TW201402589A - Fluorine-containing maleinimide compound and manufacture method therefore - Google Patents

Abstract

The invention provides a fluorine-containing maleinimide compound characterized in that a single molecule is provided with at least a fluoroalkyl and/or a perfluoropolyether and at least a residue expressed by the following general formula (1), the residue is bonded with a silicon atom. In the general formula, a is an integral number from 1 to 10. Thereby, the fluorine-based fluorine-containing maleinimide compound and a high-yield-rate manufacture method for the fluorine-containing maleinimide compound are disclosed, wherein the structure of the fluorine-containing maleinimide compound is completely under control.

Description

Fluorine-containing maleic imine compound and method for producing same

The present invention relates to a fluorine-containing maleimide compound and a process for producing the same.

Conventionally, as a fluorine compound which can be cured by light irradiation such as ultraviolet rays, a polymerizable monomer having a perfluoroalkyl group in a side chain, for example, a fluorine-containing alkyl acrylate or a fluoroalkyl methacrylate is widely used. polymer. The so-called fluorine-containing acryl compound is an additive which improves the surface characteristics of the surface of the hard coat film obtained from the ultraviolet curable hard coat material, and has been attracting attention in recent years, and the demand for high performance has also increased. For example, in Patent Documents 1, 2 and the like, a fluorine-containing acrylate or the like which is improved in functionality by a structure control by a polyfunctional Si-H compound is described.

When the fluorine-containing acrylate is blended in a very small amount in the non-fluorinated acrylate-based curable composition, the fluorine-containing acrylate is concentrated at the air interface by coating. By irradiating the coated surface with ultraviolet rays, a hardened film in which the fluorine group is present on the outermost surface is formed, and exhibits excellent functions such as water repellency, oil repellency, and scratch resistance. However, radical polymerization of an acrylic compound due to ultraviolet rays is hindered by oxygen when it is hardened in the air. Especially for the above-mentioned coated surface of the fluorinated acrylate The layer that is closer to the existing air interface tends to be more susceptible to this hardening. Therefore, in order to maximize the characteristics of the fluorine-containing acrylate to be added, it is necessary to employ a means such as hardening in an inert gas.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-053114

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-138112

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-088900

On the other hand, the maleic imine compound may be characterized by dimerization reaction, homopolymerization, or copolymerization with other radically polymerizable compound by ultraviolet irradiation, and is characterized by being less susceptible to hardening by oxygen. Therefore, the requirements for the synthesis method of the fluorine-containing maleic imine compound having a fluorine group and having a sufficiently controlled structure are increased.

A wide range of attempts have been made to introduce maleimine groups as reactive groups to synthesize novel compounds. For example, in Patent Document 3, a ring-opening addition and an intramolecular recyclization by a reaction between maleic anhydride and an amine are shown, and a maleidino group-based decane compound is introduced, but as such The introduction method of the maleimine group is mainly based on the synthesis method accompanying recyclization, and is not a sufficient method at the point of yield or structure control due to the residual or side reaction of the uncyclized product.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a fluorine-containing maleic imine compound which can form a cured product excellent in water repellency and oil repellency, which is hardly inhibited by oxygen, and the fluorine-containing horse. A manufacturing method in which the yield of the quinone imine compound is good.

In order to solve the above problems, in the present invention, there is provided a fluorine-containing maleimide compound characterized by having at least one fluoroalkyl group and/or fluoropolyether group in one molecule, having at least one bond to ruthenium a residue represented by the following formula (1) of an atom, (In the formula, a is an integer from 1 to 10).

When it is such a fluorine-containing maleic imine compound, it hardly hardens by hardening by oxygen, and can form the cured material which is excellent in water-repelling property.

Further, the fluorine-containing maleimide compound is preferably represented by the following formula (2).

(In the formula, a is the same as the above, and each of R ¹ to R ^{2 is} independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and Rf is each independently a fluoroalkyl group or a fluoropolyether group, and a Z-based divalent hydrocarbon group; A part thereof may also contain an oxygen atom, a nitrogen atom, or a ruthenium atom; each of x and y is an integer of 1 to 4, which satisfies 3≦x+y≦5).

According to such a fluorine-containing maleic imine compound, a cured product having more excellent water-repellent oil repellency can be formed, and it is less resistant to hardening by oxygen.

