JP2022000417A - Fluoroalkyl-substituted silane compound, production method of the same, and surface modification composition containing the same - Google Patents

Abstract

To provide a surface modification agent that is extremely excellent in film uniformity and water and oil repellency in surface modification and soluble in a general-purpose organic solvent, and contains only perfluoroalkyl structure of 6 or less carbons.SOLUTION: A fluoroalkyl-substituted silane compound having a terminal functional silyl group is produced by connecting with perfluoroalkyl group and perfluoroalkylene group of 4 and/or 6 carbons using a vinylene structure. A composition containing the same modifies a substrate surface.SELECTED DRAWING: None

Description

The present invention is a fluoroalkyl substituted silane compound having a carbon-carbon unsaturated bond, a method for producing the same, a surface modification composition containing the compound, and a surface modification method using the same, which are useful for surface modifiers and the like. Regarding.

Since the fluorine-carbon bond has a small polarizability, the surface free energy of fluoroalkanes is extremely low. Fluoroalkyl-based materials exhibit properties such as heat resistance, chemical resistance, water and oil repellency, low friction, and low refractive index, and are therefore widely used industrially as functional materials. In particular, in a surface-modifying functional product that imparts water repellency and oil repellency to a solid surface, the introduction of a perfluoroalkyl group on the solid surface makes it possible to impart high functionality. , A surface modifier having a covalent group to a solid surface such as a functional silyl group is generally used. Surface modification functions of the surface modifier, although perfluoroalkyl chain length of the molecule becomes significant, the effect longer, the number of carbon atoms is ₈ (C 8 F ₁₇ group) or a long-chain perfluoroalkyl group Compounds having the above have problems in harmfulness due to their residue and accumulation in the environment and the human body, and avoiding their use is internationally essential. Therefore, studies have been conducted on using a compound having a perfluoroalkyl group having 6 or less carbon atoms in the molecule to exhibit a good function for surface modification, but having a perfluoroalkyl group having 8 or more carbon atoms. Performance is generally lower than that of compounds.

As a method for improving water repellency and oil repellency by using a material having a perfluoroalkyl group having 6 or less carbon atoms in the molecule, various interactions between the molecules are performed between the perfluoroalkyl group and the group that binds to the substrate. (For example, see Patent Document 1).
By replacing a part of the fluorine atom of the perfluoroalkyl group with a hydrogen atom, it can be used as a modifier as a constituent of a perfluoroalkyl group unit having 6 or less carbon atoms, which is considered to have low bioaccumulation. It is known (see, for example, Patent Document 2 and Patent Document 3).

Further, a material having a perfluoroalkylene polyether structure such as Optool (registered trademark) is also known.
In Patent Document 4, the reaction between a diene compound having both a perfluoroalkyl group and a perfluoroalkylene group in the molecule and a hydrosilane compound is good even though it is composed of a perfluoroalkyl group unit having 6 or less carbon atoms. The synthesis of fluoroalkyl substituted silane compounds having various properties is disclosed. However, its surface modification performance is not high, and further improvement in surface modification performance has been required. Further, in terms of its production, it is not possible to obtain a good yield by a known method, so improvement of the production method has been required.

International Publication No. 2009/087981 Patent No. 5146455 Japanese Unexamined Patent Publication No. 2014-040373 International Publication No. 2017/119371

The subject of the present invention is a novel fluoroalkyl-substituted silane compound having a molecular structure composed of a perfluoroalkyl group unit having up to 6 carbon atoms and imparting a higher water-repellent and oil-repellent effect to a solid surface than before. , A high-yield production method thereof, and a surface modifier composition comprising the same.

As a result of diligent studies to solve the above problems, the inventors have linked a perfluoroalkyl chain having 6 or less carbon atoms and a perfluoroalkylene group via a carbon-carbon unsaturated double bond, and attached the perfluoroalkylene group to the solid surface. High water repellency and oil repellency can be achieved by efficiently producing a fluoroalkyl-substituted silane compound having a chemically bondable functional silyl group at the end and modifying the solid surface using a composition containing the fluoroalkyl-substituted silane compound. We have found that it can be applied to a solid surface, and have completed the present invention.

That is, the present invention has the following configuration.
[1]
General formula (1)

(In the formula, n and m are independently 4 or 6, respectively. K is 0, 1 or 2. R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when k is 2, 2 The two Rs may be the same or different. X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and when k is 1 or 0, the two or three Xs may be the same or different. ) Is a fluoroalkyl substituted silane compound.
[2]
The fluoroalkyl substituted silane compound according to [1], wherein n and m are 6 in the general formula (1).
[3]
The fluoroalkyl substituted silane compound according to [1] or [2], wherein k is 0 and X is a chlorine atom, a methoxy group or an ethoxy group in the general formula (1).
[4]
General formula (2)

(In the formula, n and m are independently 4 or 6, respectively.) The fluorine-containing diene compound represented by the formula and the general formula (3).

(In the formula, k is 0, 1 or 2. R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when k is 2, the two Rs may be the same or different. Representing a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and when k is 1 or 0, two or three Xs may be the same or different from each other), and a hydrosilylation catalyst. The general formula (1), which is characterized by using

(In the formula, n, m, k, R and X have the same meanings as described above.) A method for producing a fluoroalkyl-substituted silane compound.
[5]
The method for producing a fluoroalkyl-substituted silane compound according to [4], which comprises producing in a fluorine-containing organic solvent.
[6]
The fluorine-containing organic solvent comprises at least one selected from the group consisting of 2H, 3H-decafluoropentane, benzotrifluoride, 1,3-bis (trifluoromethyl) benzene and hexafluorobenzene, according to [5]. A method for producing a fluoroalkyl-substituted silane compound.
[7]
The method for producing a fluoroalkyl-substituted silane compound according to any one of [4] to [6], wherein the hydrosilylation catalyst is a platinum group transition metal catalyst.
[8]
The method for producing a fluoroalkyl-substituted silane compound according to claim 7, wherein the platinum group transition metal catalyst is hexachloroplatinic acid, tris (triphenylphosphine) rhodium chloride, or a 1,3-divinyltetramethyldisiloxane platinum complex [9]. ]
General formula (1b)

(In the formula, n and m are independently 4 or 6, respectively. K is 0, 1 or 2. R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when k is 2, 2 The two R's may be the same or different. X ² represents an alkoxy group having 1 to 3 carbon atoms.) Is a method for producing an alkoxy-substituted fluoroalkyl-substituted silane compound represented by the general formula (1a).

(In the formula, n, m, k and R have the same meanings as described above ^{. X 1} represents a halogen atom.) The halogen-substituted fluoroalkyl-substituted silane compound represented by the above is reacted with an alkoxy agent. Manufacturing method.
[10]
The method for producing an alkoxy-substituted fluoroalkyl-substituted silane compound according to [9], wherein the alkoxy agent comprises at least one selected from the group consisting of alcohols, metal alkoxides, trialkyl orthoformates and alkyl ethers.
[11]
A surface-modified composition comprising the fluoroalkyl-substituted silane compound according to any one of [1] to [3] and an organic solvent.
[12]
The surface modification composition according to [11], which comprises the fluoroalkyl substituted silane compound according to any one of [1] to [3], an organic solvent and an acid catalyst.
[12]
[11] A method for surface modification of a glass, metal oxide or metal substrate, which comprises applying the surface modification composition according to [11] or [12].

Hereinafter, the present invention will be described in detail.
^{First, R, X, X 1} and X ² in the general formulas (1), (1a), (1b), (2) and (3) will be described. R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they have two Rs in the molecule, they may be the same or different from each other. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group and a cyclopropyl group. Of these, a methyl group, an ethyl group or a propyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable, from the viewpoints of raw material cost, performance of a surface modifier and ease of purification.
X is a halogen atom or an alkoxy group having 1 to 3 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom, a chlorine atom or a bromine atom is preferable, a chlorine atom or a bromine atom is more preferable, and a chlorine atom is particularly preferable, from the viewpoints of performance, storage stability and economic efficiency of the surface modifier. Moreover, as the alkoxy group, a methoxy group, an ethoxy group, a propyloxy group or an isopropyloxy group can be exemplified. Of these, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable, from the viewpoint of raw material cost, performance of the surface modifier, and ease of purification. The ^{group represented by X 1} is a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom, a chlorine atom or a bromine atom is preferable, a chlorine atom or a bromine atom is more preferable, and a chlorine atom is particularly preferable from the viewpoint of yield and economy. The ^{group represented by X 2} is an alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group or an isopropyloxy group. Of these, a methoxy group or an ethoxy group is more preferable, and a methoxy group is particularly preferable, from the viewpoint of raw material cost yield and ease of purification.
Next, the fluoroalkyl substituted silane compound (1) of the present invention will be described. The fluoroalkyl substituted silane compound of the present invention has the following general formula (1).

