Perfluoropolyether-organopolysiloxane block copolymer

Abstract

To provide a perfluoropolyether-organopolysiloxane block copolymer that includes a perfluoropolyether group, enables the control of the number of siloxane units in the molecule, and exhibits superior affinity for a fluorine-free organic compound.SOLUTION: A perfluoropolyether-organopolysiloxane block copolymer includes a perfluoropolyether block and an organopolysiloxane block. The organopolysiloxane block includes, on its side chain, at least one organic group including a reactive functional group selected from an oxyalkylene group, a hydroxyalkyl group, a hydroxyaryl group, an epoxy group and a carboxylic acid anhydride group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to perfluoropolyether-organopolysiloxane block copolymers. [Background technology]

[0002] In general, perfluoropolyether group-containing compounds have very low surface free energy and therefore have chemical resistance, lubricity, releasability, water and oil repellency, etc. Taking advantage of these properties, they are widely used industrially as lubricants for magnetic recording media, oil repellents and release agents for precision instruments, water and oil repellents and stain repellents for paper, fiber, glass, resin, etc., cosmetics, protective films, etc.

[0003] However, since the surface free energy of perfluoropolyether group-containing compounds is low, their compatibility and affinity with other substances is very low. When attempts are made to impart the above-mentioned properties by adding perfluoropolyether group-containing compounds to various industrial materials, etc., problems arise in terms of dispersion stability and reactivity, making it difficult to incorporate perfluoropolyether group-containing compounds into various industrial materials, etc.

[0004] On the other hand, polysiloxane compounds also have low surface free energy and therefore have properties such as water repellency, lubricity, and mold releasability. Polysiloxane compounds have better affinity with other substances than perfluoropolyether compounds, and can be modified in various ways to further improve dispersion stability. Therefore, polysiloxane compounds can be easily added to various industrial materials to impart silicone properties, and are used as additives for improving performance in a wide range of fields. Perfluoropolyether-modified polysiloxane compounds are compounds having a perfluoropolyether group and a polysiloxane chain (Patent Document 1). However, when the fluorine modification rate of this polysiloxane compound is increased in an attempt to improve the properties of the perfluoropolyether group, the affinity for other industrial materials is significantly reduced, which can cause problems in dispersion stability, reactivity, etc.

[0005] In view of this, perfluoropolyether-organopolysiloxane block copolymers have been developed that have the properties of both perfluoropolyether and polysiloxane and have excellent affinity with non-fluorinated organic compounds (Patent Documents 2 and 3). Also, perfluoropolyether-modified organopolysiloxanes having reactive functional groups such as carbinol groups and epoxy groups in the siloxane moiety have been developed (Patent Documents 4 and 5). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2006-321764 A [Patent Document 2] JP 2008-88412 A [Patent Document 3] JP 2011-21158 A [Patent Document 4] Japanese Patent Application Publication No. 10-330487 [Patent Document 5] Japanese Patent Application Publication No. 5-43587 Summary of the Invention [Problem to be solved by the invention]

[0007] The perfluoropolyether-organopolysiloxane block copolymers disclosed in Patent Documents 2 and 3 have good affinity with non-fluorinated organic compounds, but since they do not have reactive functional groups, they cannot react with various organic compounds, and therefore cannot impart sustained water and oil repellency, etc., even when incorporated into a curable composition. In addition, the perfluoropolyether-modified organopolysiloxanes having reactive functional groups disclosed in Patent Documents 4 and 5 are limited in the number of organosiloxane units and reactive functional groups that can be introduced, making it difficult to control the compatibility with the curable composition and the crosslink density of the resulting cured product. Therefore, an object of the present invention is to provide a perfluoropolyether-organopolysiloxane block copolymer (hereinafter sometimes simply referred to as block copolymer) which has a perfluoropolyether group, and whose molecular structure can be controlled in terms of the number of each unit constituting the block copolymer and the modification rate of the group introduced into the side chain of the organopolysiloxane block, and which has functional groups in the organopolysiloxane block capable of reacting with various organic compounds and has excellent affinity with non-fluorine-based organic compounds. [Means for solving the problem]

[0008] Means of the Invention The present inventors have conducted extensive research to solve the above problems and have found that the following perfluoropolyether-organopolysiloxane block copolymer can achieve the above objects, thereby completing the present invention. That is, the present invention is as follows.