Furthermore, in the present invention, there is provided a process for producing a fluorine-containing maleimide compound, which is a process for producing the above-described fluorine-containing maleimide compound, which is characterized in that it has at least one fluorine in one molecule. An alkyl group and/or a fluoropolyether group, a halogen-containing modified organic ruthenium compound having at least one ruthenium atom and having an organic group modified by a halogen atom selected from chlorine, bromine and iodine, and the following formula (3) The compound shown is subjected to an N-alkylation reaction, and the obtained compound is heated to 100 ° C or higher to obtain the above-mentioned fluorine-containing maleimide compound.

According to such a production method, the fluorine-containing maleimide compound can be synthesized in a good yield.

Further, hydrofluorinated with a fluorine-containing Si-H compound having at least one fluoroalkyl group and/or fluoropolyether group and a hydrogen atom bonded to a halogen atom, and a compound represented by the following formula (4) The above-mentioned halogen-containing modified organic ruthenium compound, [Chemical 4] CH ₂ =CH-CH ₂ -(CH ₂ ) _a -X (4) (wherein a is the same as the above, and X is derived from chlorine , halogen atom selected from bromine and iodine).

Further, a Si-H compound having two or more hydrogen atoms bonded to a halogen atom, a compound represented by the following formula (4), and at least one fluoroalkyl group and/or a fluoropolyether group are provided. And a hydrohalogenation reaction of a fluorine-containing compound of a terminal alkenyl group to obtain the above halogen-containing modified organic ruthenium compound, [Chem. 5] CH ₂ =CH-CH ₂ -(CH ₂ ) _a -X (4) , a is the same as described above, and X is a halogen atom selected from chlorine, bromine and iodine).

By synthesizing the halogen-containing modified organic ruthenium compound by the above method, the fluorine-containing maleimide compound can be synthesized more favorably.

As described above, the fluorine-containing maleimide compound of the present invention is hardly inhibited by hardening by oxygen, and can form a cured product excellent in water repellency and oil repellency, and the yield can be improved by the production method of the present invention. This fluorine-containing maleimide compound was produced. In particular, the fluorine-containing maleic imide compound of the present invention can be blended in a monomer or various coating agents to form a water-repellent hardened material, and is suitable as an antifouling additive for hard coating.

Figure 1 is a ¹ H NMR spectrum of the compound of the formula (8).

Figure 2 is a ¹³ C NMR spectrum of the compound of the formula (8).

[Formation of the Invention]

Hereinafter, the fluorine-containing maleimide compound of the present invention will be described in detail, but the present invention is not limited thereto. As described above, the desired fluorine-containing maleimide compound can be hardly inhibited by hardening by oxygen to form a cured product excellent in water repellency.

In order to achieve the above-mentioned problems, the inventors of the present invention have repeatedly conducted intensive investigations and found that the following fluorine-containing maleimide compound is a compound which is in accordance with the above object, and can be obtained according to the production method of the present invention. The composition was well synthesized and the present invention was completed. Hereinafter, the present invention will be described in detail.

The fluorine-containing maleimide compound of the present invention has at least one fluoroalkyl group and/or fluoropolyether group in one molecule, and has at least one residue represented by the following formula (1) bonded to a ruthenium atom. Basic, (In the formula, a is an integer from 1 to 10).

The fluorine-containing maleimide compound of the present invention has at least one fluoroalkyl group and/or fluoropolyether group in one molecule, and thus, for example, by adding the fluorine-containing maleiciya of the present invention to a hard coating agent The amine compound irradiates the coated surface with ultraviolet rays to form a hardened film having a fluorine-based bias existing on the outermost surface, and exhibits excellent functions such as water repellency, oil repellency, and scratch resistance.

The residue represented by the formula (1) is bonded to a ruthenium atom, and contains at least one in one molecule, preferably two or more in one molecule. Thereby, even if it hardens in the air by ultraviolet irradiation, dimerization reaction, homopolymerization, or copolymerization with another radically polymerizable compound is possible, and it is hard to be hardened by hardening by oxygen.

In the formula, a is an integer of 1 to 10, preferably 1.

Further, the fluorine-containing maleimide compound is preferably represented by the following formula (2).

(In the formula, a is the same as the above, and each of R ¹ to R ^{2 is} independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and Rf is each independently a fluoroalkyl group or a fluoropolyether group, and a Z-based divalent hydrocarbon group; A part thereof may also contain an oxygen atom, a nitrogen atom, or a ruthenium atom; each of x and y is an integer of 1 to 4, which satisfies 3≦x+y≦5).

