Polymers containing fluoropolyether groups

Abstract

A fluoropolyether group-containing polymer represented by formula (1), after a reactive functional group has been introduced, can be a polymer containing a polysiloxane structure (in particular, a branched or cyclic polysiloxane structure) in the linking group between the fluoropolyether group and the reactive functional group. This water-and oil-repellent treatment agent is capable of imparting excellent characteristics to the surface of a cured product. # imgabs0 # (In the formula, Rf is a monovalent or divalent fluoropolyether group-containing polymer residue, X is independently a single bond or a divalent heteroatom, Y is independently a C1-20 divalent hydrocarbon group which may contain one or more elements selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom, and X is a hydrogen atom or a hydrogen atom. Z independently represents a monovalent organopolysiloxane residue having at least one silicon-hydrogen bond (SiH group) at the terminal, and may form a cyclic structure. And alpha represents 1 or 2).

Description

Technical Field

[0001] The present invention relates to a novel fluoropolyether group-containing polymer that can be converted into a fluoropolyether group-containing reactive polymer having a plurality of reactive functional groups in one molecule (hereinafter referred to as a fluoropolyether group-containing multifunctional reactive polymer). Background Art

[0002] Generally, the compound containing fluoropolyether group has water- and oil-repellent, chemical resistance, lubricity, demoulding property, antifouling property etc. because its surface free energy is very small.Utilize its property, be widely used in the water- and oil-repellent antifouling agent of paper, fiber etc., the lubricant of magnetic recording medium, oil-proof agent, demoulding agent, cosmetic material, protective film etc. of precision equipment in industry.But its property means non-adhesiveness, non-adhesiveness for other base materials simultaneously, even can be coated on the base material surface, also be difficult to make its coating close.

[0003] On the other hand, as a substance that combines the surface of a substrate such as glass or cloth with an organic compound, a silane coupling agent is well known and has been widely used as a coating agent for various substrate surfaces. A silane coupling agent has an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group causes a self-condensation reaction due to moisture in the air, etc., to form a coating. The coating is chemically and physically combined with the surface of glass, metal, etc. through the alkoxysilyl group, thereby forming a durable and firm coating.

[0004] In patent document 1 (Japanese Patent Publication No. 2016-204656), as a compound having a fluoropolyether group and an alkoxysilyl group, a polymer-modified silane containing a fluoropolyether group having a plurality of alkoxysilyl groups in one molecule is described. Since the polymer-modified silane containing a fluoropolyether group has a large number of reactive functional groups, the glass surface is treated with a cured product of a surface treatment agent containing the polymer-modified silane containing a fluoropolyether group, thereby being able to impart excellent wear resistance and water and oil repellency to the glass surface.

[0005] In addition, as a means of protecting the surface of a resin molding, a hard coating process is generally used. It forms a hard cured resin layer (hard coating) on ​​the surface of the molding, making it difficult to scratch. In recent years, with the expansion of the utilization field of resin moldings and the trend of high added value, the expectation for the high functionality of the cured resin layer (hard coating) has risen. As one of them, it is necessary to give antifouling properties to the hard coating. It is by giving properties such as water repellency and oil repellency to the surface of the hard coating, so that it is not easy to get dirty or even if it is dirty, it can be easily removed.

[0006] Patent Document 2 (Japanese Patent Application Laid-Open No. 2010-53114) discloses that a hard coat layer imparted with high antifouling properties can be produced by adding a fluoropolyether group-containing polymer-modified acrylate having a plurality of acryloyl groups in one molecule to an acrylic curable resin composition and curing the composition.

[0007] In recent years, there has been an increasing demand for the high functionality of fluoropolyether group-containing polymers such as fluoropolyether group-containing polymer-modified silanes and fluoropolyether group-containing polymer-modified acrylates for the purpose of surface protection of glass, resin molded bodies, etc., and there is a need for fluoropolyether group-containing polymers that can be easily converted into multifunctional reactive polymers containing fluoropolyether groups having multiple reactive functional groups in one molecule.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2016-204656

[0011] Patent Document 2: Japanese Patent Application Publication No. 2010-53114 Summary of the invention

[0012] Problems to be solved by the invention

[0013] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a fluoropolyether group-containing polymer that can be easily converted into a fluoropolyether group-containing multifunctional reactive polymer that can provide a water- and oil-repellent treatment agent that can impart excellent properties to the surface of a cured product.

[0014] Means for solving problems

[0015] The inventors of the present invention have conducted in-depth research to achieve the above-mentioned purpose, and found that among the above-mentioned multifunctional reactive polymers containing fluoropolyether groups, polymers containing a polysiloxane structure (especially a branched or cyclic polysiloxane structure) in the connecting group between the fluoropolyether group and the reactive functional group can become water- and oil-repellent treatment agents capable of imparting excellent properties to the surface of the cured product.

[0016] Therefore, further studies were conducted and as a result, it was found that the novel fluoropolyether group-containing polymer represented by the following general formula (1) can become a polymer containing a polysiloxane structure (especially a branched or cyclic polysiloxane structure) in the connecting group between the fluoropolyether group and the reactive functional group after the reactive functional group is introduced, thereby completing the present invention.

[0017] Therefore, the present invention provides the following fluoropolyether group-containing polymer.

[0018] [1] A fluoropolyether group-containing polymer represented by the following general formula (1).

[0019] [Chemistry 1]

[0020]

[0021] (In the formula, Rf is a monovalent or divalent polymer residue containing a fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms, and Z is independently a monovalent organopolysiloxane residue having at least one silicon-hydrogen bond (SiH group) at the terminal, which may form a cyclic structure. α is 1 or 2.)