[0009] [1] A perfluoropolyether-organopolysiloxane block copolymer having a perfluoropolyether block and an organopolysiloxane block, represented by the following formula (1), wherein the organopolysiloxane block has, on a side chain thereof, one or more organic groups containing a reactive functional group selected from an oxyalkylene group, a hydroxyalkyl group, a hydroxyaryl group, an epoxy group, and a carboxylic anhydride group. [ka] [In formula (1), Rf is expressed by the following formula (2) [ka] (In formula (2), z is a number from 1 to 4, v, w, x, and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Each repeating unit may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.) is a perfluoropolyether block represented by W1 is expressed by the following formula (A): [ka] (In formula (A), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. 2 R is one or more reactive functional groups selected from an oxyalkylene group represented by the following formula (3), an ω-hydroxyalkyl group having 3 to 12 carbon atoms, an organic group having 9 to 18 carbon atoms and a hydroxyaryl group, an organic group having 6 to 15 carbon atoms and an epoxy group, and an organic group having 4 to 32 carbon atoms and a carboxylic anhydride group. 3 represents one or more groups selected from an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the following formula (4). [ka] (In formula (3), R 4 is an alkylene group having 2 to 4 carbon atoms, j is a number from 3 to 12, and k is a number from 1 to 60. The oxyalkylene units bracketed by k are composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited and may be random or block. [ka] (In formula (4), R 4 is an alkylene group having 2 to 4 carbon atoms, and R 5 is an alkyl group having 1 to 4 carbon atoms, m is a number from 3 to 12, and n is a number from 1 to 60. The oxyalkylene units bracketed by n are composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited and may be random or block. Each of p1, q1, and r1 is a number from 0 to 1,000. The arrangement order of each repeating unit is not limited, and may be random or block. is a divalent organopolysiloxane block represented by W2 is independently represented by the following formula (B): [ka] (In formula (B), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. 2 R is one or more reactive functional groups selected from an oxyalkylene group represented by the above formula (3), an ω-hydroxyalkyl group having 3 to 12 carbon atoms, an organic group having 9 to 18 carbon atoms and a hydroxyaryl group, an organic group having 6 to 15 carbon atoms and an epoxy group, and an organic group having 4 to 32 carbon atoms and a carboxylic anhydride group. 3 R is one or more groups selected from an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the above formula (4). 1 Each of p2, q2, and r2 is independently a group selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. Each of p2, q2, and r2 is a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a monovalent organopolysiloxane block represented by the formula: However, q1 in the above formula (A) and q2 in the above formula (B) are not 0 at the same time. Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2; g is a number between 0 and 50, but when g is 0, q2 in formula (B) of W2 does not become 0. [2] The perfluoropolyether-organopolysiloxane block copolymer according to [1], having a weight average molecular weight of 4,000 to 500,000 and an organopolysiloxane block content in one molecule of 50% or more. [3] The perfluoropolyether-organopolysiloxane block copolymer according to [1] or [2], wherein the perfluoropolyether block represented by Rf is a group represented by the following formula (5): [ka] (In formula (5), v and w are each a number from 0 to 200, with the proviso that v+w=3 to 200. The repeating unit of (OC2F4) may be linear or branched. The arrangement order of the repeating units is not limited, and may be random or block.) [4] R in formula (A) or formula (B) 2 is an oxyalkylene group represented by the above formula (3), and R 4 The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to [3], wherein is an alkylene group having 2 or 3 carbon atoms. [5] R in formula (A) or formula (B) 2 The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to [3], wherein is an ω-hydroxyalkyl group having 3 to 12 carbon atoms. [6] R in formula (A) or formula (B) 2 is an organic group having a hydroxyaryl group represented by the following formula (6): [ka] (In formula (6), a is a number from 3 to 4, and R 6 is a group selected from a hydrogen atom, a methoxy group, and a hydroxy group. [7] In formula (6), R 6 is a hydrogen atom or a methoxy group. [8] R in formula (A) or formula (B) 2 The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to [3], wherein [ka] (In formula (7), j is a number from 3 to 12.) [9] R in formula (A) or formula (B) 2 The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to [3], wherein [ka]

[10] R in formula (A) or formula (B) 2 is an organic group having a carboxylic acid anhydride group represented by the following formula (9) or (10): [ka] (In formula (9), R 7 are independently a hydrogen atom, or a group selected from an alkyl group having 1 to 8 carbon atoms and a phenyl group. b is an integer of 0 to 4. [ka]

[11] The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to

[10] , wherein in formula (A) and formula (B), r1+r2>1.

[12] R in formula (A) or formula (B) 3is an oxyalkylene group represented by formula (4). Effect of the Invention

[0010] The block copolymer of the present invention has a perfluoropolyether block, a high siloxane content, and an organopolysiloxane block at both ends of the molecular chain. Furthermore, the side chain of the organopolysiloxane block has one or more groups selected from an oxyalkylene group, a hydroxyalkyl group, a hydroxyaryl group, an epoxy group, and a carboxylic anhydride group. Therefore, even though it has a perfluoropolyether block, it is easily compatible with non-fluorine-based organic compounds and can react with various organic compounds. In addition, the block copolymer of the present invention can easily control the number of organopolysiloxane units and the modification rate of the group on the side chain of the organopolysiloxane block. Furthermore, it is easy to introduce one or more groups selected from an aralkyl group and a group having an oxyalkylene unit, which have excellent affinity with non-fluorine-based organic compounds. Therefore, the block copolymer of the present invention is useful for applications such as a surface modifier for non-fluorinated organic resins. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will now be described in more detail. The perfluoropolyether-organopolysiloxane block copolymer of the present invention is represented by the following formula (1): In the block copolymer, perfluoropolyether blocks (Rf) and organopolysiloxane blocks (W1 or W2) exist alternately. [ka] The definitions of each symbol in formula (1) are the same as above.

[0012] The organopolysiloxane block has at least one organic group containing a reactive functional group selected from an oxyalkylene group, a hydroxyalkyl group, a hydroxyaryl group, an epoxy group, and a carboxylic acid anhydride group in its side chain, and is therefore capable of reacting with various organic compounds.

