WO2013071780A1 - 一种含氟乙烯基醚的制备方法 - Google Patents

一种含氟乙烯基醚的制备方法 Download PDF

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WO2013071780A1
WO2013071780A1 PCT/CN2012/080145 CN2012080145W WO2013071780A1 WO 2013071780 A1 WO2013071780 A1 WO 2013071780A1 CN 2012080145 W CN2012080145 W CN 2012080145W WO 2013071780 A1 WO2013071780 A1 WO 2013071780A1
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fluorine
vinyl ether
product
cfo
molecular weight
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PCT/CN2012/080145
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English (en)
French (fr)
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张鸣
杨旭仓
彭孝凤
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中昊晨光化工研究院有限公司
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Priority to US14/359,059 priority Critical patent/US8981162B2/en
Priority to AU2012339415A priority patent/AU2012339415B2/en
Priority to KR1020147016280A priority patent/KR101636350B1/ko
Priority to EP12850415.6A priority patent/EP2781500B1/en
Publication of WO2013071780A1 publication Critical patent/WO2013071780A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds

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  • the present invention relates to a process for the preparation of a fluorine-containing vinyl ether, and in particular to a process for preparing a fluorine-containing ethylene by using a by-product produced by a process for preparing a perfluoropolyether or a perfluorosurfactant by photooxidation of a fluorine-containing olefin.
  • a method of ether It belongs to the field of polymer chemistry. Background technique
  • Fluorine-containing vinyl ether is a widely used polymer compound. It can be copolymerized with other monomers for preparing fluoropolymers to prepare fluororesins and fluororubbers with special properties and used under special conditions. F 3p ?
  • the fluorine-containing vinyl ether can be prepared from a fluorine-containing acyl fluoride containing a -CF-CF structure, such as CF 3 -CF 2 -CF,
  • US Pat. No. 3,332,532 discloses the use of a fluorine-containing acid fluoride vapor in a nickel tube reactor through a pipe containing metal oxides (SiO 2 , CaO, ZnO, etc.) at a temperature higher than 300 ° C.
  • the perfluorovinyl ether is prepared by pyrolysis. The highest yield of perfluorovinyl ether in the example is 95%, and the preparation method is simple and the yield is high.
  • US4772756, US4554112, CN1520393A discloses a fluorine-containing acid fluoride in a solvent with K 2 C0 3 or Na 2 C0 3 salified, then lysed in a solvent to a temperature of about 120 ° C, and finally the solvent was cleaved
  • the perfluorovinyl ether evaporates.
  • the method by adding hydrazine, hydrazine-dimethylformyl
  • the amine controls the perfluorovinyl group to form a hydrogen-containing tetrafluoroethane ether.
  • the yield of these methods is further increased up to 96%.
  • US Pat. No. 3,114,778 and CN101659602 disclose the use of an acid fluoride and a base to neutralize a fluorine-containing carboxylate. After drying these salts, the cracking is carried out at about 220 ° C.
  • the fluorine-containing acyl fluoride having the general formula R fx_ Q _ GF _ G _ F can be prepared by the addition reaction of a fluorine-containing carbonyl compound Rf y — c " R fz with a hexafluoropropylene oxide under the action of a catalyst and a solvent, wherein R Fy and R fz may be -F or a fluorine-containing hydrocarbon group.
  • 4,035,388 describes the reaction of a fluorine-containing carbonyl compound with hexafluoropropylene oxide in dimethylaminodifluorophosphine and diglyme to prepare a fluorine-containing fluorinated fluoride.
  • Method; USP 3,274,239 describes the preparation of a fluorine-containing carbonyl compound by reacting ruthenium fluoride as a catalyst with hexafluoropropylene oxide in diethanol dimethyl ether; USP 3250808 for self-polymerization of hexafluoropropylene oxide
  • the object of the present invention is to provide a process for preparing a fluorine-containing vinyl ether by using a by-product produced by photooxidation of a fluorine-containing olefin to produce a perfluoropolyether or a perfluorosurfactant by a novel route.
  • a method for producing a fluorine-containing vinyl ether of the present invention which is produced by a photo-oxidation method using a fluorine-containing olefin, produces a perfluoropolyether or a perfluorosurfactant.
  • the product is subjected to hydrolysis neutralization, dried, and cracked to prepare a corresponding fluorine-containing ethane.
  • the fluorine-containing olefin may be a monomer such as perfluoropropene, tetrafluoroethylene or trifluorobromoethylene. In particular, perfluoropropylene is used.
  • the by-products for the preparation of fluorine-containing vinyl ethers mainly refer to light components in which the molecular weight is relatively small, and the light components mainly refer to compounds having a molecular weight of less than 400, and in particular to contain -0-CF. 2 (CF 3 ) CFO structure such acid fluoride.
  • the main source of the fluorine-containing acid fluoride in the present invention is a process for producing a perfluoropolyether or a perfluorosurfactant by photooxidation of perfluoropropylene or tetrafluoroethylene (for example, CN101648122A) to produce a large amount of light-weight by-products having a small molecular weight. These light components have a molecular weight of less than 400.
