CN108440748B - Synthesis method of high molecular weight perfluoropolyether peroxide with acyl fluoride groups - Google Patents
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Abstract
The invention discloses a method for synthesizing high molecular weight perfluoropolyether peroxide with acyl fluoride groups, which comprises the following steps: 1) adding one or a mixture of a plurality of peroxides such as ozone, oxygen difluoride and dichloro oxide as an auxiliary agent into a polymerization reaction using elemental fluorine or trifluoromethyl hypofluorite as an initiator; 2) using oxygen or liquid oxygen as a raw material; 3) the reaction temperature range is from-100 ℃ to-30 ℃, and the optimal temperature is from-100 ℃ to-45 ℃; 4) the reaction pressure ranges from normal pressure to 200KPa, and the optimal pressure is normal pressure to 100 KPa. The invention achieves the purposes of improving the content of the high molecular weight perfluoropolyether intermediate product and reducing the content of the low molecular weight perfluoropolyether intermediate product by adding the auxiliary agent, or changing the temperature of the added oxygen, or changing the process conditions.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a synthesis method of high molecular weight perfluoropolyether peroxide with acyl fluoride groups.
Background
A method for synthesizing perfluoropolyether peroxide having acyl fluoride group by directly reacting oxygen with a perfluoromonomer at low temperature using fluorine gas, trifluoromethyl hypofluorite, a mixture of fluorine gas and trifluoromethyl hypofluorite as an initiator has been reported in patent CN1049670A and foreign patent US 5149842.
By using the synthesis method reported in the patent, the molecular weight distribution of the obtained perfluoropolyether intermediate product (peroxide with acyl fluoride groups) is from hundreds to hundreds of thousands, and the distribution situation that the content of the perfluoropolyether intermediate product with low molecular weight (less than 1000) and high molecular weight (more than 10000) is lower and the content of the perfluoropolyether intermediate product with intermediate molecular weight (3000-4000) is higher is presented overall. Because of the large price difference between perfluoropolyether oils of different molecular weights, in particular, the final price of high molecular weight perfluoropolyether oils can be several times that of low molecular weight perfluoropolyether oils. Intermediate molecular weight perfluoropolyether oils, especially those of intermediate molecular weight, have been in low commercial demand.
Although USP4755330 teaches that higher molecular weight perfluoropolyether oils can be decomposed into lower molecular weight perfluoropolyether intermediates using a catalyst, the loss is greater and the process is not economical. In order to meet the market demand and ensure the profit margin, a suitable synthesis method must be found, so that the content of high molecular weight products with higher value in the synthesized products is increased, and the content of low molecular weight products with lower value is reduced.
Disclosure of Invention
The invention aims to provide a technical scheme of a synthesis method of high molecular weight perfluoropolyether peroxide with acyl fluoride groups aiming at the defects in the prior art, and the method achieves the purposes of increasing the content of a high molecular weight perfluoropolyether intermediate product and reducing the content of a low molecular weight perfluoropolyether intermediate product by adding an auxiliary agent, changing the temperature of added oxygen or changing process conditions.
In order to solve the technical problems, the technical scheme adopted by the invention is a synthesis method of high molecular weight perfluoropolyether peroxide with acyl fluoride groups, which is characterized by comprising the following steps:
the synthesis method is to directly synthesize the perfluoropolyether peroxide with acyl fluoride groups from oxygen and a perfluoro monomer by using an initiator and an auxiliary agent.
Further, the auxiliary agent is one or a mixture of more than two of ozone, oxygen difluoride, oxydichloride or peroxide.
Furthermore, the ratio of the addition amount of the auxiliary agent to the addition amount of the initiator is (0.01-1): 1.
Further, the oxygen comprises low-temperature oxygen or liquid oxygen, the temperature of the added oxygen is-100 ℃ to-30 ℃, the optimal temperature is-100 ℃ to-50 ℃, the oxygen can be mixed with an initiator (fluorine gas and trifluoromethyl hypofluorite) and an auxiliary agent and then added together, or the oxygen, the initiator and the auxiliary agent can be added respectively, the addition of the liquid oxygen can participate in the reaction, is also beneficial to controlling the reaction temperature, and greatly reduces the demand of refrigerants in the reaction process.
