JP5304698B2 - Fluorine-modified amino group-containing organopolysiloxane and method for producing the same - Google Patents

Description

  The present invention relates to an amino group-containing organopolysiloxane having a high fluorine content in which fluorine-modified groups are uniformly introduced and a method for producing the same.

  Introduction of a fluorine-modified group into an amino group-containing organopolysiloxane represented by the following general formula (3) is carried out as described in, for example, Japanese Patent No. 3022070 (Patent Document 1). It can be conveniently done by reaction with. Thereby, it is possible to produce an amino group-containing organopolysiloxane in which fluorine-modified groups are uniformly introduced.

［式中、Ｒ¹は炭素数１〜１０の１価炭化水素基であり、Ｒ²は結合途中に酸素原子、窒素原子、ケイ素原子又はイオウ原子を介在してもよく、アミド結合又はスルホンアミド結合を含有してもよい、置換又は非置換の炭素数１〜１５の２価炭化水素基であり、Ｘ及びＸ’は同一でも異なってもよく、水素原子、又は下記一般式（２）で表される１価のオルガノシリル基である。ｐは５〜５０、好ましくは１０〜３０の整数である。

（式中、Ｙは、

から選ばれる１価の有機基であり、Ｒ¹は前記と同様、ｅは０、１、２又は３である。）」

[Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² may have an oxygen atom, a nitrogen atom, a silicon atom or a sulfur atom in the middle of the bond, an amide bond or a sulfonamide A substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may contain a bond, and X and X ′ may be the same or different, and may be a hydrogen atom or the following general formula (2) It is a monovalent organosilyl group represented. p is an integer of 5 to 50, preferably 10 to 30.

(Where Y is

And R ¹ is the same as described above, and e is 0, 1, 2, or 3. ) "

Japanese Patent No. 3022070

  In Japanese Patent No. 3022070 (Patent Document 1), the fluorine group to be introduced was a fluorine group having 1 to 15 carbon atoms and a relatively low molecular weight. Depending on the application, the introduction of a fluorine group with a molecular weight of this level may function sufficiently, but when dispersed in a highly fluorinated perfluoropolyether oil or the like, unless a fluorine group with a higher molecular weight is introduced, There was a problem that it was not uniformly dispersed or dissolved.

  However, in order to further increase the fluorine content of the amino group-containing organopolysiloxane, even if a bulky perfluoropolyether group having 16 to 100 carbon atoms is to be directly introduced, the fluorine-containing carboxylic acid ester compound and the amino group-containing organo Since the difference in compatibility with polysiloxane becomes large, the reaction in a homogeneous system becomes difficult, and an excessively introduced fluorine-modified group and a polymer in which the amino group-containing siloxane of formula (3) is not introduced with a fluorine-modified group. As a result, a homogeneous fluorine-modified target product could not be obtained.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a fluorine-modified amino group-containing organopolysiloxane having a high fluorine content in which fluorine-modified groups are uniformly introduced and a method for producing the same.

As a result of intensive studies to achieve the above object, the present inventors have first introduced a monovalent group having 1 to 15 carbon atoms into a part of the amino group in the amino group-containing organopolysiloxane of the above formula (3). A fluorine-modified group Rf ¹ composed of a perfluoroalkyl group or a perfluoropolyether group is introduced, and then a fluorine-modified group composed of a monovalent perfluoropolyether group having 16 to 100 carbon atoms in a part of the remaining amino group It has been found that an amino group-containing organopolysiloxane having a high fluorine content, in which fluorine-modified groups are uniformly introduced, can be obtained by performing a two-step fluorine modification treatment of introducing Rf ^2. It came to make.

