CN108440748A - A kind of high molecular weight carries the synthetic method of acyl fluorides group perfluoropolyether peroxide - Google Patents
A kind of high molecular weight carries the synthetic method of acyl fluorides group perfluoropolyether peroxide Download PDFInfo
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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Abstract
The invention discloses the synthetic methods that a kind of high molecular weight carries acyl fluorides group perfluoropolyether peroxide, including：1) use element fluorine or Trifluoromethyl hypofluoride as the polymerisation of initiator in one or more of mixing of ozone, oxygen difluoride, the peroxide such as dichloroxide be added be used as auxiliary agent；2) use oxygen or liquid oxygen as raw material；3) for range of reaction temperature from 100 DEG C~30 DEG C, optimal is 100 DEG C~45 DEG C；4) for reaction pressure range from normal pressure~200KPa, optimal is normal pressure~100KPa.The present invention is by addition auxiliary agent, or changes the temperature for the oxygen being added, or changes process conditions and reach the content for improving high molecular weight perfluoropolyether intermediate product, achievees the purpose that reduction low molecular weight perfluoropolyether intermediates content.
Description
Technical field
The invention belongs to organic chemistry fileds, and in particular to a kind of high molecular weight carries acyl fluorides group perfluoropolyether peroxidating
The synthetic method of object.
Background technology
It is mixed as initiator with Trifluoromethyl hypofluoride using fluorine gas, Trifluoromethyl hypofluoride, fluorine gas, at low temperature will
Oxygen and perfluorinated monomers, the directly method of perfluoropolyether peroxide of the reaction synthesis with acyl fluorides group, in patent
CN1049670A has been reported with foreign patent US5149842.
Using the synthetic method of above-mentioned patent report, obtained perfluoropolyether intermediate product (carries the peroxide of acyl fluorides group
Compound) molecular weight distribution is from hundreds of to hundreds of thousands, and totally presentation low molecular weight (＜ 1000) and high molecular weight (＞
10000) perfluoropolyether intermediates content is relatively low, intermediate molecular weight (3000~4000) perfluoropolyether intermediates content compared with
High distribution situation.Since the price difference of the perfluoro polyether oil of different molecular weight is larger, the perfluor of especially high molecular weight is poly-
Ether oil final price may be several times as much as the perfluoro polyether oil of low molecular weight.And the perfluoro polyether oil of intermediate molecular weight, especially in
Between the perfluoro polyether oil of molecular weight demand is relatively low always in the market.
Although in USP4755330, describing and can be decomposed into the perfluoro polyether oil of higher molecular weight using catalyst
The perfluoropolyether intermediate product of low molecular weight, but loss therein is larger, this method is simultaneously uneconomical.It is needed to adapt to market
It asks, rate of guaranteeing the profit, it is necessary to find a kind of suitable synthetic method, in the product that can make synthesis, be worth higher high score
Son amount product assay rises, and is worth the content of lower low molecular weight product and reduces.
Invention content
Present invention aims at provide a kind of high molecular weight for deficiency of the prior art to carry acyl fluorides group
The technical solution of the synthetic method of perfluoropolyether peroxide, by adding auxiliary agent, or the temperature of the oxygen of change addition, or change
Process conditions reach the content for improving high molecular weight perfluoropolyether intermediate product, and reaching reduces production among low molecular weight perfluoropolyether
The purpose of object content.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that a kind of high molecular weight is complete with acyl fluorides group
The synthetic method of perfluoroalkyl polyether peroxide, it is characterised in that：
The synthetic method is that oxygen is directly synthesized to the perfluor with acyl fluorides group with perfluorinated monomers with auxiliary agent using initiator
Polyethers peroxide.
Further, auxiliary agent is the mixing of one or more of ozone, oxygen difluoride, dichloroxide or peroxide
Object.
Further, the ratio of the addition of the addition and initiator of auxiliary agent is (0.01~1):1.