Furthermore, the reaction temperature range of the synthesis method is-100 ℃ to-30 ℃.
Preferably, the reaction temperature of the synthesis method is in the range of-100 ℃ to-45 ℃.
Further, the reaction pressure range of the synthesis method is normal pressure to 200 KPa.
Preferably, the reaction pressure of the synthesis method is in the range of normal pressure to 150 KPa.
One or a mixture of a plurality of peroxides such as ozone, oxygen difluoride and dichloro oxide is added in the reaction as an auxiliary agent, so that the content of the high molecular weight perfluoropolyether intermediate product can be effectively improved, and the content of the low molecular weight perfluoropolyether intermediate product can be reduced. In addition, the content of the low molecular weight perfluoropolyether intermediate product can be effectively reduced even liquid oxygen is used by reducing the temperature of adding oxygen, and the content of the high molecular weight perfluoropolyether intermediate product is improved. The reaction temperature is reduced, the reaction pressure is increased, the content of the high molecular weight perfluoropolyether intermediate product can be increased, and the content of the low molecular weight perfluoropolyether intermediate product is reduced.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
(1) the method can be implemented without changing the original process equipment, and is simple and convenient and obvious in effect.
(2) The reaction temperature can be effectively controlled by using low-temperature oxygen or liquid oxygen, the demand of a refrigerant is reduced, and the energy consumption is reduced.
The invention provides a technical scheme of a synthesis method of high molecular weight perfluoropolyether peroxide with acyl fluoride groups, which achieves the purposes of improving the content of a high molecular weight perfluoropolyether intermediate product and reducing the content of a low molecular weight perfluoropolyether intermediate product by adding an auxiliary agent, changing the temperature of added oxygen or changing process conditions.
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The invention will be further described with reference to the accompanying drawings in which:
FIG. 1 shows the results of infrared analysis in the synthesis of high molecular weight perfluoropolyether peroxides having acyl fluoride groups in accordance with the present invention;
FIG. 2 shows GPC measurement results in the present invention;
FIG. 3 shows nuclear magnetic fluorine spectra in the present invention.
Detailed Description
The invention relates to a method for synthesizing high molecular weight perfluoropolyether peroxide with acyl fluoride groups, which comprises the following steps:
the method comprises the steps of directly synthesizing oxygen and a perfluorinated monomer into perfluoropolyether peroxide with acyl fluoride groups by using an initiator and an auxiliary agent, wherein the auxiliary agent is one or a mixture of more than two of ozone, oxygen difluoride, oxydichloride or peroxide, the ratio of the addition amount of the auxiliary agent to the addition amount of the initiator is 0.01-1: 1, the oxygen comprises oxygen or liquid oxygen, the temperature of the added oxygen is-100 ℃ to-30 ℃, the optimal temperature is-100 ℃ to-50 ℃, the oxygen can be mixed with the initiator (fluorine gas and trifluoromethyl hypofluorite) and the auxiliary agent and then added together, or the oxygen, the initiator and the auxiliary agent can be added respectively, the addition of the liquid oxygen can participate in reaction and also contribute to controlling the reaction temperature, the required amount of refrigerants in the reaction process is greatly reduced, the reaction temperature range is-100 ℃ to-30 ℃, the reaction temperature is preferably-100 ℃ to-45 ℃, the reaction pressure range of the reaction is normal pressure to 200KPa, and the reaction pressure is preferably normal pressure to 150 KPa.
The present invention is further illustrated by the following specific examples, which are provided for illustrative purposes only and do not limit the scope of the present invention.
Example 1
200g of hexafluoropropylene is condensed into a stainless steel reaction kettle with a 0.5L volume, a stirring jacket is arranged in the stainless steel reaction kettle, the upper part of the stainless steel reaction kettle is connected with a stainless steel condenser for condensing hexafluoropropylene, and an air inlet pipe inserted into the bottom is arranged in the stainless steel reaction kettle. The cooling medium is introduced into the jacket of the stainless steel reaction kettle, and the reaction temperature is kept lower than-55 ℃. Starting stirring, introducing anhydrous oxygen at-80 deg.C at a speed of 2L/h for 2.5h, respectively, adding trifluoromethyl hypofluorite (CF) at a speed of 2.5L/h3OF), a mixed gas OF fluorine and nitrogen having a fluorine gas concentration OF 20% (V%) was fed at a rate OF 0.7L/h, and ozone was fed at a rate OF 0.28L/h, while the reaction pressure was controlled to be normal pressure. After the reaction was completed, unreacted hexafluoropropylene and the reaction product were distilled to obtain 85 g of a crude product which was a colorless transparent viscous oil body.
