JPH09227685A - Novel fluorine-modified silicone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel fluorine-modified silicone improved in water repellency, oil repellency and compatibility by copolymerizing three specified compounds through ring opening and reacting the formed copolymer with an end-capping agent. SOLUTION: A compound represented by formula I [wherein (p) is 3-6; R<4> is a 2-24C hydrocarbon group optionally substituted by an atom except F or an F-free atomic group 9147/28} is copolymerized with a compound represented by formula II (wherein (q) is 3-6: (b) is 0-5; and Rf<2> is a 1-22C linear, branched or cyclic prefluoroalkyl) and optionally a compound represented by formula III (wherein (o) is (q) through ring opening to obtain a copolymer. This copolymer is reacted with an end-capping agent (e.g. chlorotrialkylsilance or methoxytrialkysilane) to obtain a fluorine-modified silicone represented by formula IV (wherein A is a group represented by formula V; B is a group represented by formula IV; (1) is 0-1,500; R<1> and R<3> are each a 1-4C linear, branched or cyclic alkyl; R<21> to R<23> and R<2x> are each R<4> ; mx is an arbitrary number; m1 +m2 +m3 +...+mx =1; (x) is 1-10; a1 to a2 and ay are each 0-5; Rf<11> to Rf<13> and Rf<y> are each Rf<2> : n1 +n2 +...+Ny =1; and (y) is 1-5).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a novel fluorine-modified silicone which can be suitably used for paints, coating agents, surface treatment agents and the like, and a novel fluorine-modified silicone.

[0002]

2. Description of the Related Art Fluorine-modified silicones are widely used as paints, coating agents, surface treatment agents and the like because they have excellent water repellency. However, the fluorine-modified silicones that have been developed so far have water repellency and oil repellency at the same time, so they are not well compatible with other materials and are composed of a plurality of raw materials, for example, compositions such as paints. In that case, it must be said that it is difficult to use in terms of compatibility with other raw materials.

Under these circumstances, attempts have been made to adjust the number of fluorine atoms introduced into silicone, for example, to introduce into the silicone an alkyl group having a low content of fluorine atoms, but there is little improvement in compatibility. However, the water repellency and other advantages may be impaired. Also, by introducing a normal methyl group in place of the fluorinated alkyl group,
Attempts have been made to improve the compatibility, but there is a problem that if the compatibility is increased, the water repellency is impaired, and if the compatibility is increased, the compatibility is impaired.

[0004]

The present invention has been made under such circumstances, and is a fluorine-modified silicone having excellent water and oil repellency and compatibility, and a method for producing a fluorine-modified silicone having the above properties. The challenge is to provide.

[0005]

In view of the above situation, the inventors of the present invention have earnestly studied for a means for improving the compatibility of the fluorine-modified silicone without impairing the water / oil repellency, and as a result, It was found that a novel fluorine-modified silicone having both compatibility and water / oil repellency can be obtained by introducing a bulky hydrocarbon group together with a perfluoroalkyl group into a part of the dimethylpolysiloxane structure. Has been completed.

That is, the present invention is a fluorine-modified silicone represented by the following general formula (I).

[0007]

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(However, in the formula (I), A is the following general formula (I
I represents a group represented by I), B represents a group represented by the following general formula (III), and 1 represents an arbitrary value of 0 to 1500.
R ¹ and R ³ each independently represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. )

[0009]

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(However, in the formula (II), R ²¹ , R ²² , R ²³ ,
· · · ·, R ^2X are each independently a hydrocarbon group of atomic carbon atoms which may be substituted with 2-24 containing no atom or a fluorine atom other than a fluorine atom, m _1, m ₂ ,
m ₃ , ..., M _x represent arbitrary numerical values, and m
_{1 + m 2 + m 3 +} ···· + m x is from 1 to 1500. Further, x is an arbitrary integer of 1 to 10. )

[0011]

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(However, in the formula (III), a₁, A_Two, A_Three,
... a_yAre each independently an integer of 0 to 5
And Rf¹¹, Rf¹², Rf¹³...., Rf^1yIs
Independently of linear, branched, or cyclic having 1 to 12 carbon atoms
Represents a perfluoroalkyl group, n₁, N_Two, N_Three, ...
.., n_yEach represents an arbitrary numerical value, and n₁+ N_Two+
n _Three+ ... ・ + n_yIs 1 to 1500. Also, y is
It is an arbitrary integer of 1 to 5. )

The present invention also provides at least one compound represented by the following general formula (IV), at least one compound represented by the general formula (V), and a general formula (VI) which is optionally added. After the ring-opening copolymerization of the mixture with the compound represented by), the obtained ring-opening copolymer is reacted with one or more compounds selected from the compounds shown in the following group A as an end capping agent, Provided is a method for producing a fluorine-modified silicone, which comprises endcapping the ring-opening copolymer. (A) Chlorotrialkylsilane, methoxytrialkylsilane, ethoxytrialkylsilane, bromotrialkylsilane, hexaalkyldisiloxane (wherein alkyl in each compound of group a is linear or branched having 1 to 4 carbon atoms, Represents a cyclic alkyl.)

[0014]

[Chemical 21]

(In the formula (IV), p represents an integer of 3 to 6, and R ⁴ has 2 to 24 carbon atoms which may be substituted with an atom other than a fluorine atom or an atomic group containing no fluorine atom. Represents a hydrocarbon group.)

[0016]

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(However, in the formula (V), q represents an integer of 3 to 6, b represents an arbitrary integer of 0 to 5, and Rf ² has 1 carbon atom.
Represents a straight chain, branched chain, or cyclic perfluoroalkyl group. )

[0018]

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(In the formula (VI), o represents an integer of 3 to 6.)

