindered amine sensitizer.
In a further aspect the present invention provides a process for the synthesis of a cyclic peroxide initiator comprising a sterically hindered amine phlegmatiser as described above, said process comprising the steps of: adding a ketone compound into a reactor, adding an acid catalyst, controlling the temperature of a reaction system, then adding a hydrogen peroxide aqueous solution, controlling the temperature of the reaction system, standing the reaction mixture for layering after the heat preservation reaction is finished, collecting an oil phase, and adding a hydrocarbon desensitizer containing a hindered amine compound into the oil phase to obtain the cyclic peroxide containing the hindered amine sensitizer.
In the above technical scheme, further, the ketone compound is one of acetone, butanone, pentanone and acetophenone; the acid catalyst is one or more of sulfuric acid, nitric acid, perchloric acid, acetic acid and p-toluenesulfonic acid; the mass concentration of the hydrogen peroxide aqueous solution is 10-70%.
In the technical scheme, the molar ratio of the ketone compound to the acid catalyst to the aqueous hydrogen peroxide solution is 1 (0.2-20): 1-10, preferably 1 (0.5-5): 1-5.
In the technical scheme, further, the reaction temperature is controlled to be in the range of-40 to 90 ℃ and preferably in the range of-10 to 50 ℃ when the acid catalyst is dropwise added; the reaction temperature is controlled within the range of-40 to 90 ℃, preferably-10 to 50 ℃ when the aqueous hydrogen peroxide solution is added dropwise.
The invention also provides an application of the cyclic peroxide initiator containing the hindered amine phlegmatizer in crosslinking reaction, free radical reaction or polypropylene plastic manufacturing.
Compared with the prior art, the invention has the beneficial effects that:
1. the addition of the phlegmatizer can effectively reduce the effective oxygen content in the reactant and the product, thereby achieving the aim of reducing the risk and ensuring and improving the safety of the technological process and the product;
2. the process is safe and reliable, and can obtain the target product with high yield and high purity;
3. the invention has mild reaction condition and simple process, and the product does not need to be purified;
4. the process is environment-friendly, is suitable for amplification and industrial production, and the byproducts are convenient to treat and recycle;
5. the cyclic peroxide molecular structure obtained by the synthesis process can be used as a free radical initiator or participate in oxidation reaction due to the existence of peroxide bonds and higher oxygen element content, and can be used in the fields of organic synthesis, fine chemical engineering and the like.
6. Compared with the like products sold in the market at present, the product obtained by the process is more suitable for adding and blending, is convenient to apply, can obtain accurate performance evaluation on the application effect of the annular peroxide, and has the advantages of obvious effect and convenient application.
Detailed Description
The treatment process according to the invention is further described below with reference to specific examples.
Unless otherwise indicated, all starting materials used in the examples of the present invention were commercially available.
Example 1
The synthesis of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is carried out according to the following synthetic route:
the feed ratio is shown in Table 1.
TABLE 1
The synthesis method comprises the following steps:
methyl ethyl ketone, trioctylamine and isododecane are added into a 500mL four-port reaction bottle, the reaction bottle is placed into a constant-temperature bath (bath temperature is 10 ℃), and mechanical stirring, a thermometer and a reflux condenser are arranged; adding sulfuric acid with the mass fraction of 75% through a dropping funnel, and controlling the reaction temperature to be lower than 30 ℃; hydrogen peroxide with the concentration of 50% is added dropwise through a dropping funnel, the temperature of the reaction system is controlled to be lower than 40 ℃ due to the heating phenomenon; after dripping, carrying out heat preservation reaction for 5hrs at 40 ℃; finishing the reaction, transferring the reaction mixture into a separating funnel, standing for 30min and layering; obtaining an oil phase and a water phase;
wherein the oil phase is 123g of product, yield: 74% (calculated as 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane).
Example 2
The synthesis of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is carried out according to the following synthetic route:
the feed ratio is shown in Table 2.
TABLE 2
The synthesis method comprises the following steps: methyl ethyl ketone, trioctylamine and isohexadecane are added into a 500mL four-port reaction bottle, the reaction bottle is placed into a constant-temperature bath (bath temperature is 10 ℃), and mechanical stirring, a thermometer and a reflux condenser are arranged; adding sulfuric acid with the mass fraction of 75% through a dropping funnel, and controlling the reaction temperature to be lower than 20 ℃; hydrogen peroxide with the concentration of 50% is added dropwise through a dropping funnel, the temperature of the reaction system is controlled to be lower than 20 ℃ due to the heating phenomenon; after dripping, the mixture is reacted for 5hrs at 20 ℃; finishing the reaction, transferring the reaction mixture into a separating funnel, standing for 30min and layering; obtaining an oil phase and a water phase;
wherein the oil phase is 120g of product, yield: 71% (calculated as 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane).
Example 3
The synthesis of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is carried out according to the following synthetic route:
the feed ratio is shown in Table 3.
