JP2023173917A - Organopolysiloxane including perfluoropolyether block and amino group, and method for producing the same - Google Patents

Abstract

[Problem] To provide an organopolysiloxane that has a perfluoropolyether block and an amino group, allows control of the number of siloxane units in the molecule, and has excellent affinity with non-fluorinated organic compounds, and a method for producing the same. .
[Solution]
An organopolysiloxane block having a perfluoropolyether block and an amino group, at least an organopolysiloxane block at both ends of the molecular chain, and at least one amino group per molecule in the side chain of the organopolysiloxane block. Polysiloxane.
[Selection diagram] None

Description

The present invention relates to an organopolysiloxane having a perfluoropolyether block and an amino group, and a method for producing the same.

In general, perfluoropolyether group-containing compounds have very low surface free energy and therefore have chemical resistance, lubricity, mold releasability, water and oil repellency, and the like. Utilizing its properties, it is used industrially as a lubricant for magnetic recording media, an oil-proofing agent for precision equipment, a mold release agent, a water-repellent, oil-repellent and stain-proofing agent for paper, fiber, glass, resin, etc., cosmetics, and protective films. It is widely used as such.

However, because the surface free energy of perfluoropolyether group-containing compounds is low, their compatibility and affinity with other substances are extremely low, and perfluoropolyether group-containing compounds are added to various industrial materials. Attempts to impart properties to the perfluoropolyether group caused problems in dispersion stability, reactivity, etc., and it was difficult to incorporate perfluoropolyether group-containing compounds into various industrial materials.

On the other hand, polysiloxane compounds also have properties such as water repellency, lubricity, and mold releasability due to their low surface free energy. Moreover, polysiloxane compounds have better affinity for other substances than perfluoropolyether compounds. Moreover, when various modifications are performed, the dispersion stability is further improved. Therefore, polysiloxane compounds can be easily added to various industrial materials to impart the properties of silicone, and are used as additives for improving performance in a wide range of fields. As a compound having a perfluoropolyether group and a polysiloxane chain, there is a perfluoropolyether-modified polysiloxane compound (Patent Document 1).
However, in this polysiloxane compound, if the fluorine modification rate is increased for the purpose of improving the properties of the perfluoropolyether group, the affinity for other materials will be significantly reduced. Therefore, problems may occur in dispersion stability, reactivity, etc.

In view of this, perfluoropolyether-organopolysiloxane block copolymers have been developed (Patent Document 2). This copolymer has the characteristics of both perfluoropolyether and polysiloxane, and has excellent affinity with non-fluorine organic compounds. However, since it does not have a reactive functional group, it could not react with or immobilize other materials.

Furthermore, a perfluoropolyether-modified amino group-containing organopolysiloxane having a perfluoropolyether group and an amino group in the siloxane side chain has also been developed (Patent Document 3). However, the perfluoropolyether-modified amino group-containing organopolysiloxane of Patent Document 3 has a limited number of siloxane units that can be introduced, and also has amino groups in all siloxane units, so it is non-fluorinated. It has been difficult to control the compatibility with organic compounds, the crosslinking density of the resulting cured product, and the physical properties when used for fiber processing.

Japanese Patent Application Publication No. 2006-321764 Japanese Patent Application Publication No. 2011-21158 JP2011-201941A

Therefore, the present invention provides an organopolysiloxane having a perfluoropolyether block and an amino group, which has excellent affinity with other substances, especially non-fluorinated organic compounds, and a method for producing the same. The purpose is to Specifically, we are developing organopolysiloxanes that can control the molecular structure, such as the number of perfluoropolyether blocks and organopolysiloxane blocks, and the degree of modification of amino groups introduced into the side chains of organopolysiloxane blocks, and their production. The purpose is to provide a method.

As a result of intensive research to solve the above-mentioned problems, the present inventors discovered that the following organopolysiloxane can achieve the above-mentioned objects, and completed the present invention.

［式（１）中、
Ｒｆは下記式（２）

（式（２）中、ｚは１～４の数であり、ｖ、ｗ、ｘ及びｙはそれぞれ独立に０～２００の数であり、ｖ＋ｗ＋ｘ＋ｙ＝３～２００である。また、各繰り返し単位は直鎖状でも分岐状であってもよい。各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）
で表されるパーフルオロポリエーテルブロックであり、
Ｗ１は下記式（Ａ）

（式（Ａ）中、Ｒ¹は独立して炭素数１～１８のアルキル基、炭素数６～１８のアリール基及び炭素数７～１８のアラルキル基から選ばれる基である。Ｒ²は独立してアミノ基を有する１価の基である。ｐ１及びｑ１はそれぞれ０～１，０００の数である。各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）
で表される２価のオルガノポリシロキサンブロックであり、
Ｗ２はそれぞれ独立に下記式（Ｂ）

