Fluorinated polyether compound and method for producing the same

Abstract

This invention provides the following formula (1): R a -R 2 -R 1 -R b [In the formula: R] a For COF, COOR 11 CH2OH or CHO; R b For COF, COOR 11 CH2OH or CHO; R 11 Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms that can be substituted with fluorine; R 1 It is an alkylene group with 2 to 10 carbon atoms that can be substituted by fluorine; R 2 -R 6a -(OR) 5a ) n -O-;R 5a It is a straight-chain or branched alkylene group with 2 to 10 carbon atoms that can be substituted with fluorine; R 6a Fluorinated polyether compounds, which are linear or branched alkylene groups with 1 to 9 carbon atoms that can be substituted by fluorine.

Description

Technical Field

[0001] The invention relates to a fluorinated polyether compound and a preparation method thereof. Background Art

[0002] Fluorinated polyether group-containing compounds are widely used as surface treatment agents, lubricants, etc., and their uses are further broadened.

[0003] As one of the methods for producing fluorinated polyether group compounds, for example, ring-opening polymerization of cyclic ethers such as tetrafluoroethylene oxide or hexafluoropropylene oxide is known. However, using such a method, a compound having a functional group only at one end of the molecular chain can usually be obtained, and it is difficult to obtain a compound having functional groups at both ends of the molecular chain.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2002-37880 Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] At present, in order to obtain a fluorinated polyether compound having functional groups at both ends of the molecular chain, a special initiator must be used (Patent Document 1). In particular, it is difficult to obtain a fluorinated polyether compound having different functional groups at both ends using such a production method.

[0009] The object of the present invention is to provide a novel fluorinated polyether compound and a method for producing the same.

[0010] Technical solutions for solving technical problems

[0011] The present invention includes the following aspects.

[0012] [1] A fluorinated polyether group-containing compound represented by the following formula (1a):

[0013] R a -R 2 -R 1 -R b (1a)

[0014] [Where:

[0015] R a COF, COOR 11 , CH2OH or CHO;

[0016] R b COF, COOR 11 , CH2OH or CHO;

[0017] Among them, R a and R b are different groups from each other;

[0018] R 11 Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine;

[0019] R 1 is an alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0020] R 2 For -R 6a -(OR 5a ) n -O-;

[0021] R 5a A linear or branched alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0022] R 6a A linear or branched alkylene group having 1 to 9 carbon atoms which may be substituted by fluorine;

[0023] n is an integer from 2 to 200. ].

[0024] [2] The fluorinated polyether group-containing compound according to [1] above, wherein R 5a is a linear or branched alkylene group having 2 to 4 carbon atoms which may be substituted with fluorine,

[0025] R 6a It is a linear or branched alkylene group having 1 to 3 carbon atoms which may be substituted with fluorine.

[0026] [3] The fluorinated polyether group-containing compound according to [1] or [2], wherein R 5a is an alkylene group having 3 carbon atoms which may be substituted with fluorine,

[0027] R 6a It is an alkylene group having 2 carbon atoms which may be substituted with fluorine.

[0028] [4] A fluorinated polyether group-containing compound represented by the following formula (1b):

[0029] R a -R 2’ -R 1 -R b (1b)

[0030] [Where:

[0031] R a COF, COOR 11, CH2OH or CHO;

[0032] R b COF, COOR 11 , CH2OH or CHO;

[0033] R 11 Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine;

[0034] R 1 is an alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0035] R 2’ For -R 6b -(OR 5b ) n -O-;

[0036] R 5b is CF2CF(CF3) or CF2CF2CH2;

[0037] R 6b is CF(CF3) or CF2CH2;

[0038] n is an integer from 2 to 200. ].

[0039] [5] The fluorinated polyether group-containing compound according to any one of [1] to [4], wherein R a COF, R b For COOR 11 , R 11 It is an alkyl group having 1 to 6 carbon atoms.

[0040] [6] The fluorinated polyether group-containing compound according to any one of [1] to [5], wherein R 1 It is a perfluoroalkylene group having 2 to 10 carbon atoms.

[0041] [7] A method for producing a compound represented by formula (A), comprising the step of reacting an acyl fluoride compound represented by the following formula (a) and a cyclic ether compound represented by the following formula (b):

[0042] FOC-R 2 -R 1 -COOR 12 (A)

[0043] [Where:

[0044] R 1 is an alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0045] R 2 For -R 6-(OR 5 ) n -O-;

[0046] R 5 A linear or branched alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0047] R 6 A linear or branched alkylene group having 1 to 9 carbon atoms which may be substituted by fluorine;

[0048] R 12 is an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine;

[0049] n is an integer from 2 to 200.]

[0050] FOC-R 13 -COOR 12 (a)

[0051] [Where:

[0052] R 13 is an alkylene group having 1 to 9 carbon atoms which may be substituted with fluorine;

[0053] R 12 It is an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine.]

[0054]

[0055] [Where R 15 It is a linear or branched alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine. ].

