(19)
(11)EP 3 178 865 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
21.11.2018 Bulletin 2018/47

(21)Application number: 16203164.5

(22)Date of filing:  09.12.2016
(51)Int. Cl.: 
C08G 65/00  (2006.01)

(54)

PROCESS FOR PRODUCING PERFLUOROPOLYOXYALKYLENE PEROXIDE COMPOUND

VERFAHREN ZUR HERSTELLUNG EINER PERFLUORPOLYOXYALKYLEN-PEROXID-VERBINDUNG

PROCÉDÉ DE PRODUCTION D'UN COMPOSÉ DE PERFLUOROPOLYOXYALKYLÈNE PÉROXYDIQUE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 10.12.2015 JP 2015241514

(43)Date of publication of application:
14.06.2017 Bulletin 2017/24

(73)Proprietor: Daikin Industries, Ltd.
Osaka-shi, Osaka 530-8323 (JP)

(72)Inventors:
  • Watanabe, Keiichirou
    Osaka, 530-8323 (JP)
  • Nakaya, Hideki
    Osaka, 530-8323 (JP)
  • Shino, Motohisa
    Osaka, 530-8323 (JP)
  • Takakuwa, Tatsuya
    Osaka, 530-8323 (JP)
  • Morimoto, Kazunori
    Osaka, 530-8323 (JP)

(74)Representative: Hoffmann Eitle 
Patent- und Rechtsanwälte PartmbB Arabellastraße 30
81925 München
81925 München (DE)


(56)References cited: : 
EP-A1- 1 702 939
EP-A2- 0 790 270
EP-A2- 0 790 269
US-B2- 7 214 833
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to a process for producing a perfluoropolyoxyalkylene peroxide compound.

    Background Art



    [0002] A perfluoropolyether compound is widely used as a lubricant, an intermediate of various polymers, or the like and its application has been further expanded. The perfluoropolyoxyalkylene peroxide compound is known as a raw material of the perfluoropolyether compound. The perfluoropolyether compound can be obtained by the degradation or the reduction of the perfluoropolyoxyalkylene peroxide compound.

    [0003] As a process for producing the perfluoropolyoxyalkylene peroxide compound, for example, a method in which tetrafluoroethylene is reacted with oxygen is known. Representatively, the reaction is performed by reacting tetrafluoroethylene with oxygen under an ultraviolet irradiation (Patent Document 1). Alternatively, a method is known wherein the reaction of tetrafluoroethylene with oxygen is started by adding a fluorine source, for example, F2, a FO-alkyl or the like without the ultraviolet irradiation (Patent Document 2).

    [0004] Processes for preparing perfluoropolyethers by photooxidation of TFE in the presence of UV light, at low temperature, and in the presence of fluorine are known (Patent Documents 3 and 4).

    Prior Art Document


    Patent Document



    [0005] 

    Patent Document 1: Japanese Laid-Open Patent Publication No. 6-128373

    Patent Document 2: Japanese Laid-Open Patent Publication No. 4-505171

    Patent Document 3: US 7 214 833

    Patent Document 4: EP 1 702 939


    Summary of the Invention


    Problem to be Solved by the Invention



    [0006] As the application of the perfluoropolyether compound is expanded, a demand to provide perfluoropolyethers having various variations of a molecular weight or a backbone structure is increased. That is, also as to the perfluoropolyoxyalkylene peroxide compound which is a raw material of the perfluoropolyether, a method is required which is able to produce a compound having various variations of a molecular weight or a backbone structure. However, it is difficult to effectively obtain the perfluoropolyoxyalkylene peroxide having various variations of a molecular weight or a backbone structure by using the methods of Patent Documents 1 and 2.

    [0007] For example, the inventors of the present invention have found that when it is tried to obtain the perfluoropolyoxyalkylene peroxide compound having a high molecular weight, a low ratio of an ethylene chain to a methylene chain, and a low amount of a reactive oxygen by the reaction of tetrafluoroethylene with oxygen, it is difficult to obtain such compound or if the compound is obtained, high effectivity cannot be achieved by the method simply performing the ultraviolet irradiation as described in Patent Document 1. In addition, they have found that it is difficult to obtain the compound having a high molecular weight by the method simply adding fluorine as described in Patent Document 2.

