WO2002088218A1 - Process for producing fluorinated polyoxyalkylene compound - Google Patents

Abstract

A process for producing fluorinated polyoxyalkylene compounds of various structures at low cost. The process comprises reacting a polyoxyalkylene compound having at least one hydroxyl group with a compound having a C2 or higher fluorinated organic group and a group which reacts with a hydroxyl group to form an ester linkage to thereby synthesize a polyoxyalkylene compound having the fluorinated organic group bonded through an ester linkage and subsequently conducting liquid-phase fluorination to thereby replace with fluorine one or more of the hydrogen atoms present in the polyoxyalkylene compound having the fluorinated organic group bonded through an ester linkage.

Description

 Technical field of producing fluorinated polyoxyalkylene compounds>

 Light

The present invention is industrially useful compounds, port ¹ which is fluorinated

The present invention relates to a method for producing a compound. Rice field

<Background technology>

 A fluorinated polymer compound obtained by fluorinating a polymer compound having a chemical structure (C-H) in which a hydrogen atom is bonded to a carbon atom, or a derivative of the fluorinated polymer compound is an industrially useful compound. In particular, fluorinated polyoxyalkylene compounds are industrially useful compounds as surfactants, surface modifiers, water / oil repellents, coating agents, lubricants, and the like.

 Conventionally, a fluorination method using fluorine gas has been known as a method for fluorinating a C-H portion to make it a C-F. Polymer compounds are solid or liquid under ordinary reaction conditions, and are difficult to react in the gas phase. Therefore, the fluorination method includes (1) a method of fluorination by contact with fluorine gas (La Mar method), and (2) a method of dissolving, suspending, or dispersing a polymer compound in a solvent, There is known a liquid phase fluorine method in which fluorine gas is introduced into the solvent to fluorinate the solvent.

Examples of the method of (1), examples of fluorination of fluorine-free polyether was initiator Pentaerisuri Torr (Kohyo _three to ₅ 0 0 1 7 3 JP), as essential Okishimechi Ren units Example of fluorinating non-fluorinated polyethers (Japanese Patent Publication No. Sho 63-501 667), Example of fluorinating hydrocarbon ethers (Japanese Patent Publication No. 63-501 297) ) It has been known. Examples of the method (2) include non-fluorinated poly An example of fluorinating ether (Japanese Patent Application Laid-Open No. 510/520) is to fluorinate a non-fluorinated polyether having a terminal hydroxyl group as an alkoxy group to have a molecular weight of about 250 to 200. Examples of producing perfluorinated polyethers in the range of (JP-A-1-225628) and examples of fluorinating partially fluorinated polyethers having terminal fluorinated alkyloxy groups (Japanese Patent Application Laid-Open No. An example of fluorinating a perfluorinable substance such as polyethylene glycol bis (trifluoroacetate) (Japanese Patent Application Laid-Open No. 50423019) has been published. Are known.

 However, in the method (1), since only the solid surface of the polymer compound is fluorinated, there are problems that a desired fluorinated product cannot be obtained in good yield and that the degree of fluorination is difficult to control.

 In the method (2), a perfluorinated organic solvent is used as a solvent during the fluorination reaction. Non-fluorinated polymer compound-low fluorine content, polymer compound has low solubility in perfluorinated organic solvent and is insoluble in fluorination reaction solvent or suspended in the solvent Will exist in a state. Therefore, the problem of performing the fluorination reaction in a heterogeneous reaction system and the problem of breaking the molecular chain were remarkably recognized, and it was difficult to obtain the desired polymer compound.

 Therefore, there is a proposal to add an auxiliary solvent (for example, black-mouthed form, etc.) for dissolving the fluorination reaction substrate in the fluorination solvent. However, it was difficult to obtain satisfactory solubility even with the use of an auxiliary solvent.

 In addition, when the fluorination of the polymer compound was carried out by the conventional method (2), a problem that the product gelled was also recognized. In addition, there was also a problem that the volumetric efficiency was low and the production efficiency was poor because the fluorination reaction was performed at a very low concentration of the substrate.

An object of the present invention is to solve the above problems and to provide a method for producing a fluorinated polyoxyalkylene compound having various structures by an industrially advantageous method. Invention disclosure>

 The present inventors synthesized a specific esterified polyoxyalkylene compound by subjecting a specific polyoxyalkylene compound and a specific fluorine-containing compound to an esterification reaction, and converted the esterified polyoxyalkylene compound into liquid phase fluorine. Thus, the present inventors have found that the above-mentioned problems can be solved, and have led to the present invention. That is, the present invention provides the following method.

 1. Esterification of a polyoxyalkylene compound having at least one hydroxyl group with a compound having a group capable of forming an ester bond by reacting with the hydroxyl group and a fluorine-containing organic group having 2 or more carbon atoms. By synthesizing a polyoxyalkylene compound and then subjecting the esterified boroxyalkylene compound to liquid-phase fluorination, one or more of the hydrogen atoms present in the esterified polyoxyalkylene compound are fluorinated. A method for producing a fluorinated polyalkylene compound, which comprises:

2. By subjecting a compound represented by R ^F1 —COX ¹ to an esterification reaction with a hydroxyl group of a polyoxyalkylene compound having at least one hydroxyl group, an esterified polyoxyalkylene compound having an R ^F1 —CO— group is obtained. By subjecting the esterified polyalkylene compound to liquid phase fluorination, one or more of the hydrogen atoms present in the esterified polyalkylene compound are fluorinated to obtain a fluorinated polyoxyalkylene having a R ^F1 —CO— group. The method according to claim 1, wherein the compound is obtained. Here, R ^F1 represents a perfluoromonovalent organic group having 2 or more carbon atoms, and X ¹ represents a halogen atom or a hydroxyl group.