[0056] [8] The production method according to [7] above, wherein R 13 It is a perfluoroalkylene group having 1 to 9 carbon atoms.

[0057] [9] The production method according to [7] or [8] above, wherein R 15 It is a linear or branched alkylene group having 2 to 4 carbon atoms which may be substituted with fluorine.

[0058]

[10] The production method according to any one of [7] to [9] above, wherein R 15 It is CF2CF2CH2 or CF2CF(CF3).

[0059] Effects of the Invention

[0060] The present invention can provide a novel fluorinated polyether group-containing compound that can be used for various applications. In addition, by using a specific initiator, a fluorinated polyether group-containing compound having functional groups at both ends can be easily produced. DETAILED DESCRIPTION

[0061] Hereinafter, the fluorinated polyether group-containing compound of the present invention will be described in detail.

[0062] The present invention provides a fluorinated polyether compound represented by the following formula (1):

[0063] R a -R 2 -R 1 -R b (1)

[0064] [Where:

[0065] R a COF, COOR 11 , CH2OH or CHO;

[0066] R b COF, COOR 11 , CH2OH or CHO;

[0067] R 11 A hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine;

[0068] R 1 is an alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0069] R 2 For -R 6a -(OR 5a ) n -O-;

[0070] R 5a A linear or branched alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0071] R 6a A linear or branched alkylene group having 1 to 9 carbon atoms which may be substituted by fluorine;

[0072] n is an integer from 2 to 200. ].

[0073] In one embodiment, the present invention provides a fluorinated polyether group-containing compound represented by the following formula (1a):

[0074] R a -R 2 -R 1 -R b (1a)

[0075] [Where:

[0076] R a COF, COOR 11 , CH2OH or CHO;

[0077] R b COF, COOR 11 , CH2OH or CHO;

[0078] Among them, R a and R b are different groups from each other;

[0079] R 11 Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine;

[0080] R 1 is an alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0081] R 2 For -R 6a -(OR 5a ) n -O-;

[0082] R 5a A linear or branched alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0083] R 6a A linear or branched alkylene group having 1 to 9 carbon atoms which may be substituted by fluorine;

[0084] n is an integer from 2 to 200. ].

[0085] In one embodiment, the present invention provides a fluorinated polyether group-containing compound represented by the following formula (1b):

[0086] R a -R 2’ -R 1 -R b (1b)

[0087] [Where:

[0088] R a COF, COOR 11 , CH2OH or CHO;

[0089] R b COF, COOR 11 , CH2OH or CHO;

[0090] R 11 Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine;

[0091] R 1 is an alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0092] R 2’ For -R 6b -(OR 5b ) n -O-;

[0093] R 5b is CF2CF(CF3) or CF2CF2CH2;

[0094] R 6b is CF(CF3) or CF2CH2;

[0095] n is an integer from 2 to 200. ].

[0096] The difference between the above formula (1a) and formula (1b) is that in formula (1a) R a and R b Different, in contrast, in formula (1b) R a and R b can be the same or different, and in formula (1a) R 2 For -R 6a -(OR 5a ) n -O-, in contrast, in formula (1b) R 2’ For -R 6b -(OR 5b ) n -O-.

[0097] In the above formula, R a COF, COOR 11 , CH2OH or CHO, preferably COF or COOR 11 , more preferably COF.

[0098] In the above formula, R b COF, COOR 11 , CH2OH or CHO, preferably COOR 11 .

[0099] In the above formula, R 11 Each of R is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine, and is preferably an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine. 11 The alkyl group having 1 to 6 carbon atoms in the group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.

[0100] In the above formula (1a), R a and R b are different groups from each other.

[0101] In the above formula (1b), Ra and R b They may be the same group or different groups. a and R b In another embodiment, R a and R b For different groups.

[0102] In one approach, R a and R b The combination of COF and COOR 11 or COOR 11 and COOR 11 , preferably COF and COOR 11 .

[0103] In the above formula, R 1 R is an alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine. 1 The alkylene group having 2 to 10 carbon atoms in the group is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms, and further preferably an alkylene group having 2 carbon atoms.

[0104] In one embodiment, the above R 1 The alkylene group in the above-mentioned group is a fluoroalkylene group, and preferably a perfluoroalkylene group.

[0105] In a preferred embodiment, the above R 1 It is a linear perfluoroalkylene group having 1 to 3 carbon atoms, and -CF2CF2- is more preferred.

[0106] In the above formula (1a), R 2 For -R 6a -(OR 5a ) n -O-.

[0107] The above R 5a It is a linear or branched alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine. Such an alkylene group having 2 to 10 carbon atoms is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an alkylene group having 3 carbon atoms.

[0108] In one embodiment, the above R 5a The alkylene group is a straight chain.

[0109] In another embodiment, the above R 5a The alkylene group is a branched chain.

[0110] In a preferred embodiment, the above R 5aIt is CF2CF2CH2, CF2CF2CF2 or CF2CF(CF3), preferably CF2CF2CH2 or CF2CF(CF3), more preferably CF2CF2CH2.