    [0008] An object of the present invention is to provide a process for producing which is able to efficiently obtain the perfluoropolyoxyalkylene peroxide compound having a specific physical property.

    Means to Solve the Problem



    [0009] As a result of intensively studying, the inventors of the present invention have found that by performing the ultraviolet irradiation and the adding of fluorine in the reaction of the perfluoroalkene with oxygen, it becomes possible to effectively obtain the perfluoropolyoxyalkylene peroxide compound having a specific physical property, and have reached the present invention.

    [0010] According to an aspect of the present invention, there is provided a process for producing a perfluoropolyoxyalkylene peroxide compound comprising a step of reacting a perfluoroalkene with oxygen, wherein the reaction of the perfluoroalkene with oxygen is performed under ultraviolet irradiation, in the presence of a fluorine source and in perfluorohexane.

    Effect of the Invention



    [0011] According to the present invention, by performing the reaction of the perfluoroalkene with oxygen under ultraviolet irradiation and in the presence of a fluorine source, the perfluoropolyoxyalkylene peroxide compound having a specific physical property can be effectively obtained

    Embodiments to Carry Out the Invention



    [0012] Hereinafter, the process for producing of the present invention will be described.

    [0013] In one embodiment, the reaction of the perfluoroalkene with oxygen is performed by introducing the perfluoroalkene, oxygen and a fluorine source into a solvent while irradiating them with an ultraviolet.

    [0014] The term "perfluoroalkene" as used herein represents a compound wherein all of hydrogen atoms of an alkene are substituted with a fluorine atom.

    [0015] The term "alkene" described above represents a straight or branched unsaturated hydrocarbon having one double bond.

    [0016] With respect to the perfluoroalkene, the number of carbon in the alkene chain is preferably 2 to 12, preferably 2 to 8, more preferably 2 to 6, particularly preferably 2.

    [0017] The perfluoroalkene used in the present invention is preferably straight. The perfluoroalkene used in the present invention is preferably a compound having the double bond at the molecular terminal of the following formula:

            R1-CF=CF2

    wherein R1 is a fluorine atom or a perfluoroalkyl group having 1 to 11 carbon atoms.

    [0018] R1 may be preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, for example trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, nonafluoro-n-butyl, undecafluoro-n-pentyl, more preferably a fluorine atom.

    [0019] The perfluoroalkene as used herein is preferably tetrafluoroethylene or hexafluoropropene, more preferably tetrafluoroethylene.

    [0020] The perfluoroalkene may further have a substituent. Examples of the substituent include, but are not particularly limited to, for example one or more groups selected from a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like); and a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C3-10 cycloalkyl group, a C3-10 unsaturated cycloalkyl group, a 5-10 membered heterocyclyl group, a 5-10 membered unsaturated heterocyclyl group, a C6-10 aryl group, and a 5-10 membered heteroaryl group, which may be substituted by one or more halogen atoms.

    [0021] In a preferable embodiment, the perfluoroalkene described above does not have the above substituent.

    [0022] The perfluoroalkene to be used in the reaction may be in a state of a gas or a liquid and is appropriately selected depending on a type of the perfluoroalkene, a reaction temperature, a reaction pressure, or the like.

    [0023] The oxygen to be used in the present invention is usually supplied to the reaction system as an oxygen (O2) gas.

    [0024] The oxygen gas to be supplied may be supplied to the reaction system as only an oxygen gas, as a mixture of oxygen and other inert gasses such as a nitrogen gas, or as air.

    [0025] An amount used of oxygen (O2) (an amount of oxygen present in the reaction system) with respect to the perfluoroalkene may be preferably 0.1 to 10 moles, more preferably 0.4 to 8 moles, for example 1 to 8 moles with respect to 1 mole of the perfluoroalkene.

    [0026] The introducing of the fluorine source may be performed by adding the fluorine source to the reaction mixture of the perfluoroalkene and oxygen, or by mixing one of the perfluoroalkene and oxygen with the fluorine source before the introducing. In one embodiment, the introducing of the fluorine source is performed by adding the fluorine source to the reaction mixture.