Further, oxygen includes cryogenic oxygen or liquid oxygen, be added oxygen temperature be -100 DEG C~-30 DEG C, optimum temperature be -
100 DEG C~-50 DEG C, oxygen is added jointly after being mixed with initiator (fluorine gas, Trifluoromethyl hypofluoride), auxiliary agent, can also
Oxygen, initiator, auxiliary agent are separately added into, and the addition of liquid oxygen can not only participate in reacting, and additionally aid controlling reaction temperature, significantly
Reduce the demand of refrigerant in reaction process.
Further, the range of reaction temperature of synthetic method is -100 DEG C~-30 DEG C.
After it is preferred that, the range of reaction temperature of synthetic method is -100 DEG C~-45 DEG C.
Further, the reaction pressure of synthetic method ranging from normal pressure~200KPa.
After it is preferred that, reaction pressure ranging from normal pressure~150KPa of synthetic method.
One or more of mixing of the peroxide such as ozone, oxygen difluoride, dichloroxide are included by being added in the reaction
Object can effectively improve the content of high molecular weight perfluoropolyether intermediate product as auxiliary agent, while can also reduce low molecule
Measure the content of perfluoropolyether intermediate product.In addition, reduce be added oxygen temperature can also effectively be reduced even with liquid oxygen it is low
The content of molecular weight perfluoropolyether intermediate product improves the content of high molecular weight perfluoropolyether intermediate product.Reduction reaction temperature,
The content of high molecular weight perfluoropolyether intermediate product can be improved by improving reaction pressure, be reduced among low molecular weight perfluoropolyether
Product assay.
The present invention is by adopting the above-described technical solution, have the advantages that：
(1) it is not necessarily to the change of original process equipment, you can implement, method is easy, with obvious effects.
(2) use cryogenic oxygen or liquid oxygen can effective controlling reaction temperature, reduce the demand of refrigerant, reduce energy
Consumption.
The present invention provides a kind of technologies of synthetic method of high molecular weight with acyl fluorides group perfluoropolyether peroxide
Scheme by addition auxiliary agent, or changes the temperature for the oxygen being added, or changes process conditions and reach raising high molecular weight perfluoropolyether
The content of intermediate product achievees the purpose that reduce low molecular weight perfluoropolyether intermediates content.
Description of the drawings
The invention will be further described below in conjunction with the accompanying drawings:
Fig. 1 is infrared point in synthetic method of kind of the high molecular weight with acyl fluorides group perfluoropolyether peroxide of the invention
Analyse result；
Fig. 2 is GPC measurement results in the present invention；
Fig. 3 is that nuclear-magnetism fluorine is composed in the present invention.
Specific implementation mode
A kind of high molecular weight of the present invention carries the synthetic method of acyl fluorides group perfluoropolyether peroxide：
This method is that oxygen is directly synthesized to the perfluoropolyether with acyl fluorides group with perfluorinated monomers with auxiliary agent using initiator
Peroxide, auxiliary agent are the mixture of one or more of ozone, oxygen difluoride, dichloroxide or peroxide, are helped
The ratio of the addition of agent and the addition of initiator is 0.01~1:1, oxygen includes oxygen or liquid oxygen, be added oxygen temperature be-
100 DEG C~-30 DEG C, most preferably -100 DEG C~-50 DEG C, oxygen can be mixed with initiator (fluorine gas, Trifluoromethyl hypofluoride), auxiliary agent
Be added jointly after conjunction, can also oxygen, initiator, auxiliary agent be separately added into, the addition of liquid oxygen can not only participate in reacting, and also help
In controlling reaction temperature, the demand of refrigerant in reaction process is greatly reduced, the range of reaction temperature of reaction is -100 DEG C~-
30 DEG C, reaction temperature is preferably -100 DEG C~-45 DEG C, and reaction pressure ranging from normal pressure~200KPa, the reaction pressure of reaction are excellent
It is selected as normal pressure~150KPa.
The present invention is further explained below by specific embodiment, these embodiments are only used for the purpose of illustration,
It is not intended to limit protection scope of the present invention.