［式中、Ｒ¹は炭素数１〜１０の１価炭化水素基であり、Ｒ²は結合途中に酸素原子、窒素原子、ケイ素原子又はイオウ原子を介在してもよく、アミド結合又はスルホンアミド結合を含有してもよい、置換又は非置換の炭素数１〜１５の２価炭化水素基であり、Ｒｆ¹は炭素数１〜１５の１価のパーフルオロアルキル基又はパーフルオロポリエーテル基であり、Ｒｆ²は炭素数１６〜１００の１価のパーフルオロポリエーテル基であり、Ｘ及びＸ’は同一でも異なってもよく、水素原子、又は下記一般式（２）で表される１価のオルガノシリル基である。

（式中、Ｙは、

から選ばれる１価の有機基であり、Ｒ¹は前記と同様、ｅは０、１、２又は３である。）
また、ｌは３〜３０の整数、ｍは１〜１０の整数、ｎは１〜１０の整数で、ｌ＋ｍ＋ｎ＝５〜５０を満足する整数である。］
で表されることを特徴とするフッ素変性アミノ基含有オルガノポリシロキサン。
請求項２：
一般式（１）において、まず、下記一般式（３）

（式中、Ｒ¹、Ｒ²、Ｘ及びＸ’は前記と同様である。ｐは５〜５０の整数である。）
で表されるアミノ基含有オルガノポリシロキサンに、下記一般式（４）
Ｒｆ¹−ＣＯＯＲ³ （４）
（式中、Ｒｆ¹は炭素数１〜１５の１価のパーフルオロアルキル基又はパーフルオロポリエーテル基であり、Ｒ³は炭素数１〜８の置換又は非置換の１価炭化水素基である。）
で表されるフッ素変性基（Ｒｆ¹−）を有するカルボン酸エステル化合物を、アミノ基の一部に付加反応してＲｆ¹基を導入し、その後、更に下記一般式（５）
Ｒｆ²−ＣＯＯＲ³ （５）
（式中、Ｒｆ²は炭素数１６〜１００の１価のパーフルオロポリエーテル基であり、Ｒ³は前記と同様である。）
で表されるフッ素変性基（Ｒｆ²−）を有するカルボン酸エステル化合物を、残余のアミノ基の一部に付加反応して、Ｒｆ²基を導入することを特徴とする２段階のフッ素変性基導入過程を有する請求項１記載のフッ素変性アミノ基含有オルガノポリシロキサンの製造方法。 That is, the present invention provides the following fluorine-modified amino group-containing organopolysiloxane and a method for producing the same.
Claim 1:
The following general formula (1)

[Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² may have an oxygen atom, a nitrogen atom, a silicon atom or a sulfur atom in the middle of the bond, an amide bond or a sulfonamide A substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may contain a bond, and Rf ¹ is a monovalent perfluoroalkyl group or perfluoropolyether group having 1 to 15 carbon atoms. Rf ² is a monovalent perfluoropolyether group having 16 to 100 carbon atoms, X and X ′ may be the same or different, and are a hydrogen atom or a monovalent group represented by the following general formula (2) This is an organosilyl group.

(Where Y is

And R ¹ is the same as described above, and e is 0, 1, 2, or 3. )
Moreover, l is an integer of 3-30, m is an integer of 1-10, n is an integer of 1-10, and is an integer satisfying l + m + n = 5-50. ]
A fluorine-modified amino group-containing organopolysiloxane characterized by:
Claim 2:
In general formula (1), first, the following general formula (3)

(In the formula, R ¹ , R ² , X and X ′ are the same as described above. P is an integer of 5 to 50.)
An amino group-containing organopolysiloxane represented by the following general formula (4)
Rf ¹ -COOR ³ (4)
(In the formula, Rf ¹ is a monovalent perfluoroalkyl group or perfluoropolyether group having 1 to 15 carbon atoms, and R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. .)
A carboxylic acid ester compound having a fluorine-modified group (Rf ^1- ) represented by the following formula is added to a part of the amino group to introduce an Rf ¹ group, and then the following general formula (5)
Rf ² -COOR ³ (5)
(In the formula, Rf ² is a monovalent perfluoropolyether group having 16 to 100 carbon atoms, and R ³ is the same as described above.)
A two-stage fluorine-modified group characterized by introducing an Rf ² group by addition reaction of a carboxylic acid ester compound having a fluorine-modified group (Rf ^2- ) represented by The method for producing a fluorine-modified amino group-containing organopolysiloxane according to claim 1, which has an introduction process.