  • fluorine-containing fluorinated fluorines are mainly perfluoropropionyl fluoride, perfluoroacetyl fluoride, fluorophosgene, CF 3 CF 2 CF 2 OCF 2 (CF 3 )CFO, CF 3 OCF 2 (CF 3 )CFO, CF 3 CF. 2 OCF 2 (CF 3 )CFO and the like, mainly including CF 3 CF 2 CF 2 OCF 2 (CF 3 )CFO, CF 3 OCF 2 (CF 3 )CFO, CF 3 CF 2 OCF 2 (CF 3 )CFO, these
  • the acyl fluoride can be detected by a method of esterification with methanol.
  • the acid fluoride which can be used as a fluorine-containing vinyl ether must have a -0-CF 2 (CF 3 ) CFO structure. If the perfluoropolypropylene is used as a raw material for photooxidation to prepare a perfluoropolyether and a perfluorosurfactant, one of the important by-products is 2-perfluoropropoxypropionyl fluoride, and according to different photooxidation.
  • the reaction conditions, the content of which is relatively large, the highest content can reach about 5%, this by-product can be used to prepare perfluoro-n-propyl vinyl ether.
  • the best method is to collect it for use as a fluorine-containing vinyl ether.
  • the inventors of the present invention have considered three different procedures for preparing a fluorine-containing propionyl fluoride in a mixed gas to prepare a fluorine-containing one. The first one is to directly purify these acid fluorides to collect various fluorine-containing propionyl fluoride-containing fractions.
  • this method is relatively complicated to operate, because the substances involved are very toxic, so the treatment device must Good airtightness and good ventilation.
  • the second is to first hydrolyze these acid fluorides into acids with little toxicity and easy control, purify the acid, and finally react with the alkali metal hydroxide to neutrality, then dry and then cleave to prepare perfluoro-n-propyl ether.
  • the method requires high corrosion resistance of the equipment.
  • the third is to directly neutralize these substances, dry and crack to prepare fluorine-containing vinyl ether mixed with impurities, and then purify the fluorine-containing vinyl ether.
  • This method is relatively simple and requires little equipment.
  • the present invention employs such a treatment process to prepare various fluorine-containing vinyl ethers.
  • the hydrolysis neutralization of the present invention converts these acid fluorides in by-products into fluorine-containing carboxylic acids.
  • the storage tank filled with the product prepared by photooxidation is heated by warm water, and the heating temperature can be controlled.
  • the product evaporated in the storage tank is passed through a reaction vessel containing an alkali metal lye and a condensing reflux device at 60 to 70 ° C.
  • the reaction vessel is stirred, and the stirring speed is controlled at 500 to 1000 rpm.
  • the hydrolysis reactor is preferably lined with a fluororesin or a Hastelloy.
  • the hydrolysis neutralization process is relatively easy, but the reaction exotherm is large, pay attention to temperature drop, usually the temperature is controlled within 100 ° C, of course, below 50 ° C is better, such as 30 ⁇ 50 ° C.
  • the temperature of the hydrolysis-neutralized product is lowered to room temperature, the product can be evolved, and then the hydrolyzed neutralized product is dried to a solid salt (a solid fluorine-containing carboxylate).
  • the pH of the fluorinated carboxylate solution neutralized by adding an alkali metal lye, especially KOH or NaOH, is preferably controlled at 8 to 10, because if the pH is too low, the acidity is strong, There may be cases where the neutralization is incomplete. If the pH is too high, there are more hydroxide remaining, which is disadvantageous for the subsequent cracking to prepare the fluorine-containing vinyl ether.
  • the fluorine-containing carboxylate salt after hydrolysis and neutralization of the present invention must be dried to remove moisture therein, and the lower the moisture content, the better, and the drying environment is not lower than 10 CTC, and it can be dried under normal pressure and reduced pressure.
  • the present invention incorporates the dried fluorine-containing carboxylate into a cracking apparatus.
  • the cracking unit is preferably provided with an agitator at a stirring speed of 50 to 100 rpm, which allows the temperature of the material to be heated uniformly.
  • the cracking temperature is controlled at not lower than 180 °C, the optimum temperature is 190 ⁇ 220 °C, the temperature is low, the cracking speed is slow, and the temperature is too high, and a large amount of by-products are generated, and the cracking time is 20 to 30 hours.
  • the resulting product was collected using a cold trap. Transfer the product collected by the cold trap to the rectification column, according to various Different fluorine-containing vinyl ethers have different boiling points, and various fluorine-containing vinyl ethers are collected by distillation.
  • the method for preparing a fluorine-containing vinyl ether of the invention utilizes by-products in the process of preparing a perfluoropolyether or a perfluorosurfactant, thereby solving the problem of discharge of industrial waste, reducing environmental pollution, and turning waste into treasure.
  • a fluorine-containing vinyl ether is produced which can be utilized.
  • the method is simple and highly operable, and provides a reliable way to solve by-product contamination after producing perfluoropolyether or perfluorosurfactant on a large scale. detailed description
  • An ultraviolet lamp (wavelength of 250 nm to 400 nm) irradiation device with a power of 250 W was placed on a pressure-resistant jacketed steel reactor having a volume of 20 L, and a reflowing device with a temperature of -70 ° C was placed on the reactor;
  • the reactor was charged with 20 kg of perfluoropropene (HFP) precooled to -45 ° C; metered oxygen (0 2 ) 20 L/h (standard) and perfluoromethyl vinyl were introduced into the bottom of the reactor.