 3. The perfluoro monovalent organic group is a group in which an alkyl group containing an etheric oxygen atom is perfluorinated, or a partially fluorinated alkyl group containing an etheric oxygen atom is a perfluorinated group. Manufacturing method.

4. The polyoxyalkylene compound having at least one hydroxyl group is — O (CH ₂ ) (Where a represents an integer of 2 or more.) The production method according to any one of claims 1 to 3, wherein the compound is a compound containing an oxyalkylene unit represented by the formula:

 5. The polyoxyalkylene compound having at least one hydroxyl group has a molecular weight of 300 to 10,000. 5. The method according to any one of items 1 to 4.

 6. The production method according to any one of claims 1 to 5, wherein the molecular weight of the esterified polyoxyalkylene compound is 1300 to 16000.

 7. The production method according to any one of claims 1 to 6, wherein the esterified polyoxyalkylene compound has a fluorine content of 25 mass% to 76 mass%.

 8. The polyoxyalkylene compound having at least one hydroxyl group is a compound containing no fluorine atom, and 95% or more of the total number of hydroxyl groups of the polyoxyalkylene compound is esterified by an esterification reaction. 7. The method according to any one of 7.

 9. The process for producing a fluorinated polyoxyalkylene compound according to any one of claims 1 to 8, wherein the liquid-phase fluorination is performed at 0.01 to 5 MPa (gauge pressure).

 10. The production method according to any one of claims 1 to 9, wherein the liquid phase fluorination reaction is carried out without using an HF scavenger.

<Best mode for carrying out the invention>

 In the present specification, “polyoxyalkylene compound having one or more hydroxyl groups” is referred to as “polyoxyalkylene compound”. A compound having a group that reacts with a hydroxyl group of the polyoxyalkylene compound to form an ester bond and a fluorinated organic group having 2 or more carbon atoms is referred to as “compound (F)”. The “polyoxyalkylene compound in which the fluorine-containing organic group is ester-bonded” is referred to as “esterified polyoxyalkylene compound”.

As used herein, the term "organic group" refers to a group that essentially requires a carbon atom, and is a saturated group. Or an unsaturated group, and is preferably a saturated group (ie, a saturated organic group). As the halogen atom, a fluorine atom or a chlorine atom is preferable

Examples of the monovalent saturated organic group include an alkyl group and an alkyl group containing an etheric oxygen atom.

And a cycloalkyl group, a cycloalkyl group containing an etheric oxygen atom, or a group in which one or more of the hydrogen atoms present in these groups is substituted with a halogen atom.

 Examples of the alkyl group include a group having a linear structure, a branched structure, and a structure partially forming a ring, and include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, Examples thereof include a tert-butyl group and a cycloalkyl group. Examples of the alkyl group containing an etheric oxygen atom include groups in which one or more etheric oxygen atoms are interposed between carbon-carbon bonds of the alkyl group (for example, alkoxyalkyl groups and the like). Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the cycloalkyl group containing an etheric oxygen atom include groups in which an etheric oxygen atom is inserted between carbon-carbon bonds of the cycloalkyl group.

 The polyoxyalkylene compound in the present invention is a compound having two or more oxyalkylene units and a hydroxyl group. The polyoxyalkylene compound is a compound obtained by ring-opening addition polymerization of an alkylene oxide using a compound having a hydroxyl group as an initiator, or a large amount of an alkylene oxide such as polyoxyethylene daricol or polyoxypropylene glycol. The body is preferred.

The oxyalkylene unit is preferably an oxyalkylene unit having 1 to 6 carbon atoms, particularly preferably an oxyalkylene unit having 2 to 6 carbon atoms, and is preferably an oxyethylene unit, an oxypropylene unit, an oxytrimethylene unit, Or, examples of oxytetramethylene unit and the like are given. Of these, fluorinated oxyalkylene units are From the viewpoint that the product is stable in the oxidation reaction and the product can be obtained in a high yield, it is preferably an oxyalkylene unit having a linear structure, and one O (CH ₂ ) _a — (where a is 2 It is preferably an oxyalkylene unit represented by the formula: and particularly preferably the unit wherein a is 2 to 6. Further, it is preferable that two or more oxyalkylene units are present in a row.

 The oxyalkylene unit may be one type or two or more types. When two or more kinds of oxyalkylene units are present, their connection is not particularly limited, and examples thereof include a random shape, a block shape, and a graft shape. The unit derived from the initiator is preferably a divalent or higher valent alcohol residue (an alcohol residue is a residue obtained by removing a hydrogen atom from a hydroxyl group of an alcohol compound).

Alcohol residues having 2 to 10 valences are preferred, and alcohol residues having 2 to 6 valences are particularly preferred.

 The molecular weight of the polyoxyalkylene compound is preferably from 300 to 10,000, particularly preferably from 300 to 400, particularly preferably from 300 to 300. When the molecular weight of the polyoxyalkylene is in the above-mentioned molecular weight range, the fluorination reaction can be performed more smoothly and with higher yield, and the fluorinated polyoxyalkylene compound having a desired molecular weight can be obtained. Can be produced in good yield.

 The polyoxyalkylene compound may or may not contain a fluorine atom, but is preferably a compound that does not contain a fluorine atom because of its advantage that various structures can be obtained at low cost.