    [0027] Examples of the fluorine source described above include F2 or R11-OF (wherein R11 is a perfluoroalkyl group having 1 to 6 carbons.). The fluorine source is preferably F2 gas.

    [0028] The fluorine source to be supplied may be in a state of a gas or a liquid and is appropriately selected depending on a type of the perfluoroalkene, a reaction temperature, a reaction pressure, or the like.

    [0029] When the fluorine source is a fluorine (F2) gas, the fluorine source may be supplied to the reaction system as only the fluorine gas, or as a mixture of the fluorine gas and other inert gasses such as a nitrogen gas.

    [0030] An amount used of fluorine (an amount of fluorine present in the reaction system) with respect to the perfluoroalkene may be preferably 0.001 to 1 mole, more preferably 0.005 to 0.1 mole, for example 0.01 to 0.1 mole with respect to 1 mole of the perfluoroalkene.

    [0031] The present invention is not bounded by any theory, although it is considered that by performing the reaction in the presence of the fluorine source, the perfluoroalkene is reacted with fluorine, and a double bond of the perfluoroalkene is cleaved to generate a perfluoroalkyl radical. It is considered that this is reacted with oxygen, as a result of which the reaction proceeds. Since this starting reaction proceeds at a relatively rapid rate, by adding the fluorine source, it becomes possible to effectively obtain the perfluoropolyoxyalkylene peroxide compound.

    [0032] The solvent used in the reaction is perfluorohexane.

    [0033] Examples of the straight or cyclic fluorocarbon include perfluorocyclohexane, and the like.

    [0034] The ultraviolet to be applied is an ultraviolet having preferably a wavelength of 200 nm to 350 nm, more preferably a wavelength of 220 nm to 280 nm. By the irradiation of the ultraviolet having such wavelength, the reaction proceeds more effectively.

    [0035] Examples of the light source having the wavelength described above include, for example, a mercury lamp, a xenon lamp, a LED lamp, an excimer lamp, a lamp of an electron beam or the like. The mercury lamp may be a low pressure mercury lamp, a medium mercury lamp, or a high pressure mercury lamp.

    [0036] A density of the light irradiation may be preferably 0.01 W/m2 to 500 W/m2, more preferably 0.01 W/m2 to 300 W/m2 on the surface of the reaction site. By making the density of irradiation of the light having the wavelength of 220 nm to 280 nm higher, the reaction rate can be controlled. That is, the EM ratio and the PO value can be controlled.

    [0037] The present invention is not bound by any theory, although it is considered that by performing the irradiation of ultraviolet, the perfluoroalkene is reacted with oxygen to generate a biradical, and by the reaction of the biradical with oxygen, the reaction is started. In addition, by performing the irradiation of ultraviolet, a - O-O- bonding in a molecular chain of a compound whose reaction is stopped can be cleaved to generate a radical again, and an extension reaction proceeds. As a result, the molecular having a higher molecular weight can be obtained.

    [0038] A reaction temperature is not limited as long as the reaction of the perfluoroalkene with oxygen can proceed, and may be, for example, -120 to 30°C, preferably -100 to 0°C.

    [0039] A reaction pressure is not limited as long as the reaction of the perfluoroalkene with oxygen can proceed, and may be, for example, 0.1 to 1.0 MPa, preferably 0.1 to 0.5 MPa.

    [0040] A reaction time (or a residence time) may be, for example, 0.1 second to 5 hours, preferably 0.1 second to 3 hours, for example, 0.1 second to 30 minutes.

    [0041] The perfluoropolyoxyalkylene peroxide compound produced by the process for producing of the present invention is a compound having a peroxide structure (-O-O-) and a perfluoropolyether structure (-(CnF2nO)m-) in its molecular. In -(CnF2nO)m- described above, n is an integer independently selected in the respective units in parentheses with the subscript m, for example an integer of 1 to 12, preferably an integer of 1 to 4, and m is an arbitrary integer, preferably an integer of 2 to 2,000, for example, an integer of 20 to 2,000.