  • HFP perfluoropropene
  • the oO.OOKg material was evaporated from the reactor by using 65 ° C warm water (the content of various materials in the material was 1 J: perfluoropropionyl fluoride 3.5%, perfluoroacetyl fluoride 2.8%, fluorophosgene 2.0%, CF 3 CF 2 CF 2 OCF 2 (CF 3 ) CFO 25.5%, CF 3 OCF 2 (CF 3 ) CFO 20.4%, CF 3 CF 2 OCF 2 (CF 3 ) CFO 16.8%, perfluoropropylene 2.9%, other impurities 26.1 %), added to a 30L hydrolyzer with a stirring device (lined with fluororesin, containing 20wt% KOH solution) for hydrolysis and neutralization, the temperature is controlled at 48 ° C, the stirring speed is controlled at 800 rev / min, appropriate supplement The pH of the solution was adjusted to 9 by 20 wt% KOH. The neutralized material was cooled to room temperature, and discharged to dryness to obtain 8.
  • the thoroughly dried fluorine-containing carboxylate was placed in a 20 L stainless steel cracking reactor equipped with a stirring device at a stirring speed of 100 rpm, heated to 220 ° C for 20 hours, and collected at -30 ° C in a cold trap.
  • An ultraviolet lamp (wavelength of 250 nm to 400 nm) irradiation device with a power of 250 W was placed on a pressure-resistant jacketed steel reactor having a volume of 20 L, and a reflowing device with a temperature of -70 ° C was placed on the reactor;
  • the reactor was charged with 20 kg of perfluoropropene (HFP) precooled to -45 ° C; metered oxygen (0 2 ) 20 L/h (standard) and chlorotrifluoroethylene (CTFE) were introduced into the bottom of the reactor.
  • HFP perfluoropropene
  • CFE chlorotrifluoroethylene
  • 10.OOKg material was evaporated from the reactor using warm water at 70 ° C (the contents of various materials in the material were: perfluoropropionyl fluoride 2.9%, perfluoroacetyl fluoride 3.7%, fluorine phosgene 1.6%, CF 3 CF 2 CF 2 OCF 2 (CF 3 )CFO 20.3%, CF 3 OCF 2 (CF 3 )CFO 26.9%, CF 3 CF 2 OCF 2 (CF 3 )CFO 23.0%, perfluoropropylene 2.6%, other impurities 19.0%), Adding to a 30L hydrolyzer with a stirring device (lined with fluororesin and containing 20wt% KOH solution) for hydrolysis and neutralization, the temperature is controlled at 60 °C, the stirring speed is controlled at 500 rev / min, and 20wt% KOH is appropriately supplemented. The pH of the solution was adjusted to 10. The neutralized material was cooled to room temperature, discharged and dried to obtain 9.1 Kg of
  • the thoroughly dried fluorine-containing carboxylate was charged into a 20 L stainless steel cracking reactor equipped with a stirring device at a stirring speed of 80 rpm, heated to 190 ° C for cracking for 20 hours, and collected at -30 ° C in a cold trap.
  • An ultraviolet lamp (wavelength of 250 nm to 400 nm) irradiation device with a power of 250 W was placed on a pressure-resistant jacketed steel reactor having a volume of 20 L, and a reflowing device with a temperature of -70 ° C was placed on the reactor; 5 L of perfluorodimethyl ether precooled to -45 ° C was added to the reactor; Amount of oxygen (0 2 ) 20L / h (standard) and hexafluoropropylene 2Kg / h mixture, keep the reaction phase at -45 ° C for 8h, then stop the UV lamp, stop the reaction; stop the refrigeration recovery HFP, the reaction material after recovering HFP is pressed into the intermediate tank for storage.
  • the oO.OOKg material was evaporated from the reactor using warm water at 60 °C (the contents of various materials in the material were: (perfluoropropionyl fluoride 2.8%, perfluoroacetyl fluoride 2.4%, fluorophosgene 1.9%, CF 3 CF) 2 CF 2 OCF 2 (CF 3 )CF029.8%, CF 3 OCF 2 (CF 3 )CF027.6%, CF 3 CF 2 OCF 2 (CF 3 )CFO 13.3%, perfluoropropylene 1.2%, other impurities 21.0 %), added to a 30L hydrolyzer with a stirring device (lined with fluororesin, containing 20wt% KOH solution) for hydrolysis and neutralization, the temperature is controlled at 30 ° C, the stirring speed is controlled at 500 rev / min, appropriate supplement The pH of the solution was adjusted to 8 by 20 wt% KOH. The neutralized material was cooled to room temperature, and discharged to dryness to obtain 9.3
  • the thoroughly dried fluorine-containing carboxylate was charged into a 20 L stainless steel cracking reactor equipped with a stirring device at a stirring speed of 50 rpm, heated to 200 ° C for cracking for 20 hours, and collected at -30 ° C in a cold trap.
  • 2.54Kg product determined to contain 34% perfluoro-n-propyl vinyl ether, 29.0% perfluoromethyl vinyl ether, 14.7% perfluoroethyl vinyl ether, other components in small amounts Hydrogen ether of vinyl ether (having a formula of Rf-OCFH-CF 3 , Rf may be CF 3 CF 2 CF 2 -, CF 3 -, CF 3 CF 2 - ), a small amount of CO 2 and a small amount of cleavage by-product fluorine
  • the acid fluoride or the like is finally subjected to distillation of the rectification column to collect perfluoro-n-propyl vinyl ether, perfluoromethyl vinyl ether and perfluoroethyl vinyl ether.