Further, the polyoxyalkylene compound in the present invention includes an oxyalkylene represented by the formula: (a structure other than a unit derived from the initiator) is represented by 1 O (CH ₂ ) _a — (where a represents an integer of 2 or more.) Compounds consisting only of units are preferred. The polyoxyalkylene compound according to the present invention can be obtained by adding a polyalkylene moiety to a compound having two or more hydroxyl groups by a known method. In the production method of the present invention, first, a compound (F) having a group that forms an ester bond by reacting with a hydroxyl group and a fluorine-containing organic group having 2 or more carbon atoms is reacted with a polyoxyalkylene compound. The compound (F) has one or more hydrogen atoms and one of the hydrogen atoms in a monovalent saturated organic group having two or more carbon atoms as the fluorine-containing organic group in the compound (F). the above is been substituted with fluorine atoms, the fluorine-containing monovalent saturated organic group (hereinafter, referred to fluorinated monovalent saturated organic group with R ^F group.) are preferred, in particular fluorinated all hydrogen atoms was Perufuruoro of monovalent saturated organic group (hereinafter, referred to Perufuruoro monovalent saturated organic group as R ^F1 group.) is rather preferred, especially pel full O b alkyl group, Perufuruoro of an alkyl group containing an etheric oxygen atom And a group in which a partially fluorinated alkyl group containing an etheric oxygen atom is perfluorinated, and the latter two groups containing an etheric oxygen atom are more preferable. The number of aethenoyloxygen atoms in the group in which the ether oxygen atom is inserted is not particularly limited, and is preferably 1 or more, and particularly preferably 1 to 5 The number of carbon atoms of the fluorinated organic group is 2 or more. Yes, 5 or more is preferable, and 5 to 10 is particularly preferable. When the number of carbon atoms of the ^RF group is 2 or more, particularly 5 or more, the yield of the product in the fluorination reaction tends to be remarkably increased. Further, when the fluorine-containing organic group is a group containing an etheric oxygen atom, the yield of the fluorination reaction increases due to the improvement in solubility in the liquid phase during the fluorination reaction, and the like. There is an advantage that decomposition of the substrate is suppressed.

In the compound (F), groups react to form an ester bond with a hydroxyl group, as the one COX ¹ groups are preferred. X ¹ represents a halogen atom or a hydroxyl group. Further, as the compound (F), a compound represented by the general formula RW—COX ¹ is preferable, and a compound represented by R ^F1 —C〇F is particularly preferable. R ^F1 and X ¹ have the same meaning as above Show. The method of obtaining an esterified polyoxyalkylene compound by the reaction of a compound represented by R ^F1 —COX ¹ is a method that is economical and can easily produce an esterified polyoxyalkylene compound having various structures.

Compound R ^F1 ° Examples of (F) - COF, or R ^{F1 ()} - COOH ^(wherein, R ^{F1 0} denotes the pel full O b alkyl group.), R ^FU - COF or R ^m - COOH (wherein R ^FU represents a group in which an alkyl group containing an etheric oxygen atom is perfluorinated, or a group in which a partially fluorinated alkyl group containing an etheric oxygen atom is perfluorinated.) And the like. R ^m —COF is preferred.

Examples of the _{^{R F10, F (CF 2)}} 2 -, C 3 F 7 one [F (CF _{2) 3} one or the _{(CF 3) 2 CF-],} C 4 F 9 - [F (CF _{2) 4 one, (CF 3) 2 CF CF} 2 -, (CF 3) 3 C-, CF 3 CF 2 (CF 3) CF- etc.], C ₅ F] One

CF (CF _{2) 5} -, _{etc.], C 6 F 13 - [} F (CF 2) 6 Chief], C ₇丄 _{5 - [F (CF 2)} 7 - , _{etc.], C 8 F 17 - [} F ( CF ₂ ) ₈ first class], C ₉ F _I9- [F (CF ₂ ) ₉ — etc.], C _{1 {)} F ₂₁ ― [F (CF ₂ ),. First class].

Examples of R ^m include CF ₃ (CF ₂ ) ₂ 〇CF (CF ₃ ), CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ), CF ₂ C 1 (CF ₂ ) ₂ OCF (CF ₃ ) ―, CF ₂ C 1 (CF ₂ ) ₂₀ [CF (CF ₃ ) CF ₂₀ ] _u CF (CF ₃ ) one, CF ₂ C 1 (CF ₂ ) ₂ 〇CF ( CF ₂ C 1) 1, CF ₂ C 1 (CF ₂ ) ₂ 〇 [CF (CF ₂ C 1) CF _z O] _u CF (CF ₂ C 1) 1, CF ₂ C 1 CFC 1 CF _2- , CF ₂ C 1 C FC 1 (CF ₂ ) ₂ OCF (CF ₃ ) ―, CF ₂ C 1 CFC 1 (CF ₂ ) ₂ 〇 [CF (CF ₃ ) CF ₂₀ ] u CF (CF ₃ ), CF ₂ C 1 CFC 1 (CF ₂ ) ₂ OCF (CF ₂ CI) ―, CF ₂ C 1 CFC 1 (CF ₂ ) ₂ 0 [CF (CF ₂ C 1) CF ₂ 〇] _u CF

