WO2009054569A1 - The neutralizing method of perfluoropolyether - Google Patents

The neutralizing method of perfluoropolyether Download PDF

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Publication number
WO2009054569A1
WO2009054569A1 PCT/KR2008/000047 KR2008000047W WO2009054569A1 WO 2009054569 A1 WO2009054569 A1 WO 2009054569A1 KR 2008000047 W KR2008000047 W KR 2008000047W WO 2009054569 A1 WO2009054569 A1 WO 2009054569A1
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Prior art keywords
perfluoropolyether
end group
acid end
neutralized
metal fluoride
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PCT/KR2008/000047
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French (fr)
Inventor
Soo-Bok Lee
In Jun Park
Dong Kwon Kim
Jeong Hun Kim
Jong-Wook Ha
Bong Jun Chang
Kwang Won Lee
Kwang Han Kim
Sang Goo Lee
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Korea Reserach Institute Of Chemical Technology
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Publication of WO2009054569A1 publication Critical patent/WO2009054569A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
    • C08G65/3233—Molecular halogen
    • C08G65/3236—Fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying

Definitions

  • the present invention relates to the neutralizing method of perfluoropoly ether.
  • An organic polymer molecule is composed of two main elements, carbon and hydrogen, and a fluorine resin is a resin in which most of hydrogen atoms are substituted with fluorine atoms.
  • a fluorine resin molecule has a structure in which fluorine atoms are bonded on an organic carbon-carbon chain.
  • a fluorine atom has bonding electrons, which are outermost electrons rotating in 2s and 2p orbitals.
  • the interaction between bonding electrons and an atomic nucleus is strong because the atomic nucleus strongly attracts the bonding atoms coming near the atomic nucleus.
  • Fluorine has low polarizability and has the highest electronegativity of all elements.
  • the fluorine atom since the fluorine atom has orbitals, in which electrons rotate, which are located near the nucleus of the fluorine atom, and which have high energy, there is a small probability of electrons deviating from the orbitals due to external stimuli, and the fluorine atom has high ionization energy. Further, since the fluorine atom has a small radius, the bond distance between a carbon atom and a fluorine atom is shorter than that between other atoms, and thus a carbon-fluorine bond has higher energy than other bonds.
  • a perfluoropolymer compound has excellent heat resistance, oxidation resistance (noncombustibility), ultraviolet resistance (weather resistance), and the like.
  • perfluoropolyether which has a similar structure to that of polyether, is a tasteless, odorless, and transparent liquid in a wide temperature range, and is an amorphous polymer having a glass transition temperature of -100 0 C.
  • perfluoropolyether is being industrially widely used for vacuum pump oil, heat medium oil, fluorine-based lubricating oil, hard disk drive lubricant, and the like, because the perfluoropolyether has high resistance to oxidation and hydrolysis and low volatility at high temperature, thus exhibiting excellent fire resistance, rhe- ological properties, and frictional properties.
  • the perfluoropolyether may have an end group including an acid component or a ketone component.
  • the neutralizing method of an acid component or a ketone component included in the end group of the perfluoropolyether have been attempted in order to realize stable use of the perfluoropolyether.
  • G.B. Patent No. 1226566 discloses the neutralizing method of perfluoropolyether's end group by reacting the perfluoropolyether with fluorine gas at a temperature of 50 ⁇ 25O 0 C, preferably 100 ⁇ 200 0 C.
  • the reaction rate of the perfluoropolyether and fluorine gas is slow at room temperature, but is increased when they are heated, thus decreasing the reaction time thereof.
  • the neutralizing method of perfluoropolyether using fluorine gas are problematic in that it is impossible to use them to neutralize low molecular weight perfluoropolyether because fluorine gas, which is injected into liquid perfluoropolyether, causes the liquid perfluoropolyether to splash.
  • perfluoropolyether in the neutralizing method of perfluoropolyether using fluorine gas, perfluoropolyether must be sufficiently reacted with fluorine gas for 70 hours or more in order to produce completely-neutralized perfluoropolyether. Furthermore, since fluorine gas is harmful to the human body and has strong corrosivity, it cannot be easily handled, and since expensive fluorine gas disposal equipment is required when the fluorine gas is used in the neutralization of perfluoropolyether, the cost of neutralizing perfluoropolyether increases.