（式（Ｂ）中、Ｒ¹は独立して炭素数１～１８のアルキル基、炭素数６～１８のアリール基及び炭素数７～１８のアラルキル基から選ばれる基である。Ｒ²は独立してアミノ基を有する１価の基である。Ｒ¹’は独立して炭素数１～１８のアルキル基、炭素数６～１８のアリール基及び炭素数７～１８のアラルキル基から選ばれる基である。ｐ２及びｑ２はそれぞれ０～１，０００の数である。各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）
で表される１価のオルガノポリシロキサンブロックであり、
但し、上記式（Ａ）のアミノ基を有するシロキサン単位の数ｑ１及び上記式（Ｂ）のアミノ基を有するシロキサン単位の数ｑ２は同時に０とならない。
Ｑは炭素数２～１２の２価の有機基であり、また、上記式（１）中、ＱはＲｆの末端の炭素原子、Ｗ１の末端のケイ素原子又はＷ２の末端のケイ素原子のいずれかと結合しており、
ｇは０～５０の数であるが、ｇが０のときＷ２の式（Ｂ）中のｑ２は０とならない。］

［２］
１分子中のオルガノポリシロキサンブロック含有量が５０％以上である、［１］に記載のパーフルオロポリエーテルブロックとアミノ基とを有するオルガノポリシロキサン。

［３］
Ｒｆで表されるパーフルオロポリエーテルブロックが、下記式（３）で表される基である、［１］又は［２］に記載のパーフルオロポリエーテルブロックとアミノ基とを有するオルガノポリシロキサン。

（式（３）中、ｖ及びｗはそれぞれ０～２００の数で、但しｖ＋ｗ＝３～２００である。また、（ＯＣ₂Ｆ₄）の繰り返し単位は直鎖状でも分岐状であってもよい。各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）

［４］
Ｒ²で表されるアミノ基を有する１価の基が、下記式（４）で表される基である、［１］～［３］のいずれか１項に記載のパーフルオロポリエーテルブロックとアミノ基とを有するオルガノポリシロキサン。

（式（４）中、ｉは３～８の数であり、ｊは１～４の数であり、ｋは０又は１である。）

［５］
（ａ）成分：下記式（５）で表されるパーフルオロポリエーテル－オルガノポリシロキサンブロック共重合体と、
（ｂ）成分：アミノ基を有するポリシロキサンと、
（ｃ）成分：フッ素化炭化水素溶媒と
を混合し、該（ａ）、（ｂ）及び（ｃ）成分の混合物を
（ｄ）成分：塩基触媒の存在下で
（ａ）成分と（ｂ）成分のシロキサン間の交換反応を行う工程を有する、［１］～［４］のいずれか１項に記載のパーフルオロポリエーテルブロックとアミノ基とを有するオルガノポリシロキサンの製造方法。

［式（５）中、Ｒｆは前記式（２）で表されるパーフルオロポリエーテルブロックであり、Ｗ３はそれぞれ独立に下記式（Ａ’）

（式（Ａ’）中、Ｒ¹は前記式（Ａ）のＲ¹と同じである。ｐ１’は０～１，０００の数である。）
で表される２価のオルガノポリシロキサンブロックであり、
Ｗ４はそれぞれ独立に下記式（Ｂ’）

（式（Ｂ’）中、Ｒ¹及びＲ¹’はそれぞれ前記式（Ｂ）のＲ¹及びＲ^1'と同じである。ｐ２’は０～１，０００の数である）
で表される１価のオルガノポリシロキサンブロックであり、
Ｑは前記式（１）のＱと同じである。また、上記式（５）中、ＱはＲｆの末端の炭素原子、Ｗ３の末端のケイ素原子又はＷ４の末端のケイ素原子のいずれかと結合しており、
ｇ’は０～５０の数である。］

［６］
（ｂ）成分が、下記式（６）又は下記式（７）で表されるアミノ基を有するポリシロキサンから選ばれる１種以上である、［５］に記載のパーフルオロポリエーテルブロックとアミノ基とを有するオルガノポリシロキサンの製造方法。

（式（６）中、Ｒ¹は独立して炭素数１～１８のアルキル基、炭素数６～１８のアリール基及び炭素数７～１８のアラルキル基から選ばれる基である。Ｒ³は独立して水素原子、炭素数１～４のアルキル基又は－ＳｉＲ¹ ₃（Ｒ¹は上記と同じである。）である。ｉは３～８の数であり、ｊは１～４の数であり、ｋは０又は１である。ｐ３は０～１，０００の数であり、ｑ３は１～１００の数である。）

（式（７）中、Ｒ¹、ｉ、ｊ及びｋは上記と同じである。ｐ４は０～６の数であり、ｑ４は１～８の数である。但し、３≦ｐ４＋ｑ４≦１４である。）
That is, the present invention is as follows.
[1]
An organopolysiloxane having a perfluoropolyether block and an amino group, represented by the following formula (1).

[In formula (1),
Rf is the following formula (2)

(In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Also, each repeating unit is It may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.)
It is a perfluoropolyether block represented by
W1 is the following formula (A)

(In formula (A), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. R ² is independently is a monovalent group having an amino group.p1 and q1 are each a number from 0 to 1,000.The arrangement order of each repeating unit is not limited and may be random or block. .)
It is a divalent organopolysiloxane block represented by
W2 is each independently expressed by the following formula (B)

(In formula (B), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. R ² is independently is a monovalent group having an amino group.R ¹ ' is a group independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. (p2 and q2 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited, and may be random or block.)
A monovalent organopolysiloxane block represented by
However, the number q1 of siloxane units having an amino group of the above formula (A) and the number q2 of siloxane units having an amino group of the above formula (B) do not become 0 at the same time.
Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2. are combined,
g is a number from 0 to 50, but when g is 0, q2 in formula (B) of W2 does not become 0. ]

[2]
The organopolysiloxane having a perfluoropolyether block and an amino group according to [1], wherein the organopolysiloxane block content in one molecule is 50% or more.