[0013] The block copolymer of formula (1) preferably has an organopolysiloxane block content in one molecule of 50% or more and 99% or less, and more preferably 60% or more and 90% or less. When the organopolysiloxane block content is equal to or more than the lower limit, the compatibility with non-fluorine-based organic compounds is excellent, and when it is equal to or less than the upper limit, the properties of the perfluoropolyether group are easily expressed. The organopolysiloxane block content of the block copolymer of formula (1) is 1 It is a value calculated by calculating the molar ratio of perfluoropolyether block Rf with known molecular weight and organosiloxy unit from the integral ratio of the peak derived from alkylene of Q in the above formula (1) and the peak derived from organic group on silicon atom in W1 and W2 in H-NMR spectrum, and converting this molar ratio into the molecular weight ratio. Note that, since the block copolymer of formula (1) usually has a distribution in structure, the above organopolysiloxane block content is the average value per molecule.

[0014] At least one of the organopolysiloxane blocks W1 and W2 preferably has a siloxane unit represented by the following formula (11). [ka]

[0015] In the above formula (11), R 2 is one or more reactive functional groups selected from an oxyalkylene group represented by the following formula (3), an ω-hydroxyalkyl group having 3 to 12 carbon atoms, an organic group having 9 to 18 carbon atoms and a hydroxyaryl group, an organic group having 6 to 15 carbon atoms and an epoxy group, and an organic group having 4 to 32 carbon atoms and a carboxylic anhydride group.

[0016] [ka] In formula (3), R 4 is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. j is a number from 3 to 12, preferably a number from 3 to 8. k is a number from 1 to 60, preferably a number from 1 to 12. The oxyalkylene units bracketed by k are composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited and may be random or block.

[0017] R 2 The ω-hydroxyalkyl group having 3 to 12 carbon atoms is preferably one having 3 to 8 carbon atoms.

[0018] R 2 A preferred example of the organic group having 9 to 18 carbon atoms and having a hydroxyaryl group is a group represented by the following formula (6). [ka] In formula (6), a is a number from 3 to 4, and preferably 3. 6 is a group selected from a hydrogen atom, a methoxy group, and a hydroxy group, and is preferably a hydrogen atom or a methoxy group.

[0019] R 2 The organic group having 6 to 15 carbon atoms and having an epoxy group is preferably exemplified by a group represented by the following formula (7) or (8). [ka] In formula (7), j is a number from 3 to 12, and preferably a number from 3 to 8.

[0020] R 2 The organic group having 4 to 32 carbon atoms and having a carboxylic acid anhydride group is preferably exemplified by a group represented by the following formula (9) or (10). [ka] In formula (9), b is an integer of 0 to 4, and preferably b=0 (single bond), b=3 (trimethylene group), or b=4 (tetramethylene group). 7 are independently a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms and a phenyl group, and are preferably a hydrogen atom. [ka]

[0021] The siloxane unit represented by the above formula (11) having a group selected from the oxyalkylene group represented by the above formula (3), an ω-hydroxyalkyl group having 3 to 12 carbon atoms, an organic group having a hydroxyaryl group, an organic group having an epoxy group, and an organic group having a carboxylic acid anhydride group is present in the above formula (1) at least one, and preferably at least two, in terms of reactivity with organic compounds. The siloxane units of the formula (11) in the organopolysiloxane blocks W1 and W2 may be the same or different, but are preferably the same.

[0022] In the above formula (1), at least one of the organopolysiloxane blocks W1 and W2 may have a siloxane unit represented by the following formula (12). [ka] In the above formula (12), R 3 represents one or more groups selected from an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the following formula (4).

[0023] [ka] In formula (4), R 4 R is an alkylene group having 2 to 4 carbon atoms, and preferably an alkylene group having 2 to 3 carbon atoms. 5is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. m is a number from 3 to 12, preferably 3. n is a number from 1 to 60, preferably 2 to 12. The repeating units of the oxyalkylene group bracketed by n are composed of one type or two or more types, and when composed of two or more types, the arrangement order of the units is not limited and may be random or block.

[0024] Also, R 3 The aralkyl group having 7 to 18 carbon atoms is preferably a group represented by the following formula (13). [ka] In formula (13), R 8 is a hydrogen atom, a methyl group or a phenyl group, and is preferably a methyl group.

[0025] Siloxane units represented by the above formula (12) having one or more groups selected from aralkyl groups, alkoxyalkyl groups, and groups having an oxyalkylene unit may be optionally present in the above formula (1), and when the block copolymer of formula (1) has the siloxane units represented by formula (12), it becomes easier to dissolve the block copolymer of formula (1) in non-fluorine-based organic compounds. The siloxane units of formula (12) in the organopolysiloxane blocks W1 and W2 may be the same or different from each other.

[0026] In the above formula (1), the organopolysiloxane block W1 is a divalent group represented by the following formula (A). [ka]

[0027] In the above formula (A), R 1 are independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, and an octadecyl group. 1Preferred examples of the alkyl group include a methyl group, an ethyl group, and a phenyl group, and a methyl group is particularly preferred.

[0028] In the above formula (A), R 2 and R 3 As an example, R in Eq. (11) 2 and R in formula (12) 3 Examples of the above-mentioned examples are the same as those given above.

[0029] In the above formula (A), p1, q1, and r1 are each a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200. The arrangement order of each repeating unit is not limited, and may be random or block.

[0030] Examples of the group represented by the above formula (A) include groups represented by the following formulae (14) to (26), but are not limited to the following formulae. [ka] [ka] [ka] [ka]

[0031] In the above formula (1), the organopolysiloxane block W2 is a monovalent group represented by the following formula (B). [ka]

[0032] In the above formula (B), R 1 , R 2 and R 3 R may be the same as those listed in formula (A) above. 1' is independently a group selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, and an octadecyl group. Preferred are a methyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group.

