CN104971774A

CN104971774A - Preparation method for hydrofluoroether and catalyst thereof

Info

Publication number: CN104971774A
Application number: CN201510406042.XA
Authority: CN
Inventors: 王琪宇; 张玲
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-07-08
Filing date: 2015-07-08
Publication date: 2015-10-14

Abstract

The present invention discloses a preparation method for hydrofluoroether and a catalyst thereof, especially a preparation method of 1,1,2,2,-tetrafluoroethyl-2,2,2-trifluoroethyl ether, wherein tetrafluoroethylene and trifluoroethanol react under catalysis of a solid composite catalyst. According to the present invention, advantages of good catalyst activity, recycling, less three-waste, and green environmental protection are provided.

Description

The preparation method of a kind of hydrogen fluorine ether and catalyst thereof

Technical field

The present invention relates to a kind of method of fluorine-containing ether compounds, particularly the preparation method of a kind of hydrogen fluorine ether and catalyst thereof.

Background technology

It is CF that Daikin and Asahi Glass are all proposed molecular formula ₃cH ₂oCF ₂cHF ₂hydrogen fluorine ether, the commercialization name of great Jin is called HFE-S7, and the commercialization name of Asahi Glass is called AE3000, be called AE3100, (having another name called HFE347pc-f) by commercialization name after ethanol dilution, the numerous characteristics of HFE-347 and CFC-113 are relatively, without the need to large adjustment in using method, but because its KB value is less than CFC-113, dissolving power is slightly poor, so, difference is had again during use, the KB value of HFE-347 is less, and dissolving power is more weak, so need during cleaning to use ultrasonic assistant.Simultaneously, suitable KB value makes it can have good compatibility with most of material, be easy to reclaim and use, the feature of the low latent heat of vaporization makes it to have in same kind solvent evaporation rate faster, be good dry solvent, but also have larger volatilization loss simultaneously, so, cleaning machine with cooling and reflux device will greatly reduce volatilization loss, cost-saving.In addition, because HFE-347 and most of solvent have good intersolubility, can be used in combination with the solvent of dissolving power strong (KB value is larger), learning from other's strong points to offset one's weaknesses, is a kind of excellent cleaning agent.

CN1651378 provides a kind of new hydrofluoro ether and preparation method thereof, in dimethyl formamide DMF or dimethyl sulfoxide (DMSO) DMSO organic solvent, potassium hydroxide or NaOH is used to be catalyst, prepare new hydrofluoro ether, raw material is trifluoro-ethylene, tetrafluoroethene, vinylidene, hexafluoropropene, CTFE and trifluoroethanol, trifluoropropanol, methyl alcohol, ethanol, propyl alcohol, butanols, 20 ~ 90 DEG C of reactions, 1 ~ 10hrs, obtained hydrogen fluorine ether.

CN102115428A provides a kind of synthetic method of hydrogen fluorine ether, according to ratio of weight and number with 20 ~ 100 parts of alcohol for raw material, described alcohols is a kind of in methyl alcohol, ethanol, propyl alcohol, trifluoro methyl alcohol, tetrafluoropropanol and octafluoropentanol, under 1 ~ 6 part of alkali catalyst exists, add 34 ~ 108 parts of Fluorine containing olefines continuously, react at 110 ~ 180 DEG C, reaction pressure is 0.6 ~ 1.2MPa, reaction time is 1 ~ 5h, after rectifying is separated, obtain target product.

Above patent and catalyst that technical literature uses are mainly alkali metal compound, and there is catalyst recovery difficulty, dregginess is high, and because solid particle is thin, the shortcomings such as product and catalyst separation difficulty, simultaneously because use a large amount of solvent, easily cause environmental pollution.

Summary of the invention

Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of good catalyst activity, reusable edible; The three wastes are few, a kind of hydrogen fluorine ether of environmental protection and the preparation method of catalyst thereof.

In order to solve above technical problem, present invention employs following technical scheme: the preparation of a kind of hydrogen fluorine ether and catalyst thereof, comprises the following steps:

(1) strong-base anion-exchange resin swells in 2-4 times of (weight ratio) water, adds the N-ethoxy perfluorinated octyl sulfuryl amine of strong-base anion-exchange resin percent 0.1-0.5 (wt%); Add strong-base anion-exchange resin percent 5-20 (wt%) 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), add strong-base anion-exchange resin percent 0.05-0.5 (wt%) disodium ethylene diamine tetraacetate (EDTA), in 40 DEG C-80 DEG C stirring reaction 10-20h, reaction terminates, obtained composite catalyst, for subsequent use;

(2) in reactor, add the obtained composite catalyst of above-mentioned steps (1) of trifluoroethanol, alcohol quality 30 ~ 100%, envelope still, with the air in nitrogen displacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, reaction temperature controls at 40 ~ 80 DEG C, when terminating reaction after the tetrafluoroethylene monomer passing into alcohol quality 300 ~ 500%, separation and recovery composite catalyst, washing, rectifying obtains 1,1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.

Described strong-base anion-exchange resin can use commercially available prod, as triumphant in Shanghai strength resin sell that Co., Ltd produces D201, the products such as 201*7.

Described N-ethoxy perfluorinated octyl sulfuryl amine can commercially availablely obtain, as the product that Sichuan Hua Gao Chemical Co., Ltd. produces.

Described 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU) can commercially availablely obtain, as the product that the biochemical (Shanghai) Co., Ltd. of gill can be adopted to produce.