Specific examples of the fluorine-modified silicone obtained by the production method of the present invention include the fluorine-modified silicone represented by the above general formula (I).

Further, the present invention is directed to a compound represented by the following general formula (VII) and a general formula (VI) optionally added.
After ring-opening copolymerization of the mixture with the compound represented by, the obtained ring-opening copolymer is reacted with one or more selected from the compounds shown in the following group A as an end capping agent, End-capping the ring-opening copolymer,
Further provided is a method for producing a fluorine-modified silicone, which comprises subjecting at least one compound represented by the following general formula (VIII) and at least one compound represented by the general formula (IX) to an addition reaction. (A) Chlorotrialkylsilane, methoxytrialkylsilane, ethoxytrialkylsilane, bromotrialkylsilane, hexaalkyldisiloxane (wherein alkyl in each compound of group a is linear or branched having 1 to 4 carbon atoms, Represents a cyclic alkyl.)

[0022]

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(In the formula (VII), r represents an integer of 3 to 6.)

[0024]

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(However, o in the formula (VI) represents an integer of 3 to 6.)

[0026]

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(However, in the formula (VIII), X ¹ , X ² , X
³ represents an atom other than a fluorine atom, R ⁵ represents an atom other than a fluorine atom, an atom other than a fluorine atom, or a carbon atom which may be substituted with an atomic group containing no fluorine atom.
22 represents a hydrocarbon group. )

[0028]

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(In the formula (IX), d represents an integer of 0 to 3 and Rf ³ represents a linear, branched or cyclic perfluoroalkyl group having 1 to 12 carbon atoms.)

Further, as the fluorine-modified silicone obtained by such a production method of the present invention, specifically, among the fluorine-modified silicone represented by the above general formula (I),
Generally a ₁ of formula _{(III), a 2, a} 3, ····, a y is 2
There may be mentioned fluorine-modified silicone, which is an arbitrary integer of 5.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
First, the fluorine-modified silicone of the present invention will be described. (1) Fluorine-modified silicone of the present invention The fluorine-modified silicone of the present invention has a structure represented by the above general formula (I).

Here, in the general formula (I), A represents an x-component type copolymer in which the ends are not blocked as shown in the general formula (II). The number of components constituting the copolymer, that is, the type x of the monomer is any of 1 to 10, and preferably 1 to 5. Further, in the general formula (II), R ²¹ , R ²² , R ²³ ,
..., R ^2X each independently represents a hydrocarbon group having 2 to 24 carbon atoms which may be substituted with an atom other than a fluorine atom or an atomic group containing no fluorine atom. Specific examples thereof include linear, branched, cyclic, mixed alkyl, alkenyl, alkynyl, aryl, and aralkyl groups thereof, and among these, alkyl, aryl, and aralkyl groups. Can be mentioned as a preferable group in the fluorine-modified silicone of the present invention.

Specific examples of the atom or atomic group substituting the hydrocarbon group include halogen atoms other than fluorine, alkoxy groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkylamino groups, alkylaminocarboxyl groups, alkylcarbonylamino groups. A group and the like can be mentioned. Moreover, the preferable carbon number in these substituents is 1-20.

Further, in the general formula (II), m ₁ , m ₂ ,
m _3, · · · ·, m _x each represent any number, these total number _{m 1 + m 2 + m 3} + ···· + m x ( hereinafter, represents the total number in m _s) is 1 1,500, but in the fluorine-modified silicone of the present invention, m _s is 5 to 1,000.
Is more preferable, and the more preferable range of m _s is 10 to 500.

In the general formula (I), B represents a y-component type copolymer having an unblocked perfluoroalkyl group as shown in the general formula (III). In the formula (III), the number of components having a perfluoroalkyl group forming the copolymer, that is, the type y of the monomer, is any one of 1 to 5, and preferably 1
~ 3. In the general formula (III), a ₁ , a ₂ , a ₃ ,
..., _ay each independently represents an arbitrary integer of 0 to 5. In the fluorine-modified silicone of the present invention, these are preferably in the range of 0 to 3, and more preferably in the range of 0 to 2.

In the general formula (III), Rf ¹¹ , R
f ¹² , Rf ^13, ..., Rf ^1y each independently represent a linear, branched, or cyclic perfluoroalkyl group having 1 to 12 carbon atoms, and the perfluoroalkyl group has 2 to 12 carbon atoms. It is preferably 10 and more preferably 3 to 9 in the fluorine-modified silicone of the present invention. When the carbon number of the perfluoroalkyl group is more than 12, the compatibility of the resulting fluorine-modified silicone may be impaired. Further, when the fluorine-modified silicone does not have a perfluoroalkyl group, the effect of water and oil repellency cannot be obtained. In addition, as described above, the perfluoroalkyl group may be linear or branched,
Alternatively, it may be cyclic, but as a preferred structure,
A straight-chain structure may be mentioned in terms of ease of production,
From the viewpoint of physical properties, a cyclic structure can be mentioned.

Further, in the general formula (III), n ₁ , n
₂ , n ₃ , ..., N _y represent arbitrary numerical values, respectively, and the total number n ₁ + n ₂ + n ₃ + ... + n _y (hereinafter, the total number is represented by n _s ) is 1 to 1500, but in the fluorine-modified silicone of the present invention, n _s is 5 to 1
It is preferably in the range of 000, more preferably n _s
The range is from 10 to 500.

In the general formula (I), l is 0 to 1
Although it represents an arbitrary numerical value of 500, in the fluorine-modified silicone of the present invention, 1 is preferably in the range of 0 to 1000, and more preferably 1 is in the range of 0 to 500.