TABLE 3 Table 3
The synthesis method comprises the following steps: methyl ethyl ketone, trioctylamine and isohexadecane are added into a 500mL four-port reaction bottle, the reaction bottle is placed into a constant-temperature bath (bath temperature is 10 ℃), and mechanical stirring, a thermometer and a reflux condenser are arranged; adding sulfuric acid with the mass fraction of 75% through a dropping funnel, and controlling the reaction temperature to be lower than 40 ℃; hydrogen peroxide with the concentration of 50% is added dropwise through a dropping funnel, the temperature of the reaction system is controlled to be lower than 40 ℃ due to the heating phenomenon; after dripping, carrying out heat preservation reaction for 5hrs at 40 ℃; finishing the reaction, transferring the reaction mixture into a separating funnel, standing for 30min and layering; obtaining an oil phase and a water phase;
wherein the oil phase is 125g of product, yield: 75% (calculated as 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane).
Example 4
The synthesis of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is carried out according to the following synthetic route:
the feed ratio is shown in Table 4.
TABLE 4 Table 4
The synthesis method comprises the following steps: methyl ethyl ketone is added into a 500mL four-port reaction bottle, the reaction bottle is placed into a constant-temperature bath (bath temperature is 10 ℃), and mechanical stirring, a thermometer and a reflux condenser are arranged; adding sulfuric acid with the mass fraction of 75% through a dropping funnel, and controlling the reaction temperature to be lower than 40 ℃; hydrogen peroxide with the concentration of 50% is added dropwise through a dropping funnel, the temperature of the reaction system is controlled to be lower than 40 ℃ due to the heating phenomenon; after dripping, the mixture is reacted for 3hrs at 40 ℃; finishing the reaction, transferring the reaction mixture into a separating funnel, standing for 30min and layering; obtaining an oil phase and a water phase; adding trioctylamine and isohexadecane into the oil phase, and stirring uniformly.
Wherein the oil phase is 125g of product, yield: 75% (calculated as 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane).
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims (9)

1. A cyclic peroxide initiator comprising a sterically hindered amine phlegmatiser, characterized in that: the initiator comprises cyclic peroxide and a hindered amine phlegmatizer, wherein the hindered amine phlegmatizer accounts for 10-80% of the weight of the cyclic peroxide.
2. The cyclic peroxide initiator containing a sterically hindered amine phlegmatiser according to claim 1, wherein: the cyclic peroxide is a six-membered ring containing 2 peroxy groups in formula (I) or a nine-membered ring containing 3 peroxy groups in formula (II):
r represents the same or different aliphatic alkyl or aromatic substituent groups.
3. The cyclic peroxide initiator containing a sterically hindered amine phlegmatiser according to claim 1, wherein: the hindered amine phlegmatizer is hydrocarbon containing a hindered amine compound, and the structure of the hindered amine compound is shown as a formula (III) or a formula (IV):
wherein R is 1 Represents various aliphatic alkyl groups of the same or different length;
the hydrocarbon comprises a linear alkane having a carbon chain length or an isomer thereof;
in the hindered amine phlegmatizer, the content of the hindered amine compound is 0.5-20% of the weight of hydrocarbon.
4. A process for the synthesis of a cyclic peroxide initiator containing a sterically hindered amine phlegmatiser as claimed in any one of claims 1 to 3, characterised in that:
the method comprises the following steps: adding a ketone compound into a reactor, adding a hydrocarbon desensitizer containing a hindered amine compound, adding an acid catalyst, controlling the temperature of a reaction system, then adding a hydrogen peroxide aqueous solution, controlling the temperature of the reaction system, standing the reaction mixture for layering after the heat preservation reaction is finished, and collecting an oil phase to obtain the cyclic peroxide containing the hindered amine sensitizer.
5. A process for the synthesis of a cyclic peroxide initiator containing a sterically hindered amine phlegmatiser as claimed in any one of claims 1 to 3, characterised in that: the method comprises the following steps: adding a ketone compound into a reactor, adding an acid catalyst, controlling the temperature of a reaction system, then adding a hydrogen peroxide aqueous solution, controlling the temperature of the reaction system, standing the reaction mixture for layering after the heat preservation reaction is finished, collecting an oil phase, and adding a hydrocarbon desensitizer containing a hindered amine compound into the oil phase to obtain the cyclic peroxide containing the hindered amine sensitizer.
6. The synthesis method according to claim 4 or 5, wherein: the ketone compound is one of acetone, butanone, pentanone and acetophenone;
the acid catalyst is one or more of sulfuric acid, nitric acid, perchloric acid, acetic acid and p-toluenesulfonic acid;
the mass concentration of the hydrogen peroxide aqueous solution is 10-70%.
7. The synthesis method according to claim 4 or 5, wherein: the molar ratio of the ketone compound to the acid catalyst to the aqueous hydrogen peroxide solution is 1 (0.2-20): 1-10.
8. The synthesis method according to claim 4 or 5, wherein: the reaction temperature range is controlled to be-40-90 ℃ when the acid catalyst is dripped; the reaction temperature is controlled to be-40-90 ℃ when the aqueous hydrogen peroxide solution is dripped.
9. Use of a cyclic peroxide initiator containing a sterically hindered amine phlegmatiser as claimed in any of claims 1 to 3 in a cross-linking reaction, a free radical reaction or in the manufacture of polypropylene plastics.
CN202211667599.5A 2022-12-23 2022-12-23 Cyclic peroxide initiator containing hindered amine phlegmatizer and synthesis method and application thereof Pending CN117229433A (en)

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