Indicated by. Here, n and m in the general formula (1) are independently 4 or 6, respectively, and the C _n F _{2n + 1} and C _m F _2m groups are a perfluoroalkyl group (monovalent group) and a perfluoroalkylene group (divalent group, respectively). Based on). As their structure, they may have a branched structure, but since it is considered that a straight-chain perfluoroalkyl group tends to have a self-association structure and easily form a monolayer on the surface of the substrate, it is straight-chain. Perfluoroalkyl groups and linear perfluoroalkylene groups are preferred. As for n and m, n is 6 and m is 4, n is 4 and m is 6, or n and m are from the point that the larger the chain length of the perfluoroalkyl group and the perfluoroalkylene group is, the higher the surface modification ability is. Both are preferably 6, and more preferably n and m are both 6. The vinylene unit (-CH = CH-) gives both E- and Z-geometric isomers, but it is considered to be an E-geometric isomer because it is considered that a monomolecular layer is easily formed on the surface of the substrate. Is preferable.
The following compounds can be exemplified as the fluoroalkyl substituted silane compound represented by the general formula (1) of the present invention. In addition, in this specification, Me, Et, Pr and ⁱ Pr represent a methyl group, an ethyl group, a propyl group and an isopropyl group, respectively.

Of these, (1a-1), (1a-2), (1b-1), (1b-2) or (1a-1), (1a-2), (1b-1), (1b-2) or (1a-1), (1a-2), (1b-1), (1b-2) or 1b-3) is preferable, (1a-1), (1a-2), (1b-1) or (1b-3) is more preferable, and (1a-1) or (1b-1) is particularly preferable.
Next, a method for producing the fluoroalkyl-substituted silane compound (1) of the present invention will be described. The fluoroalkyl-substituted silane compound (1) can be produced by the production method 1 or the production method 2 described below.
First, the manufacturing method 1 will be described. The production method 1 is a fluoroalkyl-substituted silane compound (1) by reacting a fluorine-containing diene compound represented by the general formula (2) with a hydrosilane compound represented by the general formula (3) in the presence of a hydrosilylation catalyst. It is characterized by obtaining.

(In the formula, R, X and k are synonymous with their respective definitions in the general formula (1).)
The number of carbon chains of the perfluoroalkyl group or perfluoroalkylene group represented by n or m in the general formulas (1) and (2) is 4 or 6 independently, respectively, and the raw material cost and yield are high. It is preferable that n is 6 and m is 4, n is 4 and m is 6, or n and m are all 6, and it is more preferable that n and m are all 6. Examples of the alkyl group having 1 to 3 carbon atoms represented by R in the general formulas (1) and (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group and a cyclopropyl group. Of these, a methyl group, an ethyl group or a propyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable, from the viewpoints of raw material cost, performance of a surface modifier and ease of purification. The group represented by X in the general formulas (1) and (3) is a halogen atom or an alkoxy group having 1 to 3 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of yield and stability, a fluorine atom, a chlorine atom or a bromine atom is preferable, and a chlorine atom or a bromine atom is more preferable. Chlorine atoms are particularly preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group or an isopropyloxy group, and a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable, from the viewpoint of easy yield and purification.
Examples of the fluorine-containing diene compound (2) that can be used as a raw material in the production method 1 include the following.

Of these, (2-3) or (2-4) is preferable, and (2-4) is more preferable, in terms of yield and ease of purification operation. These can be appropriately synthesized and used according to a known synthesis method (International Publication No. 2017/119371).
Examples of the hydrosilane compound (3) that can be used as a raw material in the production method 1 include the following.

Of these, from the viewpoint of economy, yield and safety, (3-1), (3-4), (3-6), (3-7), (3-8), (3-11). ), (3-12), (3-27) or (3-28), preferably (3-1), (3-4), (3-6), (3-7), (3-11). ) Or (3-27) is more preferable. These may be commercially available products or may be synthesized and used by a known synthetic method.

The production method 1 may be carried out under solvent-free conditions, but may be carried out in a fluorine-containing organic solvent if necessary. Production in a fluorine-containing organic solvent suppresses evaporation and dissipation of the hydrosilane compound (3) due to heating, and increases the reaction rate of the hydrosilylation reaction. The fluoroalkyl-containing organic solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and is a fluoroalkyl such as benzotrifluoride (α, α, α-trifluorotoluene) and 1,3-bis (trifluoromethyl) benzene. Substituted aromatic hydrocarbon solvents; fluoroaromatic hydrocarbon solvents such as pentafluorobenzene and hexafluorobenzene; 2H, 3H-decafluoropentane (Bertrel), tetradecafluorohexane, octadecafluorooctane, dodecafluorocyclohexane, 1, Examples thereof include fluoroaliphatic hydrocarbon solvents such as 3-bis (trifluoromethyl) decafluorocyclohexane and perfluorokerocene. 2H, 3H-decafluoropentane, benzotrifluoride, 1,3-bis (trifluoromethyl) benzene or hexafluorobenzene are preferable in terms of economy and yield. These fluorine-containing organic solvents may be used alone or may be used by mixing a plurality of fluorine-containing organic solvents at an arbitrary ratio. The amount of the fluorine-containing organic solvent used is preferably in the range of 0.1 to 1000% by weight, preferably 1 to 200% by weight, based on the weight of the fluorine-containing diene compound (2) from the viewpoint of yield. More preferred.
It is a feature of the present invention that the production method 1 is carried out in the presence of a hydrosilylation catalyst. Examples of the hydrosilylation catalyst include radical-generating hydrosilylation catalysts such as azobis (isobutyronitrile) (AIBN), di-tert-butyl peroxide, tert-butylhydroperoxide, and benzoyl peroxide (BPO); aluminum chloride, Hydrosilylation catalysts of Lewis acid such as gallium chloride, indium chloride, boron trifluoride, boron tris (pentafluorophenyl); metallic palladium, metallic platinum, palladium activated charcoal, platinum activated charcoal, platinum chloride acid, palladium chloride, palladium acetate, tris ( Triphenylphosphine) rhodium chloride, (1,3-divinyltetramethyldisiloxane) platinum complex, 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane) platinum complex, etc. An example is a platinum group transition metal catalyst. Platinum group transition metal catalysts are preferred in terms of safety, yield and catalytic activity, with platinum chloride acid, tris (triphenylphosphine) rhodium chloride, (1,3-divinyltetramethyldisiloxane) platinum complex or 2, A platinum complex (4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane) is more preferred, and platinum chloride acid or tris (triphenylphosphine) rhodium chloride is even more preferred.
In the production method 1, there is no limitation on the amount of the hydrosilylation catalyst used, and it can be carried out using a general molar equivalent when a person skilled in the art carries out the hydrosilylation reaction. As a specific example, it can be carried out at an equivalent amount appropriately selected from the catalytic molar equivalent range in which the molar equivalent of the catalyst is 0.00001 molar equivalent to 0.5 molar equivalent with respect to the molar equivalent of the diene compound. In terms of yield and economy, it is preferably in the range of 0.0001 molar equivalent to 0.2 molar equivalent, and even more preferably in the range of 0.001 molar equivalent to 0.1 molar equivalent.
The equivalent ratio of the fluorine-containing diene compound (2) to the hydrosilane compound (3) when the production method 1 is carried out is not particularly limited, but for example, the hydrosilane compound (3) has a molar equivalent of the fluorine-containing diene compound (2). Is preferably carried out at an equivalent amount appropriately selected from the range of 0.8 to 100 molar equivalents in terms of good yield.
The mixing order of the fluorine-containing diene compound (2), the hydrosilane compound (3) and the hydrosilylation catalyst in carrying out the production method 1 is not particularly limited, but for example, the fluorine-containing diene compound (2) is mixed with the hydrosilylation catalyst. However, the method of adding the hydrosilane compound (3) here is preferable from the viewpoint of safety. Further, when carrying out in a fluorine-containing organic solvent described later, for example, a method of mixing a fluorine-containing diene compound (2) and a fluorine-containing organic solvent with a hydrosilylation catalyst and adding a hydrosilane compound (3) to the mixture is safe. It is preferable from the viewpoint of sex.
When the production method 1 is carried out, it is preferably carried out in an inert gas atmosphere in terms of good yield. Specific examples of the inert gas include nitrogen, helium, neon, and argon. Nitrogen or argon is preferable because of its low cost.
In the production method 1, the reaction temperature and the reaction time are not limited, and general conditions for a person skilled in the art to carry out the hydrosilylation reaction can be used. As a specific example, the fluoroalkyl-substituted silane compound (1) is obtained by selecting a reaction time appropriately selected from the range of 1 minute to 120 hours at a reaction temperature appropriately selected from the temperature range of −10 ° C. to 300 ° C. It can be manufactured efficiently.
The fluoroalkyl-substituted silane compound (1) can be produced by appropriately selecting n, m, k, R and X in the production method 1. Examples of the fluoroalkyl-substituted silane compound (1) that can be produced by the production method 1 include the following compounds.