[0111] In the above formula, R 6a It is a linear or branched alkylene group having 1 to 9 carbon atoms which may be substituted with fluorine. Such an alkylene group having 1 to 9 carbon atoms is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms, for example, an alkylene group having 1 or 2 carbon atoms.

[0112] In one embodiment, the above R 6a The alkylene group is a straight chain.

[0113] In another embodiment, the above R 6a The alkylene group is a branched chain.

[0114] In a preferred embodiment, the above R 6a It is CF2CH2, CF2CF2 or CF(CF3), preferably CF2CH2 or CF(CF3), more preferably CF2CH2.

[0115] In one approach, R 5a The carbon number of the alkylene group is greater than R 6a The number of carbon atoms in the alkylene group is greater than 1. 5a When the number of carbon atoms in the alkylene group is 3, R 6a The number of carbon atoms in the alkylene group is 2.

[0116] In the above formula (1b), R 2’ For -R 6b -(OR 5b ) n -O-.

[0117] In the above formula (1b), R 5b It is CF2CF(CF3) or CF2CF2CH2.

[0118] In the above formula (1b), R 6b It is CF(CF3) or CF2CH2.

[0119] In one approach, R 5b is CF2CF(CF3), R 6b It is CF (CF3).

[0120] In another way, R 5b is CF2CF2CH2, R 6b It is CF2CH2.

[0121] In the above formula, n is an integer of 2-200, preferably an integer of 5-100, and more preferably an integer of 10-60.

[0122] In a preferred embodiment, in the fluorinated polyether group-containing compound represented by formula (1a) of the present invention,

[0123] R a is COF;

[0124] R b For COOR 11 ;

[0125] R 11 is an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine;

[0126] R 1 is a fluoroalkylene group having 2 to 6 carbon atoms;

[0127] R 2 For -R 6a -(OR 5a ) n -O-;

[0128] R 5a A linear or branched fluoroalkylene group having 2 to 4 carbon atoms;

[0129] R 6a A linear or branched alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine;

[0130] n is an integer from 5 to 100.

[0131] In a more preferred embodiment, in the fluorinated polyether group-containing compound represented by formula (1a) of the present invention,

[0132] R a is COF;

[0133] R b For COOR 11 ;

[0134] R 11 is an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine;

[0135] R 1 is a fluoroalkylene group having 2 to 6 carbon atoms;

[0136] R 2 -CF2CH2-(OCF2CF2CH2) n -O- or -CF(CF3)-(OCF2CF(CF3)) n -O-;

[0137] n is an integer from 5 to 100.

[0138] In a preferred embodiment, in the fluorinated polyether group-containing compound represented by formula (1b) of the present invention,

[0139] R a COF or COOR 11 ;

[0140] R b For COOR 11 ;

[0141] R 11 An alkyl group having 1 to 6 carbon atoms;

[0142] R 1 is a fluoroalkylene group having 2 to 6 carbon atoms;

[0143] R 2’ For -R 6b -(OR 5b ) n -O-;

[0144] R 5b is CF2CF(CF3) or CF2CF2CH2;

[0145] R 6b is CF(CF3) or CF2CH2;

[0146] n is an integer from 5 to 100.

[0147] In one embodiment, the number average molecular weight of the fluorinated polyether group-containing compound is not particularly limited, and may be, for example, 500 or more, preferably 1,000 or more, for example, 3,000 or more, 5,000 or more, or 10,000 or more. The number average molecular weight of the fluorinated polyether group-containing compound is not particularly limited, and may be, for example, 100,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

[0148] In one embodiment, the dispersity (weight average molecular weight / number average molecular weight) of the fluorinated polyether group-containing compound is not particularly limited, but is preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.2 or less, and particularly preferably 1.1 or less.

[0149] The number average molecular weight and weight average molecular weight can be determined by F-NMR or GPC.

[0150] The present invention provides a composition containing two or more compounds represented by the above formula (1).

[0151] In one embodiment, the compound represented by the above formula (1) is a fluorinated polyether group-containing compound represented by the above formula (1a) or a fluorinated polyether group-containing compound represented by the above formula (1b).

[0152] In one embodiment, the two or more compounds in the composition are a and / or R b For example, R b is -COO-alkyl, and R b It can be -COOH.

[0153] The fluorinated polyether group-containing compound of the present invention can be suitably used as a surface treatment agent, lubricating oil, etc., and an intermediate thereof.

[0154] The present invention provides a method for preparing the fluorinated polyether compound.

[0155] That is, the present invention provides a method for producing a compound represented by formula (A), comprising the step of reacting an acyl fluoride compound represented by the following formula (a) and a cyclic ether compound represented by the following formula (b):

[0156] FOC-R 2 -R 1 -COOR 12 (A)

[0157] [Where:

[0158] R 1 is an alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0159] R 2 For -R 6 -(OR 5 ) n -O-;

[0160] R 5 A linear or branched alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine;

[0161] R 6 A linear or branched alkylene group having 1 to 9 carbon atoms which may be substituted by fluorine;

[0162] R 12 It is an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine.]