  • the present invention provides a method for preparing a fluorine-containing vinyl ether, which is subjected to hydrolysis neutralization by using a small molecular weight by-product produced in the process of photo-oxidation of a fluorine-containing olefin to produce a perfluoropolyether or a perfluorosurfactant. Dry, cracked to obtain a fluorine-containing vinyl ether.
  • the method of the invention utilizes by-products in the process of preparing perfluoropolyether or perfluorosurfactant, not only solves the problem of industrial waste discharge, reduces environmental pollution, but also turns waste into treasure, and generates available fluorine-containing vinyl ether. It has industrial applicability.

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Abstract

提供了一种含氟乙烯基醚的制备方法，其采用由含氟烯烃光氧化制备全氟聚醚或全氟表面活性剂的过程中产生的小分子量的副产物，进行水解中和，干燥，裂解制备而得含氟乙烯基醚。利用制备全氟聚醚或全氟表面活性剂过程中的副产物，既解决了工业废物的排放问题，降低了环境污染，又生成可利用的含氟乙烯基醚。

Description

一种含氟乙烯基醚的制备方法 技术领域
本发明涉及一种含氟乙烯基醚的制备方法， 具体地说， 涉及一种利用由 含氟烯烃光氧化制备全氟聚醚或全氟表面活性剂的过程中产生的副产物制备 含氟乙烯基醚的方法。 属于高分子化学领域。 背景技术
含氟乙烯基醚是一种用途广泛的高分子化合物， 与其他制备氟聚合物的 单体共聚， 可制备具有特殊性能， 在特殊条件下使用的氟树脂、 氟橡胶等材 料。 F 3p ？ 含氟乙烯基醚可由含有 -CF-C-F结构的含氟酰氟制备， 如 CF3-CF2-C-F、
？ ？
F-C-F、
Figure imgf000002_0001
、 CF3-C-CF3等， 有不少的专利和文献报道了此制 备方法， 有文献认为利用含氟酰氟制备相应的醚的基本原理是全氟酰氟先与 成盐剂反应生成全氟羧酸盐， 以碳酸钠为例， 其成盐过程是：
Rf-C-F+NaO-C-ONa ~►Rf-C-O-C-ONa+NaF
然后升高温度， 羧酸盐分解出 C02和 NaF, 从而制备相应的醚。 目前制备含氟乙烯基醚的主要方法有三种：
其一， US3321532、 US3291843公开了在镍管反应器中， 以氮气流带着含 氟酰氟蒸汽经过装有金属氧化物 （ Si02, CaO, ZnO等） 的管道， 以高于 300°C 的高温裂解制备全氟乙烯基醚， 实例中全氟乙烯基醚最高收率达到 95%, 其 制备方法简单， 产率高。
其二， US4772756、 US4554112, CN1520393A公开了在溶剂中含氟酰氟 与 K2C03或Na2C03成盐， 然后在溶剂中以 120°C左右的温度进行裂解， 最后 将溶剂里裂解出的全氟乙烯基醚蒸发出来。 该方法通过加入 Ν,Ν-二甲基甲酰 胺来控制全氟乙烯基生成含氢的四氟乙烷基醚。这些方法的收率进一步提高， 最高可达 96%。
其三， US3114778、 CN101659602 公开釆用酰氟和碱中和后成为含氟羧 酸盐， 干燥这些盐后再在 220°C左右进行裂解， 该方法制备的全氟乙烯基醚 中含氢醚（是指 -0-CF=CF2基团变成了 -0-CFHCF3基团的含氟醚）最少。 通常通式为 Rfx_Q_G F_G_F的含氟酰氟可以由含氟羰基化合物 Rfy_ c" Rfz 在催化剂和溶剂作用下与六氟环氧丙烷的加成反应制备， 其中 Rfy和 Rfz可以为 -F或含氟烃基。如 US4035388描述了含氟羰基化合物在二甲胺基二氟膦和二甘 醇二甲醚中与六氟环氧丙烷反应制备含氟酰氟的方法； USP3274239叙述了含 氟羰基化合物在二乙醇二甲醚中以氟化铯为催化剂与六氟环氧丙烷反应制备 含 氟 酰 氟 ； USP3250808 对 六 氟 环 氧 丙 烷 自 聚 制 备
CF3CF2CF O-(CF-CF O)n-CF-C-F进行了较详细的叙述，同时也对其它一些含氟酰
CF3 氟与六氟环氧丙烷生成相应的 X 0 进行了描述。 因此， 可获得具有
Figure imgf000003_0001
结构的含氟酰氟。 发明内容
本发明的目的是通过一种新途径， 提供一种利用由含氟烯烃光氧化制备 全氟聚醚或全氟表面活性剂过程中产生的副产物制备含氟乙烯基醚的方法。
为了实现本发明目的， 本发明的一种制备含氟乙烯基醚的方法， 其由含 氟烯烃使用光氧化法制备全氟聚醚或全氟表面活性剂过程中产生的一些分子 量较小的副产物， 将该副产物进行水解中和， 干燥， 裂解制备相应的含氟乙 其中， 所述的含氟烯烃可以是全氟丙烯、 四氟乙烯、 三氟溴乙烯等单体, 特别是釆用全氟丙烯。