In the fluorine-modified silicone of the present invention represented by the general formula (I), the above-mentioned values of l, m _s and n _s influence the state of the obtained fluorine-modified silicone. When it is desired to use the fluorine-modified silicone of the present invention for a purpose such as a paste base which makes use of solid or semi-solid properties, the above l, m _s and n _s are 100 to 1 independently.
It is preferably in the range of 500. Moreover, 200-1000 can be mentioned as a more preferable range of l, m _s , and n _s , and 300-800 can be mentioned as a more preferable range.

[0040] Further, in the fluorine-modified silicone of the present invention, the value of _{(l + m s) / n} s to balance the compatibility and water and oil repellency is preferably in the range of 50 to 200 . In addition, more preferable (l + _ms )
The value range of / n _s can be 75 to 175, and a more preferable range is 100 to 150.

Further, in the general formula (I), R ¹ and R ³ each independently represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. ^{Both 1} and R ³ are preferably methyl groups.

The above-mentioned fluorine-modified silicone of the present invention is a copolymer compound obtained by copolymerizing several kinds of monomers as shown in the general formula (I). For example, the compound of the general formula (I) can be obtained by polycondensation reaction. After a polycondensation reaction of a mixture of various monomers to be each constitutional unit by an ordinary method, an appropriate end capping agent capable of forming the end represented by the general formula (I) is added to the reaction solution. Can be manufactured by a manufacturing method such as end-capping the copolymer.

Further, ring-opening copolymerization was carried out by a method similar to the method for producing a fluorine-modified silicone of the present invention described below, using several silicone cyclic compounds containing a cyclic silicone having a perfluoroalkyl group as starting materials. rear,
A production method such as endcapping this with an endcapping agent can be mentioned. Alternatively, ring-opening copolymerization is carried out using a silicone cyclic compound containing no fluorine atom as a starting material by a method similar to still another method for producing the fluorine-modified silicone of the present invention shown below, which is end-capped with an end-capping agent. Then, there can be mentioned a production method in which a hydrocarbon group having a perfluoroalkyl group and a bulky hydrocarbon group are introduced therein by an addition reaction or the like.

(2) Method for producing fluorine-modified silicone of the present invention The present invention provides the following method for producing fluorine-modified silicone. One of the methods for producing the fluorine-modified silicone of the present invention (hereinafter referred to as “the production method 1 of the present invention”) is
At least one compound represented by the general formula (IV), at least one compound represented by the general formula (V), and a compound represented by the general formula (VI) optionally added. After the mixture is subjected to ring-opening copolymerization, the resulting ring-opening copolymer is reacted with one or more compounds selected from the compounds shown in Group A below as an end-capping agent to give the ring-opening copolymer. Characterized by capping. (A) Chlorotrialkylsilane, methoxytrialkylsilane, ethoxytrialkylsilane, bromotrialkylsilane, hexaalkyldisiloxane (wherein alkyl in each compound of group a is linear or branched having 1 to 4 carbon atoms, Cyclic alkyl is represented.) First, the cyclic silicone represented by the general formula (VI), which is optionally used in the production method 1 of the present invention, is represented by, for example, the following reaction formula 1 (formula 28). It is obtained by condensing dichlorodimethylsilane in the presence of an alkali.

[0045]

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(In the formula, o represents an integer of 3 to 6.)

The cyclic silicone represented by the general formula (IV) is, for example, as shown in the following reaction formula 2 (Chemical formula 29):
First, by adding to the methylhydrogendichlorosilane, a hydrocarbon compound having 2 to 24 carbon atoms which may be substituted with an atom other than a fluorine atom having a double bond at the terminal or an atomic group containing no fluorine atom is added. It can be prepared by obtaining a hydrogen group-substituted methyldichlorosilane and further condensing this in the presence of an alkali. In reaction formula 2, a compound in which one of the hydrogen atoms of ethylene is replaced by the hydrocarbon group represented by R ⁶ is used as the compound to be added to methylhydrogendichlorosilane. It is also possible to use a compound in which the other three hydrogen atoms in the ethylene derivative are substituted with an atom other than a fluorine atom or an atomic group containing no fluorine atom, as long as the addition reaction is not affected. .

[0048]

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(In the formula, p represents an integer of 3 to 6, and R
⁶ represents a hydrocarbon group having 1 to 22 carbon atoms which may be substituted with an atom other than a fluorine atom, an atom other than a fluorine atom or an atomic group containing no fluorine atom. )

Further, as the cyclic silicone having a perfluoroalkyl group represented by the general formula (V), for example, as shown in the following reaction formula 3 (Chemical formula 30), first, methylhydrogendichlorosilane is first added to the terminal carbon atom. A straight chain of the numbers 1 to 12,
Hydrocarbon group-substituted methyl having a branched or cyclic perfluoroalkyl group and having a perfluoroalkyl group by adding a hydrocarbon compound having a double bond at the end opposite to the one to which the perfluoroalkyl group is bonded It can be prepared by obtaining dichlorosilane and condensing it in the presence of an alkali.

[0051]

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(In the formula, q represents an integer of 3 to 6, and e
Represents an arbitrary integer of 0 to 3, and Rf ⁴ has 1 to 12 carbon atoms.
Represents a linear, branched or cyclic perfluoroalkyl group. )

Alternatively, the cyclic silicone represented by the general formula (IV) and the cyclic silicone represented by the general formula (V) are represented by the following reaction formula 4 (formula 31) and the following reaction formula 5 (formula 32), respectively. As described above, trichloromethylsilane is reacted with a Grignard reagent derived from a halide of a corresponding hydrocarbon group or a halide of a hydrocarbon group having a perfluoroalkyl group,
It can also be produced by preparing a hydrocarbon group-substituted methyldichlorosilane compound having a hydrocarbon group or a perfluoroalkyl group, and cyclizing this in the presence of an alkali.