[0033] In the above formula (B), p2, q2 and r2 are each a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200. The arrangement order of each repeating unit is not limited and may be random or block. However, q1 in the above formula (A) and q2 in the above formula (B) are not 0 at the same time.

[0034] Examples of the group represented by formula (B) include groups represented by the following formulae (27) to (37), but are not limited to these. [ka] [ka] [ka] [ka]

[0035] The perfluoropolyether block Rf in the above formula (1) is represented by the following formula (2). [ka]

[0036] In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, preferably a number from 0 to 50, provided that v+w+x+y=3 to 200, preferably 10 to 50, and each repeating unit may be linear or branched, and the arrangement order of each repeating unit is not limited and may be random or block.

[0037] Examples of the repeating units of the above formula (2) include the following repeating units. [ka]

[0038] Among these, a perfluoropolyether block of the following formula (5) in which z=1 and x and y are 0 in the above formula (2) is preferred because it has excellent compatibility with non-fluorine-based organic compounds. [ka]

[0039] In formula (5), v and w are each a number from 0 to 200, and preferably a number from 0 to 50, with the proviso that v+w=3 to 200, and preferably 10 to 50. The repeating unit of (OC2F4) may be linear or branched, and the arrangement order of each repeating unit is not limited and may be random or block.

[0040] The perfluoropolyether blocks represented by the above formulas usually have a distribution in structure, and v, w, x and y are each average values ​​per molecule.

[0041] In the above formula (1), Q is a divalent organic group having 2 to 12 carbon atoms, preferably 3 to 6 carbon atoms. In addition, in the above formula (1), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2. Q may contain an oxygen atom or a nitrogen atom. Specific examples include an ether bond, an ester bond, an amide bond, and a secondary amino group. Specific examples of Q include the following groups. [ka] (In the formula, * represents a free group bonded to Rf, and ** represents a free group bonded to W1 or W2.)

[0042] Among the specific examples of Q above, the following is particularly preferred in that it is easy to link the organopolysiloxane block and the perfluoropolyether block: * -CH2OCH2CH2CH2- ** is preferred.

[0043] The weight average molecular weight of the block copolymer of formula (1) is preferably 4,000 to 500,000. When the weight average molecular weight is within this range, the copolymer tends to have excellent solubility in non-fluorine-based organic compounds and is easy to handle. In this specification, the weight average molecular weight is a polystyrene-equivalent value determined by GPC (gel permeation chromatography) measurement under the following conditions (hereinafter the same).

[0044] [Measurement conditions] Developing solvent: toluene Flow rate: 0.6mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperH5000(6.0mmI.D.×15cm×1) TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (toluene solution with a concentration of 0.3% by mass)

[0045] In the above formula (1), g is a number from 0 to 50, and is preferably a number such that the weight average molecular weight of the block copolymer of formula (1) is 4,000 to 500,000. Specifically, g is preferably a number from 0 to 20, and more preferably a number from 0 to 10. However, when g is 0, q2 in formula (B) of W2 is not 0.

[0046] [Method for producing perfluoropolyether-organopolysiloxane block copolymer] The block copolymer of the present invention can be produced by the method described below. Component (a): an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (38): and, Component (b): one or more compounds selected from a compound having an oxyalkylene group having a terminal carbon-carbon double bond represented by the following formula (39), an ω-hydroxy-1-alkene having 3 to 12 carbon atoms, a phenol compound having 9 to 18 carbon atoms and a terminal carbon-carbon double bond, an epoxy compound having 6 to 15 carbon atoms and a terminal carbon-carbon double bond, and a carboxylic acid anhydride compound having 4 to 32 carbon atoms and a terminal carbon-carbon double bond or an alicyclic carbon-carbon double bond: And, Component (c): Hydrosilylation reaction catalyst By carrying out a hydrosilylation reaction between the components (a) and (b) in the presence of the above, the block copolymer represented by the above formula (1) can be obtained.

[0047] [ka]

[0048] [ka] (In formula (39), R 4 , j, and k are the same as those shown in the above formula (3). The arrangement order of the repeating units bounded by k is not limited, and may be random or block. The oxyalkylene units are composed of one type or two or more types.

[0049] In the above formula (38), Rf is a perfluoropolyether block represented by the above formula (2), and g′ is a number of 0 to 50.

[0050] In formula (38), the organopolysiloxane blocks W3 are each independently a divalent group represented by the following formula (A'). [ka] In the above formula (A'), R 1 is the same as in the above formula (A). p1' and s1' are each a number from 0 to 1,000, and preferably a number from 0 to 200. The arrangement order of each repeating unit is not limited, and may be random or block.

[0051] In formula (38), the organopolysiloxane blocks W4 are each independently a monovalent group represented by the following formula (B'). [ka] In the above formula (B'), R 1 and R 1 p2' is the same as in the above formula (B). p2' and s2' are each a number from 0 to 1,000, and preferably a number from 0 to 200. The arrangement order of each repeating unit is not limited, and may be random or block. However, the number s1' of the hydrogensiloxane units in the above formula (A') and the number s2' of the hydrogensiloxane units in the above formula (B') are not 0 at the same time.