(CF ₂ C 1) one, CF ₂ C 1 CFC 1 CF (CF ₃ ) OCF (CF ₃ ) one, CF ₂ C 1 CFC 1 CF (CF ₃ ) O [CF (CF ₃ ) CF ₂₀ ] _u CF (CF ₃ ) ―, CF ₂ C 1 CFC 1 (CF ₂ ) ₂ OCF (CF ₂ C 1) one, CF ₂ C 1 CFC 1 (CF ₂ ) ₂₀ [CF (CF ₂ C 1) CF ₂ 0] _u CF (CF ₂ C 1) 1, F (CF ₂ ) ₅ OCF (CF ₃ ) ―, F [CF (CF ₃ ) CF ₂ 〇] _r CF (CF ₃ ) CF ₂ CF ₂ ―, F [CF (CF ₃ ) CF ₂ O] _u CF (CF ₃ ), F [CF (CF ₃ ) CF ₂ O] _u CF ₂ CF ₂ , F (CF ₂ CF ₂ CF ₂ O) _u CF ₂ CF ₂ , F (CF ₂ CF ₂ 〇) _u CF ₂ CF ₂ ― (r is an integer from 1 to 5, u is an integer from 1 to 6, w is an integer from 1 to 9 ), And the like.

 As the compound (F), a compound produced by the method described in WO00 / 56694 by the present applicant may be used, or a commercially available product may be used.

The esterification reaction between the polyoxyalkylene compound and the compound (F) is appropriately changed depending on the type of the group that reacts with the hydroxyl group present in the compound (F), and known reaction conditions can be employed. For example, when the compound (F) is a compound represented by R ^F1 —COX ¹ (R ^F1 and X ¹ each have the same meaning as described above), a known esterification reaction method and conditions May be applied.

 The esterification reaction is preferably carried out by dissolving the polyoxyalkylene compound in a solvent (hereinafter, referred to as an esterification solvent) and reacting with the compound (F) in the solvent. As the esterification solvent, a solvent that dissolves the polyoxyalkylene compound and is inert to the compound (F) is preferable. When the product of the esterification reaction does not dissolve in the esterification solvent, the reaction S is preferably carried out while dropping a solvent capable of dissolving the product, thereby suppressing the precipitation of the product. The amount of the esterification solvent used is preferably 50 to 500% by mass based on the total amount of the polyoxyalkylene compound and the compound (F).

When an acid (eg, HC 1, HF, etc.) is generated by the reaction of the polyoxyalkylene compound with the compound (F), an alkali metal fluoride (preferably NaF or KF) or a trialkylamine is used. Is preferably present in the reaction system. When the base is not used, it is preferable to discharge the acid out of the reaction system by accompanying the acid with a nitrogen stream. The amount of the base is preferably 1 to 10 moles per mole of the compound (F).

 In general, the reaction temperature of the esterification reaction is preferably −50 ° C. or higher, more preferably +10 o t: or lower, or lower than the boiling point of the esterification solvent. The reaction pressure (the pressure is indicated by a gauge pressure; the same applies hereinafter) is preferably from 0 to 2 MPa.

 Among the hydroxyl groups in the polyoxyalkylene compound, the proportion of the hydroxyl groups that react with the compound (F) can be appropriately changed according to the structure of the target fluorinated polyoxyalkylene compound. It is preferred that 95% or more of the number react with the compound (F). As a result, even if a hydroxyl group remains in the reaction with the compound (F), the product has a sufficient molecular weight, so that it is difficult for the product to be entrained in a gas phase in which fluorine gas is present, and carbon-carbon which easily occurs in the gas phase Cleavage of bonds can be prevented. Further, by esterifying the hydroxyl group, a structural change of the hydroxyl group in the fluorination reaction can be avoided. Furthermore, the ester bond present in the product can be converted to a 1 COF group or a 1OH group by performing thermal decomposition or hydrolysis.

When a hydroxyl group is present in the esterified polyoxyalkylene compound after the esterification reaction, a compound containing no fluorine atom in the hydroxyl group may be reacted. Examples of the compound include a compound represented by R ^H —COX ² (R ^H represents a monovalent organic group containing no fluorine atom, and X ² represents a halogen atom). R ^H is preferably an alkyl group or an alkyl group containing an etheric oxygen atom, and X ² is preferably a chlorine atom or a fluorine atom.

The amount of each compound in the esterification reaction between the polyoxyalkylene compound and the compound (F) is such that the amount of the compound (F) is 1 to 5 moles per mole of the hydroxyl groups present in the polyoxyalkylene compound. It is particularly preferable that the molar amount is 1 to 2 times. The crude product obtained by the esterification reaction may be purified according to the purpose or used as it is in the next reaction, etc., but is purified from the viewpoint of stably performing the next liquid phase fluorination reaction. Preferably, the compound (F) and the esterification solvent in the crude product are separated by a method such as drying under reduced pressure. As a purification method, both the compound (F) and the esterification solvent were dissolved, and the crude reaction product was added dropwise to the solvent for precipitating the product to reprecipitate the esterified polyoxyalkylene compound. Thereafter, a method is preferred in which the solvent is removed by drying under reduced pressure to recover the precipitate.

As the esterified polyoxyalkylene compound, a polyoxyalkylene compound having an R ^F1 —CO— group obtained by using a compound represented by R ^F1 —COX ¹ as the compound (F) (R ^F1 and X ¹ are And each has the same meaning as described above.