[0022] [2] The fluoropolyether group-containing polymer according to [1], wherein α in the formula (1) is 1, and Rf is a monovalent fluoropolyether group represented by the following general formula (2).

[0023] [Chemistry 2]

[0024]

[0025] (In the formula, A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms. d is independently an integer of 1 to 3 in each unit, and p, q, r, s, t, u, and v are each an integer of 0 to 200, and the total of p, q, r, s, t, u, and v is 3 to 200. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly combined.)

[0026] [3] The fluoropolyether group-containing polymer according to [1], wherein α in the formula (1) is 2, and Rf is a divalent fluoropolyether group represented by the following general formula (3).

[0027] [Chemistry 3]

[0028]

[0029] (W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms, d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, and the total of p, q, r, s, t, u, and v is 3 to 200. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

[0030] [4] A fluoropolyether group-containing polymer according to any one of [1] to [3], wherein, in the formula (1), when α=1, there are two Xs at one end of the molecular chain, and when α=2, there are two Xs at each end of the molecular chain (four Xs in the molecule), and one X at each end is an oxygen atom and the other X is a single bond.

[0031] [5] The fluoropolyether group-containing polymer according to any one of [1] to [4], wherein in the formula (1), Y is independently an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms.

[0032] [6] A fluoropolyether group-containing polymer according to any one of [1] to [5], wherein in the formula (1), Z is a linear, branched or cyclic monovalent organopolysiloxane residue having 2 to 10 silicon atoms and 1 to 9 silicon-hydrogen bonds (SiH groups) at the terminal.

[0033] [7] The fluoropolyether group-containing polymer according to any one of [1] to [6], wherein in the formula (1), Z is represented by any one of the following formulae.

[0034] [Chemistry 4]

[0035]

[0036] (In the formula, * is a bonding end to Y in formula (1), R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, R' is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one R' is a hydrogen atom. a is an integer of 0 to 6, b is an integer of 2 to 9, and c is 1. The repeating units shown in the brackets with a and c may be randomly bonded.)

[0037] [8] The fluoropolyether group-containing polymer according to any one of [1] to [7], wherein the polymer represented by formula (1) is selected from polymers represented by the following general formulas (4) and (5).

[0038] [Chemistry 5]

[0039]

[0040] (In the formula, d is independently an integer of 1 to 3 in each unit, p", q", r", and s" are each an integer of 0 to 100, and the total of p", q", r", and s" in each formula is 3 to 100. In addition, each repeating unit shown in the parentheses with p", q", r", and s" may be randomly combined. m and n are independently an integer of 2 to 10 in each unit. These units may be linear or branched. Z' is independently represented by any of the following formulae.)

[0041] [Chemistry 6]

[0042]

[0043] (In the formula, * is a bonding end bonded to the terminal carbon atom in formula (4) and (5).)

[0044] Effects of the Invention

[0045] The novel fluoropolyether group-containing polymer of the present invention is suitable as a precursor of a fluoropolyether group-containing multifunctional reactive polymer, and the fluoropolyether group-containing multifunctional reactive polymer obtained by converting the polymer can be a water- and oil-repellent treatment agent capable of imparting excellent properties to the surface of a cured product. DETAILED DESCRIPTION

[0046] In this specification, "about (a numerical value)" is a numerical value (approximate number) expressed by rounding, and when the last digit of the numerical value represented by it is not "0", it also includes a numerical range until it becomes a numerical value represented by rounding the last digit. For example, "about 3 equivalents" means more than 2.5 equivalents and less than 3.4 equivalents, and "about 0.02 equivalents" means more than 0.015 equivalents and less than 0.024 equivalents. In addition, when the last digit of the numerical value represented by it is "0", it includes a numerical range until it becomes a numerical value represented by rounding the last digit. For example, "about 80°C" means more than 75°C and less than 84°C.

[0047] The fluoropolyether group-containing polymer of the present invention is represented by the following general formula (1).

[0048] [Chemistry 7]

[0049]

[0050] (In the formula, Rf is a monovalent or divalent polymer residue containing a fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms, and Z is independently a monovalent organopolysiloxane residue having at least one silicon-hydrogen bond (SiH group) at the terminal, which may form a cyclic structure. α is 1 or 2.)

[0051] In the above formula (1), Rf is a monovalent or divalent polymer residue containing a fluoropolyether group. When α is 1 (i.e., when Rf is a monovalent polymer residue containing a fluoropolyether group), it is preferably a monovalent fluoropolyether group represented by the following general formula (2). When α is 2 (i.e., when Rf is a divalent polymer residue containing a fluoropolyether group), it is preferably a divalent fluoropolyether group represented by the following general formula (3).

[0052] [Chemistry 8]

[0053]

[0054] [Chemistry 9]

[0055]

[0056] (In the above formulae, A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms. d is independently an integer of 1 to 3 for each unit, and p, q, r, s, t, u, and v are each an integer of 0 to 200, and the total of p, q, r, s, t, u, and v is 3 to 200. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

[0057] In the above formula (2), A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, in particular, an alkyl group. A is preferably a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, and more preferably a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0058] In the above formulae (2) and (3), W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms, and examples thereof include CF2 units, C2F4 units, C3F6 units, C4F8 units, C5F 10 Unit, C6F 12 A group in which one or two fluorine atoms in each perfluoroalkylene group such as a unit are replaced by hydrogen atoms, and the like.

[0059] In the above formulae (2) and (3), d is independently an integer of 1 to 3, and is preferably 1 or 2, for each unit.

