JP7699899B2 - Organopolysiloxane having perfluoropolyether blocks and amino groups, and method for producing same - Google Patents

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, releasability, water and oil repellency, etc. Taking advantage of these properties, they are widely used industrially as lubricants for magnetic recording media, oil repellents and release agents for precision instruments, water and oil repellents and stain repellents for paper, fiber, glass, resin, etc., cosmetics, protective films, etc.

However, because perfluoropolyether group-containing compounds have low surface free energy, their compatibility and affinity with other substances is very low. When perfluoropolyether group-containing compounds are added to various industrial materials to impart the above properties, problems arise in terms of dispersion stability and reactivity, making it difficult to incorporate perfluoropolyether group-containing compounds into various industrial materials.

On the other hand, polysiloxane compounds also have low surface free energy, and therefore have properties such as water repellency, lubricity, and mold releasability. Polysiloxane compounds have better affinity with other substances than perfluoropolyether compounds. In addition, when various modifications are applied, the dispersion stability is further improved. Therefore, polysiloxane compounds can be easily added to various industrial materials and the like to impart silicone properties, 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, when the fluorine modification rate of this polysiloxane compound is increased in order to improve the properties of the perfluoropolyether group, the affinity for other materials is significantly reduced, which can cause problems in dispersion stability, reactivity, etc.

In light of this, a perfluoropolyether-organopolysiloxane block copolymer has been developed (Patent Document 2). This copolymer has the properties of both perfluoropolyether and polysiloxane, and has excellent affinity with non-fluorine-based organic compounds. However, since it does not have reactive functional groups, it cannot react with or be fixed to other materials.

Also, a perfluoropolyether-modified amino-group-containing organopolysiloxane that has a perfluoropolyether group and an amino group on the siloxane side chain has 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 all siloxane units have amino groups, so it was difficult to control the compatibility with non-fluorine-based organic compounds, control the crosslink density of the resulting cured product, and control the physical properties when used for fiber processing, etc.

JP 2006-321764 A JP 2011-21158 A JP 2011-201941 A

Therefore, the present invention aims to provide an organopolysiloxane having perfluoropolyether blocks and amino groups, which has excellent affinity with other substances, particularly non-fluorine-based organic compounds, and a method for producing the same. Specifically, the present invention aims to provide an organopolysiloxane and a method for producing the same, which enable control of the molecular structure, such as the number of perfluoropolyether blocks and organopolysiloxane blocks, and the modification rate of amino groups introduced into the side chains of the organopolysiloxane blocks.

As a result of intensive research into solving the above problems, the inventors discovered that the following organopolysiloxane can achieve the above objective, and thus 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 represented by 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. Each repeating unit may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.)
is a perfluoropolyether block represented by
W1 is represented by the following formula (A):

(In formula (A), ^R1 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. ^R2 is independently 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.)
is a divalent organopolysiloxane block represented by
Each W2 independently represents the following formula (B):

(In formula (B), 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 ² is independently a monovalent group having an amino group. 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. 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.)
is a monovalent organopolysiloxane block represented by
However, the number q1 of the siloxane units having an amino group of the above formula (A) and the number q2 of the siloxane units having an amino group of the above formula (B) are not 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 bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2;
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 perfluoropolyether blocks and amino groups 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, with the proviso that v+w=3 to 200. The repeating unit of (OC ₂ F ₄ ) may be linear or branched. The arrangement order of the repeating units is not limited and may be random or block.)

[4]
The organopolysiloxane having a perfluoropolyether block and an amino group 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):

(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),
Component (b): a polysiloxane having an amino group;
A method for producing an organopolysiloxane having perfluoropolyether blocks and amino groups according to any one of items [1] to [4], comprising the steps of: mixing a mixture of components (a), (b), and (c) with a fluorinated hydrocarbon solvent; and subjecting the mixture to an exchange reaction between the siloxanes of component (a) and component (b) in the presence of component (d): a base catalyst.

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

(In formula (A'), ^R1 is the same as ^R1 in formula (A). p1' is a number from 0 to 1,000.)
is a divalent organopolysiloxane block represented by
W4 each independently represents the following formula (B'):

(In formula (B'), ^R1 and ^R1 ' are the same as ^R1 and R1 ^' in formula (B), respectively. p2' is a number from 0 to 1,000.)
is a monovalent organopolysiloxane block represented by
Q is the same as Q in the formula (1). In addition, in the formula (5), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W3, or the silicon atom at the end of W4,
g' is a number from 0 to 50.

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

(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 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, j is a number from 1 to 4, and 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, with the proviso that 3≦p4+q4≦14.)