[0054]

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(In the formula, p represents an integer of 3 to 6, and X
⁴ represents a halogen atom, and R ⁷ represents a hydrocarbon group having 2 to 24 carbon atoms which may be substituted with an atom other than a fluorine atom or an atomic group containing no fluorine atom. )

[0056]

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(In the formula, q represents an integer of 3 to 6, and h
Represents an arbitrary integer of 0 to ⁵ , X ⁵ represents a halogen atom, and Rf ⁵ represents a linear, branched, or cyclic perfluoroalkyl group having 1 to 12 carbon atoms. )

In the method 1 for producing a fluorine-modified silicone of the present invention, at least one of the cyclic silicones represented by the general formula (IV) thus obtained and the cyclic silicone represented by the general formula (V) are prepared. The mixture obtained by mixing at least one kind in an appropriate ratio is subjected to ring-opening copolymerization. Alternatively, at least one kind of the cyclic silicone represented by the general formula (IV), at least one kind of the cyclic silicone represented by the general formula (V) and the cyclic silicone represented by the general formula (VI) are contained in appropriate proportions. The ring-opening copolymerization is performed on the mixture mixed in. Here, the mixing ratio of each cyclic silicone compound used in the ring-opening copolymerization may be, for example, a general formula as a mixing ratio of each compound for obtaining a fluorine-modified silicone having compatibility with water and oil repellency. The molar ratio of the total amount of the compound represented by (VI) and the compound represented by the general formula (IV) to the amount of the compound represented by the general formula (V) is 50: 1 to 200: 1. Such a mixing ratio can be mentioned. The molar ratio is more preferably 7
5: 1 to 175: 1, more preferably 100:
1 to 150: 1.

The ring-opening polymerization may be carried out by an ordinary method, for example, by mixing the above mixture with toluene, benzene,
It is dissolved in an organic solvent such as xylene, a catalyst such as trifluoromethylsulfuric acid, sulfuric acid, nitric acid is added thereto, and the reaction is carried out for an appropriate time while heating if necessary. The reaction time is adjusted depending on the molecular weight or the degree of polymerization of the target copolymer. For example, using a mixture with the above molar ratio,
In order to obtain a copolymer having a degree of polymerization of about 15 to 3000 which is easy to use, a reaction temperature of about 60 to 180 ° C. is generally used for about 2 to
The reaction may be performed for 24 hours. Moreover, the more preferable range of the degree of polymerization of the copolymer is about 20 to 2,500, and the more preferable range of the degree of polymerization is 30 to 200.
There can be about 0.

In the manufacturing method 1 of the present invention, after that,
After the lapse of time, one or more compounds selected from the compounds shown in Group A above are added as an end capping agent to the reaction solution to stop the reaction, and the reaction is carried out to end cap the ring-opening copolymer. To do. The end-capping agent used is as shown in the above group A, but the alkyl in each compound of group B is preferably methyl, and among these, more preferable end-capping agents include hexamethyldisiloxane and chloro. Examples include trimethylsilane.

The method 1 for producing a fluorine-modified silicone of the present invention is the above-mentioned production method and is suitable for producing a block copolymer. Furthermore, as the fluorine-modified silicone obtained by the above-mentioned production method 1 of the present invention,
Specific examples include fluorine-modified silicone represented by the above general formula (I).

Yet another method for producing the fluorine-modified silicone of the present invention (hereinafter referred to as "production method 2 of the present invention") is a compound represented by the above general formula (VII) and, if necessary, After ring-opening copolymerization of the mixture with the compound represented by the general formula (VI) to be added, the obtained ring-opening copolymer is endowed with one or more compounds selected from the compounds shown in the following group A. The ring-opening copolymer is end-capped by reacting as a capping agent, and at least one of the compounds represented by the following general formula (VIII) and at least one of the compounds represented by the general formula (IX) are further added thereto. It is characterized by carrying out an addition reaction. (A) Chlorotrialkylsilane, methoxytrialkylsilane, ethoxytrialkylsilane, bromotrialkylsilane, hexaalkyldisiloxane (wherein alkyl in each compound of group a is linear or branched having 1 to 4 carbon atoms, Represents a cyclic alkyl.) The cyclic silicone represented by the general formula (VI) used in the production method 2 of the present invention is as described in the production method 1 above. The cyclic silicone represented by the general formula (VII) can also be obtained by condensing methylhydrogendichlorosilane in the presence of an alkali in the same manner as the cyclic silicone represented by the general formula (VI).

In the method 2 for producing a fluorine-modified silicone of the present invention, the cyclic silicone represented by the general formula (VII) or the cyclic silicone represented by the general formula (VII) and the general formula (VI) is represented. The ring-opening copolymerization is performed on the mixture obtained by mixing the above-mentioned cyclic silicone in an appropriate ratio. The ring-opening polymerization may be carried out by a conventional method, and the above general formula (VI
Cyclic silicone represented by I) and this and general formula (VI)
The polymer raw material such as a mixture with the cyclic silicone represented in (1) is dissolved in an organic solvent such as toluene, benzene or xylene, and a catalyst such as trifluoromethyl sulfuric acid, sulfuric acid or nitric acid is added to this, While heating accordingly
React for a suitable time.

The reaction time is adjusted depending on the degree of polymerization of the desired copolymer. For example, in order to obtain an easy-to-use copolymer having a degree of polymerization of about 15 to 3000 using the above polymer raw materials, the reaction may be performed at a reaction temperature of about 60 to 180 ° C. for about 2 to 24 hours. . Moreover, the more preferable range of the degree of polymerization of the above copolymer is about 20 to 2500, and the more preferable range of the degree of polymerization is 30 to 2
000 can be mentioned.