[0163] FOC-R 13 -COOR 12 (a)

[0164] [Where:

[0165] R13 is an alkylene group having 1 to 9 carbon atoms which may be substituted with fluorine;

[0166] R 12 It is an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine.]

[0167]

[0168] [Where R 15 It is a linear or branched alkylene group having 2 to 10 carbon atoms which may be substituted with fluorine. ].

[0169] By the method of the present invention, the cyclic ether represented by formula (b) is bonded to the COF side of the acyl fluoride compound represented by formula (a). That is, in the method of the present invention, the reaction is carried out at one end side of the acyl fluoride compound represented by formula (a), and the polymer chain is extended at this end. Therefore, it is possible to obtain a polymer having different functional groups, namely, COF and COOR, at each end of the polymer chain. 12 In addition, in the production method of the present invention, since the reaction is easily controlled, it is easy to adjust the degree of polymerization, molecular weight, dispersion, etc., for example, it is easy to obtain a compound with a desired molecular weight and a compound with a small dispersion.

[0170] The above formula (A) and R a COF and R b For COOR 11 (Among them, R 11 is an alkyl group having 1 to 6 carbon atoms) corresponds to the above formula (1), in the symbols of formula (A), R 1 and R 2 The meaning of is the same as that described in formula (1).

[0171] In the above formula (A), R 12 R of the above formula (1) 11 Correspondingly, it is an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine. 12 The alkyl group having 1 to 6 carbon atoms in the group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. In one embodiment, the alkyl group is substituted with fluorine, preferably a perfluoroalkyl group. In another embodiment, the alkyl group is unsubstituted.

[0172] In the above formula (a), R 12 It is an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine and has the same meaning as defined above.

[0173] In the above formula (a), R 13 is an alkylene group having 1 to 9 carbon atoms which may be substituted with fluorine. 1 The carbon atom of COF from formula (a) and R13 The group formed by the left end of .

[0174] The above R 13 The alkylene group having 1 to 9 carbon atoms in the group is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms, and still more preferably a methylene group.

[0175] In one embodiment, the above R 13 The alkylene group in the above-mentioned group is a fluoroalkylene group, and preferably a perfluoroalkylene group.

[0176] In a preferred embodiment, the above R 13 It is a linear perfluoroalkylene group having 1 to 2 carbon atoms, and -CF2- is more preferred.

[0177] The acyl fluoride compound represented by the above formula (a) functions as a polymerization initiator in this reaction.

[0178] The acyl fluoride compound represented by the above formula (a) is commercially available or can be produced by a method known to those skilled in the art.

[0179] In the above formula (b), R 15 R is an alkylene group having 1 to 10 carbon atoms which may be substituted with fluorine. 15 The alkylene group having 2 to 10 carbon atoms in the group is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an alkylene group having 3 carbon atoms.

[0180] In one embodiment, the above R 15 The alkylene group is a straight chain.

[0181] In another embodiment, the above R 15 The alkylene group is a branched chain.

[0182] In a preferred embodiment, the above R 15 It is CF2CF2CH2, CF2CF2CF2 or CF2CF(CF3), preferably CF2CF2CH2 or CF2CF(CF3), more preferably CF2CF2CH2.

[0183] In a preferred embodiment, the cyclic ether compound represented by formula (b) is tetrafluorooxetane or hexafluoropropylene oxide, and more preferably tetrafluorooxetane.

[0184] The cyclic ether compound represented by the above formula (b) is cleaved at the C—O region and then reacts with the acyl fluoride compound represented by the above formula (a), and as a result, a fluorinated polyether group-containing compound represented by the formula (A) can be obtained. 2 part.

[0185] The cyclic ether compound represented by the above formula (b) functions as a monomer in this reaction.

[0186] The cyclic ether compound represented by the above formula (b) is commercially available or can be produced by a method known to those skilled in the art.

[0187] The ratio of the acyl fluoride compound represented by the formula (a) to the cyclic ether compound represented by the formula (b) can be appropriately set according to the molecular weight of the target compound, and can be, for example, 0.01:100 to 10:100, preferably 0.1:100 to 5:100, for example, 1:100 to 5:100 in terms of molar ratio.