  The fluorine-modified amino group-containing organopolysiloxane having a high fluorine content in which fluorine-modified groups are uniformly introduced, obtained by the production method of the present invention, is highly soluble in highly fluorinated perfluoropolyether oil. Improvement is expected. As a result, for example, when used as a cross-linking agent for room temperature curable fluoropolyether rubber compositions, the compatibility with the base polymer is remarkably improved, and even in molding with a simple mixing device such as a static mixer, it is uniform. A rubber composition having a smooth surface is obtained.

The IR spectrum of the fluorine-modified amino group containing organopolysiloxane (7) of Formula (7) in the Example of this invention is shown. In the embodiment of the present invention shows a ¹ H-NMR spectrum of Formula fluorine-modified amino group-containing organopolysiloxane (7) (7). The IR spectrum of the fluorine-modified amino group containing organopolysiloxane (8) of Formula (8) in the Example of this invention is shown. In the embodiment of the present invention shows a ¹ H-NMR spectrum of the fluorine-modified amino group-containing organopolysiloxane (8) of formula (8). The IR spectrum of the high-viscosity cloudy layer obtained from the comparative example is shown. The IR spectrum of the low-viscosity slightly cloudy layer obtained from the comparative example is shown.

TECHNICAL FIELD The present invention relates to a fluorine-modified amino group-containing organopolysiloxane having a high fluorine content and uniformly introduced with a fluorine-modified group, and a method for producing the same. First, (b) a carboxylic acid ester compound having a fluorine-modified group (Rf ^1- ) having 1 to 15 carbon atoms is reacted with a part of the amino group in the organopolysiloxane, and then (c) 16 to 100 carbon atoms. It consists of a two-step reaction process in which a carboxylic acid ester compound having a fluorine-modified group (Rf ² —) is reacted with a part of the remaining amino group. The details will be described below.

(A) Amino Group-Containing Organopolysiloxane Examples of the amino group-containing organopolysiloxane that is a raw material component of the present invention include compounds represented by the following general formula (3).

Here, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group. Group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group and other alkyl groups, vinyl group, allyl group, butenyl group, hexenyl group and other alkenyl groups, phenyl group, tolyl group and other aryl groups, benzyl And aralkyl groups such as a phenylethyl group.

（式中、Ｒ¹は前記の通りであり、ｅは０、１、２又は３である。また、Ｙは下記式から選ばれる１価有機基である。

で示される１価のオルガノシリル基である。
また、ｐは５〜５０、特に１０〜３０の整数である。 R ² is a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms, preferably 2 to 12 carbon atoms, and examples thereof include alkylene groups, alkenylene groups, arylene groups, and combinations thereof. Includes those in which one of the hydrogen atoms bonded to the carbon atom is eliminated from the specific example of the monovalent hydrocarbon group for R ¹ . R ² may be one in which one or more of the hydrogen atoms of the divalent hydrocarbon group are substituted with a chlorine atom or a halogen atom of a fluorine atom, and an oxygen atom or nitrogen atom ( -NR-: R is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, monovalent hydrocarbon groups such as phenyl group), a silicon atom (-SiR _'2 -: R' is an alkyl group having 1 to 10 carbon atoms , A monovalent hydrocarbon group such as a phenyl group), or a sulfur atom, and may contain an amide bond (—CONH—) or a sulfonamide bond (—SO ₂ NH—).
X and X ′ may be the same or different from each other, and may be a hydrogen atom or the following general formula (2)

(In the formula, R ¹ is as described above, and e is 0, 1, 2, or 3. Y is a monovalent organic group selected from the following formulas.

Is a monovalent organosilyl group.
Moreover, p is an integer of 5-50, especially 10-30.

  Examples of such amino group-containing organopolysiloxanes include the following compounds. These compounds may be used alone or in combination of two or more, and are limited to the following examples. Is not to be done.