 The fluorine content in the esterified polyoxyalkylene compound is preferably at least 25% by mass, more preferably at least 30% by mass, based on the molecular weight. The upper limit of the fluorine content is preferably 76% by mass, and particularly preferably 65% by mass. By setting the fluorine content, the solubility of the fluorination reaction in the solvent is remarkably improved. There is an advantage that the reaction yield is high. If the fluorine content is too low, the solubility in the liquid phase becomes extremely low, and the reaction system of the fluorination reaction becomes non-uniform. The upper limit of the fluorine content is not limited, but using too high a fluorine content may not be economical.

 The esterified polyoxyalkylene compound is usually soluble in the liquid phase during the liquid phase fluorination reaction described below. Here, "soluble" means that the compound is dissolved in the liquid phase in an amount of 0.1% by mass or more under the conditions of the fluorination reaction, and the dissolving power is preferably 0.5% by mass or more.

Further, the molecular weight of the esterified polyoxyalkylene compound is preferably from 130 to 160, particularly preferably from 160 to 1100. The minute An esterified polyoxyalkylene compound having a molecular weight in the range of the molecular weight has the advantage that it is not entrained in the gas phase and the breakage of carbon-carbon bonds is significantly prevented. If the molecular weight of the esterified polyoxyalkylene compound is too large, the solubility in the liquid phase tends to decrease, and the type of solvent that can be used as the liquid phase decreases.

 In the production method of the present invention, the esterified polyoxyalkylene compound is then subjected to a liquid-phase fluorination reaction to convert one or more of the hydrogen atoms present in the esterified polyoxyalkylene compound to fluorine. To obtain a fluorinated boroxyalkylene compound.

 In the present invention, fluorination is performed by a liquid phase fluorination reaction method. As a fluorination method, a cobalt fluorination method and an ECF method are known. In the present invention, a liquid phase fluorination method in which a target product is obtained with remarkable yield is used.

The liquid phase fluorination is carried out by reacting an esterified polyoxyalkylene compound, preferably a polyoxyalkylene compound having an R ^Fi- CO— group, with fluorine in a solution in a fluorinated solvent.

 In liquid-phase fluorine, fluorine gas may be used as it is, or fluorine gas diluted with an inert gas may be used. As the inert gas, nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economic reasons. The amount of fluorine gas in the nitrogen gas is not particularly limited, and is preferably 5 to 50% from the viewpoint of efficiency, and particularly preferably 5 to 20%.

 The liquid phase fluorination is preferably carried out under the condition that the amount of fluorine is always excessively equivalent to the hydrogen atom in the esterified polyoxyalkylene compound, and particularly, the amount of fluorine becomes 1.5 times or more. This is preferable from the viewpoint of selectivity. The upper limit of the amount of fluorine is preferably 3 times or less from the viewpoint of economy.

Fluorine may be dissolved in a fluorinated solvent in advance, and fluorine gas may be continuously introduced into the fluorinated solvent. This liquid phase fluorination reaction In other words, one or more of the hydrogen atoms bonded to the carbon atoms in the esterified boroxyalkylene compound are replaced with fluorine atoms, thereby producing a fluorinated polyoxyalkylene compound.

 In the fluorination reaction, C-H present in the esterified polyoxyalkylene compound is partially or completely fluorinated to produce a fluorinated polyoxyalkylene compound. When a carbon-carbon unsaturated bond is present in the esterified polyoxyalkylene compound, a reaction in which a fluorine atom is added to the bond may occur. The fluorination reaction in the present invention may be a reaction for fluorinating all of the hydrogen atoms in the C—H portion (ie, complete fluorination) or a partial fluorination. In the case of partial fluorination, 40 mol% or more of the hydrogen atoms are preferably fluorinated, and particularly preferably 90 mol% or more are fluorinated.

 As the fluorinated solvent in the liquid-phase fluorination, among the solvents capable of dissolving the esterified polyoxyalkylene compound, the solvent capable of dissolving the fluorine gas and preferably containing no CH bond is preferable. , Perfluoroalkanes (FC-72, etc.), perfluoroethers (FC-75, FC-77, etc.), perfluoropolyethers (trade names: Crytox, Fmpulin, Galden, Demnum, etc.), black mouth fluorocarbons (trade name: CFC), black mouth fluoropolyethers, perfluoroalkylamines (eg, perfluorotrialkylamine, etc.), inert fluids ( (Product name: Florinert) and the like. As the fluorinated solvent, a fluorinated polyoxyalkylene compound generated by a fluorination reaction may be used. In this case, there is an advantage that the step of separating the product from the fluorinated solvent can be omitted.

When a chlorinated solvent is used together with the fluorinated solvent, the solubility of both the esterified polyoxyalkylene compound and the fluorinated polyoxyalkylene compound in the night phase is improved, and The advantage of making the reaction in the system easier is there. As the chlorinated solvent, chlorinated fluorinated hydrocarbons are preferable, and dichloropen fluorinated propane, and chlorinated tetrafluoroethylene oligomer are exemplified.The fluorinated solvent is based on the esterified polyoxyalkylene compound. It is preferable to use a 5-fold mass or more, particularly preferably 10- to 100-fold mass. Also, the viscosity of the solution obtained by dissolving esterified poly O alkoxy polyalkylene compounds fluorinated solvent to less ^{5X 10- 4 ~0. L P a} * s can be smoothly carried out liquid phase fluorination reaction preferably reasons, particularly preferably less particularly ^{5 X 1 0- 4 ~5 X 10-} 3 P a · s.