  • an object of the present invention is to provide a neutralizing method of perfluoropolyether at high efficiency without using fluorine gas, which is harmful to the human body.
  • the present invention provides a neutralizing method of perfluoropolyether, including the steps of neutralizing perfluoropolyether having an acid end group with metal fluoride in a reactor to form a neutralized per- fluoropoly ether solution (step 1); removing metal fluoride remaining in the neutralized perfluoropolyether solution formed in step 1 by separating the neutralized perfluoro- poly ether solution into layers using distilled water (step 2); and removing water from the perfluoropolyether obtained in step 2 (step 3).
  • the neutralizing method of perfluoropolyether according to the present invention is advantageous in that perfluoropolyether is not lost, and in that the acid end group of perfluoropolyether can be neutralized at high efficiency in a short time without using fluorine gas, which is harmful to the human body, thus decreasing the production cost of perfluoropolyether and producing the perfluoropolyether in safety.
  • FIG. 1 is a graph showing the results of analysis of the perfluoropolyether prepared in Example 4 and Preparation Example 2 using FT-IR ((a) Example 4, (b) Preparation Example 2). Best Mode for Carrying Out the Invention
  • the present invention provides a neutralizing method of perfluoropolyether, including the steps for neutralization of perfluoropolyether having an acid end group with metal fluoride in a reactor to form a neutralized perfluoropolyether solution (step 1); removing metal fluoride remaining in the neutralized perfluoropolyether solution formed in step 1 by separating the neutralized perfluoropolyether solution into layers using distilled water (step 2); and removing water from the perfluoropolyether obtained in step 2 (step 3).
  • step 1 perfluoropolyether, having an acid end group, are neutralized with metal fluoride in a reactor.
  • the reactor used in the neutralization can be heated to a temperature necessary for the neutralization and simultaneously allow the reactants to be stirred, thus optimizing the neutralization.
  • the Rf is any one selected from the group consisting of -AO-(CF(CF 3 )CF 2 O)n -, -
  • the metal fluoride serving as a fluorination agent, is selected from among aluminum fluoride (AlF 3 ), antimony fluoride (SbF 5 ), and cobalt fluoride (CoF 3 ).
  • AlF 3 aluminum fluoride
  • SbF 5 antimony fluoride
  • CoF 3 cobalt fluoride
  • the acid end group or ketone group included in the perfluoropolyether can be neutralized using the metal fluoride.
  • This neutralization may be conducted at a temperature of 50 ⁇ 15O 0 C, and preferably
  • the neutralization must be performed within 50 hours.
  • the neutralization time exceeds 50 hours, there is a problem in that process time is increased, thus decreasing productivity.
  • step 2 the metal fluoride remaining in the neutralized perfluoropolyether solution formed in step 1 is removed by separating the neutralized perfluoropolyether solution into layers using distilled water.
  • the distilled water is used to separate the metal fluoride from the perfluoropolyether solution. After the neutralization is completed, the distilled water is introduced into the perfluoropolyether solution, and then the perfluoropolyether solution is stirred, and thus the metal fluoride is dissolved in the distilled water, and the perfluoropolyether solution is separated into layers. Subsequently, the separated aqueous solution layer is removed, thereby removing the metal fluoride.
  • step 3 water is removed from the perfluoropolyether obtained in step 2.
  • the distilled water, used in step 2 can be mostly removed through the layer separation, but some water may remain in the perfluoropolyether solution.
  • the water remaining in the perfluoropolyether solution can be removed using anhydrous magnesium sulfate.
  • CsF cesium fluoride
  • HFPO hexafluoropropylene oxide
  • the prepared perfluoropolyether was refined through fractional distillation, thereby preparing 41Og of perfluoropolyether (C 3F 7 O(CF(CF 3 )CF 2 O)nCF(CF 3 )COF) having an average molecular weight (Mw) of 2,000.
  • CsF cesium fluoride
  • HFPO hexafluoropropylene oxide
  • the prepared perfluoropolyether was refined through fractional distillation, thereby preparing 43Og of perfluoropolyether (C 3 F 7 O(CF(CF 3 )CF 2 O)UCF(CF 3 )COF) having an average molecular weight (Mw) of 10,830.