The organopolysiloxane of the present invention has a perfluoropolyether block, a high siloxane content, and an organopolysiloxane block at both ends of the molecular chain. Furthermore, the organopolysiloxane block has an amino group at the side chain. Therefore, even though it has a perfluoropolyether block, it is easily compatible with non-fluorine-based organic compounds, can react with epoxy compounds, etc., and has excellent adhesion to fibers, etc. In addition, the organopolysiloxane of the present invention can easily control the number of organopolysiloxane units and the modification rate of the amino group at the side chain of the organopolysiloxane block.
Therefore, the organopolysiloxane of the present invention is useful as a surface modifier for non-fluorine-containing organic resins, for 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 now be described in more detail.
The organopolysiloxane of the present invention is represented by the following formula (1), in which perfluoropolyether blocks (Rf) and organopolysiloxane blocks (W2 or W1) exist alternately.

The definitions of each symbol in formula (1) are the same as above.

The above organopolysiloxane block has amino groups on the side chains, making it possible to react with and adhere to various organic compounds.

The organopolysiloxane of formula (1) preferably has an organopolysiloxane block content of 50% or more and 99% or less, more preferably 60% or more and 90% or less, in one molecule. If the organopolysiloxane block content is equal to or more than the lower limit, the compatibility with non-fluorine-based organic compounds is excellent, and if it is equal to or less than the upper limit, the properties of the perfluoropolyether group are easily expressed. The organopolysiloxane block content is a value calculated by calculating the molar ratio of the perfluoropolyether block ^Rf of known molecular weight and the organosiloxy unit from the integral ratio of the peak derived from the alkylene of Q in formula (1) to the peak derived from the organic group on the silicon atom in W1 and W2 in the 1H-NMR spectrum of the organopolysiloxane of formula (1), and converting this molar ratio into a molecular weight ratio. Incidentally, since the organopolysiloxane of formula (1) usually has a distribution in structure, the above organopolysiloxane block content is the average value per molecule.

At least one of the organopolysiloxane blocks W1 and W2 preferably has a siloxane unit represented by the following formula (8).

In the above formula (8), R ² is a monovalent group having an amino group, and is 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, and preferably a number from 3 to 4. j is a number from 1 to 4, and preferably a number from 2 to 3. k is 0 or 1.

The siloxane unit having an amino group represented by the above formula (8) is present in the above formula (1) at least one, and preferably at least two, from the viewpoint of reactivity with organic compounds and adhesion. 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, and an octadecyl group. Examples of the aryl group having 6 to 18 carbon atoms for R ¹ include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the aralkyl group having 7 to 18 carbon atoms for ^{R 1} include a benzyl group, a 2-phenylethyl group, a 2-methyl-2-phenylethyl group, a naphthylmethyl group, and a 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 as those 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 formula (A) include groups represented by the following formulas (9) to (14), but are not limited to these.

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 in the above 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, and is preferably an alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms for R ¹ ' include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, and an octadecyl group. Examples of the aryl group having 6 to 18 carbon atoms for ^{R 1} ' include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the aralkyl group having 7 to 18 carbon atoms for R ¹ ' include a benzyl group, a 2-phenylethyl group, a 2-methyl-2-phenylethyl group, a naphthylmethyl group, and a 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. 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) are not 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 these.

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, v, w, x, and y are each independently a number from 0 to 200, preferably a number 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, and the arrangement order of each repeating unit is not limited and may be random or block.

Examples of the repeating units 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 preferred because it has excellent compatibility with non-fluorine-based organic compounds.

In formula (3), v and w are each a number from 0 to 200, preferably a number from 0 to 50, with the proviso that v+w=3 to 200, preferably 10 to 50. The repeating unit of (OC 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 distribution in structure, with v, w, x, and y each being an average value 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, and preferably a divalent organic group having 3 to 6 carbon atoms. In addition, in the above formula (1), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2. Q may contain an oxygen atom or a nitrogen atom. Specific examples include an ether bond, an ester bond, an amide bond, and a secondary amino group. Specific examples of Q include the following groups.

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

Among the above specific examples of Q, ^* --CH ₂ OCH ₂ CH ₂ CH ₂ -- ^** is preferred because it allows easy linking of 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 is easy to handle.