 Usually, the reaction temperature of the fluorination reaction is preferably not lower than 160 ° C and not higher than the boiling point of the fluorinated solvent.From the viewpoint of the reaction yield, selectivity, and the ease of industrial implementation, the reaction temperature is preferably from 150 ° C to Is particularly preferred, and a temperature of from 20 ° C to 10100 ° C is particularly preferred.

 Further, the reaction pressure of the fluorination reaction is preferably set to a pressurized condition, more preferably 0.01 to 5 MPa (gauge pressure, the same applies hereinafter). When it is necessary to remove HF, the pressure is preferably reduced to atmospheric pressure.

 The reaction system of the fluorination reaction is preferably a batch system or a continuous system, and includes the following method 1 or method 2. Among them, the following method 2 is preferable in terms of the reaction yield and the selectivity. The fluorine gas used in the following method may be diluted with an inert gas such as nitrogen gas.

 [Method 1] An esterified polyoxyalkylene compound and a fluorinated solvent are charged into a reactor, and stirring is started. Next, the reaction is performed while continuously supplying fluorine gas to the liquid phase in the reactor at a predetermined reaction temperature and reaction pressure.

[Method 2] A fluorinated solvent is charged into a reactor, and stirring is started. Next, at a predetermined reaction temperature and reaction pressure, the esterified polyoxyalkylene compound dissolved in the fluorinated solvent and fluorine gas are continuously and simultaneously added to the liquid phase in the reactor at a predetermined molar ratio. How to supply.

 In the liquid-phase fluorination reaction of the present invention, HF is by-produced because a hydrogen atom is replaced with a fluorine atom. To remove by-product HF, it is preferable to coexist with an HF scavenger in the reaction system or to contact the HF scavenger with the outlet gas at the reactor gas outlet. Of these, it is preferable that no HF scavenger is present in the reaction system, and it is particularly preferable that the HF scavenger is present at the reactor gas outlet without the HF scavenger in the reaction system. . When no HF scavenger is present in the reaction system, there is an advantage that the decomposition reaction of the ester bond can be prevented, the reaction can be carried out in good yield, and the post-treatment becomes easy.

 As the HF scavenger, those similar to those described above can be used, and NaF is preferred. The amount of the HF scavenger coexisting in the reaction system is preferably 1 to 20 times, and more preferably 1 to 5 times the mole of the total hydrogen atoms present in the esterified polyoxyalkylene compound.

When an HF scavenger is placed at the reactor gas outlet, (h) a cooler (preferably maintained at 10 ° C. to room temperature, particularly preferably maintained at about 20 ° C.) (i) Na F pellet packed bed, and (j) a cooler (preferably maintained at 78 ° C to 10 ° C, preferably maintained at 30 ° C to 0 ° C). -It is preferable to install them in series in the order of (i)-(j). In addition, a liquid return line for returning the flocculated fluorinated solvent or the like to the reactor from the cooler (j) may be provided. The use of a liquid return line is particularly preferable in that the increase in the viscosity of the reaction solution due to the scattering of the fluorinated solvent can be suppressed.In particular, when the scattering of the fluorinated solvent is remarkable, the fluorinated solvent is continued inside the reactor. In order to increase the fluorination rate in the liquid phase fluorination reaction efficiently, it is preferable to supply C-H bonds in the reaction system. Add compounds or irradiate UV And are preferred. As a result, the esterified polyoxyalkylene compound present in the reaction system can be efficiently fluorinated, and the reaction rate can be dramatically improved. The ultraviolet irradiation time is preferably from 0.1 to 3 hours.

 The C—H bond-containing compound is selected from organic compounds other than the esterified polyoxyalkylene compound, particularly preferably an aromatic hydrocarbon, particularly preferably benzene, toluene and the like. The amount of the C—H bond-containing compound to be added is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 5 mol%, based on the total number of hydrogen atoms in the esterified polyoxyalkylene compound. It is preferred that

 The C—H bond-containing compound is preferably added in a state where fluorine gas is present in the reaction system. Further, when a C—H bond-containing compound is added, it is preferable to pressurize the reaction system. The pressure at the time of pressurization is preferably from 0.01 to 5 MPa.

 It is preferable to remove the fluorinated solvent from the crude product of the fluorination reaction to obtain the product. When the same fluorinated solvent as the product is used, the crude product may be used as it is for the intended use.

 The liquid-phase fluorination reaction in the present invention is a method that can be carried out while preventing a carbon-carbon bond breaking reaction and an ester bond decomposition reaction, so that a product having a target molecular weight can be obtained.

The fluorinated polyoxyalkylene compound has an oxy (perfluoroalkylene) unit represented by —〇 (CF ₂ ) _a — (where, a represents an integer of 2 or more). Preferably, the unit has a portion in which two or more units are connected), and is a compound having an R ^Fi —CO— group. Further, when a C—H structure derived from an initiator is present in the esterified polyoxyalkylene, it is preferable that all of the C—H structures be C—F structures. The molecular weight of the fluorinated polyoxyalkylene compound is preferably from 330 to 370,000, particularly preferably from 410 to 300.000. The fluorinated polyoxyalkylene compound in the present invention is a compound that can be usefully used as it is or by derivatization to another compound. Examples of derivatization include hydrolyzing an ester bond of a fluorinated polyoxyalkylene compound into one COOH group, or decomposing the ester bond into one COF group, and further derivatizing these groups. And the like. The fluorinated polyoxyalkylene compound or a derivative obtained by chemically converting the compound is useful as a surfactant, a surface modifier, a water / oil repellent, a coating agent, and a lubricant. Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Incidentally, it referred tetramethylsilane TMS, the _{CC 1 F 2 CF 2 CHC 1} F the _{AK- 225, CC 1 2 FCC 1} 2 a R- 113 below. In addition, the NMR spectrum data was shown as an apparent chemical shift range, and the integral was expressed as a ratio.