The crude product was subjected to infrared analysis, with iodine amount analysis, chemical titration to determine number average molecular weight, molecular weight distribution by GPC, and nuclear magnetic fluorine spectroscopy to determine its structure.
The infrared analysis result is shown in the attached figure 1 of the specification in detail.
| Characteristic absorption peak position (cm)-1) | The result of the judgment |
| 1897.70 | Acyl fluorides |
| 1780.95 | Carboxylic acids |
| 1150-1030 | Alkyl peroxides may be present |
Chemical titration assay data:
the content of active oxygen is 0.85 percent by iodometry;
the number average molecular weight of the product was determined to be 6500 by chemical titration.
The GPC measurement results are shown in FIG. 2 of the specification.
The average molecular weight was approximately 6800 by area normalization.
The nuclear magnetic fluorine spectrum is shown in attached figure 3 in the specification.
The structural formula is determined by nuclear magnetism: CF (compact flash)3O-(CF(CF3)CF2O)m-(CF2O)n-(CFO(CF3))P-COF of19In the F-NMR spectrum, the signal at the chemical shift-146 ppm-represents- (CF)3)CF2the-CF-group in O) the signal at-131 ppm is- (CFO (CF)3) a-CF-group in-55 ppm is a- (CF) signal2O) middle-CF2-group, -signal at 57ppm denotes CF3In O-CF3The signals at-81 to-82 ppm of the-group are represented by- (CF)3)CF2CF in O)3And CF2-a group.
Examples 2 to 10
The experimental conditions were varied in the reactor apparatus of example 1 using 200g of hexafluoropropylene reacted for a reaction time of 2.5h, the reaction conditions are given in the following table:
after the reaction, the structure of the product is determined to be consistent with that of the product obtained in example 1 through nuclear magnetic and infrared detection, and the reaction result is shown in the following table:
| peroxide content (%) | Number average molecular weight | Average molecular weight by GPC measurement | Product quality (g) | |
| Example 1 | 0.85 | 6500 | 6800 | 85 |
| Example 2 | 0.91 | 7300 | 7500 | 87 |
| Example 3 | 1.21 | 8500 | 8600 | 88 |
| Example 4 | 1.33 | 8800 | 8900 | 87 |
| Example 5 | 1.41 | 8800 | 9000 | 88 |
| Example 6 | 1.44 | 8900 | 9200 | 88 |
| Example 7 | 1.44 | 9000 | 9200 | 88 |
| Example 8 | 1.52 | 9500 | 9500 | 87 |
| Example 9 | 1.56 | 9800 | 9800 | 89 |
| Example 10 | 1.65 | 10000 | 10000 | 88 |
From the results, it can be seen that the average molecular weight of the product was significantly increased, and the high molecular weight product content was significantly increased as measured by GPC.
Examples 11 to 20
The experimental conditions were varied in the reactor apparatus of example 1 using 100g of hexafluoropropylene reacted with 100g of tetrafluoroethylene for a reaction time of 2.5 hours, the reaction conditions are given in the following table:
the results of the reaction are shown in the following table:
| peroxide content (%) | Number average molecular weight | Average molecular weight by GPC measurement | Product quality (g) | |
| Example 11 | 1.41 | 8800 | 9000 | 88 |
| Example 12 | 1.44 | 8900 | 9200 | 89 |
| Example 13 | 1.44 | 9000 | 9200 | 90 |
| Example 14 | 1.52 | 9500 | 9500 | 90 |
| Example 15 | 1.56 | 9800 | 9800 | 89 |
| Example 16 | 1.65 | 10000 | 10000 | 89 |
| Example 17 | 1.73 | 12000 | 12000 | 89 |
| Example 18 | 1.72 | 12000 | 12000 | 90 |
| Example 19 | 1.75 | 12000 | 12000 | 90 |
| Example 20 | 1.77 | 12000 | 12000 | 90 |
The average molecular weight of the product is obviously increased, and the content of the high molecular weight product in the product measured by GPC is obviously increased.
