CN111138275B

CN111138275B - Perfluoroalkyl diacyl fluoride and preparation method thereof

Info

Publication number: CN111138275B
Application number: CN201911404655.4A
Authority: CN
Inventors: 汤峤永; 肖鑫; 姚素梅
Original assignee: Tianjin Changlu Chemical New Material Co ltd
Current assignee: Tianjin Changlu Chemical New Material Co ltd
Priority date: 2019-12-30
Filing date: 2019-12-30
Publication date: 2022-06-10
Anticipated expiration: 2039-12-30
Also published as: CN111138275A

Abstract

The present invention belongs to the field of fluorine chemical industryCyclic olefin is pre-activated in an activation chamber and then enters a cracking chamber to react with oxygen under the condition of a catalyst to generate the perfluoro diacyl fluoride through catalytic cracking, wherein n is an integer from 1 to 5, and Rf is an integer from 1 to 5₁Rf2, Rf3, Rf4, Rf5 and Rf6 are respectively one of fluoro, perfluoroalkyl and perfluoroalkyl ether. In the method, cyclic olefin is used as a raw material, and catalytic cracking is carried out under oxygen atmosphere after catalytic pre-activation by ozone, so that the cyclic olefin can almost completely react without loss, the yield is high, and the controllability is strong.

Description

Perfluoroalkyl diacyl fluoride and preparation method thereof

Technical Field

The invention belongs to the field of fluorine chemical industry, and particularly relates to perfluoroalkyl diacyl fluoride and a preparation method thereof.

Background

The diacyl fluorine hexafluoropropylene oxide polymer is a fluorine-containing organic intermediate with wide application, can be hydrolyzed, aminolyzed and alcoholyzed by utilizing the reactivity of a terminal-COF group to further synthesize fluorine-containing polyester, polyamide, polyepoxy resin, fluorosilicone resin and various compounds with polymerizable vinyl fluoride, and therefore has important development value in the fluorine-containing fine chemical engineering field.

Disclosure of Invention

The invention aims to provide perfluoroalkyl diacyl fluoride and a preparation method thereof.

In order to realize the purpose, the invention adopts the following technical scheme:

a preparation method of perfluoroalkyl diacyl fluoride comprises the steps of pre-activating cyclic olefin in an activation chamber, then allowing the cyclic olefin to enter a cracking chamber to react with oxygen under the condition of a catalyst, and catalytically cracking the cyclic olefin to generate the perfluoroalkyl diacyl fluoride, wherein the reaction formula (I) is as shown in the specification:

wherein n is an integer of 1 to 5, Rf₁Rf2 and Rf3 are respectively one of fluoro, perfluoroalkyl and perfluoroalkyl ether.

Preferably, n is 1, Rf₁Rf2 and Rf3 are all fluorine groups.

The pre-activation method comprises the specific steps of introducing cyclic olefin into an activation chamber, filling metal oxide into the activation chamber, introducing O3, and performing activation under the condition of light irradiation; the light irradiation time was: 10-90min, and the reaction temperature is-10-20 ℃.

The metal oxide is one of TiO2, Fe2O3, Fe3O4, CoO, Co3O4, Ag2O and Pd 2O.

The cracking process takes oxygen and activated cyclic olefin as raw materials, and the cyclic olefin is prepared by reaction under the action of a catalyst; wherein the molar ratio of oxygen to the cyclic olefin is 20:1-1: 10; the contact reaction time is 0.1s to 200 s; the reaction pressure is 0-1 MPa; the reaction temperature is 200-700 ℃.

The catalyst is a supported catalyst, and the active component is one or a mixture of more of AgO, Al2O3, CuO, AgF, NaF, KF, RbF and CsF.

The application also comprises perfluoroalkyl diacyl fluoride obtained by the preparation method.

Compared with the prior art, the invention has the beneficial effects that:

in the method, cyclic olefin is used as a raw material, and catalytic cracking is carried out under oxygen atmosphere after catalytic pre-activation by ozone, so that the cyclic olefin can almost completely react without loss, the yield is high, and the controllability is strong.

Detailed Description

In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.