Among these, (1a-1), (1a-2), (1b-1), (1b-2) or (1b-3) is preferable, and (1a-1) is preferable in terms of economic efficiency and excellent yield. ), (1a-2), (1b-1) or (1b-3) is more preferable, and (1a-1) or (1b-1) is particularly preferable.

The fluoroalkyl-substituted silane compound (1) produced by the production method 1 can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies a functional organic silane compound. Specific purification methods include concentration, distillation, filtration, centrifugation, washing, extraction, column chromatography separation, etc., which can be appropriately selected and used in combination for purification as necessary. You can.

Next, the manufacturing method 2 will be described. In the production method 2, among the fluoroalkyl-substituted silane compounds (1) of the present invention, the halogen atom-substituted fluoroalkyl-substituted silane compound (1a) produced in the production method 1 is reacted with an alkoxy agent to obtain an alkoxy-substituted fluoro. It is characterized by producing an alkyl substituted silane compound (1b).

(In the formula, X ¹ represents a halogen atom. n and m are independently 4 or 6, respectively. K is 0, 1 or 2. X ² represents an alkoxy group having 1 to 3 carbon atoms. R. Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
When R in the general formulas (1a) and (1b) is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and has two Rs in the molecule, a plurality of Rs may be the same or different from each other. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group and a cyclopropyl group. Of these, a methyl group, an ethyl group or a propyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable, from the viewpoint of raw material cost, yield and ease of purification. The ^{group represented by X 1} is a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom, a chlorine atom or a bromine atom is preferable, a chlorine atom or a bromine atom is more preferable, and a chlorine atom is particularly preferable, from the viewpoints of yield, operability in manufacturing and economic efficiency. The ^{group represented by X 2} is an alkoxy group having 1 to 3 carbon atoms, and examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group or an isopropyloxy group. Of these, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable, from the viewpoint of raw material cost, yield and ease of purification. The number of carbon chains of the fluoroalkyl group represented by n or m in the general formulas (1a) and (1b) is 4 or 6, respectively, and n is 6 and m is good in terms of raw material cost and yield. 4, n is 4 and m is 6, or n and m are all 6, and it is more preferable that n and m are both 6.
Examples of the halogen atom-substituted fluoroalkyl-substituted silane compound (1a) that can be used as a raw material in the production method 2 include the following.

Of these, (1a-1), (1a-2), (1a-5) or (1a-8) are preferable, and (1a-1), (1a-2) or ( 1a-8) is more preferable.
The halogen atom-substituted fluoroalkyl-substituted silane compound (1a) used in the production method 2 may be the one produced by the production method 1, and the halogen atom-substituted fluoroalkyl-substituted silane compound (1a) purified after the production method 1 may be used. It may be used, or the production mixture obtained by the production method 1 may be used as it is in the production method 2.
The production method 2 is characterized in that an alkoxylation is carried out using a halogen atom-substituted fluoroalkyl-substituted silane compound (1a) and an alkoxy agent to produce an alkoxy-substituted fluoroalkyl-substituted silane compound (1b). Examples of the alkoxide include alcohols such as methanol, ethanol, 1-propanol and 2-propanol; lithium methoxydo, sodium methoxydo, potassium methoxydo, lithium ethoxydo, sodium ethoxydo, potassium ethoxydo and sodium 1-. Metal alkoxides such as propyl oxide, potassium propyl oxide, sodium 2-propyl oxide, potassium 2-propyl oxide; orthogic acid esters such as trimethyl orthostate, triethyl orthogeate, tripropyl orthogeate; tert-butylmethyl ether, benzyl Examples thereof include alkyl ethers such as methyl ether.
The equivalent ratio between the halogen atom-substituted fluoroalkyl-substituted silane compound (1a) and the alcohol produced by using alcohol as the alkoxylating agent in the production method 2 is not particularly limited, but for example, the halogen atom-substituted fluoroalkyl-substituted silane compound (1a). ), It is preferable to carry out alcohol at an equivalent amount appropriately selected from the range of 0.8 to 100 molar equivalents with respect to 1 molar equivalent of halogen atoms in terms of good yield.
In the production method 2 in which alcohol is used as the alkoxy agent, a hydrogen halide scavenger that captures by-produced hydrogen halide may be present. Examples of the hydrogen halide trapping agent include ammonia such as gaseous ammonia, liquid ammonia and ammonia alcohol solution; aliphatic secondary amines such as dimethylamine, diethylamine and diisopropylamine; trimethylamine, triethylamine, diethylisopropylamine, triethylenediamine and the like. Examples thereof include aliphatic tertiary amines; aromatic amines such as aniline, pyridine, 4-dimethylaminopyridine, and quinoline; alkali metals such as metallic lithium, metallic sodium, metallic calcium, and metallic magnesium, and alkaline earth metals. .. Diethylamine, triethylamine, aniline or pyridine is preferable, and triethylamine or pyridine is more preferable from the viewpoint of yield, operability and safety.
In the production method 2 in which alcohol is used as the alkoxy agent, it is preferable to carry out the production in an inert gas atmosphere in terms of good yield. Specific examples of the inert gas include nitrogen, helium, neon, and argon. Nitrogen or argon is preferable because of its low cost.
In the production method 2 in which alcohol is used as the alkoxy agent, the production may be carried out in an organic solvent. Examples of the organic solvent include aliphatic hydrocarbon organic solvents such as hexane, heptane and octane; aromatic hydrocarbon organic solvents such as benzene, toluene and xylene; diethyl ether, tetrahydrofuran, 1,4-dioxane, diisopropyl ether and cyclopentylmethyl. Examples thereof include ether-based organic solvents such as ether. Tetrahydrofuran, cyclopentyl methyl ether or toluene is preferable, and tetrahydrofuran is more preferable, from the viewpoint of yield and safety. Further, it is also possible to use an alcohol as an alkoxy agent in an excessive amount and use it as a reaction reagent and an organic solvent.
In the production using an alcohol as an alkoxylating agent in the production method 2, the reaction temperature and the reaction time are not particularly limited, and general conditions for carrying out an alkoxylation reaction of silane halide by those skilled in the art can be used. I can. As a specific example, an alkoxy-substituted fluoroalkyl-substituted silane compound (1b) is obtained by selecting an appropriately selected reaction time from a range of 1 minute to 120 hours at a reaction temperature appropriately selected from a temperature range of −10 ° C. to 300 ° C. ) Can be produced in good yield.