（式中、ｐは前記と同様である。）

(In the formula, p is the same as described above.)

(B) fluorine-modified group consisting of 1 to 15 carbon atoms (Rf ¹ -) fluorine-modified group consisting of 1 to 15 carbon atoms in the carboxylic acid ester compound present invention having (Rf ¹ -) carboxylic acid ester compound having the It can be represented by the following general formula (4).
Rf ¹ -COOR ³ (4)
Wherein Rf ¹ is a monovalent perfluoroalkyl group or perfluoropolyether group having 1 to 15 carbon atoms, and R ³ is a substituted or unsubstituted 1 having 1 to 8 carbon atoms, preferably 1 to ³ carbon atoms. Valent hydrocarbon group.)

The monovalent perfluoroalkyl group and monovalent perfluoroalkyl ether group may have either a chain structure or a branched structure, and typical examples thereof include groups represented by the following general formula. However, the present invention is not limited to this.
C _g F _{2g + 1} −
(In the formula, g is an integer of 1 to 6, preferably 4 to 6.)

（式中、ｆは１〜４の整数、好ましくは２又は３であり、ｈは１〜３の整数である。）
Ｆ−（ＣＦ₂Ｏ）_c−（ＣＦ₂ＣＦ₂Ｏ）_d−ＣＦ₂−
（式中、ｃ及びｄはそれぞれ１〜４の整数、好ましくは２又は３である。）

(In the formula, f is an integer of 1 to 4, preferably 2 or 3, and h is an integer of 1 to 3.)
_{F- (CF 2 O) c -} (CF 2 CF 2 O) d -CF 2 -
(Wherein c and d are each an integer of 1 to 4, preferably 2 or 3)

（式中、ａ及びｂは、それぞれ１〜３の整数、好ましくは１又は２である。）
Ｆ−（ＣＦ₂ＣＦ₂ＣＦ₂Ｏ）_i−ＣＦ₂ＣＦ₂−
（式中、ｉは１〜４の整数、好ましくは１又は２である。）

(In the formula, a and b are each an integer of 1 to 3, preferably 1 or 2.)
_{F- (CF 2 CF 2 CF 2} O) i -CF 2 CF 2 -
(In the formula, i is an integer of 1 to 4, preferably 1 or 2.)

As described above, specific examples of the carboxylic acid ester compound having a fluorine-modified group (Rf ¹ —) having 1 to 15 carbon atoms include the following compounds, but are not limited thereto. Moreover, these compounds may be used independently or may use 2 or more types together.

(C) fluorine-modified group consisting of 16 to 100 carbon atoms (Rf ² -) consisting of 16 to 100 carbon atoms in the carboxylic acid ester compound present invention having a fluorine-modified group (Rf ² -) carboxylic acid ester compound having the following The compound represented by General formula (5) can be mentioned.
Rf ² -COOR ³ (5)
(In the formula, Rf ² is a monovalent perfluoropolyether group having 16 to 100 carbon atoms, and R ³ is the same as described above.)
The monovalent perfluoroalkyl ether group may have either a chain structure or a branched structure, and typical examples thereof include groups represented by the following general formula, but are not limited thereto. Absent.

（式中、ｊは５〜３２、好ましくは１５〜３０の整数であり、ｋは１〜３の整数である。）
Ｆ−（ＣＦ₂Ｏ）_o−（ＣＦ₂ＣＦ₂Ｏ）_q−ＣＦ₂−
（式中、ｏ及びｑは、それぞれ５〜３３、好ましくは１５〜３０の整数である。）

(In the formula, j is an integer of 5 to 32, preferably 15 to 30, and k is an integer of 1 to 3.)
_{F- (CF 2 O) o -} (CF 2 CF 2 O) q -CF 2 -
(In the formula, o and q are each an integer of 5 to 33, preferably 15 to 30.)