所述的用于制备含氟乙烯基醚的副产物， 主要是指其中分子量相对较小 的轻组分， 轻组分主要是指的分子量小于 400的化合物， 并且特别是指含有 -0-CF2 ( CF3 ) CFO结构这类酰氟。
本发明中的含氟酰氟主要来源是由全氟丙烯或四氟乙烯光氧化制备全氟 聚醚或全氟表面活性剂的过程中 （比如 CN101648122A )产生大量分子量较 小的轻组分副产物， 这些轻组分分子量小于 400。 而这些含氟酰氟主要有全 氟丙酰 氟 、 全氟 乙 酰 氟 、 氟光气 、 CF3CF2CF2OCF2(CF3)CFO 、 CF3OCF2(CF3)CFO 、 CF3CF2OCF2(CF3)CFO 等 等 ， 主 要 包 括 CF3CF2CF2OCF2(CF3)CFO、 CF3OCF2(CF3)CFO、 CF3 CF2OCF2(CF3)CFO , 这 些酰氟可釆用甲醇酯化的方法进行检测。
可以用作制备含氟乙烯基醚的酰氟必须有 -0-CF2(CF3)CFO结构。 如果以 全氟丙烯作为原料光氧化制备全氟聚醚和全氟表面活性剂的反应过程中， 其 中一种重要副产物就为 2-全氟丙氧基丙酰氟， 而且根据不同的光氧化反应条 件， 其含量有比较大的不同， 最高含量可以达到 5%左右， 这种副产物可用于 制备全氟正丙基乙烯基醚。 另外其它副产物还有 2-全氟甲氧基丙酰氟， 2-全 氟乙氧基丙酰氟，含量也在 1〜6%之间，分别可以用于制备全氟甲基乙烯基醚 和全氟乙基乙烯基醚。 这些副产物用于制备氟醚油由于分子量太小， 不合适； 用于制备含氟表面活性剂， 分子链相对较短也不太合适。 当然更不能简单的 用来作废物处理， 甚至将其排放， 不仅会增加生产成本， 而且还会造成严重 的环境污染。 就是制备全氟正丙基乙烯基醚、 全氟甲基乙烯基醚和全氟乙基乙烯基醚的重 要原料， 因此， 最好的办法是将其收集出来用作制备含氟乙烯基醚。 本发明 研究人员考虑了三种不同的工序可将混合气体中的含氟丙酰氟制备出含氟乙 其一是釆用将这些酰氟直接提纯， 收集各种含氟丙酰氟的馏分， 但是这 种方法操作相对复杂， 因为涉及物质都是毒性十分大的， 所以处理装置必须 密闭性良好， 且环境通风性能良好。
其二是先将这些酰氟都水解成毒性小易于控制的酸， 将酸进行提纯， 最 后再与碱金属氢氧化物进行反应至中性，然后干燥后裂解制备全氟正丙基醚, 这种方法对设备耐腐蚀性要求较高。
其三是将这些物质直接中和后， 干燥裂解制备成混有杂质的含氟乙烯基 醚， 然后再提纯含氟乙烯基醚， 这种方法相对简单， 对设备要求也不高。 由 此， 本发明釆用此种处理工艺制备各种含氟乙烯基醚。
本发明的水解中和是将副产物中的这些酰氟转化成含氟羧酸。 具体釆用 先对装有光氧化反应制备的产物的储罐进行温水加热， 加热温度可控制在
60〜70°C ,将储罐中蒸发出来的产物通入装有碱金属碱液并带有冷凝回流装置 的反应釜内， 反应釜带有搅拌， 搅拌速度控制在 500〜1000转 /min。 水解反应 釜材质最好内衬含氟树脂， 或者使用哈斯特合金。
水解中和过程相对容易， 但是反应放热量大， 注意降温， 通常温度控制 在 100°C以内， 当然 50°C以下则更好， 比如 30〜50°C。 当水解中和产物温度 降至室温后， 可以放出产物， 然后将水解中和产物烘干呈固体盐 （为固体的 含氟羧酸盐 )。
所述水解中和时， 釆用加入碱金属碱液， 特别是指 KOH或 NaOH, 中和 的含氟羧酸盐溶液 pH值最好控制在 8〜10, 因为如果 pH过低， 酸性强， 可 能存在中和不完全的情况， 如果 pH值过高， 则剩佘的氢氧化物多， 对于以 后的裂解制备含氟乙烯基醚不利。
本发明水解中和后的含氟羧酸盐， 必须进行干燥除掉其中的水分， 特别 是水分含量越低越好， 干燥环境不低于 10CTC条件下， 在常压、 减压干燥均 可。
本发明将干燥得到的含氟羧酸盐装入裂解装置中。 裂解装置最好带有搅 拌器， 搅拌速度为 50〜100转 /min, 这样可使物料温度加热均匀。 裂解温度控 制在不低于 180°C条件下， 最佳温度是 190〜220°C , 温度低， 裂解速度慢， 温 度过高又会产生大量的副产物， 裂解时间为 20〜30小时。
最后所得产物使用冷阱收集。 将冷阱收集的产物转入精馏塔， 根据各种 不同的含氟乙烯基醚的沸点不同， 精馏收集各种含氟乙烯基醚。
本发明制备含氟乙烯基醚的方法， 其利用制备全氟聚醚或全氟表面活性 剂过程中的副产物， 既解决了工业废物的排放问题， 降低了环境污染， 又变 废为宝， 生成可利用的含氟乙烯基醚。 该方法简单， 操作性强， 为规模化生 产全氟聚醚或全氟表面活性剂后， 提供一条有利地解决副产物污染的可靠的 途径。 具体实施方式
以下实施例用于说明本发明， 但不用来限制本发明的范围。
实施例 1
在容积为 20L的耐压的带夹套的钢制反应器上安置功率为 250W的紫外 灯（波长为 250nm〜400nm )照射装置， 反应器上带 -70°C的回流设施； 向已经 预冷的反应器里加入经预冷至 -45°C的全氟丙烯 （HFP ) 20Kg; 向反应器底 部通入经计量的氧气（ 02 )20L/h(标态）和全氟甲基乙烯基醚（ PMVE ) 2.5L/h (标态）的混合气， 保持反应相在 -45°C左右， 维持 8h; 然后停紫外灯， 停止 反应； 停止冷冻回收 HFP, 将回收 HFP后的反应物料压入中间槽中存放。