[0052] In the above formula (38), Q is a divalent organic group having 2 to 12 carbon atoms. Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W3, or the terminal silicon atom of W4.

[0053] Component (b): a phenol compound having 9 to 18 carbon atoms and a terminal carbon-carbon double bond is preferably a compound represented by the following formula (40). [ka] (In formula (40), R 6 and a are the same as those in formula (6) above.)

[0054] Component (b): the epoxy compound having 6 to 15 carbon atoms and a terminal carbon-carbon double bond is preferably a compound represented by the following formula (41) or the following formula (42). [ka] (In formula (41), j is the same as in formula (7) above.)

[0055] Component (b): a carboxylic acid anhydride compound having 4 to 32 carbon atoms and a terminal carbon-carbon double bond or an alicyclic carbon-carbon double bond is preferably a compound represented by the following formulas (43) to (45). [ka] (In formula (43), R 7 are independently the same as those in the above formula (9), and b is a number from 2 to 4. [ka] (In formula (44), R 7 are independently the same as in formula (9) above.) [ka]

[0056] Component (c): The hydrosilylation catalyst is, for example, a platinum, palladium, rhodium, or ruthenium catalyst, preferably a platinum catalyst. Examples of platinum catalysts include chloroplatinic acid, alcohol or aldehyde solutions of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinylsiloxanes, and complexes of platinum with various olefins or vinylsiloxanes.

[0057] The above-mentioned component (c): hydrosilylation reaction catalyst may be used in a so-called catalytic amount, and is preferably 0.1 to 200 ppm in terms of metal atom weight based on the total amount of the above-mentioned components (a) and (b).

[0058] In the method for producing the block copolymer of the above formula (1) by the hydrosilylation reaction of the above components (a) and (b), the hydrosilylation reaction may be carried out by optionally adding component (d): one or more selected from aralkyl compounds having 7 to 18 carbon atoms and a terminal carbon-carbon double bond, ether compounds having 3 to 12 carbon atoms and a terminal carbon-carbon double bond, and compounds having an oxyalkylene unit having 6 to 248 carbon atoms and a terminal carbon-carbon double bond represented by the following formula (46). The siloxane unit represented by the above formula (12) is introduced into the block copolymer of the above formula (1), making it more compatible with non-fluorinated organic compounds.

[0059] [ka] (In formula (46), R 4 , R 5 , m and n are the same as those shown in the above formula (4). The arrangement order of the repeating units bounded by n is not limited, and may be random or block. The oxyalkylene units are composed of one type or two or more types.

[0060] Component (d): an aralkyl compound having 7 to 18 carbon atoms and a terminal carbon-carbon double bond is preferably a compound represented by the above formula (47). [ka] (In formula (47), R 8 is the same as in the above formula (13).

[0061] Component (d): Examples of the ether compound having a terminal carbon-carbon double bond and 3 to 12 carbon atoms include, but are not limited to, the compounds represented by the following formula: [ka]

[0062] Component (d): Examples of the compound having an oxyalkylene unit having 6 to 248 carbon atoms and a terminal carbon-carbon double bond include, but are not limited to, compounds represented by the following formula: [ka]

[0063] In the method for producing the block copolymer of the above formula (1), the hydrosilylation reaction may be carried out by optionally adding an organic solvent (e). This reaction can be carried out without a solvent, but adding an organic solvent may facilitate compatibility between the components (a), (b) and (d), and the hydrosilylation reaction may proceed efficiently.

[0064] Examples of the organic solvent (e) include aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol, 2-propanol and 1-butanol; and fluorinated aromatic hydrocarbons such as (trifluoromethyl)benzene and 1,3-bis(trifluoromethyl)benzene. Of these, toluene is preferred because it has good compatibility with the components (a), (b) and (d).

[0065] The amount of the organic solvent used as component (e) is not particularly limited as long as the components (a), (b), and (d) are compatible with each other, but is preferably 10 to 300 mass % based on the total mass of the components (a), (b), and (d).

[0066] The above component (a): an organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38) can be produced by the following method or the like.

[0067] In detail, component (f): a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (48), component (g): an organohydrogenpolysiloxane, component (h): an acid catalyst, and, if necessary, component (i): one or more polysiloxanes selected from the group consisting of polysiloxanes represented by the following formulas (49) and (50) are mixed together to carry out an exchange reaction between the siloxanes of component (f), component (g), and component (i).

[0068] [ka]

[0069] [ka] (In formula (49), R 1 is the same as in the above formula (A'). t1 is a number from 3 to 10, and preferably a number from 3 to 8.

[0070] [ka] (In formula (50), R 1 is the same as that in the above formula (B'). 9 are independently a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and are preferably a hydroxy group, a methyl group, or a methoxy group. t2 is a number from 0 to 5,000, and preferably a number from 2 to 1,000.

[0071] In the above formula (48), Rf is a perfluoropolyether block represented by the above formula (2), and g″ is a number of 0 to 50. In the above formula (48), each organopolysiloxane block W5 is independently a divalent group represented by the following formula (A″). [ka] In the above formula (A"), R 1 is the same as in the above formula (A'). p" is a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200.

[0072] In the above formula (48), the organopolysiloxane block W6 is a monovalent group represented by the following formula (B″). [ka] In the above formula (B"), R 1 and R 1 is the same as in the above formula (B'). q'' is a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200.