（式中、ｒ及びｓは、それぞれ４〜２４、好ましくは１０〜２０の整数である。）
Ｆ−（ＣＦ₂ＣＦ₂ＣＦ₂Ｏ）_t−ＣＦ₂ＣＦ₂−
（式中、ｔは５〜３２、好ましくは２０〜３０の整数である。）

(In the formula, r and s are each an integer of 4 to 24, preferably 10 to 20.)
_{F- (CF 2 CF 2 CF 2} O) t -CF 2 CF 2 -
(In the formula, t is an integer of 5 to 32, preferably 20 to 30.)

As described above, specific examples of the carboxylic acid ester compound having a fluorine-modified group (Rf ² —) having 16 to 100 carbon atoms include the following compounds, but are not limited thereto. Moreover, these compounds may be used independently or may use 2 or more types together.

The first addition reaction of the amino group-containing organopolysiloxane represented by the general formula (3) and the carboxylic acid ester compound having a fluorine-modified group (Rf ^1- ) represented by the general formula (4), followed by the general By the second addition reaction with the carboxylic acid ester compound having a fluorine-modified group (Rf ² —) represented by the formula (5), the introduction of Rf ¹ group and the introduction of Rf ² group into the amino group-containing organopolysiloxane are carried out. As a method of sequentially performing, for example, the addition reaction of an amino group-containing organopolysiloxane and a fluorine-containing carboxylic acid ester compound described in, for example, Japanese Patent No. 3022070 (Patent Document 1) can be easily performed in two steps. Can be implemented.

  More specifically, both the first addition reaction and the second addition reaction are usually performed at a temperature of 200 ° C. or lower, preferably 50 to 150 ° C. The reaction time is appropriately selected in the range of several minutes to several tens of hours, but preferably 5 to 20 hours. The reaction may be performed in a solventless system or a solvent system. As the solvent, toluene, benzene, hexane, methyl ethyl ketone, methyl isobutyl ketone, metaxylene hexafluoride and the like can be suitably used.

The amount of the first carboxylic acid ester compound having a fluorine-modified group (Rf ^1- ) and the second carboxylic acid ester compound having a fluorine-modified group (Rf ^2- ) used in the reaction is the target fluorine modification. It is determined according to the fluorine-containing content of the amino group-containing organopolysiloxane.

That is, the fluorine-modified amino group-containing organopolysiloxane represented by the following general formula (1) is obtained by the first and second addition reactions, and the present invention is a fluorine-modified amino group-containing organopolysiloxane of the formula (1). Is to provide.

Here, R ¹ , R ² , X, and X ′ are as described above. L is an integer of 3-30, preferably 5-20, m is an integer of 1-10, preferably 3-9, n is an integer of 1-10, preferably 2-6, and l + m + n is 5-50. , Preferably an integer satisfying 10-35.

Therefore, the usage-amount of the said 1st and 2nd carboxylic acid ester compound is selected so that the value of said l, m, and n may be satisfied.
That is, in the first addition reaction, the first carboxylic acid having the fluorine-modified group (Rf ¹ —) represented by the general formula (4) with respect to the amino group in the amino group-containing organopolysiloxane represented by the general formula (3). The molar ratio of the acid ester is less than equimolar, and in the second addition reaction, the second ester having a fluorine-modified group (Rf ² —) represented by the general formula (5) with respect to the remaining amino group in the intermediate. The carboxylic acid ester is reacted at a molar ratio of less than equimolar.
After the completion of the addition reaction, the by-produced alcohol and solvent are distilled off to obtain the target fluorine-modified amino group-containing organopolysiloxane of formula (1), which has excellent surface properties. It is used as a fiber treatment material, a release agent, a resin modifier, and the like, and is useful as a solvent resistance and chemical resistance rubber material.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

（屈折率：１．４８、密度（２３℃）：１．０７ｇ／ｃｍ³、粘度（２３℃）：１．５４Ｐａ・ｓ）
及びトルエン５００ｍＬをフラスコにとり、Ｎ₂雰囲気下、氷浴中で撹拌した。そこに下記式