  • step 1 After the neutralization in step 1 was completed, in order to remove the antimony fluoride (SbF 5 ) remaining in the mixture, 80g of distilled water was added to the mixture, which was then stirred to form a mixed solution. Subsequently, the mixed solution was separated into an aqueous solution layer and a perfluoropolyether layer.
  • SBF 5 antimony fluoride
  • Example 1 except that 5.2g of aluminum fluoride (AlF 3 ) was used as the metal fluoride.
  • Example 1 except that 7.1g of cobalt fluoride (CoF 3 ) was used as the metal fluoride.
  • Example 4 The perfluoropolyether obtained in Example 4 was analyzed using FT-IR, and the results thereof are shown in FIG. 1. Further, the perfluoropolyether obtained in Example 4 was analyzed using 19 F-NMR.
  • Example 1 was introduced into a reactor provided with a stirrer, a gas distributor, a cooler and a CO 2 trap, while the reactor was maintained at a temperature of 6O 0 C. Subsequently, fluorine gas was supplied to the reactor at a flow rate of 10 £/h for 70 hours, thus preparing 97.8g of perfluoropolyether, the acid end group of which was neutralized.
  • the neutralizing method of perfluoropolyether of the present invention is advantageous in that, since metal fluoride is used as a flu- orinating agent instead of fluorine gas, the neutralization of perfluoropolyether is easily conducted, and the neutralization time thereof is decreased, and thus the productivity of the preparation of perfluoropolyether was improved, and the conversion ratio of the acid end group of perfluoropolyether was increased without the loss of raw materials.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Disclosed herein is a neutralizing method of perfluoropolyether having an acid end group using metal fluoride instead of fluorine gas as a fluorinating agent. The method is advantageous in that perfluoropolyether is not lost, and in that the acid end group of perfluoropolyether can be neutralized at high efficiency in a short time without using fluorine gas, which is harmful to the human body, thus decreasing the production cost of perfluoropolyether and producing the perfluoropolyether in safety.

Description

Description
THE NEUTRALIZING METHOD OF PERFLUORO-
POLYETHER
Technical Field
[1] The present invention relates to the neutralizing method of perfluoropoly ether.
Background Art
[2] An organic polymer molecule is composed of two main elements, carbon and hydrogen, and a fluorine resin is a resin in which most of hydrogen atoms are substituted with fluorine atoms.
[3] A fluorine resin molecule has a structure in which fluorine atoms are bonded on an organic carbon-carbon chain. A fluorine atom has bonding electrons, which are outermost electrons rotating in 2s and 2p orbitals. The interaction between bonding electrons and an atomic nucleus is strong because the atomic nucleus strongly attracts the bonding atoms coming near the atomic nucleus. Fluorine has low polarizability and has the highest electronegativity of all elements. Accordingly, since the fluorine atom has orbitals, in which electrons rotate, which are located near the nucleus of the fluorine atom, and which have high energy, there is a small probability of electrons deviating from the orbitals due to external stimuli, and the fluorine atom has high ionization energy. Further, since the fluorine atom has a small radius, the bond distance between a carbon atom and a fluorine atom is shorter than that between other atoms, and thus a carbon-fluorine bond has higher energy than other bonds.
[4] For this reason, of the fluorine resin, a perfluoropolymer compound has excellent heat resistance, oxidation resistance (noncombustibility), ultraviolet resistance (weather resistance), and the like.
[5] Of the perfluoropolymer compound, perfluoropolyether, which has a similar structure to that of polyether, is a tasteless, odorless, and transparent liquid in a wide temperature range, and is an amorphous polymer having a glass transition temperature of -1000C. Currently, perfluoropolyether is being industrially widely used for vacuum pump oil, heat medium oil, fluorine-based lubricating oil, hard disk drive lubricant, and the like, because the perfluoropolyether has high resistance to oxidation and hydrolysis and low volatility at high temperature, thus exhibiting excellent fire resistance, rhe- ological properties, and frictional properties.