    [0042] In a preferably embodiment, the perfluoropolyoxyalkylene peroxide compound is a compound of the following formula (I).

            Rf-[(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-(O)e]-Rf'     (I)



    [0043] In the above formula, Rf and Rf' are each independently -CF3, -CF2CF3, -COF or -CF2COF.

    [0044] In the above formula, a and b may be each independently an integer of 0 to 100, for example an integer of 1 to 100, preferably an integer of 0 to 50, more preferably an integer of 0 to 30. In the above formula, c and d may be each independently an integer of 0 to 1,000, for example an integer of 2 to 1,000, preferably an integer of 0 to 800, more preferably an integer of 2 to 600, for example, an integer of 10 to 600. The sum of a, b, c and d may be an integer 2 to 2,000, preferably an integer of 2 to 1,500, more preferably an integer of 2 to 1,000, for example an integer of 100 to 800 or an integer of 250 to 800. In the above formula, e is an integer of 1 or more or 5 or more and 250 or

    [0045] The occurrence order of the respective repeating units in parentheses with the subscript a, b, c, d or e is not limited in the formula. Among these repeating units, the - (OC4F8)- group may be any of - (OCF2CF2CF2CF2)-, - (OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, - (OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, - (OCF(C2F5)CF2)- and -(OCF2CF(C2F5)), preferably-(OCF2CF2CF2CF2)-. The - (OC3F6)- group may be any of - (OCF2CF2CF2)-, - (OCF(CF3)CF2)- and - (OCF2CF(CF3))-, preferably - (OCF2CF2CF2)-. The -(OC2F4)- group may be any of -(OCF2CF2)- and -(OCF(CF3))-, preferably -(OCF2CF2)-.

    [0046] In one embodiment, the perfluoropolyoxyalkylene peroxide compound may be a compound of the following formula.

            Rf-[(OC2F4)c-(OCF2)d-(O)e]-Rf'



    [0047] In one embodiment, a number average molecular weight of the perfluoropolyoxyalkylene peroxide compound is, for example, 5,000 or more, preferably 10,000 or more, more preferably 15,000 or more, further preferably 20,000 or more, further more preferably 25,000 or more. An upper limit of the number average molecular weight of the perfluoropolyoxyalkylene peroxide compound is not particularly limited. For example, the number average molecular weight of the perfluoropolyoxyalkylene peroxide compound may be 150,000 or less, 100,000 or less or 50,000 or less.

    [0048] In the present invention, the number average molecular weight of the perfluoropolyoxyalkylene peroxide compound is measured by a GPC (Gel permeation chromatography) analysis unless indicated otherwise.

    [0049] In one embodiment, a ratio of c to d (hereinafter, referred to as a "c/d ratio" or an "EM ratio") is 0.1 or more and 5.0 or less, preferably 0.3 or more and 4.0 or less, more preferably 0.5 or more and 3.0 or less, preferably 2.0 or less or 1.2 or less, for example 0.7 or more and 2.0 or less or 0.8 or more and 1.2 or less.

    [0050]  In the present invention, the EM ratio is measured by a 19F-NMR analysis.

    [0051] In one embodiment, a PO value of the perfluoropolyoxyalkylene peroxide compound is 6.0 or less, preferably 7.0 or less. A lower limit of the PO value is, preferably 1.0 or more, more preferably 3.0 or more. The PO value represents a mass of a reactive oxygen (one oxygen of oxygens forming -O-O-) contained in 100 g of a compound.

    [0052] In the present invention, the PO value is measured by a 19F-NMR analysis.

    [0053] In a preferable embodiment, the perfluoropolyoxyalkylene peroxide compound meets at least two, preferably all of following requirements (a) to (c):
    1. (a) the number average molecular weight is 5,000 or more, preferably 15,000 or more,
    2. (b) the EM ratio is 0.1 to 5.0, preferably 0.7 to 2.0, and
    3. (c) the PO value is 8.6 or less, preferably 7.0 or less.