[0188] The reaction of the acyl fluoride compound represented by the above formula (a) and the cyclic ether compound represented by the formula (b) is usually carried out in a solvent. Examples of the solvent include cyclic ethers such as tetrahydrofuran (THF), tetrahydropyran, and dioxane, non-cyclic ethers such as diethyl ether, diisopropyl ether, dibutyl ether, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, HMPA (hexamethylphosphoramide), DMPU (dimethylpropylene), TMEDA (tetramethylethylenediamine), toluene, xylene, trifluorotoluene, and aromatic compounds, N,N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone and other amides, hexafluoropropylene, trichlorotrifluoroethane, 1,1,1,3,3-pentafluorobutane, hexafluoro-m-xylene, perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamines (Fluorinert (trade name) etc.), perfluoroalkylethers, perfluorobutyltetrahydrofuran, polyfluoroaliphatic hydrocarbons (ASAHIKLIN AC6000 (trade name)), hydrochlorofluorocarbons (ASAHIKLIN AK-225 (trade name) etc.), hydrofluoroethers (Novec (trade name), HFE-7100 (trade name) etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorinated alcohols, perfluoroalkyl bromides, perfluoroalkyl iodides, perfluoropolyethers (Krytox (trade name), DEMNUM (trade name), Fomblin (trade name) etc.), 1,3-bistrifluoromethylbenzene, 2-(perfluoroalkyl)ethyl methacrylate, 2-(perfluoroalkyl)ethyl acrylate, perfluoroalkylethylene, Freon 134a and hexafluoropropylene oligomers and the like, or mixtures thereof.

[0189] The above reaction is preferably carried out in the presence of a catalyst. The catalyst is not particularly limited, and examples thereof include NaH, CaH2, LiH, LiAlH4, NaBH4, Cs t OBu, K t OBu、Na tOBu, Li t OBu, CsOH, KOH, NaOH, LiOH, Cs2CO3, K2CO3, Na2CO3, Li2CO3, CsHCO3, KHCO3, NaHCO3, LiHCO3, KF, CsF, tetra-n-butylammonium fluoride (TBAF) and other inorganic bases, triethylamine, pyridine, N,N-dimethyl-4-aminopyridine (DMAP), diazabicycloundecene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO) and other organic bases, n BuLi, t BuLi, lithium diisopropylamide (LDA) and other organic lithium reagents.

[0190] The reaction temperature of the above reaction can be generally -80°C to 60°C, preferably -60°C to 40°C, and more preferably -50 to 30°C.

[0191] The reaction time of the above reaction can generally be 1 hour to 5 days, for example 1 day to 3 days.

[0192] The terminal functional group of the fluorinated polyether compound represented by the above formula (A) can be converted into a desired functional group by appropriate treatment. 11 The reaction can convert the terminal functional group into COOR 11 By reducing the terminal functional group, it can be converted into CH2OH, CHO, etc., and the compound represented by the above formula (1) can be obtained.

[0193] The fluorinated polyether group-containing compound represented by formula (A) may be fluorinated. For example, the hydrogen atoms bonded to the carbon atoms of the fluorinated polyether group-containing compound may be fluorinated to convert the compound into a perfluorinated polyether group-containing compound.

[0194] Example

[0195] Example 1: (Synthesis of Compound A1)

[0196] 27.3 g of cesium fluoride, 662 mL of diethylene glycol dimethyl ether, and 198.2 g of methyl 2,2,3-trifluoro-3-oxopropionate were added to the reaction container after nitrogen substitution, and stirred at 5°C for 10 minutes under an ice bath. Then, 892.2 g of 2,2,3,3-tetrafluorooxetane was added dropwise to the reaction container using a dropping funnel at 5°C for 20 minutes under an ice bath, and stirred for 2 hours. After that, the ice bath was removed and stirred for 48 hours. After the obtained reaction solution was pressure filtered using a 5 μm PTFE filter, diethylene glycol dimethyl ether was distilled off to obtain compound A1.

[0197] (Number average molecular weight: 912 (NMR), initiation rate from acyl fluoride: 100%)

[0198] Compound A1 19 F-NMR assignment

[0199]

[0200] Chemical shifts were based on hexafluoro-m-xylene (-80.0 ppm).

[0201] a: 3.5ppm, b: -130.3ppm, c: -106.9~-106.2ppm, d: -140.4~-140.7ppm, e: -106.0ppm, f: -137.9ppm

[0202] Example 2: (Synthesis of Compound A2)

[0203] 15.4 g of cesium fluoride, 290 mL of diethylene glycol dimethyl ether, and 107.0 g of methyl 2,2,3-trifluoro-3-oxopropionate were added to the reaction container after nitrogen substitution, and stirred at 5°C for 10 minutes under an ice bath. Then, 526.0 g of 2,2,3,3-tetrafluorooxetane was added dropwise to the reaction container using a dropping funnel at 5°C for 20 minutes under an ice bath, and stirred for 2 hours. After that, the ice bath was removed and stirred for 50 hours. 60 mL of methanol was added dropwise to the obtained reaction solution over 20 minutes, and stirred for 24 hours. After distilling off the volatile components from the reaction solution under reduced pressure, 80 g of hexafluoro-m-xylene and 40 g of water were added for liquid separation and washing, and 5 g of magnesium sulfate was added to the organic layer obtained by extraction to dry it. Volatile components were distilled off from the obtained treatment solution to obtain compound A2.

[0204] (Number average molecular weight: 865 (NMR), initiation rate from acyl fluoride: 100%)

[0205] Compound A2 19 F-NMR assignment

[0206]

[0207] Chemical shifts were based on hexafluoro-m-xylene (-80.0 ppm).