[0060] In addition, p, q, r, s, t, u, and v are each an integer of 0 to 200, preferably, p is an integer of 0 to 100, q is an integer of 0 to 100, r is an integer of 0 to 100, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and v is an integer of 0 to 100, and the total of p, q, r, s, t, u, and v is 3 to 200, preferably 10 to 100. If the total of p, q, r, s, t, u, and v is less than the upper limit, the performance of a fluoropolyether group-containing multifunctional reactive polymer obtained by introducing a reactive functional group into the fluoropolyether group-containing polymer is obtained, and if it is greater than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferred.

[0061] When r, s, t, u, and v are all 0, p and q are each an integer of 5 to 100, and the total of p and q is preferably 10 to 105, and particularly preferably 15 to 60.

[0062] In the above formulae (2) and (3), each unit may be linear or branched. In addition, each repeating unit represented by a parenthesis with p, q, r, s, t, u, or v may be randomly bonded.

[0063] Specifically, as Rf, the following groups can be exemplified.

[0064] [Chemistry 10]

[0065] CF3O(CF2O) p′ CF2-

[0066] CF3O(CF2O) p′ (CF2CF2O) q′ CF2-

[0067] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2-

[0068] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O) s′ CF2-

[0069] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ CF2-

[0070] CF3O(CF2O)p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ (CF2CF2CF2CF2CF2O) t′ CF2-

[0071] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ (CF2CF2CF2CF2CF2O) t′ (CF2CF2CF2CF2CF2CF2O) u′ CF2-

[0072] CF3O(CF2CF2O) q′ CF2-

[0073] [Chemical Formula 11]

[0074] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2CF2-

[0075]

[0076] CF3CF2CF2O(CF2CF2CF2O) r′ CF2CF2-

[0077]

[0078] [Chemical Formula 12]

[0079] -CF2O(CF2O) p′ CF2-

[0080] -CF2O(CF2O) p′ (CF2CF2O) q′ CF2-

[0081] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2-

[0082] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O)s′ CF2-

[0083] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ CF2-

[0084] -CF2CF2O(CF2CF2CF2O) r′ CF2CF2-

[0085]

[0086] (In the formula, p', q', r', s', t', u', q1', r1', and r2' are each an integer greater than 1, and the total of p', q', r', s', t', u', q1', r1', and r2' in each formula is 3 to 200. In addition, each repeating unit shown in the parentheses with p', q', r', s', t', and u' may be randomly combined.)

[0087] As Rf, the following groups are preferred.

[0088] [Chemistry 13]

[0089]

[0090] CF3CF2CF2O-(CF2CF2CF2O) r′ —CF2CF2-

[0091]

[0092] CF3O-(CF2O) p′ -(CF2CF2O) q′ -(CF2CF2CF2O) r′ -CF2CF2-

[0093]

[0094] (In the formula, p', q', r' and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0095] As for the molecular weight of Rf, the number average molecular weight of the corresponding structural part can be included in the range of 400 to 40,000, preferably 2,000 to 25,000, and there is no particular limitation on its molecular weight distribution (or degree of polymerization distribution). It should be noted that in the present invention, the molecular weight (or degree of polymerization or number of repeating units) can be obtained as the polystyrene-converted number average molecular weight (or number average degree of polymerization) obtained by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as an elution solvent, preferably based on 1 H-NMR analysis and 19 The number average molecular weight (or number average degree of polymerization) (the same below) is calculated from the ratio of the characteristic peak intensities of the terminal structure and the main chain structure of the fluoropolyether group-containing polymer analyzed by F-NMR.

[0096] In the above formula (1), X is independently a single bond or a divalent heteroatom. Examples of the divalent heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom. Preferably, among the two Xs present at each end of the molecular chain (i.e., one end of the molecular chain when α=1, and both ends of the molecular chain when α=2), it is desirable that one X is an oxygen atom and the other X is a single bond.

[0097] In the above formula (1), Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms. Specific examples of Y include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, and arylene groups having 6 to 20 carbon atoms, such as phenylene, and combinations of two or more of these groups (for example, alkylene groups having 2 to 10 carbon atoms (alkylene-arylene groups having 8 to 18 carbon atoms) containing arylene groups having 6 to 8 carbon atoms), and amide bonds selected from these groups (for example, The group is formed by connecting or intervening one or more of the following bonds: an unsubstituted amide bond, an N-methyl substituted amide bond, an N-phenyl substituted amide bond), an ether bond, a carbonyl bond, an ester bond, a diorganosilylene group (for example, a dialkylsilylene group such as a dimethylsilylene group), a silylene arylene bond (for example, a silylene phenylene bond) and a silylene alkylene bond (for example, a silylene ethylene bond), preferably an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, and more preferably a straight-chain alkylene group having 3 to 6 carbon atoms.

[0098] Specific examples of Y include the following groups.

[0099] [Chemistry 14]

[0100] *-CH2CH2- ＊＊

[0101] *-CH2CH2CH2-**

[0102]

[0103] *-CH2CH2CH2CH2-**

[0104] *-CH2CH2CH2CH2CH2-**

[0105] *-CH2CH2CH2CH2CH2CH2CH2-**

[0106] *-CH2CH2CH2CH2CH2CH2CH2-**

[0107] *-CH2CH2CH2CH2CH2CH2CH2CH2-**

[0108]

[0109] [Chemistry 15]

[0110]

[0111] [Chemistry 16]

[0112]

[0113] (In the formula, * is the end bonded to X in formula (1), and ** is the end bonded to Z in formula (1).)

[0114] As Y, the following groups are more preferable.