    [0054] When the above requirements (a) and / or (c) are met, a molecular weight of the perfluoropolyether compound obtained by the degradation or the reduction of the perfluoropolyoxyalkylene peroxide compound can become higher. When the above requirement (b) is met, the perfluoropolyether compound having the similar EM ratio to that of the perfluoropolyoxyalkylene peroxide compound can be obtained. By using the perfluoropolyether compound having higher number average molecular weight and the EM ratio of 0.1 to 5.0, preferably 0.5 to 3.0, more preferably 0.7 to 2.0, for example, a perfluoropolyether group-containing silane compound providing excellent effect as a water and oil repellent can be obtained.

    [0055] According to the present invention, by using the ultraviolet and fluorine in the reaction of perfluoroalkene with oxygen, the perfluoropolyoxyalkylene peroxide compound having a high number average molecular weight, a low EM ratio and a low PO value, for example, the perfluoropolyoxyalkylene peroxide compound having the number average molecular weight of 15,000 or more, the EM ratio of 0.1 to 5.0, and/or the PO value of 8.6 or less.

    [0056] In a preferable embodiment, the reaction of the perfluoroalkene with oxygen in the present invention is performed in a microreactor.

    [0057]  The microreactor as used herein represents a reactor having a channel width which does not completely separate reaction liquids and does not generate an interface between the liquids.

    [0058] The channel width of the microreactor may be preferably 10 mm or less, more preferably 1 µm or more and 8.0 mm or less, further preferably 10 µm or more and 6.0 mm or less, further more preferably 100 µm or more and 5.0 mm or less, for example 4.9 mm or less, 4.8 mm or less, 4.5 mm or less, 4.0 mm or less or 3.0 mm or less. By making the channel width larger, throughput can be increased. By making the channel width smaller, the molecular contact (in other words, microscopic mixing) of the perfluoroalkene with oxygen can be sufficiently attained, as a result of which the reaction is allowed to rapidly proceed and the reaction time (or residence time) can be shortened. In addition, effective heat removal and strict temperature control become possible. Furthermore, by making the channel width smaller, rapid reaction or degradation of reactants (for example, tetrafluoroethylene) in the reactor can be suppressed, and even if the rapid reaction or degradation occurs, the effects can be minimized. It is noted that the channel width represents a smallest distance between opposing walls of the channel.

    [0059] The perfluoroalkene introduced into the microreactor may be in a state of gas or liquid, and the state is appropriately selected depending on the perfluoroalkene used and reaction conditions such as temperature, pressure, or the like. In one embodiment, the perfluoroalkene introduced into the microreactor is in a state of gas. In another embodiment, the perfluoroalkene introduced into the microreactor is dissolved in a following solvent.

    [0060] A flow rate of the perfluoroalkene to be introduced into the microreactor may be preferably 0.01 to 100 mL/min, more preferably 0.1 to 10 mL/min calculated in term of a state at ambient temperature (25°C) and under ambient pressure (1 atom).

    [0061] A flow rate of the oxygen (O2 gas) to be introduced into the microreator may be preferably 0.01 to 200 mL/min, more preferably 1.0 to 20 mL/min in term of a state at ambient temperature (25°C) and under ambient pressure (1 atom).

    [0062] A volume ratio of the oxygen to the perfluoroalkene to be introduced into the microreactor (an oxygen/perfluoroalkene ratio) may be, but not particularly limited to, for example, 0.1 to 20, preferably 0.1 to 10, more preferably 0.4 to 10, further preferably 1.0 to 8.0.

    [0063] In the reaction in the microreactor, a solvent is preferably used. By performing the reaction in the solvent, a polymerization between the perfluoroalkenes and a precipitation of an obtained polymer can be suppressed.

    [0064] The solvent is perfluorohexane. This is preferable in view of environmental protection.

    [0065] The solvent and the perfluoroalkene may be mixed and then, introduced into the microreactor in a state of a mixture or a solution. Alternatively the solvent and the perfluoroalkene may be introduced into the microreactor respectively and mixed or dissolved in the microreactor.

    [0066] A flow rate of the solvent is preferably 0.01 to 100 mL/min, more preferably 0.1 to 10 mL/min.

    [0067] A temperature in the microreactor is not limited as long as the reaction of the perfluoroalkene with oxygen can proceed, and may be, for example, -100 to 30°C, preferably -80 to 0°C.