[6] The perfluoropolyether may have an end group including an acid component or a ketone component. The neutralizing method of an acid component or a ketone component included in the end group of the perfluoropolyether have been attempted in order to realize stable use of the perfluoropolyether. [7] G.B. Patent No. 1226566 discloses the neutralizing method of perfluoropolyether's end group by reacting the perfluoropolyether with fluorine gas at a temperature of 50 ~ 25O0C, preferably 100 ~ 2000C. As the above method, in the neutralizing method of perfluoropolyether using fluorine gas, the reaction rate of the perfluoropolyether and fluorine gas is slow at room temperature, but is increased when they are heated, thus decreasing the reaction time thereof. However, the neutralizing method of perfluoropolyether using fluorine gas are problematic in that it is impossible to use them to neutralize low molecular weight perfluoropolyether because fluorine gas, which is injected into liquid perfluoropolyether, causes the liquid perfluoropolyether to splash. Further, in the neutralizing method of perfluoropolyether using fluorine gas, perfluoropolyether must be sufficiently reacted with fluorine gas for 70 hours or more in order to produce completely-neutralized perfluoropolyether. Furthermore, since fluorine gas is harmful to the human body and has strong corrosivity, it cannot be easily handled, and since expensive fluorine gas disposal equipment is required when the fluorine gas is used in the neutralization of perfluoropolyether, the cost of neutralizing perfluoropolyether increases.
[8] Meanwhile, it has been reported that fluorination of perfluoropolyether at a constant pressure, rather than under a heating atmosphere, have been used instead of the methods of neutralizing perfluoropolyether using fluorine gas. However, these methods also retain the problems resulting from the use of fluorine gas because fluorine gas is still used in the neutralization of perfluoropolyether.
Disclosure of Invention
Technical Problem
[9] In order to overcome the above problems occurring in the prior art, the present inventors have conducted extensive research. As a result, they have found that, when metal fluoride is used in the neutralization of perfluoropolyether instead of fluorine gas, the acid end group of perfluoropolyether can be 96% or more neutralized in a short time, and perfluoropolyether is not lost during the neutralization thereof. Based on this finding, the present inventors completed the present invention.
[10] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a neutralizing method of perfluoropolyether at high efficiency without using fluorine gas, which is harmful to the human body. Technical Solution
[11] In order to accomplish the above object, the present invention provides a neutralizing method of perfluoropolyether, including the steps of neutralizing perfluoropolyether having an acid end group with metal fluoride in a reactor to form a neutralized per- fluoropoly ether solution (step 1); removing metal fluoride remaining in the neutralized perfluoropolyether solution formed in step 1 by separating the neutralized perfluoro- poly ether solution into layers using distilled water (step 2); and removing water from the perfluoropolyether obtained in step 2 (step 3).
Advantageous Effects
[12] The neutralizing method of perfluoropolyether according to the present invention is advantageous in that perfluoropolyether is not lost, and in that the acid end group of perfluoropolyether can be neutralized at high efficiency in a short time without using fluorine gas, which is harmful to the human body, thus decreasing the production cost of perfluoropolyether and producing the perfluoropolyether in safety. Brief Description of the Drawings
[13] FIG. 1 is a graph showing the results of analysis of the perfluoropolyether prepared in Example 4 and Preparation Example 2 using FT-IR ((a) Example 4, (b) Preparation Example 2). Best Mode for Carrying Out the Invention
[14] Hereinafter, the present invention will be described in detail.
[15] The present invention provides a neutralizing method of perfluoropolyether, including the steps for neutralization of perfluoropolyether having an acid end group with metal fluoride in a reactor to form a neutralized perfluoropolyether solution (step 1); removing metal fluoride remaining in the neutralized perfluoropolyether solution formed in step 1 by separating the neutralized perfluoropolyether solution into layers using distilled water (step 2); and removing water from the perfluoropolyether obtained in step 2 (step 3).
[16] Hereinafter, the neutralizing method of perfluoropolyether according to the present invention will be described stepwise in detail.
[17] First, in step 1, perfluoropolyether, having an acid end group, are neutralized with metal fluoride in a reactor.
[18] Equipped with a stirrer, a gas distributor, a cooler and a CO2 trap, the reactor used in the neutralization can be heated to a temperature necessary for the neutralization and simultaneously allow the reactants to be stirred, thus optimizing the neutralization.
[19] In the method, the perfluoropolyether is any one selected from the group consisting of -Rf-CF2-COF, -Rf-CF2-OCOF, -Rf-CF2CF2-OCOF, -RrCF(CF3)-C0F, -Rf-CF2 - CF(CF3)-OCOF, -Rf-CF(CF3)-CF2-OCOF and -Rf-CF2-C(CF3)=O.