In the formula, a is the same as described above, and each of R ¹ to R ^{2 is} independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. R ¹ to R ² are not particularly limited, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a phenyl group.

Further, Rf each independently represents a fluoroalkyl group or a fluoropolyether group, and the Z system may contain a divalent hydrocarbon group of an oxygen atom, a nitrogen atom or a ruthenium atom in a part thereof. Further, x and y are each an integer of 1 to 4, satisfying 3≦x+y≦5, preferably an integer of 1 to 3, and preferably satisfying x+y=4.

Further, in the general formula (2), the arrangement of each repeating unit is not particularly limited and may be any.

The fluorine-containing maleimide compound of the present invention may be selected from chlorine, bromine and iodine by having at least one fluoroalkyl group and/or fluoropolyether group in one molecule, containing at least one halogen atom, and having chlorine, bromine and iodine. a halogen-containing organic ruthenium compound of an organic group modified by a halogen atom, and represented by the following formula (3) The protected maleimide derivative is subjected to an N-alkylation reaction, and the compound obtained after the reaction is heated to 100 ° C or higher to obtain deprotection.

The halogen-containing modified organic ruthenium compound has at least one fluoroalkyl group and/or fluoropolyether group in one molecule, contains at least one ruthenium atom, and has an organic group modified by a halogen atom selected from chlorine, bromine and iodine. . Therefore, the fluoroalkyl group or the fluoropolyether group may be the same as the above-described fluorine-containing maleimide compound. Further, the organic group modified by a halogen atom selected from chlorine, bromine and iodine is not particularly limited as long as the hydrogen atom in the monovalent organic group is replaced by a halogen atom selected from chlorine, bromine and iodine. The limitation is, for example, that a hydrogen atom at the end of a linear or branched alkyl group having 4 to 10 carbon atoms is replaced by a halogen atom selected from chlorine, bromine and iodine. Further, as the halogen atom, bromine is particularly preferred.

As such a halogen-containing modified organic ruthenium compound, the following compounds are preferable.

(In the formula, n and m are integers of 1 to 4, and 3≦n+m≦5 is satisfied, and Rf, X and Z are the same as described above).

(In the formula, b is an integer from 1 to 15, and Rf, X and Z are the same as described above).

(wherein Q is each independently a group which can be represented by any one of the following, and one or more of each group is required to be contained in one molecule; and Rf, X and Z are the same as described above).

Further, Rf is each independently a fluoroalkyl group or a fluoropolyether group, and specific examples thereof include the following.

CF ₃ - (CF ₃ ) ₂ CF-CF ₃ CF ₂ - CF ₃ CF ₂ CF ₂ - CF ₃ CF ₂ CF ₂ CF ₂ - CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ - C _{4 F 9 CH 2 CF 2 (CF} 2 CF 2) 2 -

Moreover, as a particularly preferable fluoropolyether group, the following is mentioned.

(However, c, d, e, f, and g are each independently an integer of 0 to 30, h is an integer of 1 to 3, and X ¹ and X ² are each independently a fluorine atom or a CF ₃ group, and the arrangement of each repeating unit There are no special restrictions, and it can be any.

These Rf groups preferably have a molecular weight of from 150 to 10,000 and a particularly preferred molecular weight of from 200 to 5,000.

Further, the Z-based divalent hydrocarbon group may further contain an oxygen atom, a nitrogen atom or a ruthenium atom in a part thereof. Further, it may contain a fluorine atom. As such Z, the following shows a preferred structure.

The halogen-containing modified organic ruthenium compound of the present invention can be obtained by any method, but specifically, by having at least one fluoroalkyl group and/or fluoropolyether group and a hydrogen atom bonded to a ruthenium atom. The fluorine-containing Si-H compound is obtained by hydrosilylation reaction with a compound represented by the following formula (4).

[Chemical Formula 16] _{CH 2 = CH-CH 2 -} (CH 2) a -X (4) ( formula, a line the same as above, X is selected based consisting of chlorine, bromine and iodine, and the halogen atom).

Hereinafter, a compound which can be used as a fluorine-containing Si-H compound is exemplified. The hydrogen atom bonded to the ruthenium atom can be hydrosilylation reaction with the alkenyl group of the formula (4) to obtain a halogen-containing modified organic ruthenium compound.