    [0068] A pressure in the microreactor is not limited as long as the reaction of the perfluoroalkene with oxygen can proceed, and may be, for example, 0.1 to 1.0 MPa, preferably 0.1 to 0.5 MPa.

    [0069] A reaction time (or a residence time) in the microreactor may be, for example, 0.1 second to 1 hour, preferably 0.1 second to 30 minutes, for example, 0.1 second to 30 minutes.

    Examples


    Examples 1 and 2



    [0070] As the reactor, a microreactor was used wherein a channel of stainless which has a channel width of 2 mm, a channel depth of 5 mm, a length of 652.8 mm, was a ditched groove which was folded per 41 mm, and was covered and sealed with a silica glass. An inlet port of the microreactor was connected to a tetrafluoroethylene (TFE) tank, an oxygen (O2) tank, a fluorine (15% of F2 in N2) tank, and a perfluorohexane (PFH) tank via a precooling section, respectively.

    [0071] From each raw material tank, TFE (1 mL/min), oxygen (6 mL/min), 15% of fluorine gas in N2 (0.11 mL/min), and PFH (0.24 mL/min) were supplied to a fine tube and were cooled to -45°C (Example 1) or -60°C (Example 2) in the precooling section, and were supplied to the microreactor. The microreactor was irradiated with a light having the wavelength of 220 nm to 280 nm at the light irradiation density of 200 W/m2 using a high pressure mercury lamp.

    Evaluation



    [0072] The obtained products were evaluated as follows, and a yield, a number average molecular weight, an EM ratio, a PO value were calculated. The results are shown in the following table.

    Yield



    [0073] From the result of a 19F-NMR analysis, a fluorine amount incorporated into the polymer in the product and a fluorine amount in TFE were determined, and the yield was calculated according to the following equation:


    Number average molecular weight



    [0074] From the result of the 19F-NMR analysis, a ratio of the number of units of CF2CF2OO, CF2CF2O, CF2OO and CF2O, and terminal CF3 in a main chain of the peroxide polymer in the product was determined, and the number average molecular weight (Mn) was calculated according to the following equations:




    EM ratio



    [0075] From the result of the 19F-NMR analysis, the number of unit CF2CF2 and the number of unit CF2 in the product were determined, and the EM ratio was calculated according to the following equation:


    PO value



    [0076] From the result of the 19F-NMR analysis, the number of unit CF2CF2OO and the number of unit CF2OO in the product were determined, a molecular weight of a reactive oxygen and a molecular weight of the polymer in the product were calculated, and the PO ratio was calculated according to the following equations:





    Table 1
    Experiment condition
     TFE (mL/min)O2 (mL/min)F2 (mL/min)PFH (mL/min)Temp. (°C)
    Example 1 1.0 6.0 0.11 0.24 -45
    Example 2 1.0 6.0 0.11 0.24 -60
    Result
     PO valueEM ratioYield (%)Mn 
      6.7 0.84 27 6,068  
      7.3 1.28 34 7,513  


    [0077] As seen from the above results, it was confirmed that by performing the reaction the perfluoroalkene with oxygen under ultraviolet irradiation and in the presence of the fluorine source, the perfluoropolyoxyalkylene peroxide compound having a relatively low EM ratio and PO value and a high molecular weight could be obtained.

    [0078] The present invention includes following embodiments:

    Embodiment 1. A process for producing a perfluoropolyoxyalkylene peroxide compound comprising a step of reacting a perfluoroalkene with oxygen, wherein the reaction of the perfluoroalkene with oxygen is performed under ultraviolet irradiation, in the presence of a fluorine source and in perfluorohexane.

    Embodiment 2. The process for producing according to Embodiment 1, wherein the fluorine source is F2.

    Embodiment 3. The process for producing according to Embodiment 1 or 2, wherein the ultraviolet irradiation is performed by irradiating the reaction mixture with a light having a wavelength of 200 nm to 350 nm.

    Embodiment 4. The process for producing according to any one of Embodiments 1-3, wherein the perfluoroalkene is tetrafluoroethylene.