[0208] b: -131.0ppm, c: -106.4~-106.8ppm, d: -140.7ppm, e: -106.0ppm, f: -138.0ppm

[0209] Example 3: (Synthesis of Compound B1)

[0210] 4.23 g of cesium fluoride, 101 g of tetraethylene glycol dimethyl ether, and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropionate were added to the reaction container after nitrogen substitution, and stirred at 0°C for 2 hours. Then, 200 g of hexafluoropropylene oxide was added at 0°C for 60 minutes in a manner of adding 10 g each time and stirred. After the obtained reaction solution was pressure filtered using a 5 μm PTFE filter, tetraethylene glycol dimethyl ether was distilled off to obtain compound B1 (COF and methyl ester).

[0211] (Number average molecular weight: 2000 (NMR), initiation rate from acyl fluoride: 40%)

[0212] Compound B1 19 F-NMR assignment

[0213]

[0214] Chemical shifts were based on hexafluoro-m-xylene (-65.0 ppm).

[0215] a: -122.4ppm, c: -145.9~-146.3ppm, d, e: -79.5~-83.3ppm, f: -131.0ppm, g: -82.2~-82.6ppm, h: 25.0ppm

[0216] Example 4: (Synthesis of Compound B2)

[0217] 10 mL of methanol was added dropwise to the obtained B1 reaction solution at 0°C for 5 minutes and stirred for 2 hours. 130 g of hexafluoro-m-xylene and 200 g of water were added for liquid separation and washing, and 5 g of magnesium sulfate was added to the organic layer obtained by extraction and dried. Volatile components were distilled off from the obtained treatment solution to obtain compound B2 (methyl ester at both ends).

[0218] (Number average molecular weight: 2000 (NMR), initiation rate from acyl fluoride: 40%)

[0219] Compound B2 19 F-NMR assignment

[0220]

[0221] Chemical shifts were based on hexafluoro-m-xylene (-65.0 ppm).

[0222] a: -122.5ppm, c: -145.4~-146.2ppm, d, e: -79.6~-82.5ppm, f: -132.5ppm, g: -83.7~-84.1ppm.

[0223] Example 5: (Synthesis of Compound B3)

[0224] To the nitrogen-substituted reaction vessel, 3.85 g of cesium fluoride, 100 g of tetraethylene glycol dimethyl ether, and 3.98 g of methyl 2,2,3-trifluoro-3-oxopropionate were added, and stirred at 0°C for 2 hours. Next, 200 g of hexafluoropropylene oxide was added at -30°C for 60 minutes, with 5 g added each time, and stirred. 10 mL of methanol was added dropwise to the obtained reaction solution at 0°C for 5 minutes, and stirred for 2 hours. 130 g of hexafluoro-m-xylene and 200 g of water were added for liquid separation and washing, and 5 g of magnesium sulfate was added to the organic layer obtained by extraction to dry it. Volatile components were distilled off from the obtained treatment solution to obtain compound B3 (methyl ester at both ends).

[0225] (Number average molecular weight: 3000 (NMR), initiation rate from acyl fluoride: 70%)

[0226] Example 6: (Synthesis of Compound B4)

[0227] 1.94 g of potassium fluoride, 13 g of tetraethylene glycol dimethyl ether, 130 g of hexafluoro-m-xylene, and 5.20 g of methyl 2,2,3-trifluoro-3-oxopropionate were added to the nitrogen-substituted reaction vessel, and stirred at 0°C for 2 hours. Next, 140 g of hexafluoropropylene oxide was added at 0°C for 60 minutes in a manner of adding 10 g each time and stirred. The obtained reaction solution was pressure filtered using a 5 μm PTFE filter, and tetraethylene glycol dimethyl ether was distilled off to obtain compound B4 (COF and methyl ester).

[0228] (Number average molecular weight: 2900 (NMR), initiation rate from acyl fluoride: 60%, Mw / Mn=1.07 (GPC))

[0229] Example 7: (Synthesis of Compound B5)

[0230] 10 mL of methanol was added dropwise to the obtained B4 reaction solution at 0°C over 5 minutes and stirred for 2 hours. 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the organic layer obtained by extraction and dried. Volatile components were distilled off from the obtained treatment solution to obtain compound B5 (methyl ester at both ends).

[0231] (Number average molecular weight: 2900 (NMR), initiation rate from acyl fluoride: 60%)

[0232] Example 8: (Synthesis of Compound B6)

[0233] To the nitrogen-substituted reaction vessel, 1.87 g of potassium fluoride, 13 g of tetraethylene glycol dimethyl ether, 130 g of hexafluoro-m-xylene, and 5.15 g of methyl 2,2,3-trifluoro-3-oxopropionate were added, and stirred at 0°C for 2 hours. Next, 140 g of hexafluoropropylene oxide was added at -30°C for 60 minutes, with 5 g added each time, and stirred. 10 mL of methanol was added dropwise to the obtained reaction solution at 0°C for 5 minutes, and stirred for 2 hours. 200 g of water was added to the obtained reaction solution for liquid separation and washing, and 5 g of magnesium sulfate was added to the organic layer obtained by extraction to dry it. The volatile components were distilled off from the obtained treatment solution to obtain compound B6 (methyl ester at both ends).