(In the formula, n and m are integers of 1 to 4, satisfying 3≦n+m≦5, and Rf and Z are the same as described above).

(In the formula, b is an integer from 1 to 15, and Rf and Z are the same as described above).

(In the formula, each of Q is independently a group which can be represented by any one of the following, and one or more of each group is required to be contained in one molecule; and Rf and Z are the same as described above).

Further, the fluorine-containing Si-H compound can be, for example, synthesized by a fluorine-containing oxoxane The equilibrium of the substance with the cyclic H oxane compound, the reaction of the fluorine-containing chlorodecane compound with the heterogeneous reaction of 1,1,3,3-tetramethyldioxane, etc., is added by hydroquinonelation reaction It is produced by a method of a polyfunctional Si-H compound and a fluorine compound having a terminal alkenyl group. The polyfunctional Si-H compound referred to herein means a compound having one or more hydrogen atoms bonded to a halogen atom in one molecule.

Further, the halogen-containing modified organic ruthenium compound may have at least one compound having two or more Si-H compounds bonded to a hydrogen atom of a halogen atom, a compound represented by the following formula (4), and A hydrohalogenation reaction of a fluorine-containing compound of a fluoroalkyl group and/or a fluoropolyether group and a terminal alkenyl group.

In this case, a synthesis procedure in which a polyfunctional Si-H compound is first reacted with a compound represented by the formula (4), and then the resulting halogen-containing Si-H compound is reacted with a fluorine compound having a terminal alkenyl group may be employed. Alternatively, the polyfunctional Si-H compound may be mixed with the compound represented by the formula (4) and the fluorine compound having a terminal alkenyl group, and the addition reaction may be carried out simultaneously.

The structure of the polyfunctional Si-H compound is not limited, but the following are exemplified as the most preferable ones.

Further, as the fluorine compound having at least one fluoroalkyl group, fluoropolyether group and terminal alkenyl group, the following may be exemplified.

Rf-CH=CH ₂ Rf-CH ₂ CH=CH ₂ Rf-CH ₂ CH ₂ CH=CH ₂ Rf-CH ₂ C(CH ₃ )=CH ₂ Rf-CH ₂ OCH ₂ CH=CH ₂

The addition reaction by hydrohydrylation may be carried out even if the solvent is not present, but may be diluted with a solvent as needed. In this case, the diluent solvent may be a generally widely used organic solvent such as toluene, xylene or isooctane. In particular, the boiling point is above the intended reaction temperature and does not hinder the reaction, and the compound formed after the reaction is preferably an organic solvent which is soluble at the reaction temperature, and for example, hexafluoro-xylene or benzotrifluoride may also be used. A partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent or a fluorine-modified ether solvent such as methyl perfluorobutyl ether.

As the addition reaction catalyst, for example, a compound containing platinum, rhodium or palladium can be used. Among them, a platinum-containing compound is preferred, and hexachloroplatinum (IV) acid hexahydrate, platinum carbonyl vinyl methyl complex, platinum-divinyltetramethyldioxane complex, platinum may be used. a cyclovinylmethyl oxime complex, a platinum-octanal/octanol complex, or a platinum supported on activated carbon. The amount of the catalyst is preferably from 0.1 to 5,000 ppm, more preferably from 1 to 1,000 ppm, based on the total weight of the fluorine-containing compound and/or the compound represented by the formula (4).

In the addition reaction, the addition ratio of the reaction is not particularly limited as long as the desired structure is obtained, and after the addition reaction is carried out at an arbitrary ratio, the additional components are distilled at a desired ratio, and the column is distilled. Refined, etc., and separated and taken out. Further, for example, when one fluoroalkyl group and/or fluoropolyether group is synthesized into one additional fluorine-containing Si-H compound, a polyfunctional Si-H compound which is excessively large relative to a fluorine compound having a terminal alkenyl group is present. The reaction is carried out. The desired fluorine-containing Si-H compound can also be obtained by removing the remaining polyfunctional Si-H compound. Conversely, it can also be used in multi-functional Si-H A compound represented by the formula (4) is added to the compound, and a Si-H compound having one halogen-modified organic group is synthesized to react a residual Si-H group with a fluorine-containing alkenyl compound. Further, all of the three compounds of the polyfunctional Si-H compound, the fluorine-containing alkenyl compound, and the compound represented by the formula (4) may be mixed and the addition reaction may be carried out simultaneously.