Embodiment 1
200g hexafluoropropenes are condensed in the stainless steel cauldron of band stirring jacketed of a 0.5L volume, stainless steel
Reaction kettle top connection stainless steel condenser has the air inlet for being inserted into bottom for condensing hexafluoropropene inside stainless steel cauldron
Pipe.Refrigerant is passed through in stainless steel cauldron chuck, maintaining reaction temperature is less than -55 DEG C always.Stirring is started, is divided in 2.5h
- 80 DEG C of anhydrous oxygen is not passed through with the speed of 2L/h, Trifluoromethyl hypofluoride (CF is added in the speed of 2.5L/h3OF),
The fluorine nitrogen mixed gas that concentration of fluorine is 20% (V%) is added in the speed of 0.7L/h, and ozone is added in the speed of 0.28L/h, and control is anti-
It is normal pressure to answer pressure.After reaction, unreacted hexafluoropropene and reaction product are distilled, obtains 85 grams of thick production
Product, crude product are the sticky oil bodies of water white transparency.
Crude product carries out infrared analysis, and with iodometric analysis, chemistry titration measures number-average molecular weight, molecule is measured by GPC
Amount distribution, is composed by nuclear-magnetism fluorine and determines its structure.
Infrared analysis is the results detailed in Figure of description 1.
| Characteristic absorption peak position (cm-1) | Judge result |
| 1897.70 | Acyl fluorides |
| 1780.95 | Carboxylic acid |
| 1150-1030 | Alkyl peroxide there may be |
Chemistry titration determination data：
Iodometric determination active o content is 0.85%；
By chemistry titration, the number-average molecular weight for measuring product is 6500.
GPC measurement results refer to Figure of description 2.
It is calculated by area normalization, average molecular weight is about 6800.
Nuclear-magnetism fluorine spectrum refers to Figure of description 3.
Nuclear-magnetism determines that its structural formula is：CF3O-(CF(CF3)CF2O)m-(CF2O)n-(CFO(CF3))P- COF,19F-NMR
In collection of illustrative plates, the signal expression at the places chemical shift -146ppm-is-(CF (CF3)CF2O-CF- the groups in), the places -131ppm
That signal indicates is-(CFO (CF3)) in-CF- groups, -55ppm place signal indicate be-(CF2O-CF in)2Group ,-
That the signal at 57ppm indicates is CF3CF in O-3Group, the signal expression at the places -81~-82ppm is-(CF (CF3)
CF2O CF in)3And CF2Group.
Example 2-10
Change experimental condition in the reaction unit of example 1, is reacted using 200g hexafluoropropenes, reaction time 2.5h, reaction
Condition see the table below：
By nuclear-magnetism and infrared detection after reaction, determine that its structure is consistent with the product that example 1 obtains, reaction result is seen below
Table：
| Peroxide content (%) | Number-average molecular weight | GPC measures average molecular weight | 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 |
As can be seen from the results, the average molecular weight of product obviously rises, and GPC, which is measured, finds high molecular weight product content
Rise apparent.
Example 11-20
Change experimental condition in the reaction unit of example 1, reacted with 100g tetrafluoroethene using 100g hexafluoropropenes,
Reaction time 2.5h, reaction condition see the table below：
Reaction result see the table below：
| Peroxide content (%) | Number-average molecular weight | GPC measures average molecular weight | 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 product rises obviously, while GPC measures high molecular weight product content in product and rises obviously.
Example 21-23
Change experimental condition in the reaction unit of example 1, solvent, 100g tetrafluoro second are done using 100g Freon 13s
Alkene is reacted, and reaction time 1.5h, reaction condition see the table below：
Reaction result see the table below：
| Peroxide content (%) | Number-average molecular weight | GPC measures average molecular weight | 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 present invention provides a kind of technologies of synthetic method of high molecular weight with acyl fluorides group perfluoropolyether peroxide
Scheme by addition auxiliary agent, or changes the temperature for the oxygen being added, or changes process conditions and reach raising high molecular weight perfluoropolyether
The content of intermediate product achievees the purpose that reduce low molecular weight perfluoropolyether intermediates content.