[0073] In the above formula (42), Q is a divalent organic group having 2 to 12 carbon atoms. Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W5, or the terminal silicon atom of W6.

[0074] The component (g): organohydrogenpolysiloxane may be linear, branched, or cyclic, and examples thereof include the following siloxanes. [ka]

[0075] There are no particular limitations on the acid catalyst used as component (h) as long as it is capable of hydrolyzing the siloxane bonds in components (f) and (g) above. Preferred are sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like.

[0076] Component (i) above: Examples of the polysiloxanes represented by formula (49) and formula (50) above include the following siloxanes. [ka]

[0077] In the method for producing the organohydrogenpolysiloxane of formula (38) by the exchange reaction between siloxanes, the exchange reaction between siloxanes may be carried out by optionally adding component (j): an organic solvent. This reaction can be carried out without a solvent, but adding an organic solvent makes it easier for component (f): the perfluoropolyether-organopolysiloxane block copolymer to become compatible with component (g) and component (i): the polysiloxane, and allows the exchange reaction between siloxanes to proceed efficiently.

[0078] Component (j): The amount of organic solvent used is not particularly limited as long as the components (f), (g), and (i) are compatible with each other, but it is preferably 10 to 300 mass % based on the total mass of components (f), (g), and (i). EXAMPLES

[0079] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, the weight average molecular weight is a polystyrene equivalent value determined by GPC measurement under the above-mentioned measurement conditions. In the following examples, the number of repeating units (g) is 29 In the Si-NMR spectrum, the Si(R 1' The integral value M derived from Si in the )3-O- structure and the -Q-Si(R 1 )2-O-structure Si-derived integral value M', and g = (M' / M)-1.

[0080] [Example 1] Synthesis of block copolymer (1-1) 2.2 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (38-1), 0.39 g of ethylene glycol monoallyl ether, and 2.5 g of toluene as a solvent were placed in a reaction vessel and stirred at 80° C. for 5 minutes. Next, 0.01 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 110° C. for 4 hours. Next, the excess ethylene glycol monoallyl ether and the toluene solvent were distilled off under reduced pressure to obtain 2.3 g of a liquid product. [ka]

[0081] The results of measuring the NMR spectra of the products obtained are shown in Tables 1 to 3. [Table 1] [Table 2] [Table 3]

[0082] From the above results, it was found that the product had the structure represented by the following formula (1-1), and was a block copolymer with an organopolysiloxane block content of 77% in the molecule. In addition, the weight average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 12,440. [ka]

[0083] [Example 2] Synthesis of block copolymer (1-2) A reaction vessel was charged with 2.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1), 0.89 g of a compound having a hydroxyl group with a terminal carbon-carbon double bond represented by the following formula (46-2), and 2.9 g of toluene as a solvent, and the mixture was stirred at 85° C. for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100° C. for 3 hours. Next, the toluene solvent was distilled off under reduced pressure to obtain 2.5 g of a liquid product.

[0084] [ka]

[0085] The results of measuring the NMR spectra of the products obtained are shown in Tables 4 to 6. [Table 4] [Table 5] [Table 6]

[0086] From the above results, it was found that the product had the structure represented by the following formula (1-2), and was a block copolymer with an organopolysiloxane block content of 83% in the molecule. In addition, the weight average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 16,600. [ka]

[0087] [Example 3] Synthesis of block copolymer (1-3) 3.5 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (38-2), 0.58 g of 2-allylphenol, and 3.5 g of toluene as a solvent were placed in a reaction vessel and stirred at 100° C. for 5 minutes. Next, 0.01 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100° C. for 4 hours. Next, the excess 2-allylphenol and the toluene solvent were distilled off under reduced pressure to obtain 3.7 g of a liquid product.

[0088] [ka]

[0089] The results of measuring the NMR spectra of the products obtained are shown in Tables 7 to 9. [Table 7] [Table 8] [Table 9]

[0090] From the above results, it was found that the product had the structure represented by the following formula (1-3), and was a block copolymer with an organopolysiloxane block content of 62% in the molecule. In addition, the weight average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 8,850.

[0091] [ka]

[0092] [Example 4] Synthesis of block copolymer (1-4) 3.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1), 0.51 g of allyl glycidyl ether, and 3.0 g of toluene as a solvent were placed in a reaction vessel and stirred at 100° C. for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100° C. for 7 hours. Next, the excess allyl glycidyl ether and the toluene solvent were distilled off under reduced pressure to obtain 2.8 g of a liquid product.

[0093] The results of measuring the NMR spectra of the products obtained are shown in Tables 10 to 12. [Table 10] [Table 11] [Table 12]

[0094] From the above results, it was found that the product had the structure represented by the following formula (1-4), and was a block copolymer with an organopolysiloxane block content of 78% in the molecule. In addition, the weight average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 8,680.

[0095] [ka]

[0096] [Example 5] Synthesis of block copolymer (1-5) 3.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1), 0.52 g of allylsuccinic anhydride, and 3.0 g of toluene as a solvent were placed in a reaction vessel and stirred at 105° C. for 5 minutes. Then, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 105° C. for 8 hours. Next, the excess allylsuccinic anhydride and the toluene solvent were distilled off under reduced pressure to obtain 3.1 g of a liquid product.

[0097] The NMR spectra of the resulting product were as follows: [Table 13] [Table 14] [Table 15]

[0098] From the above results, it was found that the product had the structure represented by the following formula (1-5), and was a block copolymer with an organopolysiloxane block content of 78% in the molecule. In addition, the weight average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 9,220.