使用 65°C温水从反应器中蒸发出 lO.OOKg物料（物料中各种物料含量分 另1 J为 ： 全氟丙酰氟 3.5% , 全氟 乙酰氟 2.8% , 氟光气 2.0% , CF3CF2CF2OCF2(CF3)CFO 25.5% 、 CF3OCF2(CF3)CFO 20.4% 、 CF3 CF2OCF2(CF3)CFO 16.8%, 全氟丙烯 2.9%, 其它杂质 26.1% ), 加入到带有搅 拌装置的 30L水解釜中（内衬含氟树脂， 内装 20wt%KOH溶液 )进行水解中 和， 温度控制在 48°C , 搅拌速度控制在 800转 /min, 适当补充 20wt%KOH调 节溶液 pH为 9。 将中和物料降至室温， 放出进行烘干， 得到干燥含氟羧酸盐 8.6Kg。
将彻底干燥的含氟羧酸盐装入带有搅拌装置的 20L 不锈钢裂解反应釜 内，搅拌速度为 100转 /min,加热至 220 °C进行裂解 20小时， -30°C冷阱收集， 得到 2.13Kg 产物， 经测定， 含有 32%的全氟正丙基乙烯基醚， 21.7%的全氟 甲基乙烯基醚， 17.4%的全氟乙基乙烯基醚， 其他成分为少量的各种对应的乙 烯基醚的含氢醚（分子式为 Rf-OCFH-CF3, Rf 可以是 CF3CF2CF2-， CF3-， CF3CF2- )、 少量 C02及少量裂解副产物含氟酰氟等。 最后经精馏塔精馏收集 全氟正丙基乙烯基醚、 全氟甲基乙烯基醚和全氟乙基乙烯基醚。
实施例 2
在容积为 20L的耐压的带夹套的钢制反应器上安置功率为 250W的紫外 灯（波长为 250nm〜400nm )照射装置， 反应器上带 -70°C的回流设施； 向已经 预冷的反应器里加入经预冷至 -45°C的全氟丙烯（HFP ) 20Kg; 向反应器底部 通入经计量的氧气 （02 ) 20L/h (标态） 和三氟氯乙烯 （CTFE ) 1.5L/h (标 态）的混合气，保持反应相在 -45°C左右， 维持 8h; 然后停紫外灯，停止反应； 停冷冻回收 HFP, 将回收 HFP后的反应物料压入中间槽中存放。
使用 70°C温水从反应器中蒸发出 lO.OOKg物料（物料中各种物料含量分 别为 ： 全氟丙酰氟 2.9% , 全氟 乙酰氟 3.7% , 氟光气 1.6% , CF3CF2CF2OCF2(CF3)CFO 20.3% 、 CF3OCF2(CF3)CFO 26.9% 、 CF3 CF2OCF2(CF3)CFO 23.0%, 全氟丙烯 2.6%, 其它杂质 19.0% ), 加入到带有搅 拌装置的 30L水解釜中（内衬含氟树脂， 内装 20wt%KOH溶液 )进行水解中 和， 温度控制在 60 °C , 搅拌速度控制在 500转 /min, 适当补充 20wt%KOH调 节溶液 pH为 10。 将中和物料降至室温， 放出进行烘干， 得到干燥含氟羧酸 盐 9.1Kg。
将彻底干燥的含氟羧酸盐装入带有搅拌装置的 20L不锈钢裂解反应釜内， 搅拌速度为 80转 /min, 加热至 190°C进行裂解 20小时， -30°C冷阱收集， 得到 2.13Kg产物， 经测定， 含有 23.0%的全氟正丙基乙烯基醚， 0.5%的全氟甲基 乙烯基醚、 25.8%的全氟乙基乙烯基醚， 其他成分为少量的各种对应的乙烯基 醚的含氢醚（分子式为 Rf-OCFH-CF3, Rf可以是 CF3CF2CF2-， CF3-， CF3CF2- )、 少量 C02及少量裂解副产物含氟酰氟等， 最后经精馏塔精馏收集全氟正丙基 乙烯基醚、 全氟甲基乙烯基醚和全氟乙基乙烯基醚。
实施例 3
在容积为 20L的耐压的带夹套的钢制反应器上安置功率为 250W的紫外 灯（波长为 250nm〜400nm )照射装置， 反应器上带 -70°C的回流设施； 向已经 预冷的反应器里加入经预冷至 -45°C的全氟二甲醚 5L;向反应器底部通入经计 量的氧气（02 ) 20L/h (标态）和六氟丙烯 2Kg/h的混合气， 保持反应相在温 度 -45°C左右， 维持 8h, 然后停紫外灯， 停止反应； 停冷冻回收 HFP, 将回收 HFP后的反应物料压入中间槽中存放。
使用 60 °C温水从反应器中蒸发出 lO.OOKg物料 (物料中各种物料含量分别 为 ： （ 全氟丙酰氟 2.8% , 全氟 乙酰氟 2.4% , 氟光气 1.9% , CF3CF2CF2OCF2(CF3)CF029.8% 、 CF3OCF2(CF3)CF027.6% 、 CF3 CF2OCF2(CF3)CFO 13.3%, 全氟丙烯 1.2%, 其它杂质 21.0%), 加入到带有搅 拌装置的 30L水解釜中（内衬含氟树脂， 内装 20wt%KOH溶液 )进行水解中 和， 温度控制在 30°C , 搅拌速度控制在 500转 /min, 适当补充 20wt%KOH调 节溶液 pH为 8。 将中和物料降至室温， 放出进行烘干， 得到干燥含氟羧酸盐 9.3Kg。
将彻底干燥的含氟羧酸盐装入带有搅拌装置的 20L不锈钢裂解反应釜内， 搅拌速度为 50转 /min, 加热至 200°C进行裂解 20小时， -30°C冷阱收集， 得到 2.54Kg 产物， 经测定， 含有 34%的全氟正丙基乙烯基醚、 29.0%的全氟甲基 乙烯基醚、 14.7%的全氟乙基乙烯基醚， 其他成分为少量的各种对应的乙烯基 醚的含氢醚（分子式为 Rf-OCFH-CF3, Rf可以是 CF3CF2CF2-， CF3-， CF3CF2- )、 少量 C02及少量裂解副产物含氟酰氟等， 最后经精馏塔精馏收集全氟正丙基 乙烯基醚、 全氟甲基乙烯基醚和全氟乙基乙烯基醚。
虽然， 上文中已经用一般性说明及具体实施方案对本发明作了详尽的描 述， 但在本发明基础上， 可以对之作一些修改或改进， 这对本领域技术人员 而言是显而易见的。 因此， 在不偏离本发明精神的基础上所做的这些修改或 改进， 均属于本发明要求保护的范围。 工业实用性