In the production using a metal alkoxide as an alkoxide in the production method 2, lithium methoxide, sodium methoxide, lithium ethoxide or sodium ethoxide is preferable, and sodium methoxide or sodium ethoxide is preferable from the viewpoint of economy and yield. Is more preferable. It is preferable to use 0.8-1.2 equivalents of these metal alkoxides with respect to the molar equivalent of the halogen atom of the halogen atom substituted fluoroalkyl substituted silane compound (1a) from the viewpoint of yield. In the production using a metal alkoxide as an alkoxy agent, the halogen atom-substituted fluoroalkyl-substituted silane compound (1a) and the metal alkoxide are mixed and produced in an organic solvent. The organic solvent is not limited as long as it does not inhibit the reaction, and is an aliphatic hydrocarbon organic solvent such as hexane, heptane and octane; an aromatic hydrocarbon organic solvent such as benzene, toluene and xylene; diethyl ether and tetrahydrofuran. , 1,4-Dioxane, diisopropyl ether, cyclopentylmethyl ether and other ether-based organic solvents can be exemplified. Tetrahydrofuran, cyclopentyl methyl ether or toluene is preferable, and tetrahydrofuran is more preferable, from the viewpoint of yield and safety. Further, the metal alkoxide can also be used as a solution (alcolate) to an alcohol corresponding to the protonated product.
In the production using trialkyl orthoformate as the alkoxy agent in the production method 2, lower orthoformate esters such as trimethyl orthoformate and triethyl orthoformate can be used, and trimethyl orthoformate is preferable from the viewpoint of yield. The amount of the trialkyl orthoformate used is preferably 0.8-10 equivalents with respect to the molar equivalent of the halogen atom of the halogen atom-substituted fluoroalkyl-substituted silane compound (1a) from the viewpoint of yield. In the production using trialkyl orthoformate as an alkoxyagent, the halogen atom-substituted fluoroalkyl-substituted silane compound (1a) and trialkyl orthoformate are mixed, and the reaction temperature is appropriately selected from the range of 0 ° C to 200 ° C for 1 minute. By selecting an appropriately selected reaction time from the range of 120 hours to 120 hours, the alkoxy-substituted fluoroalkyl-substituted silane compound (1b) can be produced in good yield.
In the production using alkyl ethers as the alkoxy agent in the production method 2, alkyl ethers such as tert-butyl methyl ether, tert-butyl ethyl ether, benzyl methyl ether, benzyl ethyl ether, and (diphenylmethyl) methyl ether are used. Therefore, tert-butyl methyl ether is preferable from the viewpoint of economy and operability. The amount of the alkyl ethers used is preferably 0.8-3 equivalents with respect to the molar equivalent of the halogen atom of the halogen atom substituted fluoroalkyl substituted silane compound (1a) from the viewpoint of yield. A Lewis acid catalyst is indispensable for production using alkyl ethers as an alkoxylating agent. As the Lewis acid catalyst, metal halide Lewis acids such as anhydrous bismuth chloride, anhydrous aluminum chloride, and indium chloride can be used. The equivalent of the Lewis acid catalyst is preferably an equivalent selected appropriately from the range of 0.001 equivalent to 1 equivalent with respect to the halogen-substituted fluoroalkyl-substituted silane compound (1a) from the viewpoint of yield and economy. .. Halogen-substituted fluoroalkyl-substituted silane compound (1a), alkyl ethers and Lewis acid catalyst are mixed, and a reaction appropriately selected from the range of 1 minute to 120 hours at a reaction temperature appropriately selected from the range of -20 ° C to 200 ° C. By selecting the time, the alkoxy-substituted fluoroalkyl-substituted silane compound (1b) can be produced in good yield.

In the production method 2, n, m, k, R, by appropriately selecting the ^{X 1} and ^{X 2,} alkoxy-substituted fluoroalkyl-substituted silane compound (1b) the can be produced in good yield. Examples of the alkoxy-substituted fluoroalkyl-substituted silane compound (1b) that can be produced by the production method 2 include the following compounds.

Of these, (1b-1), (1b-2), (1b-3), (1b-5), (1b-13) or (1b-14) are preferable in terms of good yield. 1b-1), (1b-2) or (1b-13) is more preferable.
The alkoxy-substituted fluoroalkyl-substituted silane compound (1b) produced by the production method 2 can be purified by appropriately selecting and using a general purification method for purifying alkoxylated silanes by those skilled in the art. Specific purification methods include filtration, concentration, extraction, centrifugation, washing, distillation and the like.

Next, the surface-modified composition of the present invention (hereinafter, also referred to as the composition of the present invention) will be described. The composition of the present invention comprises the fluoroalkyl substituted silane compound (1) of the present invention and an organic solvent. Further, it may contain an acid catalyst, water, and other auxiliaries that facilitate the surface modification action. The fluoroalkyl-substituted silane compound in the composition of the present invention is represented by the general formula (1). Examples of the fluoroalkyl-substituted silane compound (1) that can be used in the composition of the present invention include the following.

Of these, (1a-1), (1a-2), (1a-3), (1a-8), and (1b-1) are excellent in surface modification properties, stability of the composition, and economy. ), (1b-2) or (1b-3) is preferable, and (1a-1), (1a-2), (1b-1) or (1b-2) is more preferable. As these fluoroalkyl-substituted silane compounds (1), one type may be used alone, or a plurality of fluoroalkyl-substituted silane compounds (1) may be mixed and used in an arbitrary ratio.
The concentration of the fluoroalkyl-substituted silane compound (1) in the composition of the present invention is selected from the range of 0.0001% by weight to 50% by weight with respect to the total amount of the composition from the viewpoint of economic efficiency and film homogeneity. It is preferable that the concentration is selected from 0.01% to 20% by weight, and more preferably.
As a component constituting the composition of the present invention, an organic solvent for dissolving the fluoroalkyl-substituted silane compound (1) is used. The organic solvent is not particularly limited as long as it dissolves the fluoroalkyl-substituted silane compound (1), and is a lower alcohol solvent such as methanol, ethanol and 2-propanol; acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone ( Ketones such as MIBK); ester solvents such as methyl acetate, ethyl acetate, butyl acetate; hydrocarbon solvents such as hexane, octane, benzene, toluene, xylene; 1,2-dimethoxyethane, digrim, 1,4- Examples of ether solvents such as dioxane, diethyl ether, dibutyl ether, tert-butylmethyl ether, tetrahydrofuran, and diisopropyl ether can be exemplified. Further, a fluorine-based organic solvent such as hydrofluorocarbons, perfluorocarbons, perfluoroethers or hydrofluoroalkyl ethers can also be used. As specific examples, benzotrifluoride (α, α, α-trifluorotoluene), 1,3-bis (trifluoromethyl) benzene, pentafluorobenzene, hexafluorobenzene, 2H, 3H-decafluoropentane (Bertrel), Examples thereof include tetradecafluorohexane, octadecafluorooctane, dodecafluorocyclohexane, and 1,3-bis (trifluoromethyl) decafluorocyclohexane. Of these, lower alcohol solvents such as ethanol and 2-propyl alcohol and fluorine-based organic solvents such as 1,3-bis (trifluoromethyl) benzene have high solubility of fluoroalkylsilane compounds and acid catalysts, and further. It is preferable because the coatability (easiness of spreading) and the drying time (working time) of the water-repellent liquid become appropriate. As these organic solvents, one kind may be used alone, or a plurality of organic solvents may be mixed and used in an arbitrary ratio.
The amount of the organic solvent added is preferably 50 to 99.999% by mass, more preferably 80 to 99.99% by mass, based on the total amount of the composition of the present invention. If it is less than 80% by mass, the amount of the fluoroalkyl-substituted silane compound adhered to the substrate becomes too large, and the coatability (easiness of spreading) of the composition is lowered. On the other hand, if it exceeds 99.999% by mass, the amount of the fluoroalkyl-substituted silane compound adhered to the substrate is reduced, and it becomes difficult to sufficiently develop water repellency and smoothness.
Water may be contained in the composition of the present invention. The water used in the composition of the present invention is a component for partially hydrolyzing the fluoroalkyl-substituted silane compound and smoothly chemically bonding it to the solid surface. The amount of the water added is preferably 0.1 to 200 times the number of moles of the fluoroalkyl-substituted silane compound (1), more preferably 1 to 50 times. Further, in order to adjust the water content in the composition, a dehydrating agent may be added to the water-repellent liquid and dehydration treatment may be performed for a predetermined time. As the dehydrating agent, silica gel, synthetic zeolite, activated alumina or the like can be used.
An acid catalyst that facilitates surface treatment may be added to the composition of the present invention. As the acid catalyst, either an inorganic acid or an organic acid can be used. Examples of the inorganic acid include hydrohalogenated acids such as hydrochloric acid, hydrobromic acid, and hydroiodic acid; inorganic oxo acids such as sulfuric acid, nitric acid, and perchloric acid; and organic carboxylic acids such as formic acid, acetic acid, propionic acid, and oxalic acid. Acids; methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, 2-propane sulfonic acid, butane sulfonic acid, 2-butane sulfonic acid, pentan sulfonic acid, trifluoromethane sulfonic acid, 2-hydroxyethane-1-sulfonic acid (Isetion). Acid), allyl sulfonic acid, 1,3-propanedisulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, p-xylene-2-sulfonic acid, 2-sulfobenzoic acid, 5 Examples thereof include organic sulfonic acids such as −sulfosalicylic acid and p-phenolsulfonic acid. Of these, acetic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid are preferable from the viewpoints of economy, safety, handleability and high-quality surface modification. , Methane sulfonic acid, benzene sulfonic acid or p-toluene sulfonic acid are more preferable.
The concentration of the acid catalyst in the composition of the present invention is 0.0001% by weight to 50% by weight based on the total amount of the composition in terms of economy, stability of the composition (pot life) and homogeneity of the film. The concentration is preferably selected from the range, and more preferably the concentration is selected from the range of 0.01% to 20% by weight.
The composition of the present invention may contain another silane additive having a surface modifying action. The silane additive is a functional silane having a binding action on the solid surface, such as chlorotrimethylsilane, methoxytrimethylsilane, triethoxymethylsilane, hexamethyldisilazane, tetramethyldisilazane, dichlorodimethylsilane, and dimethoxydimethylsilane. , Diethoxydimethylsilane, trichlorooctylsilane, trimethoxyoctylsilane, triethoxyoctylsilane, chlorodimethyloctylsilane, chlorodimethyloctadecylsilane, trichlorooctadecylsilane, triethoxyoctadecylsilane, triethoxy (3,3,4,4,5) , 5,6,6,7,7,8,8,8-tridecafluorooctyl) silane, triethoxy (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane, Trimethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silane, trimethoxy (3,3,4,4,5,5,6) , 6,6-nonafluorohexyl) silane, trichloro (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silane, trichloro (3,3) 3,4,4,5,5,6,6,6-nonafluorohexyl) silane and the like can be exemplified.