[0099] [ka]

[0100] [Example 6] Synthesis of block copolymer (1-6) In a reaction vessel, 3.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1), 0.15 g of isopropenylbenzene, and 3.0 g of toluene as a solvent were placed and stirred at 100°C for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added and stirred at 100°C for 3 hours. Next, 0.30 g of allyl glycidyl ether was added and stirred at 100°C for 7 hours. Next, the excess allyl glycidyl ether and the toluene solvent were distilled off under reduced pressure to obtain 3.1 g of a liquid product.

[0101] The NMR spectra of the resulting product were as follows: [Table 16] [Table 17] [Table 18]

[0102] From the above results, it was found that the product had the structure represented by the following formula (1-6), and was a block copolymer with an organopolysiloxane block content of 76% in the molecule. In addition, the weight average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 8,950.

[0103] [ka]

[0104] [Example 7] Synthesis of block copolymer (1-7) In a reaction vessel, 3.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1), 0.77 g of a compound having an oxyalkylene unit having a terminal carbon-carbon double bond represented by the following formula (46-7), and 3.5 g of toluene as a solvent were placed and stirred at 100°C for 5 minutes. Then, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added and stirred at 100°C for 1 hour. Then, 0.30 g of allyl glycidyl ether was added and stirred at 100°C for 7 hours. Then, the excess allyl glycidyl ether and the toluene solvent were distilled off under reduced pressure to obtain 3.7 g of a liquid product. [ka]

[0105] The NMR spectra of the resulting product were as follows: [Table 19] [Table 20] [Table 21]

[0106] From the above results, it was found that the product had the structure represented by the following formula (1-7), and was a block copolymer with an organopolysiloxane block content of 81% in the molecule. In addition, the weight average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 11,170.

[0107] [ka]

[0108] [Comparative Example 1 (Organopolysiloxane Block Content in Molecule: 0%)] Perfluoropolyether diol (manufactured by Solvay Specialty Polymers, trade name: Fomblin D2).

[0109] [Comparative Example 2 (Organopolysiloxane Block Content in Molecule: 25%)] 0.59g of 2-allylphenol and 0.59g of 1,3-bis(trifluoromethyl)benzene were placed in a reaction vessel and stirred at 100°C for 5 minutes, followed by the addition of 0.01g of a toluene solution of a platinum vinylsiloxane complex. Next, a mixed solution of 4.4g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (51) and 4.4g of 1,3-bis(trifluoromethyl)benzene was added dropwise over 15 minutes at 100°C, and further stirred for 2 hours at 100°C. Next, the excess amount of 2-allylphenol and the solvent 1,3-bis(trifluoromethyl)benzene were distilled off under reduced pressure to obtain 4.6g of a block copolymer represented by the following formula (52).

[0110] [ka]

[0111] [Comparative Example 3 (Organopolysiloxane Block Content in Molecule: 24%)] 0.59g of allyl glycidyl ether and 0.59g of 1,3-bis(trifluoromethyl)benzene were added to a reaction vessel, and the mixture was stirred at 100°C for 5 minutes, followed by the addition of 0.01g of a toluene solution of a platinum vinylsiloxane complex. Next, a mixed solution of 4.4g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (51) and 4.4g of 1,3-bis(trifluoromethyl)benzene was added dropwise over 15 minutes at 100°C, and the mixture was further stirred at 100°C for 3 hours. Next, the excess amount of allyl glycidyl ether and the solvent 1,3-bis(trifluoromethyl)benzene were distilled off under reduced pressure to obtain 4.6g of a block copolymer represented by the following formula (53).

[0112] [ka]

[0113] [Comparative Example 4 (Organopolysiloxane Block Content in Molecule: 26%)] 0.60g of allyl succinic anhydride and 0.60g of 1,3-bis(trifluoromethyl)benzene were added to a reaction vessel, and the mixture was stirred at 100°C for 5 minutes, followed by the addition of 0.01g of a toluene solution of a platinum vinylsiloxane complex. Next, a mixed solution of 4.4g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (51) and 4.4g of 1,3-bis(trifluoromethyl)benzene was added dropwise at 105°C over 15 minutes, and the mixture was further stirred at 105°C for 4 hours. Next, the excess amount of allyl glycidyl ether and the solvent 1,3-bis(trifluoromethyl)benzene were distilled off under reduced pressure to obtain 4.6g of a block copolymer represented by the following formula (54).

[0114] [ka]

[0115] [Evaluation of solubility in non-fluorinated organic compounds] 1 g of the block copolymer of the above Examples and Comparative Examples was mixed with 9 g of the following non-fluorinated organic compound, and the mixture was visually observed to evaluate the solubility according to the following criteria.

[0116] Evaluation criteria ○: The mixture is transparent. △: The mixture is cloudy. ×: The mixture is separated into two phases.

[0117] [Table 22]

[0118] The results in Table 22 show that the perfluoropolyether-organopolysiloxane block copolymer of the present invention has better solubility in non-fluorinated organic compounds than perfluoropolyether compounds not containing organopolysiloxane and the block copolymers of the comparative examples having a low siloxane content. In addition, the perfluoropolyether-organopolysiloxane block copolymer of the present invention is useful for applications such as a surface modifier for non-fluorine-based organic resins because it is easy to control the number of organosiloxane units, the number of siloxane units having one or more groups selected from a hydroxy group, a phenol group, an epoxy group, and a carboxylic anhydride group, and the number of siloxane units having one or more groups selected from an aralkyl group and a group having an oxyalkylene unit. This makes it possible to control the compatibility and the crosslink density of the cured product.