Examples 21 to 23
The experimental conditions were varied in the reaction apparatus of example 1, using 100g of trifluoromonochloromethane as solvent and 100g of tetrafluoroethylene for 1.5h, and the reaction conditions are given in the following table:
the results of the reaction are shown in the following table:
| peroxide content (%) | Number average molecular weight | Average molecular weight by GPC measurement | Product quality (g) | |
| Example 21 | 1.81 | 13000 | 13000 | 67 |
| Example 22 | 1.84 | 13000 | 13000 | 67 |
| Example 23 | 1.84 | 14000 | 14000 | 69 |
The invention provides a technical scheme of a synthesis method of high molecular weight perfluoropolyether peroxide with acyl fluoride groups, which achieves the purposes of improving the content of a high molecular weight perfluoropolyether intermediate product and reducing the content of a low molecular weight perfluoropolyether intermediate product by adding an auxiliary agent, changing the temperature of added oxygen or changing process conditions.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple variations, equivalent substitutions or modifications based on the present invention to achieve substantially the same technical effects are within the scope of the present invention.
Claims (7)
1. A method for synthesizing perfluoropolyether peroxide with high molecular weight and acyl fluoride groups is characterized in that: the synthesis method is to directly synthesize oxygen and a perfluorinated monomer into perfluoropolyether peroxide with acyl fluoride groups by using an initiator and an auxiliary agent, wherein the auxiliary agent is one or a mixture of more than two of ozone, oxygen difluoride, oxydichloride or peroxide.
2. The method for synthesizing a high molecular weight perfluoropolyether peroxide having acyl fluoride groups according to claim 1, wherein: the ratio of the addition amount of the auxiliary agent to the addition amount of the initiator is (0.01-1): 1.
3. The method for synthesizing a high molecular weight perfluoropolyether peroxide having acyl fluoride groups according to claim 1, wherein: the oxygen comprises oxygen gas or liquid oxygen.
4. The method for synthesizing a high molecular weight perfluoropolyether peroxide having acyl fluoride groups according to claim 1, wherein: the reaction temperature range of the synthesis method is-100 ℃ to-30 ℃.
5. The method for synthesizing the perfluoropolyether peroxide with high molecular weight and acyl fluoride groups according to claim 4, wherein the method comprises the following steps: the reaction temperature range of the synthesis method is-100 ℃ to-45 ℃.
6. The method for synthesizing a high molecular weight perfluoropolyether peroxide having acyl fluoride groups according to claim 1, wherein: the reaction pressure range of the synthesis method is normal pressure to 200 KPa.
7. The method for synthesizing the perfluoropolyether peroxide with high molecular weight and acyl fluoride groups according to claim 6, wherein the method comprises the following steps: the reaction pressure range of the synthesis method is normal pressure to 150 KPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047313A (en) * | 1989-04-20 | 1990-11-28 | 奥西蒙特公司 | The method for preparing peroxide perfluoropolyethers |
| CN1167124A (en) * | 1996-02-14 | 1997-12-10 | 奥西蒙特公司 | Process for preparing peroxidic perfluoropolyoxyalkylenes |
| US10029981B2 (en) * | 2015-12-10 | 2018-07-24 | Daikin Industries, Ltd. | Process for producing perfluoropolyoxyalkylene peroxide compound |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047313A (en) * | 1989-04-20 | 1990-11-28 | 奥西蒙特公司 | The method for preparing peroxide perfluoropolyethers |
| CN1049670A (en) * | 1989-04-20 | 1991-03-06 | 奥西蒙特公司 | The method for preparing peroxide perfluoropolyethers |
| CN1167124A (en) * | 1996-02-14 | 1997-12-10 | 奥西蒙特公司 | Process for preparing peroxidic perfluoropolyoxyalkylenes |
| US10029981B2 (en) * | 2015-12-10 | 2018-07-24 | Daikin Industries, Ltd. | Process for producing perfluoropolyoxyalkylene peroxide compound |
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