In the manufacturing method 2 of the present invention, after that,
After the lapse of time, one or more compounds selected from the compounds shown in Group A above are added as an end capping agent to the reaction solution to stop the reaction, and the reaction is carried out to end cap the ring-opening copolymer. To do. The end-capping agent used is as shown in the above group A, but the alkyl in each compound of group B is preferably methyl, and among these, more preferable end-capping agents include hexamethyldisiloxane and chloro. Examples include trimethylsilane.

In the production method 2 of the present invention, the copolymer obtained by endcapping the ring-opening copolymer as described above is further prepared by further adding at least one compound represented by the general formula (VIII) and At least one compound represented by the general formula (IX) is subjected to an addition reaction. The addition reaction may be carried out according to a conventional method. For example, the copolymer and the compound represented by the general formula (VIII), the compound represented by the general formula (IX) may be treated with a catalyst such as platinum chloride. It suffices to carry out the addition reaction under pressure and heating conditions.

Here, with respect to the mixing ratio of each cyclic silicone compound and the mixing ratio of each unsaturated compound used in the addition reaction in the method 2 for producing a fluorine-modified silicone of the present invention, for example, compatibility, water repellency and oil repellency are included. As a mixing ratio of each of the above compounds to obtain a fluorine-modified silicone having also, the mixing ratio of the cyclic silicone represented by the general formula (VI) and the cyclic silicone represented by the general formula (VII) is s: where t is the general formula (VII
When the ratio of the amount of the compound represented by I) to the amount of the compound represented by the general formula (IX) is u: w in molar ratio, s + (t × u
/ (U + w)): The value of t × w / (u + w) is 50: 1 to
A mixing ratio of 200: 1, preferably 75: 1 to 175: 1, and more preferably 100: 1 to 150: 1 can be mentioned.

The method 2 for producing a fluorine-modified silicone of the present invention is the above-mentioned method for producing a copolymer in which groups containing a hydrocarbon group and a perfluoroalkyl group are randomly arranged in the copolymer. It is suitable for

Further, as the fluorine-modified silicone obtained by the production method 2 of the present invention as described above, specifically,
Among the fluorine-modified silicones represented by the above general formula (I), fluorine-modified one in which a ₁ , a ₂ , a ₃ , ..., A _{y in} the general formula (III) is any integer of 2 to 5 Mention may be made of silicone.

Manufacturing method 1 and manufacturing method 2 of the present invention
Among the fluorine-modified silicone of the present invention obtained by
For example, a compound having a good compatibility with a solvent for chromatography such as the fluorine-modified silicone represented by the above general formula (I) can be easily purified by silica gel column chromatography, alumina color chromatography, etc. In addition to this, the fluorine-modified silicone of the present invention obtained by the above-mentioned production method of the present invention can be purified by a usual method such as vacuum distillation.

[0071]

EXAMPLES Examples of the present invention will be described below, but it goes without saying that the present invention is not limited to these examples.

[0072]

Example 1 1,1,1,2,2,3,3,4,4,5,5,6,6 dissolved in 300 ml of diethyl ether
-Tridecafluoro-8-iodooctane was added to a Grignard reagent derived from 50 g and magnesium 3 g, and trichloromethylsilane 20 was added under cooling with dry ice acetone.
g solution in 100 ml of diethyl ether,
Added dropwise. The temperature of this mixed solution was gradually raised to room temperature and reacted for 24 hours. The reaction solution obtained is treated with 500 m of water.
It was dripped into 1 and hydrolyzed at 50 ° C for 1 hour. After cooling the hydrolysis reaction liquid, add diethyl ether 500 m to it.
1 was added and liquid-liquid extraction was performed, and the diethyl ether layer was taken out. Next, the taken-out diethyl ether layer was washed with dilute hydrochloric acid and water, and dried over magnesium sulfate. The obtained liquid is concentrated and purified by silica gel column chromatography (elution solvent; normal hexane: diethyl ether = 100: 0 → 50: 50) to obtain 29 g of cyclic silicone 1 represented by the following formula (1a). It was
The structure of this compound was confirmed by performing NMR, IR, and mass spectrometry.

[0073]

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Next, 50 g of methyldichlorosilane and H ₂
0.1g of PtCl ₆ and 0.5g of SnCl ₂ · 2H ₂ O
Was heated to reflux, 70 g of styrene was added dropwise thereto, and the mixture was reacted at 80 ° C. for 24 hours. The obtained reaction solution was hydrolyzed in the same manner as the above-mentioned cyclic silicone 1, and then purified to give 43 parts of the cyclic silicone 2 represented by the following formula (2a).
g was obtained.

[0075]

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After hydrolyzing 50 g of dichlorodimethylsilane in the same manner as the cyclic silicone 1,
After purification, 24 g of cyclic silicone 3 represented by the following formula (3a) was obtained.

[0077]

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12 of the cyclic silicone 1 obtained above
g, 5 g of cyclic silicone 2, and cyclic silicone 3
Was dissolved in 100 ml of toluene and heated to 80 ° C. A catalytic amount of trifluoromethylsulfuric acid was added to this mixed solution and reacted for 8 hours. After that, 1 g of hexamethyldisiloxane was further added to this reaction solution, and end capping was performed. The reaction product was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off, followed by silica gel column chromatography (elution solvent, hexane: diethyl ether =
1: 0 → 50: 50), and the following formula (1B)
8 g of Silicone 1 represented by The structure of the obtained Silicone 1 was confirmed by measuring NMR and IR. The degree of polymerization was determined by measuring the viscosity.

[0079]

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[0080]

Example 2 Cyclic silicone 1 and cyclic silicone 3 were produced in the same manner as in Example 1 above. Furthermore, 20 g of methyldichlorosilane and 30 g of 1 were prepared in exactly the same manner as in the production of the cyclic silicone 2 in Example 1 above.
16 g of cyclic silicone 4 represented by the following formula (4a) was produced from decene.