    Embodiment 5. The process for producing according to any one of Embodiments 1-4, wherein the perfluoropolyoxyalkylene peroxide compound is a compound of the formula (I):

            Rf-[(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-(O)e]-Rf'     (I)

    wherein:

    Rf and Rf' are each independently -CF3, -CF2CF3, -COF or -CF2COF,

    a and b are each independently an integer of 0 to 100,

    c and d are each independently an integer of 2 to 1,000,

    the sum of a, b, c and d is a integer of 2 to 2,000,

    e is an integer of 1 to 250, and

    the occurrence order of the respective repeating units in parentheses with the subscript a, b, c, d or e is not limited in the formula.

    Embodiment 6. The process for producing according to Embodiment 5, wherein a c/d ratio of the perfluoropolyoxyalkylene peroxide compound is 5.0 or less.

    Embodiment 7. The process for producing according to any one of Embodiments 1-6, wherein a PO value of the perfluoropolyoxyalkylene peroxide compound is 8.6 or less Z as measured by 19F-NMR.

    Embodiment 8. The process for producing according to any one of Embodiments 1-7, wherein a number average molecular weight of the perfluoropolyoxyalkylene peroxide compound is 5,000 or more as measured by gel permeation chromatography.


    Industrial Applicability



    [0079] According to the present invention, the perfluoropolyoxyalkylene peroxide compound can be suitably produced.


    Claims

    1. A process for producing a perfluoropolyoxyalkylene peroxide compound comprising a step of reacting a perfluoroalkene with oxygen, wherein the reaction of the perfluoroalkene with oxygen is performed under ultraviolet irradiation, in the presence of a fluorine source, and in perfluorohexane.
     
    2. The process for producing according to claim 1, wherein the fluorine source is F2.
     
    3. The process for producing according to claim 1 or 2, wherein the ultraviolet irradiation is performed by irradiating the reaction mixture with a light having a wavelength of 200 nm to 350 nm.
     
    4. The process for producing according to any one of claims 1-3, wherein the perfluoroalkene is tetrafluoroethylene.
     
    5. The process for producing according to any one of claims 1-4, wherein the perfluoropolyoxyalkylene peroxide compound is a compound of the formula (I):

            Rf-[(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-(O)e]-Rf'     (I)

    wherein:

    Rf and Rf' are each independently -CF3, -CF2CF3, -COF or - CF2COF,

    a and b are each independently an integer of 0 to 100,

    c and d are each independently an integer of 2 to 1,000,

    the sum of a, b, c and d is a integer of 2 to 2,000,

    e is an integer of 1 to 250, and

    the occurrence order of the respective repeating units in parentheses with the subscript a, b, c, d or e is not limited in the formula.


     
    6. The process for producing according to claim 5, wherein a c/d ratio of the perfluoropolyoxyalkylene peroxide compound is 5.0 or less.
     
    7. The process for producing according to any one of claims 1-6, wherein a PO value of the perfluoropolyoxyalkylene peroxide compound is 8.6 or less as measured by 19F-NMR.
     
    8. The process for producing according to any one of claims 1-7, wherein a number average molecular weight of the perfluoropolyoxyalkylene peroxide compound is 5,000 or more as measured by gel permeation chromatography.
     


    Ansprüche

    1. Verfahren zur Herstellung einer Perfluorpolyoxyalkylenperoxid-Verbindung, umfassend einen Schritt des Umsetzens eines Perfluoralkens mit Sauerstoff, wobei die Reaktion des Perfluoralkens mit Sauerstoff unter Ultraviolettbestrahlung in Gegenwart einer Fluorquelle und in Perfluorhexan durchgeführt wird.
     
    2. Verfahren zur Herstellung gemäß Anspruch 1, bei dem die Fluorquelle F2 ist.
     
    3. Verfahren zur Herstellung gemäß Anspruch 1 oder 2, bei dem die Ultraviolettbestrahlung mittels Bestrahlens der Reaktionsmischung mit einem Licht mit einer Wellenlänge von 200 nm bis 350 nm durchgeführt wird.
     