[20] The Rf is any one selected from the group consisting of -AO-(CF(CF3)CF2O)n -, -
AO-(CF2-CF(CF3)O)m-(CF2O)n-(CF(CF3)O)r-, -AO-(CF2-CF2O)t-(CF2O)p- and - AO-(CF2-CF2O)t-(CF2O)n-(CF(CF3)O)r-(CF2CF(CF3)O)m-, in which A is any one selected from the group consisting of -CF3, -C2F5, -C3F7 and -CF(CF3)2. [21] Each of m, n and r is an integer of 1 ~ 50, and each of t and p is an integer of 0 ~ 200.
[22] Further, the metal fluoride, serving as a fluorination agent, is selected from among aluminum fluoride (AlF3), antimony fluoride (SbF5), and cobalt fluoride (CoF3). The acid end group or ketone group included in the perfluoropolyether can be neutralized using the metal fluoride.
[23] This neutralization may be conducted at a temperature of 50 ~ 15O0C, and preferably
100 ~ 15O0C. When the temperature is above 15O0C, there is a problem in that the metal fluoride decomposes the perfluoropolyether into low molecular weight polymer. In contrast, when the temperature is below 50 0C, there is a problem in that the end group of the perfluoropolyether is not neutralized.
[24] Further, the neutralization must be performed within 50 hours. When the neutralization time exceeds 50 hours, there is a problem in that process time is increased, thus decreasing productivity.
[25] Second, in step 2, the metal fluoride remaining in the neutralized perfluoropolyether solution formed in step 1 is removed by separating the neutralized perfluoropolyether solution into layers using distilled water.
[26] The distilled water is used to separate the metal fluoride from the perfluoropolyether solution. After the neutralization is completed, the distilled water is introduced into the perfluoropolyether solution, and then the perfluoropolyether solution is stirred, and thus the metal fluoride is dissolved in the distilled water, and the perfluoropolyether solution is separated into layers. Subsequently, the separated aqueous solution layer is removed, thereby removing the metal fluoride.
[27] Third, in step 3, water is removed from the perfluoropolyether obtained in step 2.
[28] The distilled water, used in step 2, can be mostly removed through the layer separation, but some water may remain in the perfluoropolyether solution. In step 3, the water remaining in the perfluoropolyether solution can be removed using anhydrous magnesium sulfate. Mode for the Invention
[29] Hereinafter, the present invention will be described in detail with reference to
Examples.
[30] A better understanding of the present invention may be obtained through the following examples, which are set forth to illustrate, but are not to be construed as the limit of the present invention.
[31] <Preparation Example 1> Preparation of perfluoropolyether having acid end group
[32] 2g of cesium fluoride (CsF), serving as an initiator, was added to 3g of a diethyl- eneglycol dimethylether solvent to form a mixed solution, and then the mixed solution was stirred at a temperature of -350C while 500g of hexafluoropropylene oxide (HFPO) was added to the mixed solution for 9 hours, thus preparing 500g of perfluoropolyether having an acid end group (-CFO). Subsequently, the prepared perfluoropolyether was refined through fractional distillation, thereby preparing 41Og of perfluoropolyether (C 3F7O(CF(CF3)CF2O)nCF(CF3)COF) having an average molecular weight (Mw) of 2,000.
[33] <Preparation Example 2> Preparation of perfluoropolyether having acid end group
[34] 2g of cesium fluoride (CsF), serving as an initiator, was added to 3g of a diethyl- eneglycol dimethylether solvent to form a mixed solution, and then the mixed solution was stirred at a temperature of -350C while 500g of hexafluoropropylene oxide (HFPO) was added to the mixed solution for 36 hours, thus preparing 500g of perfluoropolyether having an acid end group (-CFO). Subsequently, the prepared perfluoropolyether was refined through fractional distillation, thereby preparing 43Og of perfluoropolyether (C3F7O(CF(CF3)CF2O)UCF(CF3)COF) having an average molecular weight (Mw) of 10,830.