It these are only specific embodiments of the present invention, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, for the technique effect for realizing essentially identical, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (8)
1. a kind of high molecular weight carries the synthetic method of acyl fluorides group perfluoropolyether peroxide, it is characterised in that：
The synthetic method is that oxygen is directly synthesized to the perfluoropolyether with acyl fluorides group with perfluorinated monomers with auxiliary agent using initiator
Peroxide.
2. a kind of high molecular weight according to claim 1 carries the synthetic method of acyl fluorides group perfluoropolyether peroxide,
It is characterized in that：The auxiliary agent is the mixing of one or more of ozone, oxygen difluoride, dichloroxide or peroxide
Object.
3. a kind of high molecular weight according to claim 1 carries the synthetic method of acyl fluorides group perfluoropolyether peroxide,
It is characterized in that：The ratio of the addition of the auxiliary agent and the addition of the initiator is (0.01~1):1.
4. a kind of high molecular weight according to claim 1 carries the synthetic method of acyl fluorides group perfluoropolyether peroxide,
It is characterized in that：The oxygen includes oxygen or liquid oxygen.
5. a kind of high molecular weight according to claim 1 carries the synthetic method of acyl fluorides group perfluoropolyether peroxide,
It is characterized in that：The range of reaction temperature of the synthetic method is -100 DEG C~-30 DEG C.
6. a kind of high molecular weight according to claim 5 carries the synthetic method of acyl fluorides group perfluoropolyether peroxide,
It is characterized in that：The range of reaction temperature of the synthetic method is -100 DEG C~-45 DEG C.
7. a kind of high molecular weight according to claim 1 carries the synthetic method of acyl fluorides group perfluoropolyether peroxide,
It is characterized in that：The reaction pressure of the synthetic method ranging from normal pressure~200KPa.
8. a kind of high molecular weight according to claim 7 carries the synthetic method of acyl fluorides group perfluoropolyether peroxide,
It is characterized in that：The reaction pressure of the synthetic method ranging from normal pressure~150KPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109384911A (en) * | 2018-11-15 | 2019-02-26 | 四川科源精诚新材料科技有限公司 | A kind of perfluorinated surfactant and preparation method thereof |
| CN112159506A (en) * | 2020-08-19 | 2021-01-01 | 浙江巨化技术中心有限公司 | Preparation method of multi-anchor brush-shaped perfluoropolyether anti-fingerprint agent |
| CN114395117A (en) * | 2021-12-31 | 2022-04-26 | 西安近代化学研究所 | Double-end perfluoropolyether and preparation method thereof |
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| 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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2018
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Patent Citations (4)
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| 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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109384911A (en) * | 2018-11-15 | 2019-02-26 | 四川科源精诚新材料科技有限公司 | A kind of perfluorinated surfactant and preparation method thereof |
| CN109384911B (en) * | 2018-11-15 | 2019-08-27 | 四川科源精诚新材料科技有限公司 | A kind of perfluorinated surfactant and preparation method thereof |
| EP3872115A4 (en) * | 2018-11-15 | 2022-01-05 | Inner Mongolia Huansheng Technology Co., Ltd. | Perfluoro surfactant and preparation method therefor |
| CN112159506A (en) * | 2020-08-19 | 2021-01-01 | 浙江巨化技术中心有限公司 | Preparation method of multi-anchor brush-shaped perfluoropolyether anti-fingerprint agent |
| CN112159506B (en) * | 2020-08-19 | 2023-01-10 | 浙江巨化技术中心有限公司 | Preparation method of multi-anchor brush-shaped perfluoropolyether anti-fingerprint agent |
| CN114395117A (en) * | 2021-12-31 | 2022-04-26 | 西安近代化学研究所 | Double-end perfluoropolyether and preparation method thereof |
| CN114395117B (en) * | 2021-12-31 | 2023-10-20 | 西安近代化学研究所 | Double-end perfluoropolyether and preparation method thereof |
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