[0081]

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10 of the cyclic silicone 1 obtained above
g, cyclic silicone 3 2 g, cyclic silicone 4 5 g
Was dissolved in 100 ml of toluene, and 1 was added in the same manner as in Example 1.
After treatment for 6 hours, it was endcapped with hexamethyldisiloxane. The obtained reaction product was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off, followed by purification by silica gel column chromatography (elution solvent, hexane: diethyl ether = 100: 0 → 50: 50), and the following formula was used. 5 g of Silicone 2 represented by (2B) was obtained. The structure of the obtained Silicone 2 was confirmed by measuring NMR and IR. The degree of polymerization was determined by measuring the viscosity.

[0083]

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[0084]

Example 3 Cyclic silicone 1 and cyclic silicone 3 were produced in the same manner as in Example 1 above. Further, 7 g of cyclic silicone 5 represented by the following formula (5a) was produced from 10 g of cyclohexene and 20 g of methyldichlorosilane in the same manner as in the production of cyclic silicone 2 in Example 1 above.

[0085]

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5 g of the cyclic silicone 1 obtained above,
1 g of cyclic silicone 3 and 7 g of cyclic silicone 5
It was dissolved in 0 ml of toluene, treated in the same manner as in Example 1 for 4 hours, and then end-capped with hexamethyldisiloxane. The obtained reaction product was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off, followed by purification by silica gel column chromatography (elution solvent, hexane: diethyl ether = 100: 0 → 50: 50), and the following formula was used. 4 g of Silicone 3 represented by (3B) was obtained. The structure of the obtained Silicone 3 was confirmed by measuring NMR and IR. The degree of polymerization was determined by measuring the viscosity.

[0087]

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[0088]

Example 4 Cyclic silicone 3 was produced in the same manner as in Example 1 above. In addition, the cyclic silicone 1 of Example 1 above
In the manufacture of 1,1,1,2,2,3,3,4,
27 g of cyclic silicone 6 represented by the following formula (6a) was produced in exactly the same manner except that perfluorooctyl bromide was used instead of 4,5,5,6,6-tridecafluoro-8-iodooctane. did.

[0089]

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Further, 16 g of cyclic silicone 7 represented by the following formula (7a) was produced from 20 g of 1-tetradecene and 20 g of methyldichlorosilane in the same manner as in the production of cyclic silicone 2 in Example 1 above. .

[0091]

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2 g of the cyclic silicone 3 obtained above,
5 g of cyclic silicone 6 and 10 g of cyclic silicone 7 were dissolved in 200 ml of toluene, treated in the same manner as in Example 1 for 10 hours, and then end-capped with hexamethyldisiloxane. The obtained reaction product was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off, followed by purification by silica gel column chromatography (elution solvent, hexane: diethyl ether = 100: 0 → 50: 50),
12 g of Silicone 4 represented by the following formula (4B) was obtained.
The structure of the obtained Silicone 4 was confirmed by measuring NMR and IR. The degree of polymerization was determined by measuring the viscosity.

[0093]

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[0094]

Example 5 Cyclic silicone 1, cyclic silicone 2 and cyclic silicone 3 were produced in the same manner as in Example 1 above. Further, in the same manner as in Example 4 above, the cyclic silicone 7
Was manufactured.

7 g of cyclic silicone 1 thus obtained, 5 g of cyclic silicone 2 and 2 of cyclic silicone 3 were obtained.
g and 10 g of cyclic silicone 7 were dissolved in 100 ml of toluene, treated in the same manner as in Example 1 for 6 hours, and endcapped with hexamethyldisiloxane. The obtained reaction product was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off, followed by silica gel column chromatography (eluting solvent, hexane: diethyl ether =
1: 0 → 50: 50) to obtain 6 g of Silicone 5 represented by the following formula (5B). The structure of the obtained Silicone 5 was confirmed by measuring NMR and IR. The degree of polymerization was determined by measuring the viscosity.

[0096]

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[0097]

Example 6 Cyclic silicone 3 was produced in the same manner as in Example 1 above. Further, in the same manner as in the production of the cyclic silicone 2 in the above-mentioned Example 1, 3, 3, 4,
4,5,5,6,6,7,7,8,8,9,9,10,
21 g of a cyclic silicone 8 represented by the following formula (8a) was produced from 50 g of 10,10-heptadecafluoro-1-decene and 30 g of methyldichlorosilane.

[0098]

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Furthermore, the cyclic silicone 1 of Example 1 above
In the manufacture of 1,1,1,2,2,3,3,4,
26 g of cyclic silicone 9 represented by the following formula (9a) was produced in exactly the same manner except that 30 g of monochlorobenzene was used instead of 50 g of 4,5,5,6,6-tridecafluoro-8-iodooctane. did.

[0100]

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2 g of the cyclic silicone 3 obtained above,
5 g of cyclic silicone 8 and 7 g of cyclic silicone 9
It was dissolved in 0 ml of toluene, treated in the same manner as in Example 1 for 3 hours, and then endcapped with hexamethyldisiloxane. The obtained reaction product was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off, followed by purification by silica gel column chromatography (elution solvent, hexane: diethyl ether = 100: 0 → 50: 50), and the following formula was used. 3 g of Silicone 6 represented by (6B) was obtained. The structure of the obtained Silicone 6 was confirmed by measuring NMR and IR. The degree of polymerization was determined by measuring the viscosity.

[0102]

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[0103]

Comparative Example 1 Cyclic silicone 1 was produced in the same manner as in Example 1 above. 50 g of the obtained cyclic silicone 1 was added.
After dissolving in ml of toluene, adding sulfuric acid and reacting for 4 hours, trimethylchlorosilane was added to terminate the polymerization reaction. The obtained reaction product was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent, hexane: diethyl ether = 100: 0 → 50: 50), and 5 g of control silicone 1 represented by the formula (7B) was obtained.