[3]
The organopolysiloxane having a perfluoropolyether block and an amino group according to [1] or [2], wherein the perfluoropolyether block represented by Rf is a group represented by the following formula (3).

(In formula (3), v and w are each a number from 0 to 200, provided that v+w = 3 to 200. Also, the repeating unit of (OC ₂ F ₄ ) may be linear or branched. (The arrangement order of each repeating unit is not limited, and may be random or block.)

[4]
The perfluoropolyether block according to any one of [1] to [3], wherein the monovalent group having an amino group represented by R ² is a group represented by the following formula (4); An organopolysiloxane having an amino group.

(In formula (4), i is a number from 3 to 8, j is a number from 1 to 4, and k is 0 or 1.)

[5]
Component (a): a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5),
(b) Component: polysiloxane having an amino group,
Component (c): fluorinated hydrocarbon solvent is mixed, and the mixture of components (a), (b), and (c) is mixed with component (d): component (a) and (b) in the presence of a base catalyst. The method for producing an organopolysiloxane having a perfluoropolyether block and an amino group according to any one of [1] to [4], which comprises a step of performing an exchange reaction between the component siloxanes.

[In formula (5), Rf is a perfluoropolyether block represented by the above formula (2), and W3 is each independently represented by the following formula (A')

(In formula (A'), R ¹ is the same as R ¹ in formula (A) above. p1' is a number from 0 to 1,000.)
It is a divalent organopolysiloxane block represented by
W4 is each independently expressed by the following formula (B')

(In formula (B'), R ¹ and R ¹ ' are respectively the same as R ¹ and R ^1' in formula (B) above. p2' is a number from 0 to 1,000)
A monovalent organopolysiloxane block represented by
Q is the same as Q in the above formula (1). Furthermore, in the above formula (5), Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W3, or the terminal silicon atom of W4,
g' is a number from 0 to 50. ]

[6]
The perfluoropolyether block and amino group according to [5], wherein the component (b) is one or more selected from polysiloxanes having an amino group represented by the following formula (6) or the following formula (7). A method for producing an organopolysiloxane comprising:

(In formula (6), R ¹ is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. R ³ is independently is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -SiR ¹ ₃ (R ¹ is the same as above). i is a number from 3 to 8, and j is a number from 1 to 4. (k is 0 or 1, p3 is a number from 0 to 1,000, and q3 is a number from 1 to 100.)

(In formula (7), R ¹ , i, j and k are the same as above. p4 is a number from 0 to 6, and q4 is a number from 1 to 8. However, 3≦p4+q4≦14 be.)

The organopolysiloxane of the present invention has perfluoropolyether blocks, has a high siloxane content, and has organopolysiloxane blocks at both ends of the molecular chain. Furthermore, the organopolysiloxane block has an amino group in its side chain. Therefore, even though it has a perfluoropolyether block, it is easily compatible with non-fluorine organic compounds, can react with epoxy compounds, and has excellent adhesion to fibers and the like. Furthermore, in the organopolysiloxane of the present invention, the number of organopolysiloxane units and the modification rate of amino groups in the side chains of the organopolysiloxane blocks can be easily controlled.
Therefore, the organopolysiloxane of the present invention is useful as a surface modifier for non-fluorine organic resins, fiber treatment, and the like.

式（１）中の各符号の定義は前記と同じである。 The present invention will be explained in more detail below.
The organopolysiloxane of the present invention is represented by the following formula (1), and perfluoropolyether blocks (Rf) and organopolysiloxane blocks (W2 or W1) are present alternately.

The definition of each symbol in formula (1) is the same as above.

Since the organopolysiloxane block has an amino group in its side chain, it can react with and attach to various organic compounds.

The organopolysiloxane of formula (1) above preferably has an organopolysiloxane block content in one molecule of 50% or more and 99% or less, more preferably 60% or more and 90% or less. When the organopolysiloxane block content is at least the above lower limit, it has excellent compatibility with non-fluorine organic compounds, and when it is at most the above upper limit, the properties of perfluoropolyether groups are easily expressed. The organopolysiloxane block content is determined by the ¹ H-NMR spectrum of the organopolysiloxane of formula (1). The molar ratio between the perfluoropolyether block Rf of known molecular weight and the organosiloxy unit is determined from the integral ratio with the peak derived from the group, and this molar ratio is calculated by converting it into a molecular weight ratio. In addition, since the organopolysiloxane of formula (1) usually has a distribution in its structure, the above organopolysiloxane block content is an average value per molecule.

It is preferable that one or more of the organopolysiloxane blocks W1 and W2 have a siloxane unit represented by the following formula (8).

In the above formula (8), R ² is a monovalent group having an amino group, preferably a monovalent group having an amino group represented by the following formula (4).

式（４）中、ｉは３～８の数であり、好ましくは３～４の数である。ｊは１～４の数であり、好ましくは２～３の数である。ｋは０又は１である。

In formula (4), i is a number from 3 to 8, preferably from 3 to 4. j is a number from 1 to 4, preferably from 2 to 3. k is 0 or 1.