[0115] [Chemistry 17]

[0116] *-CH2CH2-**

[0117] *-CH2CH2CH2-**

[0118]

[0119] *-CH2CH2CH2CH2-**

[0120] *-CH2CH2CH2CH2CH2-**

[0121] *-CH2CH2CH2CH2CH2CH2CH2-** (wherein * is the end bonded to X in formula (1), and ** is the end bonded to Z in formula (1).)

[0122] In the formula (1), Z is independently a monovalent organopolysiloxane residue having at least one silicon-hydrogen bond (SiH group) at the terminal, and may form a cyclic structure. Z is preferably a monovalent organopolysiloxane residue having 1 to 9, particularly 2 to 7 silicon-hydrogen bonds (SiH groups) at the terminal, and having 2 to 10 silicon atoms in a linear chain or 3 to 10 silicon atoms in a branched or cyclic structure.

[0123] Specific examples of Z include the following groups.

[0124] [Chemistry 18]

[0125]

[0126] (In the formula, * is a bonding end bonded to Y in formula (1), R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, R' is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one R' is a hydrogen atom. a is an integer of 0 to 6, b is an integer of 2 to 9, and c is 1. The repeating units shown in the brackets with a and c may be randomly bonded.)

[0127] Here, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, or an aryl group having 6 to 10 carbon atoms such as phenyl, and more preferably a methyl group. R may be the same or different.

[0128] In addition, R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, or an aryl group having 6 to 10 carbon atoms such as phenyl, and more preferably a hydrogen atom. R' may be the same or different, at least one R' is a hydrogen atom, preferably two or more R' are hydrogen atoms, and more preferably all R' are hydrogen atoms.

[0129] As Z, the following groups are preferred.

[0130] [Chemistry 19]

[0131]

[0132] (In the formula, * is the end that is bound to Y in formula (1).)

[0133] Examples of the fluoropolyether group-containing polymer represented by the above formula (1) include polymers represented by the following general formulas (4) and (5).

[0134] [Chemistry 20]

[0135]

[0136] [In the formula, d is independently an integer of 1 to 3 in each unit, p", q", r", s" are each an integer of 0 to 100, and the total of p", q", r", s" in each formula is 3 to 100. In addition, each repeating unit shown in the brackets with p", q", r", s" can be randomly combined. m and n are independently an integer of 2 to 10 in each unit. These units may be linear or branched. Z' is independently represented by any of the following formulas.

[0137] [Chemistry 21]

[0138]

[0139] (In the formula, * is a bonding end bonded to the terminal carbon atom in formula (4) and (5).)]

[0140] Examples of the fluoropolyether group-containing polymer represented by the above formula (1) include polymers represented by the following formulas.

[0141] [Chemistry 22]

[0142]

[0143] [Chemistry 23]

[0144]

[0145] [Chemistry 24]

[0146]

[0147] [Chemistry 25]

[0148]

[0149] [Chemistry 26]

[0150]

[0151] [Chemistry 27]

[0152]

[0153] [Chemistry 28]

[0154]

[0155] [Chemistry 29]

[0156]

[0157] [Chemistry 30]

[0158]

[0159] (In the formula, p', q', r', and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0160] Examples of methods for producing a fluoropolyether group-containing polymer represented by the above formula (1) where α is 1 (i.e., when Rf is a monovalent fluoropolyether group-containing polymer residue) or α is 2 (i.e., when Rf is a divalent fluoropolyether group-containing polymer residue) include the following methods.

[0161] First, let the following general formula (6)

[0162] [Chemistry 32]

[0163]

[0164] (In the formula, Rf and α are the same as above, and M is a leaving monovalent group.)

[0165] The fluoropolyether group-containing polymer having a carbonyl group at the terminal and an organometallic reagent having an aliphatic unsaturated double bond (olefin moiety) at the terminal and having a β hydrogen atom (i.e., a hydrogen atom bonded to a carbon atom at the β position of a metal atom) are preferably reacted in the presence of a solvent.

[0166] In the above formula (6), M is a removable monovalent group, and examples thereof include a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a thiol group, an alkylthio group, and an acyl group.

[0167] Examples of such M include the following groups.

[0168] [Chemistry 33]

[0169]

[0170] Specific examples of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (6) include the following polymers.

[0171] [Chemistry 34]

[0172]

[0173] [Chemistry 35]

[0174]

[0175] (In the formula, p', q', r' and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' can be randomly combined. R3' and r4' are each an integer greater than 1, and the total of r3' and r4' is 2 to 199.)

[0176] As the above-mentioned organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β hydrogen atom, specifically, organolithium reagents, Grignard reagents, organozinc reagents, organoboron reagents, organotin reagents, etc. can be listed, and Grignard reagents and organozinc reagents are particularly preferably used from the aspect of ease of handling. As such an organometallic reagent, the following reagents can be particularly preferably used.

[0177] [Chemistry 36]

[0178]

[0179] The amount of the organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β-hydrogen atom is preferably 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and further preferably about 3 equivalents, relative to 1 equivalent of the reactive terminal group (detachable monovalent group) of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (6).

[0180] A solvent can be used in the reaction of a polymer containing a fluoropolyether group having a carbonyl group at the end represented by the above formula (6) and an organic metal reagent having an aliphatic unsaturated double bond at the end and having a β hydrogen atom. The solvent used at this time is not particularly limited. From the perspective that the reaction compound is a fluorine compound, a fluorine-based solvent is preferably used. As a fluorine-based solvent, 1,3-bistrifluoromethylbenzene, trifluoromethylbenzene, a perfluoro-based solvent sold by AGC (AsahiklinAC2000, AsahiklinAC6000, etc.), a hydrofluoroether (HFE)-based solvent sold by 3M (NOVEC7100: C4F9OCH3, NOVEC7200: C4F9OC2H5, NOVEC7300: C2F5-CF(OCH3)-CF(CF3)2, etc.), and a perfluoro-based solvent also sold by 3M (PF5080, PF5070, PF5060, etc.) can be cited. The fluorine-based solvents may be used alone or in combination.