Next, N-alkylation by reaction of a halogen-containing modified organic ruthenium compound containing a fluoroalkyl group and/or a fluoropolyether group and a ruthenium atom with a compound represented by the formula (3) in the molecule thus obtained .

Here, the N-alkylation can be easily carried out by heating and stirring and mixing the halogen-containing modified organic hydrazine compound and the compound represented by the formula (3) in the presence of potassium carbonate. Here, the addition ratio of the compound represented by the formula (3) is preferably a molar amount such as a halogen-modified organic group contained in the halogen-containing modified organic ruthenium compound, or more than necessary. The remaining compound represented by the formula (3) may be optionally removed by distillation under reduced pressure, liquid separation, column purification, or the like, or may be used as a mixture as it is.

The potassium carbonate is preferably used in an amount of more than or equal to the molar amount of the halogen atom, preferably 3 to 10 moles.

Further, the N-alkylation reaction can be carried out without a solvent, but can be diluted with any solvent as needed, particularly from the viewpoint of reactivity, ethers, ketones, acetonitrile, DMF (dimethyl group). Methotrexate, DMSO (dimethyl hydrazine) A non-protic polar solvent is suitable.

Further, the reaction temperature is preferably from 0 ° C to 80 ° C, particularly preferably from 20 ° C to 60 ° C. When it is 0 ° C or more, the progress of the reaction is not too slow, and if it is 80 ° C or less, the possibility that the protective group-containing furan is detached from the compound represented by the general formula (3) can be suppressed. The reaction time is also affected by the structure of the target compound, the amount of the solvent, etc., but usually ends in 1 to 72 hours.

The compound obtained by N-alkylation can be usually heated by heating at 100 ° C to 180 ° C, preferably at 150 to 170 ° C, and the furan is easily removed to obtain the desired fluorine-containing maleimide compound. The heating system can be carried out separately or as needed in any solvent dilution. The solvent to be used herein is suitably an object having a boiling point in the heating temperature range of the object, and is capable of dissolving the object before and after the reaction, and is also inert to the substance, and specifically, anisole or DMF.

[Examples]

Hereinafter, the present invention will be described in more detail by showing examples and comparative examples, but the invention is not limited thereto.

[Example 1]

In a flask equipped with a stirring and refluxing apparatus, 20.0 g of the following compound (5), 10.6 g of 4-bromo-1-butene, and 20 g of xylene hexafluoride were heated to 90 ° C to mix chloroplatinic acid/ethylene. 0.040 g of a toluene solution of a base oxane complex (containing 1.0 × 10 ^-7 mol as a Pt monomer), and heating and stirring for 12 hours. After the heating was stopped, 1 part by mass of activated carbon was added to the obtained mixed solution, and the mixture was stirred for 1 hour, and then subjected to pressure filtration. The organic solvent was volatilized from the filtrate with an evaporator at 110 ° C / 2 Torr to obtain 29.5 g of a pale yellow transparent liquid. The obtained liquid was identified as the compound of the following (6) according to ¹ H NMR and ¹³ C NMR.

Into a flask equipped with a stirring apparatus and a reflux apparatus, 10.0 g of the obtained compound (6), 4.24 g of the compound represented by the formula (3), 17.3 g of potassium carbonate, and 30 g of DMF were stirred at 50 ° C for 48 hours. 50 ml of ethyl acetate was added to the solution after the stirring was stopped, and the mixture was washed three times with 100 ml of water. After washing the upper layer, the solvent was distilled off under reduced pressure at 80 ° C / 2 Torr to obtain 9.2 g of a translucent brown and highly viscous liquid. The obtained liquid was identified as the compound of the following (7) based on ¹ H NMR and ¹³ C NMR.

7.2 g of the compound (7) and 21.3 g of anisole were placed in a flask equipped with a stirring apparatus and a reflux apparatus, and the mixture was heated in an oil bath at 160 ° C, and heated under stirring with anisole for 30 minutes. Then, the volatile matter was removed from the reaction solution by distillation under reduced pressure at 150 ° C / 2 Torr to obtain 6.0 g of a translucent red and highly viscous liquid. The obtained liquid was identified as the compound of the following (8) based on ¹ H NMR and ¹³ C NMR. Shown in Figure 1. This ¹ H NMR, FIG. 2 shows the ¹³ C NMR.