One or more siloxane units having an amino group represented by the above formula (8) are present in the above formula (1), and preferably two or more siloxane units are present from the viewpoint of reactivity and adhesion with organic compounds. . Note that the siloxane units of formula (8) in the organopolysiloxane blocks W1 and W2 may be the same or different, but are preferably the same.

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

In formula (A), R ¹ is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms for R ¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, dodecyl group, and octadecyl group. Examples of the aryl group having 6 to 18 carbon atoms for R ¹ include phenyl group, tolyl group, xylyl group, and naphthyl group. Examples of the aralkyl group having 7 to 18 carbon atoms for R ¹ include benzyl group, 2-phenylethyl group, 2-methyl-2-phenylethyl group, naphthylmethyl group, and 2-naphthylethyl group. R ¹ is preferably a methyl group or a phenyl group.

In the above formula (A), examples of R ² include the same ones as exemplified for R ² in formula (8).

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

Examples of the group represented by the above formula (A) include groups represented by the following formulas (9) to (14), but are not limited to the following formulas.

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

In the above formula (B), R ¹ and R ² are the same as those listed for the above formula (A). R ¹ ' is a group independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms. It is. Examples of the alkyl group having 1 to 18 carbon atoms for R ¹ ' include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, dodecyl group, and octadecyl group. Examples of the aryl group having 6 to 18 carbon atoms for R ¹ ' include phenyl group, tolyl group, xylyl group, and naphthyl group. Examples of the aralkyl group having 7 to 18 carbon atoms for R ¹ ' include benzyl group, 2-phenylethyl group, 2-methyl-2-phenylethyl group, naphthylmethyl group, and 2-naphthylethyl group. R ¹ ' is more preferably a methyl group, a butyl group, a hexyl group, an octyl group or a dodecyl group.

In the above formula (B), p2 and q2 are each a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200. Note that the arrangement order of each repeating unit is not limited, and may be random or block. However, the number q1 of siloxane units having an amino group in the above formula (A) and the number q2 of siloxane units having an amino group in the above formula (B) do not become 0 at the same time.

Examples of the group represented by formula (B) include groups represented by the following formulas (15) to (19), but are not limited to the following formulas.

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

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

Examples of each repeating unit of the above formula (2) include the following repeating units.

Among these, a perfluoropolyether block of the following formula (3) in which z=1 and x and y are 0 in the above formula (2) is preferable because it has excellent compatibility with non-fluorine organic compounds.

In formula (3), v and w are each a number from 0 to 200, preferably each from 0 to 50, provided that v+w=3 to 200, preferably 10 to 50, and (OC The repeating unit of ₂ F ₄ ) may be linear or branched, and the arrangement order of each repeating unit is not limited and may be random or block.

The perfluoropolyether blocks represented by the above formulas usually have a distributed structure, and v, w, x, and y are each average values per molecule.

（式中、＊はＲｆに結合する遊離基、＊＊はＷ１またはＷ２に結合する遊離基を示す。） In the above formula (1), Q is a divalent organic group having 2 to 12 carbon atoms, preferably a divalent organic group having 3 to 6 carbon atoms. In the above formula (1), Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2. Note that Q may contain an oxygen atom or a nitrogen atom. Specific examples include ether bonds, ester bonds, amide bonds, and secondary amino groups. Specific examples of Q include the following groups.

(In the formula, * represents a free group that binds to Rf, and ** represents a free group that binds to W1 or W2.)

Among the specific examples of Q above, ^* -CH ₂ OCH ₂ CH ₂ CH ₂ - ^** is preferred in that it is easy to connect the organopolysiloxane block and the perfluoropolyether block.

In the above formula (1), g is a number from 0 to 50, preferably a number from 0 to 20, and more preferably a number from 0 to 10. When g is in this range, the viscosity becomes easy to handle.

[Method for producing organopolysiloxane]
The present invention also relates to a method for producing an organopolysiloxane having the above perfluoropolyether block and an amino group. The organopolysiloxane of the present invention can be produced, for example, by the method described below.

(a) component: perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5), (b) component: polysiloxane having an amino group, (c) component: fluorinated hydrocarbon (d) component: in the presence of a base catalyst, the mixture of components (a), (b) and (c) is mixed with a solvent,
The organopolysiloxane represented by the above formula (1) can be obtained by carrying out an exchange reaction between the siloxanes of component (a) and component (b).

Component (a): The perfluoropolyether-organopolysiloxane block copolymer represented by formula (5) can be produced using the method described in Patent No. 4,900,854.

Specifically, an organohydrogenpolysiloxane having one hydrosilyl group at one end for deriving W4, and an organohydrogenpolysiloxane having one hydrosilyl group at each end for deriving W3 and/or W4. One or more hydrogen polysiloxanes and a compound having a group Q' having an unsaturated group on both sides of Rf represented by the following formula (20) are subjected to a hydrosilylation reaction in the presence of a platinum catalyst. When only an organohydrogenpolysiloxane having one hydrosilyl group at both ends is subjected to a hydrosilylation reaction with a compound represented by the following formula (20), an unsubstituted or substituted terminal unsubstituted compound having 1 to 18 carbon atoms is further added. A saturated hydrocarbon is subjected to a hydrosilylation reaction to deactivate the terminal hydrosilyl group. By deactivating the terminal hydrosilyl group, gelation during the exchange reaction between siloxanes can be prevented.