[0181] In addition, as a solvent, in addition to the above-mentioned fluorine-based solvents, an organic solvent can be used. As an organic solvent, an ether solvent such as tetrahydrofuran (THF), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane, etc. can be used. The organic solvent can be used alone or mixed with a fluorine-based solvent.

[0182] The amount of the solvent used is 10 to 600 parts by mass, preferably 50 to 400 parts by mass, and more preferably 200 to 350 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having a terminal carbonyl group represented by the above formula (6).

[0183] The reaction conditions of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (6) and the organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β-hydrogen atom can be set to 0 to 80° C., preferably 45 to 70° C., more preferably about 50° C., for 1 to 12 hours, preferably 5 to 7 hours.

[0184] After the reaction is carried out under the above conditions, the reaction is stopped, and the water layer and the fluorine solvent layer are separated by liquid separation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the end of the molecular chain represented by the following general formula (7).

[0185] [Chemistry 37]

[0186]

[0187] (In the formula, Rf and α are the same as above, and Y' is independently a single bond, or a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms.)

[0188] In the above formula (7), Y' is a single bond, or a divalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 12 carbon atoms, which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms. Specifically, there can be mentioned a single bond, methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene and other alkylene groups having 1 to 18 carbon atoms, and alkylene groups having 1 to 10 carbon atoms (e.g., alkylene-arylene groups having 7 to 18 carbon atoms, etc.) including arylene groups having 6 to 8 carbon atoms such as phenylene. As Y', a linear alkylene group having 1 to 4 carbon atoms is preferred.

[0189] Examples of such Y' include the following groups.

[0190] [Chemistry 38]

[0191] *-CH2-**

[0192] *-CH2CH2-**

[0193] *-CH2CH2CH2-**

[0194] *-CH2CH2CH2CH2-**

[0195] *-CH2CH2CH2CH2CH2-**

[0196] *-CH2CH2CH2CH2CH2CH2CH2-**

[0197]

[0198] (In the formula, * is the bonding end bonded to the carbon atom to which Rf in the formula (7) is bonded, and ** is the bonding end bonded to the vinyl group in the formula (7).)

[0199] Specific examples of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the formula (7) include the following polymers.

[0200] [Chemistry 39]

[0201]

[0202] [Chemistry 40]

[0203]

[0204] (In the formula, p', q', r', r3', r4' and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0205] Next, the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the formula (7) obtained above and an olefin introducing agent are aged at 0 to 90° C., preferably 40 to 60° C., more preferably about 50° C. for 1 to 48 hours, preferably 10 to 40 hours, more preferably about 24 hours in the presence of a base and, if necessary, an additive or solvent for improving reactivity.

[0206] Examples of the olefin-introducing agent that reacts with the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the formula (7) include halides, and specific examples thereof include allyl bromide, allyl chloride, and 3-butenyl bromide.

[0207] The amount of the olefin-introducing agent used is 1 to 15 equivalents, more preferably 3 to 6 equivalents, and even more preferably about 4 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (7).

[0208] As the base used in the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (7) and the olefin-introducing agent, for example, amines, alkali metal bases, etc. can be used. Specifically, among the amines, triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, etc. can be mentioned. Among the alkali metal bases, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, tert-butoxy potassium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, etc. can be mentioned.

[0209] The base can be used in an amount of 1 to 20 equivalents, more preferably 4 to 8 equivalents, and even more preferably about 6 equivalents, per 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (7).

[0210] In the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (7) with an olefin introducing agent, tetrabutylammonium halide, alkali metal halide, etc. can be used as an additive to improve reactivity. Specifically, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, crown ether, etc. can be cited as the additive. These additives catalyze the halogen exchange with the olefin introducing agent in the reaction system, thereby improving reactivity, and the crown ether coordinates with the metal to improve reactivity.

[0211] The amount of the additive used is 0.005 to 0.1 equivalents, more preferably 0.01 to 0.05 equivalents, and even more preferably about 0.02 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (7).

[0212] In the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (7) and the olefin introduction agent, a solvent may be used. A solvent may not necessarily be used. As the solvent used, as a fluorine-based solvent, fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, hydrofluoroether (HFE) solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name: Novec series), and perfluoro solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series) can be listed. Furthermore, as an organic solvent, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran (THF), etc. can be used.

[0213] When a solvent is used, the amount used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, more preferably about 50 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (7).

[0214] By reacting the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (7) with an olefin-introducing agent, a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminal represented by the following general formula (8) is obtained.

[0215] [Chemistry 41]

[0216]

[0217] (In the formula, Rf, Y', and α are the same as above. Multiple Y's may be the same or different.)

[0218] Preferred examples of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the formula (8) include the following polymers.

[0219] [Chemistry 42]

[0220]

[0221] [Chemistry 43]

[0222]

[0223] (In the formula, p', q', r', r3', r4' and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0224] Next, the polymer containing fluoropolyether groups represented by formula (8) obtained above and having two olefin sites at the ends of the molecular chain is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organic silicon compound having two or more SiH groups in the molecule such as 2,4,6,8-tetramethylcyclotetrasiloxane is mixed, and the mixture is aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, thereby obtaining the polymer containing fluoropolyether groups represented by formula (1) above.