 [Example 1] Production example of fluorinated polyoxypropylene compound

(Example 11-1) Production Example of Polyoxypropylene Compound Introducing Fluorine-Containing Organic Group Commercially available polyoxypropylene glycol (20 g) (HO [CH (CH ₃ ) CH ₂₀ ] _n H (n = l 8. 1 (average value)), AK-225 (54 g), and NaF (3.41 g) were placed in a flask, and the mixture was stirred vigorously while maintaining the internal temperature at 25 ° C to bubble nitrogen. (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (41 g) was added dropwise over 1.0 hour while maintaining the internal temperature at 25 ° C or higher. After stirring at room temperature for 12 hours and then at room temperature for 24 hours, the crude solution was collected by filtration under reduced pressure, and the collected solution was then filtered using a vacuum dryer (100 ° C, 5.0 torr). Dry for 2 hours to obtain 26.9 g of polymer, liquid at room temperature Was. 'Η—NMR, ¹⁹ F—As a result of NMR analysis, the obtained polymer was CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) C (〇) O [CH (CH ₃ ) CH _{20 ] n C OCF (CF 3)} OCF 2 CF (CF 3) OCF 2 CF 2 CF 3 (n is. as defined above) it was confirmed to be a compound represented by.

Ή-NMR (300. 4MHz, solvent: CDC 1 _3, reference: TMS) δ (ppm): .. 0. 9~1 4, 3. 3~3 8, 5. 3.

¹⁹ F- NMR (282. 7MHz, solvent: CDC 1 _{3, reference: CFC 1 3) δ (ppm} ): - 76. 0 81. 0, - 81. 0 82. 0, - 82. 0~-

82.5, 1 82.5--85.0,-128.0--129.2, -131.1, 1 147.7.

 (Example 1-2) Production example of fluorinated polyoxypropylene compound with fluorine-containing organic group introduced

 R-113 (312 g) was added to a 50 OmL Hastelloy autoclave, and the mixture was stirred and kept at 25 ° C. At the autoclave gas outlet, a cooler kept at 20 ° C, a packed bed of NaF pellets, and a cooler kept at 120 ° C were installed in series. In addition, a liquid return line was installed to return the condensed liquid from the cooler kept at 20 ° C to the autoclave. After blowing nitrogen gas for 1.0 hour, fluorine gas diluted to 20% with nitrogen gas (hereinafter referred to as 20% fluorine gas) was blown at a flow rate of 5.63 L / h for 1 hour.

 Next, a solution prepared by dissolving the product obtained in Example 11 (1.20 g) in R-113 (59.5 g) was injected for 3.25 hours while blowing 20% fluorine gas at the same flow rate. And injected.

Next, 6 mL of the R-113 solution was injected while blowing 20% fluorine gas at the same flow rate. Furthermore, nitrogen gas was blown for 1.0 hour. After completion of the reaction, the solvent was removed by vacuum drying (60 ° C, 6.0 hr), and 1.28 g of the liquid product was removed at room temperature. Obtained. As a result of the analysis, it was confirmed that 81.9% of the total number of hydrogen atoms in the product obtained in Example 1 was a compound in which fluorine atoms were substituted.

 Ή-NMR (300.4 MHz, solvent: R-113, standard: TMS, internal standard: nitrobenzene) δ (ppm): 1.4, 4.9 to 5.2, 5.9 to 6.4

. ¹⁹ F- NMR (282. 7MHz, solvent: R- 113, reference: CFC 1 _3, internal standard: to hexa Full O b benzene) <5 (p pm): -77 5~ one 92.0, -

120. 0 135.0, -142. 0 to 1 146.0.

 [Example 2]

 (Example 2-1) Example of esterification of pentaerythritol-1 6 EO adduct

 A Penyu erythritol-to-6EO adduct (manufactured by Asahi Glass Co., Ltd.) was prepared by adding Pentan Erythritol as an initiator and adding ethylene oxide on average 6 times.

A 20-OmL round-bottomed flask sufficiently purged with nitrogen was prepared, and a solution prepared by dissolving pentaerythritol-16 EO adduct (10. Og) in R-225 (100.0 g) was charged. Nitrogen gas was flowed at a flow rate of 100 ml min, the temperature was raised to 25 ° C with vigorous stirring, and CF ₃ CF ₂ CF ₂ 〇CF (CF ₃ ) CF ₂ OCF was passed through a dropping funnel installed at the top of the device. (CF ₃₎ was added COF (1 00. O g). After completion of the dropwise addition, the mixture was kept for 15 hours, and then cooled to room temperature to recover a crude liquid.

?? The recovered crude liquid was dried under reduced pressure, and R- 2 25, excess _{3 2 2} 〇 _{CF (CF 3) CF 2 OCF} (CF 3) After evaporation of the COF, the residual liquid R - 22 5 (100 g) and the operation of dropping in hexane (500 g) was performed twice. Next, the product was dried under reduced pressure (100 ° (:, 24 hours) to obtain a liquid product (56.32 g) at room temperature. It was confirmed that the component was the title compound. The number average molecular weight measured by gel permeation chromatography was 2620.

Ή-NMR (300. 40MHz, solvent CDC 1 _3, reference ·· TMS) δ (p pm) :. 3. 45~ 3. 95, 4. 3~4 8.