Example 1: ozone is led into an activation chamber with an ozone irradiation lamp arranged at the upper part, a temperature-controllable material storage tank is arranged in the activation chamber, a vertical irradiation mode is adopted during irradiation, namely the direction of a particle beam is vertical to the surface of liquid, metal oxide is arranged in the material storage tank, the raw material perfluorocyclopentene is added, the reaction temperature is controlled to be-10-20 ℃, the irradiation time is 10-90min, a liquid discharge valve at the bottom of the material storage tank is opened after irradiation is finished, the activated perfluorocyclopentene is put into a vaporization chamber to be slowly vaporized, and the temperature rise process of the vaporization chamber adopts the programmed temperature rise: keeping the temperature at 20 ℃ for 5-10min, and then increasing the temperature to 30-40 ℃ at the speed of 0.5-1 ℃/min. The gasified raw material enters a cracking chamber to be heated and cracked in the presence of oxygen, and the feeding molar ratio of the gasified raw material to the oxygen is controlled to be 20:1-1:10 by a gas flow meter in the cracking process. The contact reaction time is 0.1s to 200 s; the reaction pressure is 0-1 MPa; the reaction temperature is 200-700 ℃. And (3) the product obtained after cracking firstly enters a cold trap at 30 ℃ for collecting the diacyl fluoride generated by cracking, and the obtained diacyl fluoride is rectified and purified to obtain a high-purity diacyl fluoride product, wherein the parameters and the yield of different embodiments are shown in table 1.

Comparative example 1: the comparative example differs from example 2 only in that perfluorocyclopentene was added directly to the cracking chamber without pre-activation to react with oxygen.

TABLE 1

	Example 1	Example 2	Example 3	Example 4	Comparative example 1
						Metal oxides	TiO2	Ag2O	TiO2	Ag2O	/
Catalyst and process for preparing same	NaF	NaF	KF	KF	NaF
						Perfluoro cyclopentene: oxygen gas	20:1	1:1	1:1	1:10	1:1
Reaction temperature/. degree.C	200	350	350	700	350
						Contact time/s	30	60	100	200	100
Yield of	76.2％	85.1％	86.9％	92.3％	62.3％

The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.

Claims

1. A preparation method of perfluoroalkyl diacyl fluoride is characterized by comprising the following steps: the cyclic olefin is pre-activated by an activation chamber, enters a cracking chamber and reacts with oxygen under the condition of a catalyst, and is catalytically cracked to generate perfluorodiacyl fluoride, wherein the reaction formula is shown as (I):

（I）

wherein n is an integer of 1 to 5, Rf₁Rf2, Rf3, Rf4, Rf5 and Rf6 are respectively one of fluoro, perfluoroalkyl and perfluoroalkyl ether.

2. The process for producing a perfluoroalkyldiacyl fluoride according to claim 1, wherein n =1, Rf₁All of Rf2, Rf3, Rf4, Rf5 and Rf6 are fluorine groups.

3. The method for preparing perfluoroalkyldiacyl fluoride according to claim 1, wherein the pre-activation comprises the steps of introducing cyclic olefin into an activation chamber, filling metal oxide into the activation chamber, introducing O3, and performing activation under light irradiation; the light irradiation time was: 10-90min, and the reaction temperature is-10-20 ℃.

4. The method of claim 3, wherein the metal oxide is one of TiO2, Fe2O3, Fe3O4, CoO, Co3O4, Ag2O, and Pd 2O.

5. The method for preparing perfluoroalkyldiacyl fluoride according to claim 1, wherein the cracking process is carried out by reacting oxygen with activated cyclic olefin as raw material under the action of catalyst; wherein the molar ratio of oxygen to the cyclic olefin is 20:1-1: 10; the contact reaction time is 0.1s to 200 s; the reaction pressure is 0-1 MPa; the reaction temperature is 200-700 ℃.

6. The method for preparing perfluoroalkyldiacyl fluoride according to claim 5, wherein the catalyst is a supported catalyst, and the active ingredient is one or a mixture of more of AgO, Al2O3, CuO, AgF, NaF, KF, RbF and CsF.