[0104]

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[0105]

Comparative Example 2 A commercially available 100 cs polydimethylsiloxane was used as a control silicone 2.

[0106]

Comparative Example 3 Cyclic silicone 8 was produced in the same manner as in Example 6 above. 1 g of 12 g of the obtained cyclic silicone 8
It was dissolved in 00 ml of toluene, nitric acid was added and the reaction was carried out for 4 hours, and then hexamethyldisiloxane was added to stop the polymerization reaction. The obtained reaction product was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent, hexane: diethyl ether = 100: 0 → 50: 50), and 7 g of Control Silicone 3 represented by the formula (8B) was obtained.

[0107]

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[0108]

Comparative Example 4 Commercially available 100 cs polymethylphenyl siloxane was used as a control silicone 4.

<Evaluation of Fluorine-Modified Silicone of the Present Invention>
The compatibility, water repellency, and oil resistance of the fluorine-modified silicone of the present invention were evaluated using the various silicone compounds obtained in the above Examples and Comparative Examples.

(1) Solubility Test Phases of each of the silicones 1 to 5 obtained in the above Examples and the control silicones 1 and 2 obtained in Comparative Examples 1 and 2 described above and various solvents shown in Table 1. The solubility was investigated. That is, after stirring 9 parts of the solvent and 1 part of the silicone and leaving them still for 1 hour,
Compatibility was determined. The results are shown in Table 1. Table 1
In the above, ∘ indicates that they are completely compatible with each other and compatible, and x indicates that they are separated into two layers and are incompatible.

[0111]

[Table 1]

As is clear from these results, the fluorine-modified silicone obtained by the production method of the present invention is a fluorine-modified silicone (control silicone 1) in which the repeating unit in the polymer is composed only of units having a perfluoroalkyl group. It is found that the compatibility is better than that of the above, and the compatibility is about the same as the silicone containing no fluorine (control silicone 2).

(2) Water repellency test For the silicones 1 to 5 obtained in each of the above Examples and the control silicones 1 and 2 obtained in the above Comparative Examples 1 and 2,
The water repellent treatment effect was investigated. That is, silicone was prepared to be a 1 wt% normal hexane solution, and the obtained solution was impregnated with gauze. Then, the gauze is taken out of the solution and dried to remove the solvent, and then washed in a washing machine.
Washing was performed 0 times. The water repellency of the above-mentioned various silicone-treated gauze after washing 20 times was judged by the shape of the water droplets dropped on the gauze, and it was judged on the basis of +: water repellency, ±: slightly water repellency, −: no water repellency. . Regarding Control Silicone 1, an insoluble matter remained when it was attempted to be dissolved in normal hexane at the above concentration. Table 2 shows the results.

[0114]

[Table 2]

As is clear from these results, the fluorine-modified silicone obtained by the production method of the present invention has excellent water repellency as compared with the fluorine-free silicone (control silicone 2), and its water repellency is It can be seen that the repeating unit in the polymer is as good as the fluorine-modified silicone (Control Silicone 1) composed only of units having a perfluoroalkyl group.

(3) Water repellency and oil resistance test The water repellency and oil resistance test was performed on the silicone 6 obtained in Example 6 above and the control silicones 2-4 obtained in Comparative Examples 2-4 above. That is, lead yellow and silicone were kneaded at a ratio of 1: 1 with a Hoover Mahler and coated on a glass plate with a doctor blade. Water was allowed to flow for 5 minutes, and the water repellency was evaluated based on the remaining condition of the coating film, based on the criteria of +: water repellency, ±: slightly water repellency, and-: no water repellency. Similarly, olive oil was allowed to flow for 5 minutes, and the oil resistance was evaluated based on the degree of remaining of the coating film on the basis of +: oil resistance, ±: slightly oil resistance, and −: no oil resistance. The results are shown in Table 3.

[0117]

[Table 3]

As is clear from these results, the fluorine-modified silicone obtained by the production method of the present invention differs from the fluorine-free silicones (control silicone 2 and control silicone 4) in that the repeating unit in the polymer is perfluoro. It can be seen that it is excellent in both water repellency and oil resistance, like the fluorine-modified silicone (control silicone 3) composed only of units having an alkyl group.

[0119]

INDUSTRIAL APPLICABILITY According to the present invention, a fluorine-modified silicone having excellent water repellency and oil repellency as well as compatibility is obtained.

Claims (5)