[0225] Among them, the organosilicon compound having two or more SiH groups in the molecule to be reacted with the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the above formula (8) is preferably a compound represented by the following formula.

[0226] [Chemistry 44]

[0227]

[0228] (In the formula, R, R', a, b, and c are the same as above. The repeating units shown in the parentheses with a and c may be randomly combined.)

[0229] Examples of such an organic silicon compound having two or more SiH groups in a molecule include compounds such as 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, methyltris(dimethylsiloxy)silane, and tetrakis(dimethylsiloxy)silane.

[0230] When the fluoropolyether group-containing polymer having two olefin sites at the molecular chain terminals represented by the above formula (8) is subjected to an addition reaction with an organosilicon compound having two or more SiH groups in the molecule, the amount of the organosilicon compound having two or more SiH groups in the molecule used is 2 to 10 equivalents, more preferably 3 to 6 equivalents, and even more preferably about 5 equivalents, relative to 1 equivalent of the reactive terminal group (terminal olefin site) of the fluoropolyether group-containing polymer having two olefin sites at the molecular chain terminals.

[0231] In the reaction of the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends represented by the above formula (8) and the organosilicon compound having two or more SiH groups in the molecule, the solvent used is preferably a fluorine-based solvent. Examples of the fluorine-based solvent include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and perfluoro solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series).

[0232] The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably 100 to 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the above formula (8).

[0233] In the reaction of the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends represented by the above formula (8) and the organosilicon compound having two or more SiH groups in the molecule, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakistriphenylphosphine palladium and tristriphenylphosphine rhodium chloride. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0234] The amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the above formula (8).

[0235] Then, the solvent and unreacted products are distilled off under reduced pressure to obtain the target compound.

[0236] For example, as the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends represented by the above formula (8), a compound represented by the following formula is used:

[0237] [Chemistry 45]

[0238]

[0239] When 2,4,6,8-tetramethylcyclotetrasiloxane is used as the organic silicon compound having two or more SiH groups in the molecule, a compound represented by the following formula is obtained.

[0240] [Chemistry 46]

[0241]

[0242] In addition, for example, as the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends, a compound represented by the following formula is used:

[0243] [Chemistry 47]

[0244]

[0245] When 2,4,6,8-tetramethylcyclotetrasiloxane is used as the organic silicon compound having two or more SiH groups in the molecule, a compound represented by the following formula is obtained.

[0246] [Chemistry 48]

[0247]

[0248] Since the fluoropolyether group-containing polymer represented by the above formula (1) of the present invention has multiple Si-H bonds in one molecule, multiple functional groups can be easily introduced by hydrosilylation with a compound having an aliphatic unsaturated bond and a functional group.

[0249] Among them, examples of the functional groups that can be introduced include hydrolyzable silyl groups (e.g., alkoxysilyl groups), alkyl groups, phenyl groups, vinyl groups, allyl groups, acyl groups, carboxyl groups, ester groups, (meth)acryloyl groups, amido groups, isocyanate groups, isocyanurate groups, isothiocyanate groups, hydroxyl groups, amino groups, thiol groups, polyether groups, silyl groups, siloxane groups, thioester groups, phosphate groups, and phosphoric acid groups.

[0250] Example

[0251] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In the following examples, the repeating units shown in parentheses in the fluoropolyether group in the formula may be randomly bonded.

[0252] [Example 1]

[0253] 272 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 1.4 × 10 -1 mol), stirred. Then, 200 g (4.5 × 10 -2 mol) is represented by the following formula (A)

[0254] [Chemistry 49]

[0255]

[0256] A mixture of the compound represented by, 400g Asahiklin AC6000, and 200g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (B):

[0257] [Chemistry 50]

[0258]

[0259] 193 g of a polymer containing a fluoropolyether group was expressed.

[0260] In a reaction container, 100 g (2.3 × 10 -2 mol), allyl bromide 11g (9.2×10 -2mol), tetrabutylammonium iodide 0.17 g (4.6×10 -4 Next, 18 g (1.4 × 10 -1 mol), and then heated at 50°C for 24 hours. After heating, it was cooled to room temperature and a hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation operation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining the following formula (C):

[0261] [Chemistry 51]

[0262]

[0263] The amount of the polymer containing fluoropolyether groups was 97 g.

[0264] 80 g (1.8 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, 2,4,6,8-tetramethylcyclotetrasiloxane 43 g (1.8×10 -1 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (as a single substance of Pt, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (D):

[0265] [Chemistry 52]

[0266]

[0267] 84 g of the polymer containing fluoropolyether groups was expressed.

[0268] [Example 2]

[0269] In a reaction container, the following formula (C) obtained in the same manner as in Example 1 was added

[0270] [Chemistry 53]

[0271]

[0272] The compound represented by 80g (1.8×10 -2 mol), 120 g 1,3-bis(trifluoromethyl)benzene, 54 g 2,4,6,8,10-pentamethylcyclopentasiloxane (1.8×10 -1mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (as a single substance of Pt, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (E):

[0273] [Chemistry 54]

[0274]

[0275] 84 g of the polymer containing fluoropolyether groups was expressed.

[0276] [Example 3]

[0277] In a reaction container, the following formula (C) obtained in the same manner as in Example 1 was added

[0278] [Chemistry 55]

[0279]

[0280] The compound represented by 80g (1.8×10 -2 mol), 120 g 1,3-bis(trifluoromethyl)benzene, 48 g methyltris(dimethylsiloxy)silane (1.8×10 -1 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (as a single substance of Pt, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (F):

[0281] [Chemistry 56]

[0282]

[0283] 84 g of the polymer containing fluoropolyether groups was expressed.