本发明提供一种含氟乙烯基醚的制备方法， 其釆用由含氟烯烃光氧化制 备全氟聚醚或全氟表面活性剂的过程中产生的小分子量的副产物， 进行水解 中和， 干燥， 裂解制备而得含氟乙烯基醚。 本发明的方法利用制备全氟聚醚 或全氟表面活性剂过程中的副产物， 既解决了工业废物的排放问题， 降低了 环境污染， 又变废为宝， 生成可利用的含氟乙烯基醚。 具有工业实用性。

Claims

权 利 要 求 书
1. 一种含氟乙烯基醚的制备方法， 其特征在于， 其釆用由含氟烯烃光 氧化法制备全氟聚醚或全氟表面活性剂时产生的小分子量的副产物， 将所述 副产物进行水解中和， 干燥， 裂解而得含氟乙烯基醚。
2. 根据权利要求 1所述的方法， 其特征在于， 所述小分子量的副产物 为分子量小于 400的化合物。
3. 根据权利要求 1或 2所述的方法， 其特征在于， 所述小分子量的副产物 中含有 -0-CF2 ( CF3 ) CFO结构的酰氟。
4. 根据权利要求 3所述的方法， 其特征在于， 所述酰氟包括： CF3CF2CF2OCF2(CF3)CFO、 CF3OCF2(CF3)CFO或 CF3CF2OCF2(CF3)CFO。
5. 根据权利要求 4所述的方法， 其特征在于， 所述的小分子量副产物釆 用将光氧化法制备全氟聚醚或全氟表面活性剂的产物经 60〜70°C加热，蒸发而 得到。
6. 根据权利要求 1-5任意一项所述的方法， 其特征在于， 所述水解中和 在碱金属碱液中进行水解， 并控制 pH值 8〜10。
7. 根据权利要求 6所述的方法， 其特征在于， 所述水解中和在搅拌下进 行， 搅拌速度控制在 500〜1000转 /min。
8. 根据权利要求 1-7任意一项所述的方法， 其特征在于， 所述水解中和 的温度控制在 100°C以内， 优选为 30〜50°C。
9. 根据权利要求 1-8任意一项所述的方法， 其特征在于， 所述裂解温度 不低于 180°C , 优选 190〜220°C , 裂解时间为 20〜30小时。
10. 根据权利要求 1-9任意一项所述的方法， 其特征在于， 所述光氧化法 制备全氟聚醚或全氟表面活性剂时， 所釆用的含氟烯烃单体为全氟丙烯、 四 氟乙烯或三氟溴乙烯， 优选为全氟丙烯。
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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516039A (zh) * 2011-11-16 2012-06-27 中昊晨光化工研究院 一种含氟乙烯基醚的制备方法
CN103467242B (zh) * 2013-09-05 2015-01-21 中昊晨光化工研究院有限公司 一种光氧化反应残液中六氟丙烯的回收方法
CN105418908B (zh) * 2015-12-31 2019-03-29 天津市长芦化工新材料有限公司 一种全氟聚醚酰氟水解过程乳化现象解决方法
CN106748740A (zh) * 2016-11-22 2017-05-31 天津市长芦化工新材料有限公司 一种制备全氟丙酰氟的方法
CN109422628B (zh) * 2017-08-31 2021-11-19 中化近代环保化工(西安)有限公司 一种全氟甲基乙烯基醚的制备方法
CN108689811B (zh) * 2018-03-23 2021-05-18 金华永和氟化工有限公司 一种制备全氟烷基乙烯基醚的方法和反应***
CN114031762A (zh) * 2021-09-30 2022-02-11 四川弘氟新材料有限公司 全氟聚醚表面活性剂的制备工艺及全氟聚醚表面活性剂
CN115322078A (zh) * 2022-08-19 2022-11-11 浙江巨圣氟化学有限公司 一种全氟正丙基乙烯基醚的制备方法
CN115651184A (zh) * 2022-09-28 2023-01-31 四川弘氟新材料有限公司 一种含氟聚醚羧酸型表面活性剂及其制备方法
CN116178218B (zh) * 2022-12-15 2023-10-17 福建科润世纪氢能材料有限公司 一种新型氟磺酰基二氟亚甲基三氟乙烯基醚的制备方法

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3114778A (en) 1963-12-17 Fluorinated vinyl ethers and their
US3250808A (en) 1963-10-31 1966-05-10 Du Pont Fluorocarbon ethers derived from hexafluoropropylene epoxide
US3274239A (en) 1962-08-31 1966-09-20 Du Pont Fluorocarbon ethers
US3291843A (en) 1963-10-08 1966-12-13 Du Pont Fluorinated vinyl ethers and their preparation
US3321532A (en) 1963-10-08 1967-05-23 Du Pont Fluorocarbon ethers
US4035388A (en) 1974-12-24 1977-07-12 Hoechst Aktiengesellschaft Process for preparing perfluoro-alkoxy-propionic acid fluorides