[35] <Example 1> Neutralization of perfluoropolyether
[36] Step 1: Neutralization of perfluoropolyether having acid end group
[37] lOOg of the perfluoropolyether having an acid end group (-CFO), prepared in Preparation Example 1, and 8.0g of antimony fluoride (SbF5) were put into a reactor, and were then stirred at a temperature of 15O0C for 48 hours to form a mixture.
[38] Step 2: Removal of metal fluoride
[39] After the neutralization in step 1 was completed, in order to remove the antimony fluoride (SbF5) remaining in the mixture, 80g of distilled water was added to the mixture, which was then stirred to form a mixed solution. Subsequently, the mixed solution was separated into an aqueous solution layer and a perfluoropolyether layer.
[40] Step 3: Removal of water
[41] Water present in the separated perfluoropolyether layer was removed using 2Og of magnesium sulfate.
[42] As the result of analysis of the perfluoropolyether obtained in Example 1 using 19 F-
NMR and IR, it was found that 96% of the acid end group of the perfluoropolyether was neutralized, and none of the neutralized perfluoropolyether was lost, compared to perfluoropolyether having an acid end group.
[43] <Example 2> Neutralization of perfluoropolyether
[44] The neutralization of pefluoropolyether was conducted using the same method as in
Example 1, except that 5.2g of aluminum fluoride (AlF3) was used as the metal fluoride.
[45] As the result of analysis of the perfluoropolyether obtained in Example 2 using 19 F-
NMR and IR, it was found that 100% of the acid end group of the perfluoropolyether was neutralized, and none of the neutralized perfluoropolyether was lost, compared to perfluoropoly ether having an acid end group.
[46] <Example 3> Neutralization of perfluoropolyether
[47] The neutralization of pefluoropolyether was conducted using the same method as in
Example 1, except that 7.1g of cobalt fluoride (CoF3) was used as the metal fluoride.
[48] As the result of analysis of the perfluoropolyether obtained in Example 3 using 19 F-
NMR and IR, it was found that 97% of the acid end group of the perfluoropolyether was neutralized, and none of the neutralized perfluoropolyether was lost, compared to perfluoropolyether having an acid end group.
[49] <Example 4> Neutralization of perfluoropolyether
[50] The neutralization of pefluoropolyether was conducted using the same method as in
Example 3, except that the perfluoropolyether prepared in Preparation Example 2 was used.
[51] The perfluoropolyether obtained in Example 4 was analyzed using FT-IR, and the results thereof are shown in FIG. 1. Further, the perfluoropolyether obtained in Example 4 was analyzed using 19F-NMR.
[52] As shown in FIG. 1, a peak corresponding to a -COF group was detected at 1890 cm- i on the spectrum of the perfluoropolyether of Preparation Example 2 (spectrum a), but disappeared on the spectrum of the compound of Example 4 (spectrum b), which indicated that 100% of the acid end group of the perfluoropolyether obtained in Preparation Example 2 was neutralized. Further, 19F-NMR analysis showed that the neutralized perfluoropolyether was retained in the same amount as in the perfluoropolyether having an acid end group.
[53] <Comparative Example 1> Neutralization of perfluoropolyether using fluorine gas
[54] lOOg of the perfluoropolyether having an acid end group, prepared in Preparation
Example 1, was introduced into a reactor provided with a stirrer, a gas distributor, a cooler and a CO2 trap, while the reactor was maintained at a temperature of 6O0C. Subsequently, fluorine gas was supplied to the reactor at a flow rate of 10 £/h for 70 hours, thus preparing 97.8g of perfluoropolyether, the acid end group of which was neutralized.
[55] As the result of analysis of the perfluoropolyether obtained in Comparative Example
1 using 19F-NMR and IR, it was found that 12% of the acid end group of the perfluoropolyether was neutralized, and 2% of the neutralized perfluoropolyether was lost, compared to perfluoropolyether having an acid end group.
[56] <Comparative Example 2> Neutralization of perfluoropolyether using fluorine gas
[57] 94g of perfluoropolyether, the acid end group of which was neutralized, was prepared using the same method as in Comparative Example 1, except that the reactor was maintained at a temperature of 16O0C, and the reaction was conducted for 50 hours. [58] As the result of analysis of the perfluoropolyether obtained in Comparative Example 2 using 19F-NMR and IR, it was found that 26% of the acid end group of the perfluoropolyether was neutralized, and 2% of the neutralized perfluoropolyether was lost because the fluorine gas cause the perfluoropolyether to splash, compared to perfluoropolyether having an acid end group.