[0234] (Number average molecular weight: 4000 (NMR), initiation rate from acyl fluoride: 86%)

[0235] Example 9: (Synthesis of Compound B7)

[0236] To the nitrogen-substituted reaction vessel, 4.23 g of cesium fluoride, 11 g of tetraethylene glycol dimethyl ether, 120 g of hexafluoro-m-xylene, and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropionate were added, and stirred at 0°C for 2 hours. Next, 200 g of hexafluoropropylene oxide was added at 0°C for 60 minutes, adding 10 g each time, and stirred. 10 mL of methanol was added dropwise to the obtained reaction solution at 0°C for 5 minutes, and stirred for 2 hours. 200 g of water was added to the obtained reaction solution for liquid separation and washing, and 5 g of magnesium sulfate was added to the organic layer obtained by extraction to dry it. The volatile components were distilled off from the obtained treatment solution to obtain compound B7 (methyl ester at both ends).

[0237] (Number average molecular weight: 3500 (NMR), initiation rate from acyl fluoride: 43%)

[0238] Example 10: (Synthesis of Compound B8)

[0239] To the nitrogen-substituted reaction vessel, 4.23 g of cesium fluoride, 11 g of tetraethylene glycol dimethyl ether, 120 g of Novec7200 (manufactured by 3M), and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropionate were added, and stirred at 0°C for 2 hours. Next, 200 g of hexafluoropropylene oxide was added at 0°C for 60 minutes, with 10 g added each time, and stirred. 10 mL of methanol was added dropwise to the obtained reaction solution at 0°C for 5 minutes, and stirred for 2 hours. 200 g of water was added to the obtained reaction solution for liquid separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer to dry it. The volatile components were distilled off from the obtained treatment solution to obtain compound B8 (methyl ester at both ends).

[0240] (Number average molecular weight: 3400 (NMR), initiation rate from acyl fluoride: 45%)

[0241] Example 11: (Synthesis of Compound B9)

[0242] To the nitrogen-substituted reaction vessel, 4.23 g of cesium fluoride, 11 g of tetraethylene glycol dimethyl ether, 135 g of Novec7100 (manufactured by 3M), and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropionate were added, and stirred at 0°C for 2 hours. Next, 200 g of hexafluoropropylene oxide was added at 0°C for 60 minutes, with 10 g added each time, and stirred. 10 mL of methanol was added dropwise to the obtained reaction solution at 0°C for 5 minutes, and stirred for 2 hours. 200 g of water was added to the obtained reaction solution for liquid separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer to dry it. The volatile components were distilled off from the obtained treatment solution to obtain compound B9 (methyl ester at both ends).

[0243] (Number average molecular weight: 3500 (NMR), initiation rate from acyl fluoride: 45%)

[0244] Example 12: (Synthesis of Compound B10)

[0245] To the nitrogen-substituted reaction vessel, 4.23 g of cesium fluoride, 11 g of tetraethylene glycol dimethyl ether, 115 g of 1,1,1,3,3-pentafluorobutane, and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropionate were added, and stirred at 0°C for 2 hours. Next, 200 g of hexafluoropropylene oxide was added at 0°C for 60 minutes, with 10 g added each time, and stirred. 10 mL of methanol was added dropwise to the obtained reaction solution at 0°C for 5 minutes, and stirred for 2 hours. 200 g of water was added to the obtained reaction solution for liquid separation and washing, and 5 g of magnesium sulfate was added to the organic layer obtained by extraction to dry it. Volatile components were distilled off from the obtained treatment solution to obtain compound B10 (methyl ester at both ends).

[0246] (Number average molecular weight: 2500 (NMR), initiation rate from acyl fluoride: 40%)

[0247] Example 13: (Synthesis of Compound B11)

[0248] To the nitrogen-substituted reaction vessel, add 2.9 g of potassium fluoride, 101 g of tetraethylene glycol dimethyl ether, and 9 g of methyl 2,2,3-trifluoro-3-oxopropionate, and stir at 0°C for 2 hours. Next, add 200 g of hexafluoropropylene oxide in a total of 10 g additions at 0°C for 60 minutes and stir. To the obtained reaction solution, add 10 mL of methanol dropwise at 0°C for 5 minutes and stir for 2 hours. Add 200 g of water to the obtained reaction solution for liquid separation and washing, and add 5 g of magnesium sulfate to the organic layer obtained by extraction to dry it. The volatile components are distilled off from the obtained treatment solution to obtain compound B11 (methyl ester at both ends).