^{1 9 F-NMR (282. 7} MH z, _{solvent: R- 1 1 3 (C 2} F 3 C 1 3), _{reference: CFC 1 3) δ (p} pm): - 80. 2 (3 F), -81.3 (5 F), 1 82.3 (3 F), 1 78.2 to 1 85.6 (IF),-129.3 (2 F),-1 31.2 (IF), -14.4.7 (1F).

 (Example 2-2) Example of fluorination of the product of Example 2-1

 Prepare the same reactor as in Example 2-1 except that the 20% fluorine gas in Example 2-1 is changed to fluorine gas diluted to 10% with nitrogen gas (hereinafter referred to as 10% fluorine gas). Prepared for the same conditions.

 While injecting 10% fluorine gas into the autoclave at the same flow rate, a solution of the product of Example 2-1 (10.3 g) dissolved in R-113 (206 g) was taken for 5.0 hours. Injected. Further, while blowing 10% fluorine gas at the same flow rate, 6 mL of the R-113 solution was injected. In addition, nitrogen gas was blown for 1.0 hour.

 After the completion of the reaction, the crude liquid was recovered and dried under reduced pressure (60, 6.0 hours) to remove R-113, thereby obtaining a viscous liquid product (12.32) at room temperature. As a result of analyzing the product, it was confirmed that 99.7 mol% of hydrogen atoms in the polymer obtained in Example 2-1 were replaced with fluorine atoms. The average molecular weight measured by GPC was 2,890.

H—NMR (300.4 MHz, solvent: R—113, standard: TMS, internal standard: nitrobenzene) <5 (pm): 5.9 to 6.1, 6 to 3 to 6.6 ^{1 F-NMR (282. 7 MH} z, solvent: R_L 13, reference ·· CDC 1 _3, internal _{standard: C 6 F 6) δ (} ppm):. -63 5~- 65. 0, - 67. 5 to 1 68.3, --77.0 to 18.4, 1 86.7 to 18.8, 190 to 5 to 92.0, -128.5-1 to 13.0, 1 130.5.0-1 131.0, 1-142. 0-145.0. Industrial applicability>

 In the present invention, fluorinated polyoxyalkylene compounds having various structures can be produced using polyoxyalkylene compounds having various structures as starting materials. According to the production method of the present invention, by using a specific esterified polyoxyalkylene compound, a molecular chain scission reaction during a liquid phase fluorination reaction is prevented, and a desired fluorinated polyoxyalkylene compound is obtained. Compounds can be produced. Further, the fluorinated polyxylene compound produced by the reaction can be obtained without gelling. The fluorinated polyoxylen compound can be used as various functional materials as it is or after derivatization to another compound by chemical conversion of an ester bond.

Claims

The scope of the claims 1. An esterified polyoxyalkylene compound having at least one hydroxyl group is subjected to an esterification reaction with a compound having a group that forms an ester bond by reacting with the hydroxyl group and a fluorinated organic group having 2 or more carbon atoms. Fluorinating one or more of the hydrogen atoms present in the esterified polyoxyalkylene compound by synthesizing the oxyalkylene compound and then subjecting the esterified polyoxyalkylene compound to liquid phase fluorination. A method for producing a fluorinated polyoxyalkylene compound, comprising: . 2 hydroxyl groups in R ^F1 hydroxyl poly O alkoxy polyalkylene compounds having one or more - C 0 by esterifying a compound represented by X ^1, R ^F1 - CO- to have a group esterified polyoxyalkylene A liquid phase fluorination of the esterified polyoxyalkylene compound, thereby fluorinating one or more of the hydrogen atoms present in the esterified polyoxyalkylene compound to form a fluorinated compound having a R ^F1 —CO— group. 2. The method according to claim 1, wherein a polyoxyalkylene compound is obtained. Here, R ^F1 represents a perfluoro monovalent organic group having 2 or more carbon atoms, and X ¹ represents a halogen atom or a hydroxyl group. 3. The perfluoro monovalent organic group is a group in which an alkyl group containing an etheric oxygen atom is perfluorinated, or a partially fluorinated alkyl group containing an etheric oxygen atom is a perfluorinated group. Manufacturing method. 4. The polyoxyalkylene compound having at least one hydroxyl group contains an oxyalkylene unit represented by 10 (CH ₂ ) _a 1 (where a represents an integer of 2 or more). 4. The production method according to claim 1, wherein the compound is a compound. 5. The method according to any one of claims 1 to 4, wherein the polyoxyalkylene compound having at least one hydroxyl group has a molecular weight of 300 to 10,000. 6. The production method according to any one of claims 1 to 5, wherein the molecular weight of the esterified polyoxyalkylene compound is 1300 to 16000. 7. The fluorine content of the esterified polyoxyalkylene compound is 25 mass. /. The production method according to any one of claims 1 to 6, wherein the content is from 76 to 76% by mass. 8. The polyoxyalkylene compound having at least one hydroxyl group is a compound containing no fluorine atom, and 95% or more of the total number of hydroxyl groups of the polyoxyalkylene compound is esterified by an esterification reaction. The production method according to any one of 1 to 7. 9. The method for producing a fluorinated polyoxyalkylene compound according to any one of claims 1 to 8, wherein the liquid phase fluorination is performed at 0.01 to 5 MPa (gauge pressure). 10. The production method according to any one of claims 1 to 9, wherein the liquid phase fluorination reaction is performed without using an HF scavenger.