[0284] [Example 4]

[0285] In a reaction container, the following formula (C) obtained in the same manner as in Example 1 was added

[0286] [Chemistry 57]

[0287]

[0288] The compound represented by 80g (1.8×10 -2mol), 1,3-bis(trifluoromethyl)benzene 120 g, tetrakis(dimethylsiloxy)silane 59 g (1.8×10 -1 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (as a single substance of Pt, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (G):

[0289] [Chemistry 58]

[0290]

[0291] 84 g of the polymer containing fluoropolyether groups was expressed.

[0292] [Example 5]

[0293] 132 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 6.6 × 10 -2 mol), stirred. Then, 100 g (2.2 × 10 -2 mol) is represented by the following formula (H)

[0294] [Chemistry 59]

[0295]

[0296] A mixture of the compound represented by, 200g Asahiklin AC6000, and 100g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (I):

[0297] [Chemistry 60]

[0298]

[0299] 96 g of the polymer containing fluoropolyether groups was expressed.

[0300] In a reaction container, 20 g (4.4 × 10 -3 mol), allyl bromide 2.2g (1.8×10 -2 mol), tetrabutylammonium iodide 0.03 g (8.1 × 10 -5Next, 3.5 g (2.6 × 10 -2 mol), and then heated at 50°C for 24 hours. After heating, it was cooled to room temperature and a hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation operation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining the following formula (J):

[0301] [Chemistry 61]

[0302]

[0303] 19 g of a polymer containing a fluoropolyether group was expressed.

[0304] In a reaction vessel, 10 g (2.2 × 10 -3 mol), 15 g 1,3-bis(trifluoromethyl)benzene, 6.6 g 2,4,6,8,10-pentamethylcyclopentasiloxane (2.2×10 -2 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 1.0×10 -2 g (as a single substance of Pt, containing 3.0×10 -8 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (K):

[0305] [Chemistry 62]

[0306]

[0307] 11 g of the fluoropolyether group-containing polymer is shown.

[0308] [Example 6]

[0309] 132 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 6.6 × 10 -2 mol), stirred. Then, 100 g (2.2 × 10 -2 mol) is represented by the following formula (L)

[0310] [Chemistry 63]

[0311]

[0312] A mixture of the compound represented by, 200g Asahiklin AC6000, and 100g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (M):

[0313] [Chemistry 64]

[0314]

[0315] 96 g of the polymer containing fluoropolyether groups was expressed.

[0316] In a reaction container, 20 g (4.4 × 10 -3 mol), allyl bromide 2.2g (1.8×10 -2 mol), tetrabutylammonium iodide 0.03 g (8.1 × 10 -5 Next, 3.5 g (2.6 × 10 -2 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (N):

[0317] [Chemistry 65]

[0318]

[0319] 19 g of a polymer containing a fluoropolyether group was expressed.

[0320] In a reaction vessel, 10 g (2.2 × 10 -3 mol), 15 g 1,3-bis(trifluoromethyl)benzene, 6.6 g 2,4,6,8,10-pentamethylcyclopentasiloxane (2.2×10 -2 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 1.0×10 -2 g (as a single substance of Pt, containing 3.0×10 -8 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (O):

[0321] [Chemistry 66]

[0322]

[0323] 12 g of a fluoropolyether group-containing polymer was expressed.

[0324] [Example 7]

[0325] 126 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 6.3 × 10 -2 mol), stirred. Then, 100 g (2.1 × 10 -2 mol) is represented by the following formula (P)

[0326] [Chemistry 67]

[0327]

[0328] A mixture of the compound represented by, 200g Asahiklin AC6000, and 100g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (Q):

[0329] [Chemistry 68]

[0330]

[0331] 96 g of the polymer containing fluoropolyether groups was expressed.

[0332] In a reaction vessel, 20 g (4.2 × 10 -3 mol), allyl bromide 2.1 g (1.7 × 10 -2 mol), tetrabutylammonium iodide 0.03 g (8.1 × 10 -5 Next, 3.5 g (2.6 × 10 -2 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (R):

[0333] [Chemistry 69]

[0334]

[0335] 19 g of a polymer containing a fluoropolyether group was expressed.

[0336] In a reaction vessel, 10 g (2.1×10 -3 mol), 10 g of 1,3-bis(trifluoromethyl)benzene, 6.3 g of 2,4,6,8,10-pentamethylcyclopentasiloxane (2.1×10 -2 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 1.0×10 -2 g (as a single substance of Pt, containing 3.0×10 -8 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (S):

[0337] [Chemistry 70]

[0338]

[0339] The amount of the fluoropolyether group-containing polymer was 9.7 g.

[0340] [Example 8]

[0341] 126 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 6.3 × 10 -2 mol), stirred. Then, 100 g (2.1 × 10 -2 mol) is represented by the following formula (T)

[0342] [Chemistry 71]

[0343]

[0344] A mixture of the compound represented by, 200g Asahiklin AC6000, and 100g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (U):

[0345] [Chemistry 72]

[0346]

[0347] 96 g of the polymer containing fluoropolyether groups was expressed.

[0348] In a reaction vessel, 20 g (4.2 × 10 -3mol), allyl bromide 2.1 g (1.7 × 10 -2 mol), tetrabutylammonium iodide 0.03 g (8.1 × 10 -5 Next, 3.4 g (2.5 × 10 -2 mol), and then heated at 50°C for 24 hours. After heating, it was cooled to room temperature and a hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation operation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining the following formula (V):

[0349] [Chemistry 73]

[0350]

[0351] 19 g of a polymer containing a fluoropolyether group was expressed.