In the composition of the present invention, if necessary, an amine-based neutralizing agent such as triethylamine, triethanolamine, tris (2-hydroxyethyl) amine, morpholine, an ionic system for improving the wettability of the composition, and a non-ionic composition are included. Various surfactants such as systems, silicone oil that further improves lubricity, silicone varnish, and the like can also be added. These can be used in a proportion of about 0.001 to 300% by weight based on the weight of the fluoroalkyl-substituted silane compound (1) in the composition of the present invention.
The method for formulating the composition is carried out by mixing an appropriately determined amount of each component and an organic solvent. This may be stored after mixing and used as appropriate, or may be mixed immediately before coating and used for coating.
The coating of the composition of the present invention on a substrate is usually used for surface modification of a fluoroalkyl surface modifier such as a dipping method, a spraying method, an aerosol injection method, a brush coating method, and a coating method using an impregnated cloth. It can be done by any method. From the viewpoint of uniformity of surface modification, high liquid repellency, and economy, a dipping method, a brush coating method, or a coating method using an impregnated cloth is preferable, and a dipping method or a coating method using an impregnated cloth is more preferable. Further, after coating, a film curing (annealing) by heating and a washing step may be added as needed.
The surface-modifiable base material according to the composition of the present invention has a hydroxyl group to which a fluoroalkyl-substituted silane compound can be bonded to the solid surface. The shape may be a flat surface or a three-dimensional object. Further, it may be a powder or a molded body. The material of the base material may be an inorganic base material or an organic polymer base material. Examples of the inorganic base material include inorganic glass material base materials such as quartz glass, soda glass, lead glass, borosilicate glass, and phosphate glass; silicon dioxide material base materials such as single crystal quartz, polycrystalline quartz, and silica gel; zeolite. , Mulite, mica, aluminosilicate material base material such as clay minerals; metal oxide material base material such as alumina (aluminum oxide), titania (titanium oxide), zirconia (zinc oxide); double oxidation of spinel, iron ferrite, etc. A material material base material can be exemplified.
Further, since the metal surface has a hydroxyl group structure, it can also be used for surface modification treatment of the metal surface. Examples of the metal material include aluminum, titanium, iron, manganese, chromium, nickel, copper, zinc, silicon, germanium and alloys thereof.

By using the fluoroalkyl substituted silane compound of the present invention and the composition containing the same as a surface modifier, extremely high liquid repellency can be imparted to the surface of the substrate. In particular, it is suitable for water-repellent, oil-repellent, and antifouling surface modification of inorganic glass substrates.

The fluoroalkyl substituted silane compound of the present invention is useful for surface modification to glass, metal or metal oxide materials as a surface modifier capable of imparting transparent and high water repellency and oil repellency to a solid surface. Such surface-modified materials can be used as contact-type devices such as touch panels, optical window materials, water-repellent / stain-resistant materials, and mold release molds. In particular, it can be suitably used for windowpanes and mirrors for aircraft and automobiles, and for water-repellent and antifouling treatment of vehicle bodies.
Further, since the fluoroalkyl-substituted silane compound has a reactive functional group at one end, it can be used as an amphipathic molecule and as a fluorus phase surfactant. Furthermore, by converting a reactive functional group and converting it to another group, it can be used as a raw material for a surface modifier having a new molecular structure, such as a completely condensed type or an incompletely condensed type silsesquioxane. You can expect to use it.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention should not be construed as being limited by the specific examples shown below.
All the productions described in Examples and Comparative Examples were carried out in an argon atmosphere. Instrumental analysis includes ¹ H-NMR (proton nuclear magnetic resonance spectrum), ¹³ C-NMR (carbon 13 nuclear magnetic resonance spectrum), ¹⁹ F-NMR (fluoronuclear magnetic resonance spectrum) and ²⁹ Si-NMR (silicon 29 nuclear magnetic resonance). (Resonance spectrum) The measurement was performed using Bruker's Avance series Ascend 400 nuclear magnetic resonance spectrometer. Heavy chloroform is used as the solvent for nuclear magnetic resonance spectrum measurement, tetramethylsilane is used as the internal standard for ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR, and hexafluorobenzene is used as the secondary external for ^{19 F-NMR.} A chemical shift was sought as a reference material. The IR (infrared absorption) spectrum was measured using an FT-720 spectrophotometer manufactured by HORIBA, Ltd. and a DuraSamplIRII (reflection type) measuring cell manufactured by SensIR technologies.
In the surface modification test, a soda glass plate (short side 26 mm, long side 76 mm) that had been thoroughly washed and cleaned was used as a base material, and after surface modification, the surface was washed and visually observed for surface contamination and the like. For the contact angle in the liquid repellency test, 10 μL droplets dispensed from a microsyringe were placed on the surface-modified substrate at five locations with respect to two liquids, water and n-hexadecane, and the droplets were promptly applied. Photographed from the horizontal direction of the surface-modified substrate with a horizontal optical axis 10x macrophotographer equipped with an xyzφ stage (objective lens: Fotar 25 mm manufactured by Ernstritz, flange back 220 mm), and θ / from the aspect ratio of the droplets. The contact angle was obtained by two methods, and the average value and standard deviation were calculated from the measured values at five locations. For the water slip angle, 50 μL of water droplets dispensed from a microsyringe are placed on a surface-modified substrate, and the tilt stage is slowly tilted to determine the critical angle at which the water droplets start moving 5 times, and the average value and standard deviation are obtained. Was calculated.
(9E) -3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15 used in manufacturing , 15, 16, 16, 16-pentacosafluorohexadeca-1,9-diene (Compound (2-4)) was synthesized according to the method described in International Publication No. WO2017 / 119371. Hexafluorobenzene (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1,3-bis (trifluoromethyl) benzene (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), trichlorosilane (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), tris (triphenyl) Hosphin) rhodium chloride (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), p-toluenesulfonic acid (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), trichloro (3,3,4,4,5,5,6,6,7,7) , 8,8,8-Tridecafluorooctyl) Silane (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8) -Tridecafluorooctyl) silane (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), triethylamine (reagent manufactured by Fujifilm Wako Junyaku Co., Ltd.), toluene (reagent manufactured by Fujifilm Wako Junyaku Co., Ltd.), dehydrated tetrahydrofuran (Fujifilm Wako Jun) Yakuhin Co., Ltd. reagent), dehydrated methanol (Fujifilm Wako Junyaku Co., Ltd. reagent), 2-propanol (Fujifilm Wako Junyaku Co., Ltd. reagent), chloroform (Kanto Chemical Co., Ltd. reagent) and dichloromethylsilane (reagent manufactured by Kanto Chemical Co., Ltd.) Sigma Aldrich Japan Co., Ltd.'s reagent) was purchased as a commercial product and used as it was. For chloroplatinic acid hexahydrate, a product of Tanaka Kikinzoku Co., Ltd. was purchased and dried under reduced pressure immediately before use.
(Example 1) (9E) -Trichloro (3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14 , 15, 15, 16, 16, 16-pentacosafluoro-9-hexadecene-1-yl) silane (compound (1a-1)).