[0249] (Number average molecular weight: 900 (NMR), initiation rate from acyl fluoride: 74%)

[0250] Example 14: (Synthesis of Compound B12)

[0251] To the nitrogen-substituted reaction vessel, add 2.9 g of potassium fluoride, 20 g of tetraethylene glycol dimethyl ether, 120 g of hexafluoro-m-xylene, and 9 g of methyl 2,2,3-trifluoro-3-oxopropionate, and stir at 0°C for 2 hours. Next, add a total of 200 g of hexafluoropropylene oxide at 0°C for 60 minutes, adding 10 g each time, and stir. To the obtained reaction solution, add 10 mL of methanol dropwise at 0°C for 5 minutes and stir for 2 hours. Add 200 g of water to the obtained reaction solution for liquid separation and washing, and add 5 g of magnesium sulfate to the extracted organic layer to dry it. The volatile components are distilled off from the obtained treatment solution to obtain compound B12 (methyl ester at both ends).

[0252] (Number average molecular weight: 2100 (NMR), initiation rate from acyl fluoride: 76%)

[0253] Example 15: (Synthesis of Compound B13)

[0254] To the nitrogen-substituted reaction vessel, add 2.9 g of potassium fluoride, 20 g of tetraethylene glycol dimethyl ether, 120 g of Novec7200 (manufactured by 3M), and 9 g of methyl 2,2,3-trifluoro-3-oxopropionate, and stir at 0°C for 2 hours. Next, add a total of 200 g of hexafluoropropylene oxide at 0°C in a manner of adding 10 g each time for 60 minutes and stir. To the obtained reaction solution, 10 mL of methanol was added dropwise at 0°C for 5 minutes and stirred for 2 hours. 200 g of water was added to the obtained reaction solution for liquid separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer to dry it. The volatile components were distilled off from the obtained treatment solution to obtain compound B13 (methyl ester at both ends).

[0255] (Number average molecular weight: 1900 (NMR), initiation rate from acyl fluoride: 75%)

[0256] Industrial Applicability

[0257] According to the production method of the present invention, a fluorinated polyether group-containing compound having functional groups at both ends can be easily produced.

Claims

1. A fluorinated polyether compound, characterized in that: It is represented by the following formula (1a): R a -R 2 -R 1 -R b (1a) In formula (1a): R a COF, COOR 11 , CH2OH or CHO; R b COF, COOR 11 , CH2OH or CHO; Among them, R a and R b are different groups from each other; R 11 Each of R is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine; 1 is a perfluoroalkylene group having 2 carbon atoms; R 2 is -R 6a -(OR 5a ) n -O-; R 5a is CF2CF2CH2; R 6a is CF2CF2; n is an integer from 10 to 60, The weight average molecular weight / number average molecular weight of the fluorinated polyether group-containing compound is 1.1 or less.

2. A fluorinated polyether compound, characterized in that: It is represented by the following formula (1b): R a -R 2’ -R 1 -R b (1b) In formula (1b): R a COF, COOR 11 , CH2OH or CHO; R b COF, COOR 11 , CH2OH or CHO; R 11 Each of R is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine; 1 is a perfluoroalkylene group having 2 carbon atoms; R 2’ is -R 6b -(OR 5b ) n -O-; R 5b is CF2CF2CH2; R 6b is CF2CH2; n is an integer from 10 to 60, The weight average molecular weight / number average molecular weight of the fluorinated polyether group-containing compound is 1.1 or less.

3. The fluorinated polyether compound according to claim 1 or 2, characterized in that: R a COF, R b For COOR 11 , R 11 It is an alkyl group having 1 to 6 carbon atoms.

4. A method for producing a compound represented by formula (A), characterized in that: The method comprises reacting an acyl fluoride compound represented by the following formula (a) with a cyclic ether compound represented by the following formula (b), FOC-R 2 -R 1 -COOR 12 (A) In formula (A): R 1 is a perfluoroalkylene group having 2 carbon atoms; R 2 is -R 6 -(OR 5 ) n -O-; R 5 is CF2CF2CH2; R 6 is CF2CF2; R 12 is an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine; n is an integer from 10 to 60, FOC-R 13 -COOR 12 (to) In formula (a): R 13 is perfluoromethylene; R 12 is an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine, In formula (b), R 15 is CF2CF2CH2, The weight average molecular weight / number average molecular weight of the compound represented by the formula (A) is 1.1 or less.

5. The manufacturing method according to claim 4, characterized in that: The method comprises reacting an acyl fluoride compound represented by the following formula (a) with tetrafluorooxetane to obtain a compound represented by the formula (A), The reaction temperature of the reaction is -50 to 30°C. The reaction time of the reaction is 1 to 3 days; FOC-R 2 -R 1 -COOR 12 (A) In the compound represented by formula (A), R 12 Methyl, R 1 is a perfluoroalkylene group having 2 carbon atoms, R 2 For -R 6a -(OR 5a ) n -O-, R 5a is CF2CF2CH2, R 6a is CF2CF2, n is an integer from 10 to 60; The compound represented by formula (a) is: FOC-R 13 -COOR 12 (a) In formula (a), R 13 is perfluoromethylene, R 12 It is methyl.

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