で表される含フッ素カルボン酸メチルエステル３２３ｇ（０．６３３モル）を１．５時間かけてゆっくり滴下した。滴下終了後、３０分間撹拌した。３０分後、反応溶液の赤外吸収スペクトルを測定し、含フッ素カルボン酸メチルエステルに由来するカルボニル基（＞Ｃ＝Ｏ）の特性吸収（１，７９０ｃｍ^-1）が消失していることから、含フッ素カルボン酸メチルエステルが消費され、反応が終了していることを確認した。次いで、反応溶液を減圧ストリップすることにより、トルエン、副生したメタノールを除去し、無色透明のフッ素変性アミノ基含有オルガノポリシロキサン５８５ｇを得た。 [Example 1]
300 g (0.169 mol) of an amino group-containing organopolysiloxane represented by the following formula (6)

(Refractive index: 1.48, density (23 ° C.): 1.07 g / cm ³ , viscosity (23 ° C.): 1.54 Pa · s)
And 500 mL of toluene was placed in a flask and stirred in an ice bath under N ₂ atmosphere. There the following formula

323 g (0.633 mol) of a fluorine-containing carboxylic acid methyl ester represented by the above was slowly added dropwise over 1.5 hours. It stirred for 30 minutes after completion | finish of dripping. After 30 minutes, the infrared absorption spectrum of the reaction solution was measured, and the characteristic absorption (1,790 cm ⁻¹ ) of the carbonyl group (> C═O) derived from the fluorine-containing carboxylic acid methyl ester disappeared. It was confirmed that the fluorine-containing carboxylic acid methyl ester was consumed and the reaction was completed. Next, the reaction solution was stripped under reduced pressure to remove toluene and by-produced methanol to obtain 585 g of a colorless and transparent fluorine-modified amino group-containing organopolysiloxane.

Infrared absorption spectrum: A chart is shown in FIG.
(Characteristic absorption)
1,000 to 1,400 cm ^-1 : (C-F)
1,540, 3,350 cm ⁻¹ : (N—H)
1,590 cm ⁻¹ : (NH ₂ )
1,720 cm ⁻¹ : (C═O)
(Refractive index) 1.41
(Density, 23 ° C.) 1.34 g / cm ³
(Viscosity, 23 ° C.) 102 Pa · s

で表されることを確認した（フッ素含有率：３３．２％）。 ¹ H-NMR measurement was performed, and the composition ratio was estimated from the integral ratio of b and d in FIG. 2. As a result, the obtained fluorine-modified amino group-containing organopolysiloxane represented by the following formula (7)

(Fluorine content: 33.2%).

ｂ／ｄの積分比：１．００／０．７６より、ｕ／ｗ＝０．７６／０．２４ ¹ H-NMR spectrum of FIG.

b / d integration ratio: From 1.00 / 0.76, u / w = 0.76 / 0.24

で表される含フッ素カルボン酸メチルエステル１，５７０ｇ（０．３７８モル）を１，３−ビス（トリフルオロメチル）ベンゼン５００ｇにて希釈を行った溶液を４時間かけてゆっくり滴下した。滴下終了後、３０分間撹拌した。３０分後、反応溶液の赤外吸収スペクトルを測定し、含フッ素カルボン酸メチルエステルに由来するカルボニル基（＞Ｃ＝Ｏ）の特性吸収（１，７９０ｃｍ^-1）が完全に消失していることから、含フッ素カルボン酸メチルエステルが全て消費し、反応が終了していることを確認した。次いで、反応溶液を減圧ストリップすることにより、１，３−ビス（トリフルオロメチル）ベンゼン、副生したメタノールを除去し、淡黄色透明のフッ素変性アミノ基含有オルガノポリシロキサン１，９９０ｇを得た。 Next, 450 g (0.126 mol) of the obtained fluorine-modified amino group-containing organopolysiloxane (7) and 1.00 kg of 1,3-bis (trifluoromethyl) benzene were placed in a flask and 75 ° C. under N ₂ atmosphere. In an oil bath. There the following formula