In the above formula (20), Rf is a perfluoropolyether block represented by the above formula (2), and Q' is, for example, a group containing an unsaturated group at the terminal shown below.

In the above formula (5), Rf is a perfluoropolyether block represented by the above formula (2).

In formula (5), the organopolysiloxane blocks W3 are each independently a divalent group represented by the following formula (A').

In the above formula (A'), R ¹ is the same as described in the above formula (A). p1' is a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200.

In the above formula (5), the organopolysiloxane block W4 is a monovalent group represented by the following formula (B').

In the above formula (B'), R ¹ and R ¹ ' are the same as those described in the above formula (B). p2' is a number from 0 to 1,000, preferably from 0 to 500, more preferably from 0 to 200.

In the above formula (5), Q is a divalent organic group having 2 to 12 carbon atoms, preferably a divalent organic group having 3 to 6 carbon atoms. Further, Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W3, or the terminal silicon atom of W4. Note that Q may contain an oxygen atom or a nitrogen atom. Specific examples include ether bonds, ester bonds, amide bonds, and secondary amino groups. Specific examples of Q include the following groups.

（式中、＊はＲｆに結合する遊離基、＊＊はＷ３またはＷ４に結合する遊離基を示す。）

(In the formula, * represents a free group that binds to Rf, and ** represents a free group that binds to W3 or W4.)

Among the specific examples of Q above, ^* -CH ₂ OCH ₂ CH ₂ CH ₂ - ^** is preferred in that it is easy to connect the organopolysiloxane block and the perfluoropolyether block.

In the above formula (5), g' is a number from 0 to 50, preferably a number from 0 to 20, and more preferably a number from 0 to 10. When g' is within this range, the viscosity is easy to handle.

In formula (5), examples of the organohydrogenpolysiloxane having one hydrosilyl group at one end for inducing W4 include the following siloxanes, but are not limited to the following formula. .

（式中、各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）

(In the formula, the arrangement order of each repeating unit is not limited and may be random or block.)

In the above formula (5), examples of the organohydrogenpolysiloxane having one hydrosilyl group at both ends for deriving W3 and/or W4 include the following siloxanes, but are limited to the following formulas. It is not something that will be done.

（式中、各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）

(In the formula, the arrangement order of each repeating unit is not limited and may be random or block.)

Component (b): The polysiloxane having an amino group is not particularly limited, but is preferably a polysiloxane represented by the following formula (6) or the following formula (7).

（式（６）中、Ｒ¹、ｉ、ｊ及びｋはそれぞれ上記式（Ａ）及び上記式（４）に記載のものと同じである。Ｒ³は独立して水素原子、炭素数１～４のアルキル基、又は－ＳｉＲ¹ ₃（Ｒ¹は上記と同じである。）であり、好ましくは水素原子、メチル基又は－Ｓｉ（ＣＨ₃）₃である。ｐ３は０～１，０００の数であり、好ましくは０～５００である。ｑ３は１～５００の数であり、好ましくは１～２００の数である。）

(In formula (6), R ¹ , i, j and k are the same as those described in the above formula (A) and the above formula (4), respectively. R ³ is independently a hydrogen atom, a carbon number of 1 to p3 is an alkyl group of 4 or -SiR ¹ ₃ (R ¹ is the same as above), preferably a hydrogen atom, a methyl group or -Si(CH ₃ ) _3. p3 is an alkyl group of 0 to 1,000. (q3 is a number from 1 to 500, preferably from 1 to 200.)

（式（７）中、Ｒ¹、ｉ、ｊ及びｋはそれぞれ上記式（６）に記載のものと同じである。ｐ４は０～６の数であり、好ましくは０である。ｑ４は１～１４の数であり、好ましくは１～８の数である。但し、３≦ｐ４＋ｑ４≦１４である。）

(In formula (7), R ¹ , i, j and k are each the same as those described in formula (6) above. p4 is a number from 0 to 6, preferably 0. q4 is 1 ~14, preferably a number from 1 to 8. However, 3≦p4+q4≦14.)

Examples of the polysiloxane represented by the above formula (6) include polysiloxanes of the following formula, but are not limited to the following formula.

Examples of the polysiloxane represented by the above formula (7) include polysiloxanes of the following formula, but are not limited to the following formula.

(c) Component: Fluorinated hydrocarbon solvent is composed of (a) component: perfluoropolyether-organopolysiloxane block copolymer, (b) component: polysiloxane having an amino group, and (d) component: base. This is necessary to make the catalyst compatible and to advance the exchange reaction between siloxanes. Component (c): The fluorinated hydrocarbon solvent is not particularly limited as long as it does not deactivate the component (d): the base catalyst, but it is preferably one with a high boiling point in order to carry out the exchange reaction between siloxanes at a high temperature. . For example, (trifluoromethyl)benzene, 1,3-bis(trifluoromethyl)benzene, 1,3,5-tris(trifluoromethyl)benzene, 1-fluorohexane, 1-fluorooctane, 1-fluorodecane, etc. can be mentioned. Among them, component (a): 1,3-bis(tris), which has good compatibility between the perfluoropolyether-organopolysiloxane block copolymer represented by the above formula (5) and the polysiloxane of component (b). Fluoromethyl)benzene is preferred.