[Embodiment 2]

In a flask equipped with a stirring and refluxing apparatus, 20.0 g of the following compound (11), 13.5 g of 4-bromo-1-butene, and 20 g of xylene hexafluoride were heated to 90 ° C, and mixed with chloroplatinic acid/vinyl The toluene solution of the oxime complex was 0.040 g (as a Pt monomer, containing 1.0 × 10 ^-7 mol), and heating and stirring were continued for 12 hours. Then, the volatile matter was removed from the reaction solution by distillation under reduced pressure at 110 ° C / 2 Torr to obtain 30.2 g of a pale yellow transparent liquid. The obtained liquid was identified as the following compound (12) by ¹ H-NMR and ¹³ C-NMR.

In a flask equipped with a stirring apparatus and a reflux apparatus, 10.0 g of the obtained compound (12), 4.92 g of a compound represented by the formula (3), 20.6 g of potassium carbonate, and 30 g of DMF were stirred at 50 ° C for 48 hours. 50 ml of ethyl acetate was added to the solution after the stirring was stopped, and the mixture was washed three times with 100 ml of water. The organic layer after washing was distilled off under reduced pressure at 80 ° C / 2 Torr to obtain 11.1 g of a translucent brown and highly viscous liquid. The obtained liquid was identified as the compound of the following (13) by ¹ H-NMR and ¹³ C-NMR.

8.0 g of the compound (13) and 24 g of anisole were placed in a flask equipped with a stirring apparatus and a reflux apparatus, and the mixture was heated in an oil bath at 160 ° C, and heated under stirring in an anisole for 30 minutes. Then, the volatile matter was removed from the reaction solution by distillation under reduced pressure at 150 ° C / 2 Torr to obtain 6.4 g of a translucent red liquid. ¹ H-NMR of the obtained liquid and the spectrum of the following Table 1 were obtained, and it was identified as the compound of the following (14).

[Example 3]

In a flask equipped with a stirring and refluxing apparatus, 20.0 g of the following compound (15), 15.0 g of 4-bromo-1-butene, and 20 g of xylene hexafluoride were heated to 90 ° C, and mixed with chloroplatinic acid/vinyl The toluene solution of the oxime complex was 0.040 g (as a Pt monomer, containing 1.0 × 10 ^-7 mol), and heating and stirring were continued for 12 hours. Then, the volatile matter was removed from the reaction solution by distillation under reduced pressure at 110 ° C / 2 Torr to obtain 33.4 g of a pale yellow transparent liquid. The obtained liquid was identified as the following compound (16) based on ¹ H-NMR and ¹³ C-NMR.

In a flask equipped with a stirring apparatus and a reflux apparatus, 10.0 g of the obtained compound (16), 3.49 g of a compound represented by the formula (3), 14.6 g of potassium carbonate and 30 g of DMF were stirred at 50 ° C for 48 hours. 50 ml of ethyl acetate was added to the solution after the stirring was stopped, and the mixture was washed three times with 100 ml of water. The organic layer after washing was distilled off under reduced pressure at 80 ° C / 2 Torr to obtain 11.1 g of a translucent brown and highly viscous liquid. The obtained liquid was identified as the compound of the following (17) based on ¹ H NMR and ¹³ C NMR.

8.0 g of the compound (17) and 24 g of anisole were placed in a flask equipped with a stirring apparatus and a reflux apparatus, and the mixture was heated in an oil bath at 160 ° C, and heated under stirring with anisole for 30 minutes. Then, the volatile matter was removed from the reaction solution by distillation under reduced pressure at 150 ° C / 2 Torr to obtain 6.3 g of a translucent red liquid. ¹ H NMR of the obtained liquid and the spectrum of the following Table 2 were obtained, and it was identified as the compound of the following (18).

[Comparative Example 1]

The reaction was carried out by the same procedure as the synthesis method of (6) of Example 1, except that instead of 4-bromo-1-butene, using 9.52 g of 3-bromo-1-propane, but no addition reaction was carried out. , directly recycle raw materials (5).