    4. Verfahren zur Herstellung gemäß einem der Ansprüche 1 bis 3, bei dem das Perfluoralken Tetrafluorethylen ist.
     
    5. Verfahren zur Herstellung gemäß einem der Ansprüche 1 bis 4, bei dem die Perfluorpolyoxyalkylenperoxid-Verbindung eine Verbindung der Formel (I) ist:

            Rf-[(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-(O)e]-Rf'     (I)

    worin:

    Rf und Rf' jeweils unabhängig voneinander -CF3, -CF2CF3, -COF oder -CF2COF sind,

    a und b jeweils unabhängig voneinander eine ganze Zahl von 0 bis 100 sind,

    c und d jeweils unabhängig voneinander eine ganze Zahl von 2 bis 1.000 sind,

    die Summe von a, b, c und d eine ganze Zahl von 2 bis 2.000 ist,

    e eine ganze Zahl von 1 bis 250 ist, und

    die Reihenfolge des Auftretens der jeweiligen Wiederholungseinheiten in Klammern mit dem Index a, b, c, d oder e in der Formel nicht beschränkt ist.


     
    6. Verfahren zur Herstellung gemäß Anspruch 5, bei dem ein c/d-Verhältnis der Perfluorpolyoxyalkylenperoxid-Verbindung 5,0 oder weniger beträgt.
     
    7. Verfahren zur Herstellung gemäß einem der Ansprüche 1 bis 6, bei dem ein PO-Wert der Perfluorpolyoxyalkylenperoxid-Verbindung, gemessen durch 19F-NMR, 8,6 oder weniger beträgt.
     
    8. Verfahren zur Herstellung gemäß einem der Ansprüche 1 bis 7, bei dem ein zahlenmittleres Molekulargewicht der Perfluorpolyoxyalkylenperoxid-Verbindung, gemessen durch Gelpermeationschromatographie, 5.000 oder mehr beträgt.
     


    Revendications

    1. Procédé de production d'un composé peroxyde de perfluoropolyoxyalkylène comprenant une étape de réaction d'un perfluoroalcène avec de l'oxygène, dans lequel la réaction du perfluoroalcène avec de l'oxygène est effectuée sous irradiation aux ultraviolets, en présence d'une source de fluor, et dans du perfluorohexane.
     
    2. Procédé de production selon la revendication 1, dans lequel la source de fluor est F2.
     
    3. Procédé de production selon la revendication 1 ou 2, dans lequel l'irradiation aux ultraviolets est effectuée en irradiant le mélange réactionnel avec une lumière ayant une longueur d'onde de 200 nm à 350 nm.
     
    4. Procédé de production selon l'une quelconque des revendications 1 à 3, dans lequel le perfluoroalcène est du tétrafluoroéthylène.
     
    5. Procédé de production selon l'une quelconque des revendications 1 à 4, dans lequel le composé peroxyde de perfluoropolyoxyalkylène est un composé de formule (I) :

            Rf-[(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-(O)e]-Rf'     (I)

    dans lequel :

    Rf et Rf' sont chacun indépendamment -CF3, -CF2CF3, -COF ou -CF2COF,

    a et b sont chacun indépendamment un nombre entier de 0 à 100,

    c et d sont chacun indépendamment un nombre entier de 2 à 1 000,

    la somme de a, b, c et d est un nombre entier de 2 à 2 000,

    e est un nombre entier de 1 à 250, et

    l'ordre de survenance des motifs de répétition respectifs entre parenthèses avec l'indice a, b, c, d ou e n'est pas limité dans la formule.


     
    6. Procédé de production selon la revendication 5, dans lequel un rapport c/d du composé peroxyde de perfluoropolyoxyalkylène est de 5,0 ou moins.
     
    7. Procédé de production selon l'une quelconque des revendications 1 à 6, dans lequel une valeur PO du composé peroxyde de perfluoropolyoxyalkylène est de 8,6 ou moins, telle que mesurée par 19F-RMN.
     
    8. Procédé de production selon l'une quelconque des revendications 1 à 7, dans lequel une masse moléculaire moyenne en nombre du composé peroxyde de perfluoropolyoxyalkylène est de 5 000 ou plus telle que mesurée par chromatographie par perméation sur gel.
     




    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description