Component (c): The amount of the fluorinated hydrocarbon solvent used is not particularly limited as long as the above components (a), (b) and (d) are compatible with each other. It is preferably 10 to 300% by mass based on the total of component b) and component (d).

(d) Component: The base catalyst is not particularly limited as long as it can hydrolyze the siloxane bonds of the above (a) and (b) components, but it is compatible with the above (a) and (b) components. Polysiloxanes having a silanolate structure with good solubility are preferred.

Component (d) above: Examples of the base catalyst include polysiloxanes having a silanolate structure of the following formula, but are not limited to the following formula.

In the method for producing organopolysiloxane of the above formula (1), if necessary, component (e): one or more selected from polysiloxanes represented by the following formula (21) and the following formula (22) is added, An exchange reaction between siloxanes may also be performed. By adding and reacting component (e), the number of organosiloxy units in the above formula (1) can be controlled, and compatibility with non-fluorine organic compounds can be easily controlled.

（式（２１）中、Ｒ¹は上記と同じである。ｒ１は３～１４の数であり、好ましくは３～８の数である。）

(In formula (21), R ¹ is the same as above. r1 is a number from 3 to 14, preferably a number from 3 to 8.)

（式（２２）中、Ｒ¹は上記と同じである。ｒ２は０～５，０００の数であり、好ましくは２～１，０００の数である。）

(In formula (22), R ¹ is the same as above. r2 is a number from 0 to 5,000, preferably a number from 2 to 1,000.)

Among component (e), cyclic polysiloxanes represented by formula (21) are preferred, and octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are particularly preferred.

In the method for producing the organopolysiloxane of the above formula (1), for the purpose of increasing the boiling point and for the purpose of separating and purifying the organopolysiloxane of the above formula (1) from the cyclic polysiloxane having an amino group as a by-product. Optionally, component (f): non-fluorine organic solvent may be added. Although this reaction is possible in the presence of only component (c): a fluorinated hydrocarbon solvent, the temperature can be easily raised by adding component (f), a non-fluorinated organic solvent, to raise the boiling point. , and the exchange reaction between siloxanes and the decomposition reaction of component (d): base catalyst may be able to proceed efficiently. In addition, the organopolysiloxane of formula (1) above is dissolved, a non-fluorinated organic solvent that does not dissolve the cyclic polysiloxane having an amino group, which is a by-product, is added to the reaction product and filtered. The organopolysiloxane of formula (1) above can be purified by distilling off the organic solvent.

Component (f): Non-fluorine organic solvents include, for example, aromatic hydrocarbons such as toluene, xylene, and mesitylene; aliphatic hydrocarbons such as hexane, heptane, decane, and n-tetradecane; and diisopropyl ketone and diisobutyl ketone. Ketones; examples include esters such as butyl acetate and isobutyl acetate. For the purpose of increasing the boiling point, component (a): perfluoropolyether-organopolysiloxane block copolymer represented by the above formula (5), and polysiloxane as component (b) and component (e). Preferred is n-tetradecane, which has good compatibility and a high boiling point. If the purpose is to separate and purify the organopolysiloxane of the above formula (1) from the by-product cyclic polysiloxane having amino groups, the organopolysiloxane of the above formula (1) is easily soluble and does not contain amino groups. Preferred are aliphatic hydrocarbons in which the cyclic polysiloxane contained therein is difficult to dissolve, and more preferred is hexane, which has a low boiling point and is easily distilled off.

Component (f): The amount of non-fluorine-based organic solvent to be used is the amount that allows the exchange reaction between siloxanes to proceed and the separation of the organopolysiloxane of formula (1) above from the by-product cyclic polysiloxane having an amino group. There is no particular restriction as long as the amount is possible, but it is preferably 10 to 300% by mass based on the total of component (a), component (b), component (d), and component (e).

In the above production method, the reaction temperature is a temperature at which the exchange reaction between the siloxane of the perfluoropolyether-organopolysiloxane block copolymer (component (a)) and the siloxanes of components (b) and (e) proceeds. Although there are no particular limitations, the temperature is preferably 90 to 180°C. When the reaction temperature is at least the above lower limit, the reaction tends to proceed quickly, and when it is at or below the above upper limit, side reactions are less likely to occur.

In the above production method, the reaction time is not particularly limited as long as the exchange reaction between the component (a) and the siloxanes of the components (b) and (e) reaches an equilibrium state; Preferably it is 12 hours.

The organopolysiloxane of the above formula (1) obtained by the above production method usually has a distribution in structure, and in the formula (1), g is an average value per molecule.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below. In the following example, the number of repeating units g is determined by the integral value M derived from Si of the Si(R ^1' ) ₃ -O- structure based on the above formula (1) in the ²⁹ Si-NMR spectrum and the above formula (1). ) based on the -Q-Si(R ¹ ) ₂ -O- structure and the integral value M' derived from Si, and g=(M'/M)-1.