[Claims] 1. A fluorine modification represented by the following general formula (I):
silicone. [Chemical 1](However, in the formula (I), A is represented by the following general formula (II).
Represents a group, and B represents a group represented by the following general formula (III).
However, 1 represents an arbitrary numerical value of 0 to 1500. Also,
R¹, R^ThreeAre each independently a straight-chain or
Represents a cyclic alkyl group. )(However, in the formula (II), R^{twenty one}, R^{twenty two}, R^{twenty three}, ..., R
^2XAre each independently an atom other than a fluorine atom or a fluorine atom.
Number of carbon atoms that may be substituted with an atomic group that does not contain elementary atoms
Represents a hydrocarbon group of 2 to 24, m₁, M_Two, M_Three...
., M_xEach represents an arbitrary numerical value, and m₁+ M_Two+ M_Three
+ ・ ・ ・ ・ + M_xIs 1 to 1500. Also, x is 1
It is an arbitrary integer of -10. )(However, in the formula (III), a₁, A_Two, A_Three, ..., a_y
Each independently represent an arbitrary integer of 0 to 5, Rf
¹¹, Rf¹², Rf¹³...., Rf^1yAre independent
And straight chain, branched or cyclic perfluoro having 1 to 12 carbon atoms
Represents an alkyl group, n₁, N_Two, N_Three, ..., n_yIs
Each represents an arbitrary numerical value, n₁+ N_Two+ N _Three+ ...
+ N_yIs 1 to 1500. Further, y is an arbitrary value of 1 to 5.
Is an integer. ) 2. At least one compound represented by the following general formula (IV), at least one compound represented by the general formula (V), and at least one compound represented by the general formula (VI). After the ring-opening copolymerization of the mixture with the compound to be obtained, the resulting ring-opening copolymer is reacted with one or more compounds selected from the compounds shown in the following group A as an end-capping agent, and the ring-opening is performed. A method for producing a fluorine-modified silicone, which comprises endcapping a copolymer. (A) Chlorotrialkylsilane, methoxytrialkylsilane, ethoxytrialkylsilane, bromotrialkylsilane, hexaalkyldisiloxane (wherein alkyl in each compound of group a is linear or branched having 1 to 4 carbon atoms, Represents a cyclic alkyl.) (However, in the formula (IV), p represents an integer of 3 to 6, and R ⁴ is a hydrocarbon group having 2 to 24 carbon atoms which may be substituted with an atom other than a fluorine atom or an atomic group containing no fluorine atom. Is represented.) (However, in the formula (V), q represents an integer of 3 to 6, and b represents 0 to
5 represents an arbitrary integer of 5 and Rf ² represents a linear, branched or cyclic perfluoroalkyl group having 1 to 12 carbon atoms. ) (However, o in Formula (VI) represents an integer of 3 to 6.) 3. A mixture of a compound represented by the following general formula (VII) and a compound represented by the general formula (VI), which is optionally added, is subjected to ring-opening copolymerization and then obtained. The ring copolymer is reacted with one or more kinds selected from the compounds shown in the following group A as an end capping agent to endcap the ring-opened copolymer, and further to the following general formula (VIII) A method for producing a fluorine-modified silicone, which comprises subjecting at least one compound represented by the formula (II) and at least one compound represented by the general formula (IX) to an addition reaction. (A) Chlorotrialkylsilane, methoxytrialkylsilane, ethoxytrialkylsilane, bromotrialkylsilane, hexaalkyldisiloxane (wherein alkyl in each compound of group a is linear or branched having 1 to 4 carbon atoms, Represents a cyclic alkyl.) (However, in the formula (VII), r represents an integer of 3 to 6.) (However, o in formula (VI) represents an integer of 3 to 6.) (However, in the formula (VIII), X ¹ , X ² , and X ³ represent an atom other than a fluorine atom, and R ⁵ is an atom other than a fluorine atom, an atom other than a fluorine atom, or an atomic group containing no fluorine atom. Represents a hydrocarbon group having 1 to 22 carbon atoms which may be substituted with. (However, in the formula (IX), d represents an integer of 0 to 3, and Rf ³ represents a linear, branched, or cyclic perfluoroalkyl group having 1 to 12 carbon atoms.) 4. At least one compound represented by the following general formula (IV), at least one compound represented by the general formula (V), and at least one compound represented by the general formula (VI). After the ring-opening copolymerization of the mixture with the compound to be obtained, the resulting ring-opening copolymer is reacted with one or more compounds selected from the compounds shown in the following group A as an end-capping agent, and the ring-opening is performed. The fluorine-modified silicone according to claim 1, which is obtained by end-capping a copolymer. (A) Chlorotrialkylsilane, methoxytrialkylsilane, ethoxytrialkylsilane, bromotrialkylsilane, hexaalkyldisiloxane (wherein alkyl in each compound of group a is a straight-chain, branched chain having 1 to 4 carbon atoms, Represents a cyclic alkyl.) (However, in the formula (IV), p represents an integer of 3 to 6, and R ⁴ is a hydrocarbon group having 2 to 24 carbon atoms which may be substituted with an atom other than a fluorine atom or an atomic group containing no fluorine atom. Is represented.) (However, in the formula (V), q represents an integer of 3 to 6, and b represents 0 to
5 represents an arbitrary integer of 5 and Rf ² represents a linear, branched or cyclic perfluoroalkyl group having 1 to 12 carbon atoms. ) [Chemical 13] (However, o in Formula (VI) represents an integer of 3 to 6.) 5. A ring-opening copolymerization of a mixture of a compound represented by the following general formula (VII) and a compound represented by the general formula (VI), which is optionally added, and then obtained. The ring copolymer is reacted with one or more kinds selected from the compounds shown in the following group A as an end capping agent to endcap the ring-opened copolymer, and further to the following general formula (VIII) The fluorine-modified silicone according to claim 1, which is obtained by addition-reacting at least one compound represented by the formula (I) and at least one compound represented by the general formula (IX). (A) Chlorotrialkylsilane, methoxytrialkylsilane, ethoxytrialkylsilane, bromotrialkylsilane, hexaalkyldisiloxane (wherein alkyl in each compound of group a is a straight-chain, branched chain having 1 to 4 carbon atoms, Represents a cyclic alkyl.) (However, in the formula (VII), r represents an integer of 3 to 6.) (However, o in formula (VI) represents an integer of 3 to 6.) (However, in the formula (VIII), X ¹ , X ² , and X ³ represent an atom other than a fluorine atom, and R ⁵ is an atom other than a fluorine atom, an atom other than a fluorine atom, or an atomic group containing no fluorine atom. Represents a hydrocarbon group having 1 to 22 carbon atoms which may be substituted with. (However, in the formula (IX), d represents an integer of 0 to 3, and Rf ³ represents a linear, branched, or cyclic perfluoroalkyl group having 1 to 12 carbon atoms.)