[Comparative Example 2]

In a flask equipped with a stirring and refluxing apparatus, 20.0 g of the compound (5), 16.2 g of the following compound (9), and 20 g of m-xylene hexafluoride were heated to 90 ° C, and mixed with chloroplatinic acid/vinyl oxyalkylene. The toluene solution of the compound was 0.040 g (as a Pt monomer, containing 1.0 × 10 ^-7 mol), and heating and stirring were continued for 12 hours. When the ¹ H NMR of the reaction solution was measured, the addition reaction of the desired allyl group was not carried out, and the compound (10) shown below was obtained, and the objective compound was not obtained.

According to the above, the method for producing a fluorine-containing maleimide compound of the present invention shows that the fluorine-containing maleimide compound of the present invention can be obtained in a good yield.

Further, in order to show that the fluorine-containing maleic imine compound of the present invention is hardly inhibited by hardening by oxygen, a cured product excellent in water repellency and oil repellency can be formed, and the fluorine-containing male fluorene synthesized in the first embodiment can be prepared. The imine compound and the fluorine-containing acrylate composition of Comparative Example 3 (manufactured by Tokyo Chemical Industry Co., Ltd.: 100 parts by mass of acrylic acid 1H, 1H-pentafluoro-n-octyl ester, and 3 parts by mass of Irgacure 184 manufactured by BASF Corporation). The mixture was diluted to 40% by weight with methyl ethyl ketone, and spin-coated on a glass plate, and irradiated with ultraviolet rays of 1.6 J/cm ² in a nitrogen atmosphere by a transport type ultraviolet irradiation device (manufactured by PANASONIC Electric Co., Ltd.) to form a hardening. The film was confirmed to be in a hardened state. The results are shown in Table 3 below.

According to the above-described results, the fluorine-containing maleic imine compound of the present invention exhibits hardening by hardening by oxygen, and can form a cured product excellent in water repellency. On the other hand, in the case of using a fluorine-containing acrylate, a hardening inhibition by oxygen occurs.

Furthermore, the present invention is not limited to the above embodiment. The above-described embodiments are exemplified, and those having substantially the same effects as those of the technical idea described in the claims of the present invention are included in the technical scope of the present invention.

Claims (5)

A fluorine-containing maleic imine compound characterized by having at least one fluoroalkyl group and/or fluoropolyether group in one molecule, and having at least one bond represented by the following formula (1) bonded to a ruthenium atom Residues, (In the formula, a is an integer from 1 to 10). The fluorine-containing maleimide compound according to claim 1, which is represented by the following formula (2), (In the formula, a is the same as the above, and each of R ¹ to R ^{2 is} independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and Rf is each independently a fluoroalkyl group or a fluoropolyether group, and a Z-based divalent hydrocarbon group; A part thereof may also contain an oxygen atom, a nitrogen atom, or a ruthenium atom; each of x and y is an integer of 1 to 4, which satisfies 3≦x+y≦5). A method for producing a fluorine-containing maleic imine compound, which is a method for producing a fluorine-containing maleimide compound according to claim 1 or claim 2, which comprises at least one halothane in one molecule And a fluoropolyether group, a halogen-containing modified organic ruthenium compound having at least one ruthenium atom and having an organic group modified by a halogen atom selected from chlorine, bromine and iodine, and the following general formula (3) The compound shown is subjected to an N-alkylation reaction, and the obtained compound is heated to 100 ° C or higher to obtain the above-mentioned fluorine-containing maleimide compound. The method for producing a fluorine-containing maleimide compound according to claim 3, wherein the fluorine-containing Si-H compound having at least one fluoroalkyl group and/or fluoropolyether group and a hydrogen atom bonded to a halogen atom is obtained , with the following general formula (4) silicon hydrogen compound represented by the alkylation reaction, to give the modified organic silicon compound containing a halogen, [Chemical 4] _{CH 2 = CH-CH 2 -} (CH 2) a -X ( 4) (In the formula, a is the same as described above, and X is a halogen atom selected from chlorine, bromine and iodine). The method for producing a fluorine-containing maleimide compound according to claim 3, wherein the Si-H compound having two or more hydrogen atoms bonded to a halogen atom is represented by the following formula (4) Hydrogenation reaction of a compound and a fluorine-containing compound having at least one fluoroalkyl group and/or a fluoropolyether group and a terminal alkenyl group to obtain the aforementioned halogen-containing modified organic ruthenium compound, [Chem. 5] CH ₂ =CH-CH _2- (CH ₂ ) _a -X (4) (wherein a is the same as described above, and X is a halogen atom selected from chlorine, bromine and iodine).