A solution obtained by diluting 1,570 g (0.378 mol) of the fluorinated carboxylic acid methyl ester represented by the formula (1) with 500 g of 1,3-bis (trifluoromethyl) benzene was slowly added dropwise over 4 hours. It stirred for 30 minutes after completion | finish of dripping. After 30 minutes, the infrared absorption spectrum of the reaction solution was measured, and the characteristic absorption (1,790 cm ⁻¹ ) of the carbonyl group (> C═O) derived from the fluorine-containing carboxylic acid methyl ester had completely disappeared. Thus, it was confirmed that all of the fluorine-containing carboxylic acid methyl ester was consumed and the reaction was completed. Next, the reaction solution was stripped under reduced pressure to remove 1,3-bis (trifluoromethyl) benzene and by-produced methanol to obtain 1,990 g of a pale yellow transparent fluorine-modified amino group-containing organopolysiloxane.

Infrared absorption spectrum: A chart is shown in FIG.
(Characteristic absorption)
1,000 to 1,400 cm ^-1 : (C-F)
1,540, 3,350 cm ⁻¹ : (N—H)
1,590 cm ⁻¹ : (NH ₂ )
1,720 cm ⁻¹ : (C═O)
(Refractive index) 1.33
(Density, 23 ° C.) 1.73 g / cm ³
(Viscosity, 23 ° C.) 918 Pa · s

で表されることを確認した（フッ素含有率：５９．０％）。 As a result of performing ¹ H-NMR measurement and estimating the composition ratio from the integral ratio of b and d in FIG. 4, the obtained fluorine-modified amino group-containing organopolysiloxane has the following formula (8):

(Fluorine content: 59.0%).

ｂ／ｄの積分比：１．００／０．６１より、ｖ／ｗ／ｙ＝０．６１／０．２４／０．１５ ¹ H-NMR spectrum of FIG.

b / d integration ratio: From 1.00 / 0.61, v / w / y = 0.61 / 0.24 / 0.15

及びトルエン５００ｍＬをフラスコにとり、Ｎ₂雰囲気下、室温中で撹拌した。そこに下記式

で表される含フッ素カルボン酸メチルエステル９３．８ｇ（０．０２３モル）を１，３−ビス（トリフルオロメチル）ベンゼン３００ｇにて希釈を行った溶液を１時間かけてゆっくり滴下した。滴下終了後、３０分間撹拌した。３０分後、反応溶液の赤外吸収スペクトルを測定し、含フッ素カルボン酸メチルエステルに由来するカルボニル基（＞Ｃ＝Ｏ）の特性吸収（１，７９０ｃｍ^-1）が完全に消失していることから、含フッ素カルボン酸メチルエステルが全て消費し、反応が終了していることを確認した。次いで、反応溶液を減圧ストリップすることによりトルエン、１，３−ビス（トリフルオロメチル）ベンゼン、副生したメタノールを除去し、高粘度の白濁層と低粘度の微白濁層からなる、不均一なフッ素変性アミノ基含有オルガノポリシロキサン３８５ｇを得た。 [Comparative Example 1]
300 g (0.169 mol) of an amino group-containing organopolysiloxane represented by the following formula (6)

And 500 mL of toluene was placed in a flask and stirred at room temperature under N ₂ atmosphere. There the following formula

A solution obtained by diluting 93.8 g (0.023 mol) of a fluorinated carboxylic acid methyl ester represented by the formula (1) with 300 g of 1,3-bis (trifluoromethyl) benzene was slowly added dropwise over 1 hour. It stirred for 30 minutes after completion | finish of dripping. After 30 minutes, the infrared absorption spectrum of the reaction solution was measured, and the characteristic absorption (1,790 cm ⁻¹ ) of the carbonyl group (> C═O) derived from the fluorine-containing carboxylic acid methyl ester had completely disappeared. Thus, it was confirmed that all of the fluorine-containing carboxylic acid methyl ester was consumed and the reaction was completed. Next, the reaction solution is stripped under reduced pressure to remove toluene, 1,3-bis (trifluoromethyl) benzene, and by-produced methanol, and consists of a high-viscosity cloudy layer and a low-viscosity slightly cloudy layer. 385 g of a fluorine-modified amino group-containing organopolysiloxane was obtained.