[59] The above results are given in Table 1. [60] Table 1 [Table 1] [Table ]
Figure imgf000009_0001
[61] As given in Table 1, it can be seen that the neutralizing method of perfluoropolyether of the present invention is advantageous in that, since metal fluoride is used as a flu- orinating agent instead of fluorine gas, the neutralization of perfluoropolyether is easily conducted, and the neutralization time thereof is decreased, and thus the productivity of the preparation of perfluoropolyether was improved, and the conversion ratio of the acid end group of perfluoropolyether was increased without the loss of raw materials.

Claims

Claims
[ 1 ] A neutralizing method of perfluoropolyether, comprising: neutralizing perfluoropolyether having an acid end group with metal fluoride in a reactor to form a neutralized perfluoropolyether solution (step 1); removing metal fluoride remaining in the neutralized perfluoropolyether solution formed in step 1 by separating the neutralized perfluoropolyether solution into layers using distilled water (step 2); and removing water from the perfluoropolyether obtained in step 2 (step 3).
[2] The neutralizing method of perfluoropolyether according to claim 1, wherein the perfluoropolyether is any one selected from the group consisting of -Rf-CF2 - COF, -RrCF2-OCOF, -Rf-CF2CF2-OCOF, -Rf-CF(CF3)-COF, -Rf-CF2-CF(CF3 )-OCOF, -RrCF(CF3)-CF2-OCOF and -Rf-CF2-C(CF3)=O, in which Rf is any one selected from the group consisting of -AO-(CF(CF3)CF2O)n -, -AO-(CF2 - CF(CF3)O)m-(CF2O)n-(CF(CF3)O)r-, -AO-(CF2-CF2O)t-(CF2O)p- and -AO-(CF2 -CF2O)t-(CF2O)n-(CF(CF3)O)r-(CF2CF(CF3)O)m-, in which A is any one selected from the group consisting of -CF3, -C2F5, -C3F7 and -CF(CF3)2; each of m, n and r is an integer from 1 to 50; and each of t and p is an integer from 0 to 200.
[3] The neutralizing method of perfluoropolyether according to claim 1, wherein the metal fluoride is selected from among aluminum fluoride (AlF3), antimony fluoride (SbF5), and cobalt fluoride (CoF3).
[4] The neutralizing method of perfluoropolyether according to claim 1, wherein the step for neutalization of the perfluoropolyether having an acid end group with the metal fluoride is performed at a temperature of 50 ~ 15O0C.
[5] The neutralizing method of perfluoropolyether according to claim 1, wherein the step for neutalization of the perfluoropolyether having an acid end group with the metal fluoride is performed at a temperature of 100 ~ 15O0C.
[6] The neutralizing method of perfluoropolyether according to claim 1, wherein the step for neutalization of the perfluoropolyether having an acid end group with the metal fluoride is performed within 50 hours.
[7] The neutralizing method of perfluoropolyether according to claim 1, wherein a conversion ratio of the acid end group of the pefluoropolyether is in the range of 96 ~ 100%.
PCT/KR2008/000047 2007-10-25 2008-01-04 The neutralizing method of perfluoropolyether WO2009054569A1 (en)

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KR101681211B1 (en) 2014-10-29 2016-12-01 니카코리아 (주) Method for regeneration of polymerization catalyst of perfluoropolyether
KR101725910B1 (en) 2015-10-29 2017-04-11 니카코리아 (주) Method for regeneration of solvent in manufacturing of perfluoropolyether
CN112876669B (en) * 2019-11-29 2023-10-17 东莞东阳光科研发有限公司 Method for fluorinating end group of perfluoropolyether

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EP0548743B1 (en) * 1991-12-23 2001-07-04 AUSIMONT S.p.A. Process for the neutralization of perfluoropolyoxyalkylenes

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US4523039A (en) * 1980-04-11 1985-06-11 The University Of Texas Method for forming perfluorocarbon ethers
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US4847427A (en) * 1988-04-13 1989-07-11 E. I. Du Pont De Nemours And Company Process for preparing fluorocarbon polyethers
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