The inside of the pressure-resistant reaction tube made of glass equipped with a magnetic stirrer was replaced with argon to (9E) -3,3,4,4,5,6,6,7,7,8,8,11,11,12. , 12,13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (compound (2-4)) 1.01 g (1.50 mmol), hexa Fluorobenzene 0.5 mL, chloroplatinic acid hexahydrate 0.018 g (3.48 × ^10-5 mol, 3 mol% with respect to compound (2-4)) and trichlorosilane (compound (3-1)) 0. It contained 905 g (6.68 mmol) and was stirred at 50-60 ° C. for 2 hours. After 2 hours, excess trichlorosilane and hexafluorobenzene were distilled off under reduced pressure, and the obtained mixture was distilled under reduced pressure (distillation temperature 130 ° C./800 Pa) with a Kugelrohr distillation apparatus to obtain (9E) -trichloro (9E) -trichloro (9E). 3,3,4,4,5,5,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16- 1.10 g (yield 90.4%) of pentacosafluoro-9-hexadecene-1-yl)silane (compound (1a-1)) as a colorless crystalline solid was obtained.
^{1 1} H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.49 to 1.69 (m, 2H), 2.25 to 2.38 (m, 2H), 6.48 to 6.52 (m) , 2H); ¹³ C-NMR (101 MHz, CDCl ₃ ) δ (ppm): 14.93 (s), 24.86 (t, ² J ( ¹³ CF) = 23.7 Hz), 105-130 ( m, 14C, tridecafluorohexyl group, dodecafluorohexane-1,6-diyl group and vinylene carbon)); ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): -126.20 to -126.11 (M, 2F), 123.35-123.54 (m, 4F), -123.22 (br, 2F), -122.88 (br, 2F), -121.83 (br, 2F) , -121.64 to -121.52 (m, 4F), -115.61--115.54 (m, 2F), -113.84 (br, 4F), -80.78 (t, J = 9.8Hz, 3F); ²⁹ Si-NMR (79MHz, CDCl ₃ ) δ (ppm): 11.51; IR (net, cm ^-1 ): 1441,1365,1306,1232,1194,1138,1111,1070 , 1014,970,947,897,847,808,800,769,746,723,698,640.
(Example 2)
A 30 mL two-necked flask equipped with a magnetic stirrer and a Dimroth condenser was replaced with argon and (9E) -3,3,4,4,5,5,6,6,7,7,8,8,11,11. , 12, 12, 13, 13, 14, 14, 15, 15, 16, 16, 16-pentacosafluorohexadeca-1,9-diene (Compound (2-4)) 2.00 g (2.98 mmol) , 42 mg of platinum chloride hexahydrate (8.11 × ^10-5 mol, 2.7 mol% with respect to compound (2-4)) and 1.01 g (7.46 mmol) of trichlorosilane (compound (3-1)). ), 1.5 mL of 1,3-bis (trifluoromethyl) benzene was charged, and the mixture was heated and stirred at 55 to 65 ° C. for 2 hours. Further, 20 mg of platinum chloride acid (3.86 × ^10-5 mol, 1.3 mol% with respect to compound (2-4)) and 2.40 g (17.7 mmol) of trichlorosilane were added to the mixture, and the temperature was further 55 to 65 ° C. The mixture was heated and stirred for 1 hour and 40 minutes. ^{From 1} H-NMR of the reaction mixture, the raw material is completely consumed and (9E) -trichloro (3,3,4,4,5,5,6,6,7,7,8,8,11,11 , 12, 12, 13, 13, 14, 14, 15, 15, 16, 16, 16-pentacosafluoro-9-hexadecene-1-yl) silane (compound (1a-1)) is selectively produced. It was confirmed that it was.
(Comparative Example 1)
The production was carried out under exactly the same conditions as in Example 2 except that 1.5 mL of m-xylene was used instead of 1,3-bis (trifluoromethyl) benzene as a solvent. As a result, in the ^{analysis of the reaction mixture by 1} H-NMR, 58 mL% of the residual raw material (Compound (2-4)), 33 mL of the product (Compound (1a-1)) and 8.7 mL were used as the fluorine-containing components. % By-products (3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15, It was found that 16,16,16-pentacosafluoro-9-hexadecene) was contained.
(Example 3)
The inside of the pressure resistant reaction tube made of glass equipped with a magnetic stirrer was replaced with argon, and (9E) -3,3,4,4,5,6,6,7,7,8,8,11,11,12 , 12,13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (compound (2-4)) 1.01 g (1.50 mmol), hexa Contains 0.5 mL of fluorobenzene, 44 mg (4.62 × ^10-5 mol, 3 mol%) of tris (triphenylphosphine) rhodium chloride and 0.992 g (7.32 mmol) of trichlorosilane (compound (3-1)). The mixture was stirred at 80 to 100 ° C. for 14 hours. Excess trichlorosilane and hexafluorobenzene are distilled off under reduced pressure, and the obtained mixture is distilled under reduced pressure (distillation temperature 130 ° C./6 mmHg) with a Kugelrohr distillation apparatus to obtain (9E) -trichloro (3,3). 4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosafluoro- 1.09 g (yield 90.5%) of 9-hexadecene-1-yl)silane (compound (1a-1)) as a colorless crystalline solid was obtained. The spectroscopic data were the same as those obtained in Example 1.
(Example 4)
A glass pressure resistant reaction tube equipped with a magnetic stirrer was replaced with argon to (9E) -3,3,4,4,5,5,6,6,7,7,8,8,11,11,12. , 12,13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (Compound (2-4)) 0.999 g (1.49 mmol), 1 , 3-Bis (trifluoromethyl) benzene 0.5 mL, platinum chloride hexahydrate 0.022 g (4.25 × ^10-5 mol, 3 mol% with respect to compound (2-4)) and trichlorosilane (compound) (3-1)) 1.02 g (7.55 mmol) was contained, and the mixture was stirred at 50 to 65 ° C. for 2 hours. Excess trichlorosilane and 1,3-bis (trifluoromethyl) benzene were distilled off under reduced pressure, and the obtained mixture was distilled under reduced pressure (distillation temperature 130 ° C./6 mmHg) with a Kugelrohr distillation apparatus (9E). ) -Trichloro (3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16, 1.08 g (yield 89.8%) of 16,16-pentacosafluoro-9-hexadecene-1-yl)silane (compound (1a-1)) as a colorless crystalline solid was obtained. The spectroscopic data were the same as those obtained in Example 1.
(Example 5)
The inside of the pressure resistant reaction tube made of glass equipped with a magnetic stirrer was replaced with argon, and (9E) -3,3,4,4,5,6,6,7,7,8,8,11,11,12 , 12,13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (Compound (2-4)) 1.00 g (1.49 mmol), chloride Containing 0.022 g (4.25 × ^10-5 mol, 3 mol%) of platinum acid hexahydrate and 1.54 g (11.4 mmol) of trichlorosilane (compound (3-1)), 2 at 50-65 ° C. The mixture was heated and stirred for hours. Excess trichlorosilane is distilled off under reduced pressure, and the obtained mixture is distilled under reduced pressure (distillation temperature 130 ° C./6 mmHg) with a Kugelrohr distillation apparatus to obtain (9E) -trichlorosilane (3,3,4,4). 5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosafluoro-9-hexadecene- 1.08 g (yield 89.8%) of 1-yl)silane (compound (1a-1)) as a colorless crystalline solid was obtained. The spectroscopic data were the same as those obtained in Example 1.
(Comparative Example 2)
A Schlenk tube equipped with a magnetic stirrer was replaced with argon to (9E) -3,3,4,4,5,6,6,7,7,8,8,11,11,12,12, 13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (compound (2-4)) 1.00 g (1.49 mmol), tris (triphenyl) Phosphine) Contains 142 mg of rhodium chloride (14.9 × ^10-5 mol, 10 mol% with respect to compound (2-4)) and 0.908 g (6.70 mmol) of trichlorosilane (compound (3-1)) from 50 to 50. The mixture was heated and stirred at 60 ° C. for 6 hours. The NMR spectrum of the reaction mixture was measured, but the formation of compound (1a-1) could not be confirmed at all.
(Comparative Example 3)
A Schlenk tube equipped with a magnetic stirrer was replaced with argon to (9E) -3,3,4,4,5,6,6,7,7,8,8,11,11,12,12, 13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (compound (2-4)) 2.00 g (2.98 mmol), triphenyl (triphenyl) Phosphine) Rodium chloride 14 mg (1.47 × ^10-5 mol, 0.5 mol% with respect to compound (2-4)) and trichlorosilane (compound (3-1)) 2.01 g (14.8 mmol), toluene 5 mL was contained and heated and stirred at 85 ° C. for 3 days. The NMR spectrum of the reaction mixture was measured, but the formation of compound (1a-1) could not be confirmed at all.
(Example 6) (9E) -Dichloromethyl (3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14, Production of 14,15,15,16,16,16-pentacosafluoro-9-hexadecene-1-yl) silane (compound (1a-2))