Compared with prior art, the present invention has following beneficial effect:

1) as alkaline enhanced aid, 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), N-ethoxy perfluorinated octyl sulfuryl amine is organic alkali, can resin surface be adsorbed on, the comprehensive alkalescence of composite catalyst is strengthened.

2) catalyst reusable edible, is easy to and other separating substances, and the composite catalyst of recovery can recycle, and effectively can reduce the pollution of traditional volatile organic solvent to environment;

Detailed description of the invention

Below in conjunction with specific embodiment, illustrate the present invention further, but these embodiments are only for explaining the present invention, instead of for limiting the scope of the invention.

In embodiment, strong-base anion-exchange resin adopts D201 strong-base anion-exchange resin, and strength triumphant resin in Shanghai is sold Co., Ltd and produced.

Embodiment 1

A preparation method for hydrogen fluorine ether and catalyst thereof, comprises the following steps:

Step 1: add D201 strong-base anion-exchange resin 100Kg in 500L reactor respectively, the N-ethoxy perfluorinated octyl sulfuryl amine of 300Kg water, 0.3Kg, 10Kg 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), add 0.2Kg disodium ethylene diamine tetraacetate (EDTA), in 60 DEG C of stirring reaction 15h, reaction terminates, obtained composite catalyst, for subsequent use.

Step 2: disposablely in 1000L stainless steel autoclave add 100Kg trifluoroethanol, the composite catalyst that the above-mentioned steps (1) of 70Kg is obtained, close charge door, with the air in nitrogen displacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, reaction temperature controls at 60 DEG C, metering passes into the tetrafluoroethene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 400Kg, filtered and recycled composite catalyst, filtrate obtains 1 through washing to refine, 1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.Yield and selective in table 1.

Embodiment 2

Step 1: add D201 strong-base anion-exchange resin 100Kg in 500L reactor respectively, the N-ethoxy perfluorinated octyl sulfuryl amine of 200Kg water, 0.1Kg, 5Kg 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), add 0.05Kg disodium ethylene diamine tetraacetate (EDTA), in 40 DEG C of stirring reaction 20h, reaction terminates, obtained composite catalyst, for subsequent use.

Step 2: disposablely in 1000L stainless steel autoclave add 100Kg trifluoroethanol, the composite catalyst that the above-mentioned steps (1) of 30Kg is obtained, close charge door, with the air in nitrogen displacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, reaction temperature controls at 40 DEG C, metering passes into the tetrafluoroethene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 300Kg, filtered and recycled composite catalyst, filtrate obtains 1 through washing to refine, 1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.Yield and selective in table 1.

Embodiment 3

Step 1: add D201 strong-base anion-exchange resin 100Kg in 500L reactor respectively, the N-ethoxy perfluorinated octyl sulfuryl amine of 400Kg water, 0.5Kg, 20Kg 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), add 0.5Kg disodium ethylene diamine tetraacetate (EDTA), in 80 DEG C of stirring reaction 10h, reaction terminates, obtained composite catalyst, for subsequent use.

Step 2: disposablely in 1000L stainless steel autoclave add 100Kg trifluoroethanol, the composite catalyst that the above-mentioned steps (1) of 100Kg is obtained, close charge door, with the air in nitrogen displacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, reaction temperature controls at 80 DEG C, metering passes into the tetrafluoroethene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 500Kg, filtered and recycled composite catalyst, filtrate obtains 1 through washing to refine, 1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.Yield and selective in table 1.

Comparative example 1

Step 1 does not add N-ethoxy perfluorinated octyl sulfuryl amine, the other the same as in Example 1.Obtain 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ether products, yield and selective in table 1.

Comparative example 2

Step 1 does not add 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), the other the same as in Example 1.Obtain 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ether products, yield and selective in table 1.Comparative example 3

The potassium hydroxide adding 15% of trifluoroethanol quality in step 2 replaces composite catalyst, the other the same as in Example 1.Obtain 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ether products, yield and selective in table 1.

Table 1: the yield of embodiment 1 ~ 3 and comparative example 1 ~ 3 and selective.

Embodiment	Yield %	Selective .%
			1	95	99
2	93	97
			3	97	99
Comparative example 1	86	95
			Comparative example 2	89	92
Comparative example 3	81	87

Claims

1. a preparation method for hydrogen fluorine ether and catalyst thereof, is characterized in that, described preparation method comprises the following steps:

(1) strong-base anion-exchange resin swells in 2-4 times of (weight ratio) water, adds the N-ethoxy perfluorinated octyl sulfuryl amine of strong-base anion-exchange resin percent 0.1-0.5 (wt%); Percent 5-20 (wt%) 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), percent 0.05-0.5 (wt%) disodium ethylene diamine tetraacetate (EDTA), in 40 DEG C-80 DEG C stirring reaction 10-20h, reaction terminates, obtained composite catalyst, for subsequent use;

2. the preparation method of a kind of hydrogen fluorine ether according to claim 1 and catalyst thereof, it is characterized in that adding N-ethoxy perfluorinated octyl sulfuryl amine described in step (1), 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), disodium ethylene diamine tetraacetate (EDTA) is as alkaline enhanced aid.

3. the preparation method of a kind of hydrogen fluorine ether according to claim 1 and catalyst thereof, is characterized in that using trifluoroethanol and tetrafluoroethene as raw material in step (2), with this etherification reaction of composite catalyst catalysis obtained in the present invention.