[Example 1] Synthesis of organopolysiloxane (1-1) A perfluoropolyether-organopolysiloxane represented by the following formula (5-1) synthesized according to Patent No. 4,900,854 was placed in a reaction vessel. 3.3 g of a block copolymer, 0.25 g of a mixture of polysiloxanes having amino groups represented by the following formulas (6-1) and (7-1), and 1,3-bis(trifluoromethyl) 2.4 g of benzene, 1.2 g of n-tetradecane, and 0.077 g of polysiloxane having a silanolate structure represented by the following formula (23-1) were added, and the mixture was stirred at 150° C. for 6 hours under a nitrogen atmosphere. . Next, the mixture in the reaction vessel was cooled to 100°C, 0.012 g of 2-chloroethanol was added to the reaction vessel for the purpose of neutralizing the silanolate, and the mixture was stirred at 100°C for 2 hours. The resulting mixture was filtered, and the solvents 1,3-bis(trifluoromethyl)benzene and n-tetradecane, as well as excess 2-chloroethanol, were distilled off under reduced pressure to obtain a pale yellow, translucent liquid product. 2.6g was obtained.

The measurement results of each NMR spectrum of the obtained product are shown in Tables 1 to 3.

From the above results, it was found that the product had a structure represented by the following formula (1-1), and the organopolysiloxane block content in the molecule was 78%.

[Example 2] Synthesis of organopolysiloxane (1-2) 3.0 g of perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5-2) and the following formula (6) were placed in a reaction vessel. -2) and a mixture of 0.30 g of polysiloxane having an amino group represented by the following formula (7-2), 2.4 g of 1,3-bis(trifluoromethyl)benzene, and the following formula (23-2) 0.32 g of a polysiloxane having a silanolate structure shown by was added thereto, and the mixture was stirred at 100° C. for 3 hours under a nitrogen atmosphere. Next, 3.0 g of n-tetradecane was added to the reaction vessel and stirred at 150° C. for 2 hours to decompose the base catalyst. After distilling off the solvents 1,3-bis(trifluoromethyl)benzene and n-tetradecane under reduced pressure, 5.0 g of n-hexane was added and the solution was filtered. Polysiloxane was removed. N-hexane was distilled off under reduced pressure to obtain 2.3 g of a white translucent liquid product.

The measurement results of each NMR spectrum of the obtained product are shown in Tables 4 to 6.

From the above results, it was found that the product had a structure represented by the following formula (1-2), and the organopolysiloxane block content in the molecule was 79%.

[Example 3] Synthesis of organopolysiloxane (1-3) 3.5 g of perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5-3) and the above formula (6) were placed in a reaction vessel. -1) and 0.35 g of a mixture of polysiloxanes having amino groups represented by the above formula (7-1), 2.6 g of 1,3-bis(trifluoromethyl)benzene, and 1.3 g of n-tetradecane. , and 0.042 g of polysiloxane having a silanolate structure represented by the above formula (23-1) were added and stirred at 150° C. for 6 hours under a nitrogen atmosphere. Next, the mixture in the reaction vessel was cooled to 100°C, 0.013 g of 2-chloroethanol was added to the reaction vessel for the purpose of neutralizing the silanolate, and the mixture was stirred at 100°C for 2 hours. The resulting mixture was filtered, and the solvents 1,3-bis(trifluoromethyl)benzene and n-tetradecane, as well as excess 2-chloroethanol, were distilled off under reduced pressure to obtain a pale yellow, translucent liquid product. 2.7g was obtained.

The measurement results of each NMR spectrum of the obtained products are shown in Tables 7 to 9.

From the above results, it was found that the product had a structure represented by the following formula (1-3), and the organopolysiloxane block content in the molecule was 55%.

[Comparative example 1 (organopolysiloxane block content in molecule: 23%)]
In a reaction vessel, 21.5 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (24), 21.5 g of 1,3-bis(trifluoromethyl)benzene, and platinum vinylsiloxane were placed. 0.60 g of a toluene solution of the complex was added, and the mixture was stirred at 60° C. for 5 minutes. Next, 1.25 g of allylamine was added dropwise to the mixture in the reaction vessel over 15 minutes, and the mixture was stirred at 80° C. for 2 hours. The solvent 1,3-bis(trifluoromethyl)benzene and excess allylamine were distilled off under reduced pressure to obtain 20.8 g of organopolysiloxane represented by the following formula (25).

[Evaluation of solubility in non-fluorine organic compounds]
0.1 g of the organopolysiloxanes of the above Examples and Comparative Examples were mixed with 0.9 g of the non-fluorine organic compound described below, and the mixture was visually observed to evaluate solubility according to the following criteria.
Evaluation criteria ○: The mixed liquid is transparent.
△: The mixed liquid is slightly cloudy.
×: The liquid mixture is cloudy or separated into two phases.

From the results in Table 10, the organopolysiloxane having a perfluoropolyether block and an amino group of the present invention has better solubility in non-fluorinated organic compounds than the organopolysiloxane of the comparative example with a low siloxane content. I understand.

[Comparative example 2]
The reaction between siloxane was carried out in the same manner as in Example 1, except that the reaction was carried out in the absence of a solvent, without using 2.4 g of 1,3-bis(trifluoromethyl)benzene and 1.2 g of n-tetradecane as reaction solvents. Although an exchange reaction was carried out, the reaction did not proceed, and it was confirmed that the reaction raw material, polysiloxane having an amino group represented by the above formula (6-1), remained.