Infrared absorption spectrum measurement was performed for each of the high-viscosity cloudy layer and the low-viscosity slightly cloudy layer. In the high-viscosity cloudy layer, characteristic absorption of amide bonds (1,710 cm ⁻¹ ) was confirmed, In the cloudy layer, characteristic absorption of amide bonds (1,710 cm ⁻¹ ) was not confirmed, but characteristic absorption of amino groups (1,590 cm ⁻¹ ) was confirmed (FIGS. 5 and 6).

  As described above, in Example 1, a high fluorine-containing amino group-containing organopolysiloxane in which fluorine-modified groups were uniformly introduced was obtained, whereas in Comparative Example 1, the fluorine-modified groups were non-uniform. The introduced fluorine-containing amino group-containing organopolysiloxane was obtained.

[Example 2]
10 g of the fluorine-modified amino group-containing organopolysiloxane (8) obtained in Example 1 was put in a glass bottle, and 20 g of fomblin Y45 (perfluoropolyether oil manufactured by Solvay Solexis Co., Ltd.) was added thereto and stirred well. As a result, a colorless transparent uniform solution was obtained.

[Comparative Example 2]
In Example 2, the fluorine-modified amino group-containing organopolysiloxane was changed to the fluorine-modified amino group-containing organopolysiloxane (7) obtained from Example 1, and the same experiment was conducted. As a result, the solution became cloudy for a while. Separated layers were confirmed upon standing.

  From the above, the fluorine-modified amino group-containing organopolysiloxane (8) having a high fluorine content in which the fluorine-modified group obtained in Example 1 is uniformly introduced is a highly fluorinated perfluoropolyether oil. It was confirmed that the solubility of was improved.

Claims (2)

The following general formula (1)

[Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² may have an oxygen atom, a nitrogen atom, a silicon atom or a sulfur atom in the middle of the bond, an amide bond or a sulfonamide A substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms which may contain a bond, and Rf ¹ is a monovalent perfluoroalkyl group or perfluoropolyether group having 1 to 15 carbon atoms. Rf ² is a monovalent perfluoropolyether group having 16 to 100 carbon atoms, X and X ′ may be the same or different, and are a hydrogen atom or a monovalent group represented by the following general formula (2) This is an organosilyl group.

(Where Y is

And R ¹ is the same as described above, and e is 0, 1, 2, or 3. )
Moreover, l is an integer of 3-30, m is an integer of 1-10, n is an integer of 1-10, and is an integer satisfying l + m + n = 5-50. ]
A fluorine-modified amino group-containing organopolysiloxane characterized by: In general formula (1), first, the following general formula (3)

(In the formula, R ¹ , R ² , X and X ′ are the same as described above. P is an integer of 5 to 50.)
An amino group-containing organopolysiloxane represented by the following general formula (4)
Rf ¹ -COOR ³ (4)
(In the formula, Rf ¹ is a monovalent perfluoroalkyl group or perfluoropolyether group having 1 to 15 carbon atoms, and R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. .)
A carboxylic acid ester compound having a fluorine-modified group (Rf ^1- ) represented by the following formula is added to a part of the amino group to introduce an Rf ¹ group, and then the following general formula (5)
Rf ² -COOR ³ (5)
(In the formula, Rf ² is a monovalent perfluoropolyether group having 16 to 100 carbon atoms, and R ³ is the same as described above.)
A two-stage fluorine-modified group characterized by introducing an Rf ² group by addition reaction of a carboxylic acid ester compound having a fluorine-modified group (Rf ^2- ) represented by The method for producing a fluorine-modified amino group-containing organopolysiloxane according to claim 1, which has an introduction process.

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