A glass pressure resistant reaction tube equipped with a magnetic stirrer was replaced with argon to (9E) -3,3,4,4,5,5,6,6,7,7,8,8,11,11,12. , 12,13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (compound (2-4)) 1.00 g (1.49 mmol), hexa Fluorobenzene 0.5 mL, platinum chloride hexahydrate 0.015 g (2.90 × ^10-5 mol, 2 mol%) and dichloromethylsilane (compound (3-4)) 0.768 g (6.68 mmol). The reaction was carried out at 50 to 60 ° C. for 1.5 hours. After the reaction, excess dichloromethylsilane and hexafluorobenzene were removed under reduced pressure, and the obtained reaction mixture was distilled under reduced pressure (distillation temperature 110 ° C./667 Pa) using a Kugelrohr distillation apparatus to obtain (9E) -dichloromethyl (9E) -dichloromethyl (9E). 3,3,4,4,5,5,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16- 1.02 g (yield 86.6%) of pentacosafluoro-9-hexadecene-1-yl)silane (compound (1a-2)) as a colorless solid was obtained.
^{1 1} H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 0.86 (s, 3H), 1.34 to 1.38 (m, 2H), 2.17 to 2.33 (m, 2H), 6.48 to 6.52 (m, 2H); ¹³ C-NMR (101 _{MHz, CDCl 3} ) δ (ppm): 4.98 (s), 11.84 (s), 24.94 (t, ¹ J) ( ^13C -F) = 23.4Hz), 105-130 (m, 14C, tridecafluorohexyl group, ^{dodecafluorohexane-1,6-diyl group and vinylene carbon); 19} F-NMR (376MHz, CDCl _3). ) Δ (ppm): −126.22 to −126.12 (m, 2F), −123.56 to -123.26 (m, 6F), −122.89 (br, 2F), −121.87 (Br, 2F), -121.59 (br, 4F), -115.73--115.65 (m, 2), -113.88 (s, 2F), -113.85 (s, 2F) , -80.80 (t, J = 9.6Hz, 3F); ²⁹ Si-NMR (79MHz, CDCl ₃ ) δ (ppm): 31.57; IR ( ^{net, cm -1} ): 1442, 1414, 1365 , 1306, 1261, 1232, 1194, 1138, 1132, 111, 1070, 1016, 970, 947, 895, 829, 783, 746, 702, 685, 634,613.
(Embodiment 7) (9E)-(3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14, Production of 15,15,16,16,16-pentacosafluoro-9-hexadecene-1-yl) trimethoxysilane (compound (1b-1))

A 50 mL three-necked flask equipped with a magnetic stirrer, a dropping funnel, a Dimroth condenser and a three-way cock was replaced with argon to (9E) -3,3,4,4,5,5,6,6,7,7, 8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (Compound (2-4)) 10 0.0 g (14.9 mmol), hexafluorobenzene 5 mL, platinum chloride hexahydrate 0.023 g (4.44 × ^10-5 mol, (0.4 mol% with respect to compound (2-4)) and trichlorosilane. (Compound (3-1)) 8.65 g (63.9 mmol) was charged and the reaction was carried out at 60 to 70 ° C. for 6 hours. Then, excess trichlorosilane and hexafluorobenzene were concentrated and distilled off under reduced pressure. To the mixture containing the obtained compound (1a-1), 5 mL of dehydrated tetrahydrofuran and 7.55 g (74.8 mmol) of triethylamine were added. The reaction vessel was cooled to 0 ° C. A 2.63 g, 82.2 mmol) solution was added dropwise. After the addition was completed, the mixture was returned to room temperature and reacted for 1 hour. The precipitate was filtered off with a Schlenk tube equipped with a sintered glass filter. The obtained reaction mixture was concentrated. After that, by performing vacuum distillation (distillation temperature 130 ° C./80 Pa) with a Cugel roll distillation apparatus, (9E)-(3,3,4,4,5,5,6,6,7,7,8,8, 11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosafluoro-9-hexadecene-1-yl) trimethoxysilane (compound (1b-1)) 10.0 g (yield 84.7%) was obtained as a colorless liquid.
^{1 1} H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 0.83 to 0.87 (m, 2H), 2.06 to 2.20 (m, 2H), 3.59 (s, 9H), 6.43 to 6.56 (m, 2H); ¹³ C-NMR (101 _{MHz, CDCl 3} ) δ (ppm): -0.47 (s), 25.23 (t, ² J ( ¹³ C-F)) = 23.8 Hz), 50.82 (s), 105-130 (m, 14C, tridecafluorohexyl group, ^{dodecafluorohexane-1,6-diyl group and vinylene carbon); 19} F-NMR (376 MHz, CDCl) ₃ ) δ (ppm): -126.12 (m, 2F), -123.55--123.36 (m, 6F) -122.86 (br, 2F), -121,88 (br, 2F) , -121.58 (br, 4F), -116.70 (t, 2F, J = 12.7Hz), 113.87 to -113.77 (m, 4F), -80.77 (t, 3F) , J = ^{9.7Hz); 29} _{Si-NMR (79MHz, CDCl 3} ) δ (ppm): -44.21; IR (net, cm ^-1 ): 2951, 2848, 1444, 1245, 1365, 1240, 1190 , 1142,1090, 972,899,835,810,791,746,719,710,700,651,627.
(Example 8) (9E) -Trimethoxy (3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14 , 15, 15, 16, 16, 16-pentacosafluoro-9-hexadecene-1-yl) Silane (Compound (1b-1))

A reaction tube made of Pylex glass having a diameter of 8 mm was replaced with argon, and (9E) -3,3,4,4,5,5,6,6,7,7,8,8,11,11,12 was placed in the reaction tube. , 12,13,13,14,14,15,15,16,16,16-pentacosafluorohexadeca-1,9-diene (compound (2-4)) 1.00 g (1.49 mmol), hexa 1 mL of fluorobenzene, 0.075 g (20 wt% platinum, 7.7 × ^10-5 mol platinum) of 1,3-divinyltetramethyldisiloxane solution of 1,3-divinyltetramethyldisiloxane platinum complex, and trimethoxysilane (Compound (3-1)) 1.50 g (12.3 mmol) was contained, and the reaction was carried out at 60 to 70 ° C. for 24 hours. After concentrating the obtained reaction mixture, it was distilled under reduced pressure (distillation temperature 130 ° C./80 Pa) in a Kugelrohr distillation apparatus to obtain (9E) -trimethoxy (3,3,4,4,5,5,6,6). 7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosafluoro-9-hexadecene-1-yl) silane (compound ( 1b-1)) was used as a colorless liquid to obtain 1.14 g (yield 96.6%). The spectroscopic data were the same as those synthesized in Example 7.
(Example 9) (9E) -Chlorodimethyl (3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14, Production of 14,15,15,16,16,16-pentacosafluoro-9-hexadecene-1-yl) silane (compound (1a-8))