[Comparative example 3]
The reaction between siloxane was carried out in the same manner as in Example 1, except that 3.6 g of n-tetradecane was used instead of 2.4 g of 1,3-bis(trifluoromethyl)benzene and 1.2 g of n-tetradecane as reaction solvents. An exchange reaction was carried out to obtain 2.7 g of a non-uniform liquid product consisting of a high viscosity white cloudy layer and a low viscosity slightly white cloudy layer. No residual polysiloxane having an amino group represented by the above formula (6-1), which is a reaction raw material, could be confirmed.
The high viscosity cloudy white layer was hardly soluble in toluene, and the low viscosity slightly cloudy layer was easily soluble in toluene.

As described above, in Example 1 in which the reaction was carried out in a fluorinated hydrocarbon solvent, an organopolysiloxane having amino groups into which perfluoropolyether blocks were uniformly introduced was obtained. On the other hand, in Comparative Example 2 in which the reaction was carried out without a solvent, an organopolysiloxane having a perfluoropolyether block and an amino group was not obtained. Furthermore, in Comparative Example 3, in which the reaction was carried out in a non-fluorine organic solvent, an organopolysiloxane having amino groups in which perfluoropolyether blocks were non-uniformly introduced was obtained. From these facts, it is clear that a fluorinated hydrocarbon solvent is necessary for the reaction to proceed uniformly.

In the organopolysiloxane having a perfluoropolyether block and an amino group according to the present invention, the number of perfluoropolyether blocks and organopolysiloxane blocks and the number of siloxane units having an amino group can be easily controlled. Therefore, it is possible to control the compatibility, the crosslinking density of the cured product, and the adhesion to fibers, etc., and it is useful for applications such as surface modifiers for non-fluorine-based organic resins and fiber treatment agents.

Claims (6)

An organopolysiloxane having a perfluoropolyether block and an amino group, represented by the following formula (1).

[In formula (1),
Rf is the following formula (2)

(In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Also, each repeating unit is It may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.)
It is a perfluoropolyether block represented by
W1 is the following formula (A)

(In formula (A), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. R ² is independently is a monovalent group having an amino group.p1 and q1 are each a number from 0 to 1,000.The arrangement order of each repeating unit is not limited and may be random or block. .)
It is a divalent organopolysiloxane block represented by
W2 is each independently expressed by the following formula (B)

(In formula (B), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. R ² is independently is a monovalent group having an amino group.R ¹ ' is a group independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. (p2 and q2 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited, and may be random or block.)
A monovalent organopolysiloxane block represented by
However, the number q1 of siloxane units having an amino group of the above formula (A) and the number q2 of siloxane units having an amino group of the above formula (B) do not become 0 at the same time.
Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2. are combined,
g is a number from 0 to 50, but when g is 0, q2 in formula (B) of W2 does not become 0. ]
The organopolysiloxane having a perfluoropolyether block and an amino group according to claim 1, wherein the organopolysiloxane block content in one molecule is 50% or more.
The organopolysiloxane having a perfluoropolyether block and an amino group according to claim 1, wherein the perfluoropolyether block represented by Rf is a group represented by the following formula (3).

(In formula (3), v and w are each a number from 0 to 200, provided that v+w = 3 to 200. Also, the repeating unit of (OC ₂ F ₄ ) may be linear or branched. (The arrangement order of each repeating unit is not limited, and may be random or block.)
The organopolysiloxane having a perfluoropolyether block and an amino group according to claim 1, wherein the monovalent group having an amino group represented by R ² is a group represented by the following formula (4).

(In formula (4), i is a number from 3 to 8, j is a number from 1 to 4, and k is 0 or 1.)
Component (a): a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5),
(b) Component: polysiloxane having an amino group,
Component (c): fluorinated hydrocarbon solvent is mixed, and the mixture of components (a), (b), and (c) is mixed with component (d): component (a) and (b) in the presence of a base catalyst. A method for producing an organopolysiloxane having a perfluoropolyether block and an amino group according to any one of claims 1 to 4, which comprises a step of performing an exchange reaction between the component siloxanes.

[In formula (5), Rf is a perfluoropolyether block represented by the above formula (2), and W3 is each independently represented by the following formula (A')

(In formula (A'), R ¹ is the same as R ¹ in formula (A) above. p1' is a number from 0 to 1,000.)
It is a divalent organopolysiloxane block represented by
W4 is each independently expressed by the following formula (B')

(In formula (B'), R ¹ and R ¹ ' are respectively the same as R ¹ and R ¹ ' in formula (B) above. p2' is a number from 0 to 1,000)
A monovalent organopolysiloxane block represented by
Q is the same as Q in the above formula (1). Furthermore, in the above formula (5), Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W3, or the terminal silicon atom of W4,
g' is a number from 0 to 50. ]
The perfluoropolyether block and amino group according to claim 5, wherein the component (b) is one or more selected from polysiloxanes having an amino group represented by the following formula (6) or the following formula (7). A method for producing an organopolysiloxane comprising:

(In formula (6), R ¹ is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. R ³ is independently is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -SiR ¹ ₃ (R ¹ is the same as above). i is a number from 3 to 8, and j is a number from 1 to 4. (k is 0 or 1, p3 is a number from 0 to 1,000, and q3 is a number from 1 to 100.)

(In formula (7), R ¹ , i, j and k are the same as above. p4 is a number from 0 to 6, and q4 is a number from 1 to 8. However, 3≦p4+q4≦14 be.)