Claims

1. The perfluoropolyether-organopolysiloxane block copolymer has a perfluoropolyether block and an organopolysiloxane block, and is represented by the following formula (1), and the organopolysiloxane block has, on a side chain thereof, one or more organic groups containing a reactive functional group selected from an oxyalkylene group, a hydroxyalkyl group, a hydroxyaryl group, an epoxy group, and a carboxylic acid anhydride group. 【Chemistry 1】 [In formula (1), Rf is represented by the following formula (2) 【Chemistry 2】 (In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Each repeating unit may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.) is a perfluoropolyether block represented by W1 is represented by the following formula (A): 【Chemistry 3】 (In formula (A), R 1 are independently selected from alkyl groups having 1 to 18 carbon atoms and phenyl groups. 2 R is one or more reactive functional groups selected from an oxyalkylene group represented by the following formula (3), an ω-hydroxyalkyl group having 3 to 12 carbon atoms, an organic group having 9 to 18 carbon atoms and a hydroxyaryl group, an organic group having 6 to 15 carbon atoms and an epoxy group, and an organic group having 4 to 32 carbon atoms and a carboxylic anhydride group. 3 represents one or more groups selected from an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the following formula (4): 【Chemistry 4】 (In formula (3), R 4 is an alkylene group having 2 to 4 carbon atoms, j is a number from 3 to 12, and k is a number from 1 to 60. The oxyalkylene units bracketed by k are composed of one type or two or more types, and when composed of two or more types, the arrangement order of the units is not limited and may be random or block. 【Chemistry 5】 (In formula (4), R 4 is an alkylene group having 2 to 4 carbon atoms, R 5 is an alkyl group having 1 to 4 carbon atoms, m is a number from 3 to 12, and n is a number from 1 to 60. The oxyalkylene units bracketed by n are composed of one type or two or more types, and when composed of two or more types, the arrangement order of the units is not limited and may be random or block. Each of p1, q1, and r1 is a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a divalent organopolysiloxane block represented by Each W2 independently represents the following formula (B): 【Chemistry 6】 (In formula (B), R 1 are independently selected from alkyl groups having 1 to 18 carbon atoms and phenyl groups. 2 R is one or more reactive functional groups selected from the group consisting of an oxyalkylene group represented by the above formula (3), an ω-hydroxyalkyl group having 3 to 12 carbon atoms, an organic group having 9 to 18 carbon atoms and containing a hydroxyaryl group, an organic group having 6 to 15 carbon atoms and containing an epoxy group, and an organic group having 4 to 32 carbon atoms and containing a carboxylic anhydride group. 3 R is one or more groups selected from an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the above formula (4). 1 Each ' is independently a group selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. p2, q2 and r2 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a monovalent organopolysiloxane block represented by However, q1 in the above formula (A) and q2 in the above formula (B) are not 0 at the same time. Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2; g is a number from 0 to 50, but when g is 0, q2 in formula (B) of W2 does not become 0.]

2. 2. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, which has a weight average molecular weight of 4,000 to 500,000 and an organopolysiloxane block content in one molecule of 50% or more.

3. 3. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein the perfluoropolyether block represented by Rf is a group represented by the following formula (5): 【Chemistry 7】 In formula (5), v and w are each a number from 0 to 200, and v+w=3 to 200. 2 F 4 The repeating units of may be linear or branched. The arrangement order of the repeating units is not limited and may be random or block.

4. R in formula (A) or formula (B) 2 is an oxyalkylene group represented by formula (3), and R 4 2. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein is an alkylene group having 2 or 3 carbon atoms.

5. R in formula (A) or formula (B) 2 2. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein is an ω-hydroxyalkyl group having 3 to 12 carbon atoms.

6. R in formula (A) or formula (B) 2 The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein is an organic group having a hydroxyaryl group represented by the following formula (6): 【Chemistry 8】 (In formula (6), a is a number from 3 to 4, and R 6 is a group selected from a hydrogen atom, a methoxy group, and a hydroxy group.

7. In formula (6), R 6 The perfluoropolyether-organopolysiloxane block copolymer according to claim 6, wherein is a hydrogen atom or a methoxy group.

8. R in formula (A) or formula (B) 2 The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein is an organic group having an epoxy group represented by the following formula (7): 【Chemistry 9】 (In formula (7), j is a number from 3 to 12.)

9. R in formula (A) or formula (B) 2 The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein is an organic group having an epoxy group represented by the following formula (8): 【Chemistry 10】

10. R in formula (A) or formula (B) 2 The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein is an organic group having a carboxylic acid anhydride group represented by the following formula (9) or (10): 【Chemistry 11】 (In formula (9), R 7 are independently a hydrogen atom, or a group selected from an alkyl group having 1 to 8 carbon atoms and a phenyl group; and b is an integer of 0 to 4. 【Chemistry 12】

11. 2. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein in formula (A) and formula (B), r1+r2>1.

12. R in formula (A) or formula (B) 3 The perfluoropolyether-organopolysiloxane block copolymer according to claim 11, wherein is an oxyalkylene group represented by formula (4).

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