[0352] In a reaction vessel, 10 g (2.1 × 10 -3 mol), 10 g of 1,3-bis(trifluoromethyl)benzene, 6.3 g of 2,4,6,8,10-pentamethylcyclopentasiloxane (2.1×10 -2 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 1.0×10 -2 g (as a single substance of Pt, containing 3.0×10 -8 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (W):

[0353] [Chemistry 74]

[0354]

[0355] The amount of the fluoropolyether group-containing polymer was 9.7 g.

[0356] [Example 9]

[0357] 282 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 1.4 × 10 -1 mol), stirred. Then, 100 g (2.4 × 10 -2 mol) is represented by the following formula (X)

[0358] [Chemistry 75]

[0359]

[0360] A mixture of the compound represented by, 200g Asahiklin AC6000, and 100g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (Y):

[0361] [Chemistry 76]

[0362]

[0363] 94 g of the polymer containing fluoropolyether groups was expressed.

[0364] In a reaction container, 20 g (4.7 × 10 -3 mol), allyl bromide 4.6 g (3.8 × 10 -2 mol), tetrabutylammonium iodide 0.07 g (1.9×10 -4 Next, 7.5 g (5.6 × 10 -2 mol), and then heated at 50°C for 24 hours. After heating, it was cooled to room temperature and a hydrochloric acid aqueous solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation operation and then washed with acetone. The washed lower layer, i.e., the fluorine compound layer, was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining the following formula (Z):

[0365] [Chemistry 77]

[0366]

[0367] 21 g of a fluoropolyether group-containing polymer is shown.

[0368] 20 g (4.6 × 10 -3 mol), 30 g 1,3-bis(trifluoromethyl)benzene, 22 g 2,4,6,8-tetramethylcyclotetrasiloxane (9.2×10 -2 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 4.8×10 -2 g (as a single substance of Pt, containing 1.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (a):

[0369] [Chemistry 78]

[0370]

[0371] 22g of a polymer containing a fluoropolyether group was represented.

[0372] [Example 10]

[0373] In a reaction container, the compound of the following formula (Z) obtained in the same manner as in Example 9 was placed.

[0374] [Chemistry 79]

[0375]

[0376] The compound represented by 20g (4.6×10 -3 mol), 30 g 1,3-bis(trifluoromethyl)benzene, 28 g 2,4,6,8,10-pentamethylcyclopentasiloxane (9.2×10 -2 mol)、

[0377] and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 4.8×10 -2 g (as a single substance of Pt, containing 1.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (b):

[0378] [Chemistry 80]

[0379]

[0380] 18 g of the polymer containing fluoropolyether groups was expressed.

Claims

1. A fluoropolyether group-containing polymer represented by the following general formula (1), [Chemistry 1] In the formula, Rf is a monovalent or divalent polymer residue containing a fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms, Z is independently a monovalent organopolysiloxane residue having at least one silicon-hydrogen bond, i.e., SiH group, at the end, which may form a cyclic structure, and α is 1 or 2.

2. The fluoropolyether group-containing polymer according to claim 1, wherein In the formula (1), α is 1, and Rf is a monovalent fluoropolyether group represented by the following general formula (2): [Chemistry 2] In the formula, A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, and the total of p, q, r, s, t, u, and v is 3 to 200. Each of these units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly combined.

3. The fluoropolyether group-containing polymer according to claim 1, wherein In the formula (1), α is 2, and Rf is a divalent fluoropolyether group represented by the following general formula (3): [Chemistry 3] In the formula, W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, and the total of p, q, r, s, t, u, and v is 3 to 200. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly combined.

4. The fluoropolyether group-containing polymer according to claim 1, wherein In the formula (1), when α=1, there are two Xs at one end of the molecular chain, and when α=2, there are two Xs at each of the two ends of the molecular chain (four in the molecule), and one X at each end is an oxygen atom and the other X is a single bond.

5. The fluoropolyether group-containing polymer according to claim 1, wherein In the above formula (1), Y is independently an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms.

6. The fluoropolyether group-containing polymer according to claim 1, wherein In the above formula (1), Z is a linear monovalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic monovalent organopolysiloxane residue having 3 to 10 silicon atoms and having 1 to 9 silicon-hydrogen bonds, i.e., SiH groups, at the terminal.

7. The fluoropolyether group-containing polymer according to claim 1, wherein In the formula (1), Z is represented by any of the following formulas: [Chemistry 4] In the formula, * is a bonding end bonded to Y in formula (1), R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, R' is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, at least one R' is a hydrogen atom, a is an integer of 0 to 6, b is an integer of 2 to 9, c is 1, and each repeating unit shown in the brackets with a and c can be randomly bonded.

8. The fluoropolyether group-containing polymer according to claim 1, wherein The polymer represented by formula (1) is selected from polymers represented by the following general formulas (4) and (5), [Chemistry 5] In the formula, d is independently an integer of 1 to 3 in each unit, p", q", r", and s" are each an integer of 0 to 100, and the total of p", q", r", and s" in each formula is 3 to 100. In addition, each repeating unit shown in the parentheses with p", q", r", and s" may be randomly combined, m and n are independently an integer of 2 to 10 in each unit, and each of these units may be linear or branched, and Z' is independently represented by any of the following formulas, [Chemistry 6] In the formula, * is a bonding end bonded to the terminal carbon atom in formula (4) or (5).

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