US4554112A (en) 1980-10-16 1985-11-19 The Dow Chemical Company Method for the preparation of vinyl compounds
US4772756A (en) 1986-09-19 1988-09-20 Ausimont S.P.A. Process for the preparation of fluoroalkyl perfluorovinyl ethers
US5777179A (en) * 1996-05-24 1998-07-07 E. I. Du Pont De Nemours And Company Co-production of perfluoromethyl perfluorovinyl ether and perfluoroethyl perfluorovinyl ether
CN1520393A (zh) 2001-06-29 2004-08-11 ������������ʽ���� 氟化乙烯基醚的制造方法
CN101213168A (zh) * 2005-06-30 2008-07-02 3M创新有限公司 氟化乙烯基醚的制备方法
CN101215225A (zh) * 2007-12-26 2008-07-09 中昊晨光化工研究院 一种全氟烷基乙烯醚的生产方法
CN101659602A (zh) 2008-08-29 2010-03-03 中昊晨光化工研究院 一种含氟乙烯基醚的制备方法
CN101817728A (zh) * 2009-10-21 2010-09-01 山东东岳神舟新材料有限公司 一种生产六氟环氧丙烷联产全氟乙烯基醚的方法
CN102516039A (zh) * 2011-11-16 2012-06-27 中昊晨光化工研究院 一种含氟乙烯基醚的制备方法

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3114778A (en) 1963-12-17 Fluorinated vinyl ethers and their
US3274239A (en) 1962-08-31 1966-09-20 Du Pont Fluorocarbon ethers
US3291843A (en) 1963-10-08 1966-12-13 Du Pont Fluorinated vinyl ethers and their preparation
US3321532A (en) 1963-10-08 1967-05-23 Du Pont Fluorocarbon ethers
US3250808A (en) 1963-10-31 1966-05-10 Du Pont Fluorocarbon ethers derived from hexafluoropropylene epoxide
US4035388A (en) 1974-12-24 1977-07-12 Hoechst Aktiengesellschaft Process for preparing perfluoro-alkoxy-propionic acid fluorides
US4554112A (en) 1980-10-16 1985-11-19 The Dow Chemical Company Method for the preparation of vinyl compounds
US4772756A (en) 1986-09-19 1988-09-20 Ausimont S.P.A. Process for the preparation of fluoroalkyl perfluorovinyl ethers
US5777179A (en) * 1996-05-24 1998-07-07 E. I. Du Pont De Nemours And Company Co-production of perfluoromethyl perfluorovinyl ether and perfluoroethyl perfluorovinyl ether
CN1520393A (zh) 2001-06-29 2004-08-11 ������������ʽ���� 氟化乙烯基醚的制造方法
CN101213168A (zh) * 2005-06-30 2008-07-02 3M创新有限公司 氟化乙烯基醚的制备方法
CN101215225A (zh) * 2007-12-26 2008-07-09 中昊晨光化工研究院 一种全氟烷基乙烯醚的生产方法
CN101659602A (zh) 2008-08-29 2010-03-03 中昊晨光化工研究院 一种含氟乙烯基醚的制备方法
CN101817728A (zh) * 2009-10-21 2010-09-01 山东东岳神舟新材料有限公司 一种生产六氟环氧丙烷联产全氟乙烯基醚的方法
CN102516039A (zh) * 2011-11-16 2012-06-27 中昊晨光化工研究院 一种含氟乙烯基醚的制备方法

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CN102516039A (zh) 2012-06-27
EP2781500A1 (en) 2014-09-24
AU2012339415A1 (en) 2014-07-10
EP2781500B1 (en) 2017-11-08
US20140330046A1 (en) 2014-11-06
EP2781500A4 (en) 2015-07-01

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