A 30 mL two-necked flask equipped with a Dimroth condenser and a magnetic stir bar was replaced with argon to (9E) -3,3,4,4,5,5,6,6,7,7,8,8,11,11. , 12, 12, 13, 13, 14, 14, 15, 15, 16, 16, 16-pentacosafluorohexadeca-1,9-diene (Compound (2-4)) 5.00 g (7.44 mmol) , 2 mL of dehydrated toluene, 0.050 g (5.40 × ^10-5 mol, 0.7 mol%) of tris (triphenylphosphine) rhodium chloride and 1.41 g (14.9 mmol) of chlorodimethylsilane (compound (3-6)). ), And the reaction was carried out at 100 ° C. for 7 hours. After the reaction, excess chlorodimethylsilane and solvent are removed under reduced pressure, and the obtained reaction mixture is distilled under reduced pressure (distillation temperature 120 ° C./6 mmHg) with a Kugelrohr distillation apparatus to obtain (9E) -chlorodimethyl (3,). 3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosa 5.02 g (yield 88.0%) of fluoro-9-hexadecene-1-yl) silane (compound (1a-8)) as a colorless liquid was obtained.
^{1 1} H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 0.477 (s, 6H), 1.00 to 1.10 (m, 2H), 2.08 to 2.23 (m, 2H), 6.46 to 6.52 (m, 2H); ¹³ C-NMR (101 _{MHz, CDCl 3} ) δ (ppm): -0.13 (s), 1.28 (s), 8.84 (s), ^{25.49 (t, 1 J (13} C-F) = 23.7Hz), 105~130 (m, 14C, tridecafluorohexyl group, dodecafluoro-1,6-diyl group and vinylene ^{carbons); 19} F-NMR (376MHz, CDCl ₃ ) δ (ppm): -126.58 (s, 2F), -123.83 to -123.23 (m, 8F), -122.16 to -121.83 (m) , 6F), -116.20 (br, 2F), -114.30 (br, 4F), -81.36 (s, 3F); ²⁹ Si-NMR (79MHz, CDCl ₃ ) δ (ppm): 31 .40; IR ( ^{net, cm -1} ): 1240, 1190, 1140, 1068, 972, 849, 708.
<Surface modification evaluation>
(Evaluation example 1)
A 26 × 76 mm soda glass plate surface-modified substrate was immersed in 15 mL of a 1,3-bis (trifluoromethyl) benzene solution having a concentration of 0.05% by weight of the compound (1a-1), and the room temperature was maintained for 2 hours with stirring. Left underneath. This was washed with a hexafluorobenzene: chloroform 1: 3 solution and then poured with distilled water. Subsequently, the cells were immersed in 100 mL of chloroform, washed for 10 minutes while being irradiated with ultrasonic waves (28 kHz + 38 kHz, 340 W), and then washed by pouring acetone over them. When the water contact angle, hexadecane contact angle and water sliding angle of the obtained surface-modified substrate were determined, the water contact angle was 115 degrees (standard deviation 4 degrees) and the hexadecane contact angle was 73 degrees (standard deviation 1.7 degrees). The water sliding angle was 14.9 degrees (standard deviation 1.5 degrees).
(Comparative Example 4)
Trichloro (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) 1,3-bis (trifluoro) at a concentration of 0.05% by weight of silane A 26 × 76 mm soda glass plate surface-modified substrate was immersed in 15 mL of a methyl) benzene solution and left at room temperature for 2 hours with stirring. This was washed with a hexafluorobenzene: chloroform 1: 3 solution and then poured with distilled water. Subsequently, the cells were immersed in 100 mL of chloroform, washed for 10 minutes while being irradiated with ultrasonic waves (28 kHz + 38 kHz, 340 W), and then washed by pouring acetone over them. When the water contact angle, hexadecane contact angle and water sliding angle of the obtained surface-modified substrate were determined, the water contact angle was 105 degrees (standard deviation 2.5 degrees) and the hexadecane contact angle was 73 degrees (standard deviation 0). The water sliding angle was 16.3 degrees (standard deviation 1.6 degrees).
(Evaluation example 2)
A 26 × 76 mm soda glass plate surface-modified substrate was immersed in 15 mL of a chloroform solution having a 0.05 wt% concentration of compound (1a-2), and the mixture was allowed to stand at room temperature for 36 hours with stirring. This was washed with a hexafluorobenzene: chloroform 1: 3 solution and then poured with distilled water. Subsequently, the cells were immersed in 100 mL of chloroform, washed for 10 minutes while being irradiated with ultrasonic waves (28 kHz + 38 kHz, 340 W), and then washed by pouring acetone over them. When the water contact angle, hexadecane contact angle and water sliding angle of the obtained surface-modified substrate were determined, the water contact angle was 106 degrees (standard deviation 3 degrees) and the hexadecane contact angle was 63 degrees (standard deviation 2 degrees). The water sliding angle was 14.0 degrees (standard deviation 0.9 degrees).
(Evaluation example 3)
Immediately after mixing 10 g of a 5 wt% 2-propanol solution of compound (1b-1) and 600 mg of a 10 wt% 2-propanol solution of p-toluenesulfonic acid monohydrate, take 0.5 mL and clean with cellulose tissue paper. The surface of the soda glass substrate was wiped and coated. This was allowed to stand at room temperature for 16 hours. This was washed with a hexafluorobenzene / chloroform 1: 3 solution, then flushed with distilled water, then immersed in 100 mL of chloroform, and washed with ultrasonic irradiation (28 kHz + 38 kHz, 340 W) for 10 minutes to make it homogeneous and transparent. A surface-modified glass substrate was obtained. The contact angle of this treated glass substrate with water and hexadecane was determined by the θ / 2 method. The contact angle with water is 110 degrees (standard deviation 1.8 degrees), the contact angle with hexadecane is 66 degrees (standard deviation 1.9 degrees), and the water sliding angle is 12 degrees (standard deviation 0.6 degrees). rice field.
(Comparative Example 5)
10 g of a 5 wt% 2-propanol solution of triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silane and p-toluenesulfonic acid. Immediately after mixing 600 mg of a 10 wt% 2-propanol solution of hydrate, 0.5 mL was taken and wiped onto a clean soda glass plate surface with cellulose tissue paper. This was allowed to stand at room temperature for 16 hours. This was rinsed with a hexafluorobenzene / chloroform 1: 3 solution and then with distilled water, further immersed in chloroform and washed by ultrasonic irradiation (28 kHz + 38 kHz, 340 W). This treated glass substrate did not show a smooth surface, and a heterogeneously turbid film with a large haze adhered.

Claims (13)

General formula (1)

(In the formula, n and m are independently 4 or 6, respectively. K is 0, 1 or 2. R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when k is 2, 2 The two Rs may be the same or different. X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and when k is 1 or 0, the two or three Xs may be the same or different. ) Is a fluoroalkyl substituted silane compound. The fluoroalkyl-substituted silane compound according to claim 1, wherein n and m are 6 in the general formula (1). The fluoroalkyl substituted silane compound according to claim 1 or 2, wherein k is 0 and X is a chlorine atom, a methoxy group or an ethoxy group in the general formula (1). General formula (2)

(In the formula, n and m are independently 4 or 6, respectively.) The fluorine-containing diene compound represented by the formula and the general formula (3).

(In the formula, k is 0, 1 or 2. R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when k is 2, the two Rs may be the same or different. Representing a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and when k is 1 or 0, two or three Xs may be the same or different from each other), and a hydrosilylation catalyst. The general formula (1), which is characterized by using

(In the formula, n, m, k, R and X have the same meanings as described above.) A method for producing a fluoroalkyl-substituted silane compound. The method for producing a fluoroalkyl-substituted silane compound according to claim 4, wherein the compound is produced in a fluorine-containing organic solvent. The fifth aspect of claim 5, wherein the fluorine-containing organic solvent comprises at least one selected from the group consisting of 2H, 3H-decafluoropentane, benzotrifluoride, 1,3-bis (trifluoromethyl) benzene and hexafluorobenzene. A method for producing a fluoroalkyl-substituted silane compound. The method for producing a fluoroalkyl-substituted silane compound according to any one of claims 4 to 6, wherein the hydrosilylation catalyst is a platinum group transition metal catalyst. The method for producing a fluoroalkyl-substituted silane compound according to claim 7, wherein the platinum group transition metal catalyst is hexachloroplatinic acid, tris (triphenylphosphine) rhodium chloride or a 1,3-divinyltetramethyldisiloxane platinum complex. General formula (1b)

(In the formula, n and m are independently 4 or 6, respectively. K is 0, 1 or 2. R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when k is 2, 2 The two R's may be the same or different. X ² represents an alkoxy group having 1 to 3 carbon atoms.) Is a method for producing an alkoxy-substituted fluoroalkyl-substituted silane compound represented by the general formula (1a).

(In the formula, n, m, k and R have the same meanings as described above ^{. X 1} represents a halogen atom.) The halogen-substituted fluoroalkyl-substituted silane compound represented by the above is reacted with an alkoxy agent. Manufacturing method. The method for producing an alkoxy-substituted fluoroalkyl-substituted silane compound according to claim 9, wherein the alkoxy agent comprises at least one selected from the group consisting of alcohols, metal alkoxides, trialkyl orthoformates and alkyl ethers. A surface modification composition comprising the fluoroalkyl substituted silane compound according to any one of claims 1 to 3 and an organic solvent. The surface modification composition according to claim 11, which comprises the fluoroalkyl substituted silane compound according to any one of claims 1 to 3, an organic solvent and an acid catalyst. A method for surface modification of glass, metal oxide or metal substrate, which comprises applying the surface modification composition according to claim 11 or 12.