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

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

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

In detail, one or more of organohydrogenpolysiloxanes having one hydrosilyl group at one end to derive W4 and organohydrogenpolysiloxanes having one hydrosilyl group at each end to derive W3 and/or W4 are subjected to a hydrosilylation reaction in the presence of a platinum catalyst. When only an organohydrogenpolysiloxane having one hydrosilyl group at each end is subjected to a hydrosilylation reaction with a compound having a group Q' having an unsaturated group on both sides of Rf represented by the following formula (20), a non-substituted or substituted terminally unsaturated hydrocarbon having 1 to 18 carbon atoms is further subjected to a hydrosilylation reaction to inactivate the hydrosilyl group at the end. By inactivating the hydrosilyl group at the end, 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 end, as 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'), ^R1 is the same as that 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'), ^R1 and ^R1 ' are the same as those described in the above formula (B). p2' 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), Q is a divalent organic group having 2 to 12 carbon atoms, and preferably a divalent organic group having 3 to 6 carbon atoms. Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W3, or the silicon atom at the end of W4. Q may contain an oxygen atom or a nitrogen atom. Specific examples include an ether bond, an ester bond, an amide bond, and a secondary amino group. 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 bonded to Rf, and ** represents a free group bonded to W3 or W4.)

Among the above specific examples of Q, ^* --CH ₂ OCH ₂ CH ₂ CH ₂ -- ^** is preferred because it allows easy linking of 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 in this range, the viscosity is easy to handle.

In formula (5), examples of organohydrogenpolysiloxanes having one hydrosilyl group at one end to derive W4 include, but are not limited to, the following siloxanes:

（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 the repeating units is not limited, and may be random or block.)

In the above formula (5), examples of organohydrogenpolysiloxanes having one hydrosilyl group at each end to derive W3 and/or W4 include, but are not limited to, the following siloxanes:

（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 the repeating units 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 (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 defined in formula (A) and formula (4) above. R ³ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -SiR ¹ ₃ (R ¹ is the same as above), and is preferably a hydrogen atom, a methyl group, or -Si(CH ₃ ) _3. p3 is a number from 0 to 1,000, and preferably a number from 0 to 500. q3 is a number from 1 to 500, and preferably a number 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 the same as those defined in formula (6) above. p4 is a number from 0 to 6, and preferably 0. q4 is a number from 1 to 14, and preferably a number from 1 to 8, with the proviso that 3≦p4+q4≦14.)

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

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

The (c) component: fluorinated hydrocarbon solvent is necessary to make the (a) component: perfluoropolyether-organopolysiloxane block copolymer, the (b) component: polysiloxane having amino groups, and the (d) component: base catalyst compatible to promote the exchange reaction between siloxanes. There are no particular limitations on the (c) component: fluorinated hydrocarbon solvent as long as it does not inactivate the (d) component: base catalyst, but a high boiling point solvent is preferred in order to carry out the exchange reaction between siloxanes at high temperatures. Examples include (trifluoromethyl)benzene, 1,3-bis(trifluoromethyl)benzene, 1,3,5-tris(trifluoromethyl)benzene, 1-fluorohexane, 1-fluorooctane, and 1-fluorodecane. Among these, 1,3-bis(trifluoromethyl)benzene, which has good compatibility with the (a) component: perfluoropolyether-organopolysiloxane block copolymer represented by the above formula (5) and the (b) component polysiloxane, is preferred.

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

Component (d): There are no particular limitations on the base catalyst as long as it can hydrolyze the siloxane bonds of components (a) and (b), but polysiloxanes with a silanolate structure that are highly compatible with components (a) and (b) are preferred.

Component (d) above: An example of the base catalyst is polysiloxane having a silanolate structure of the following formula, but is not limited to the following formula.

In the method for producing the organopolysiloxane of the above formula (1), if necessary, component (e): one or more selected from polysiloxanes represented by the following formulas (21) and (22) may be added to carry out an exchange reaction between siloxanes. By adding and reacting component (e), it is possible to control the number of organosiloxy units in the above formula (1), making it easier to control the compatibility with non-fluorine-based organic compounds.

（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), ^R1 is the same as above. r1 is a number from 3 to 14, and 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), ^R1 is the same as above. r2 is a number from 0 to 5,000, preferably a number from 2 to 1,000.)

Among the (e) components, 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), a non-fluorine-based organic solvent (f) may be added as an option 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 by-product cyclic polysiloxane having amino groups. This reaction is possible in the presence of only the component (c): fluorinated hydrocarbon solvent, but by adding the non-fluorine-based organic solvent of the component (f) to increase the boiling point, the temperature can be easily increased, and the exchange reaction between siloxanes and the decomposition reaction of the base catalyst (d) can be efficiently promoted. In addition, the organopolysiloxane of the above formula (1) can be purified by adding a non-fluorine-based organic solvent that dissolves the organopolysiloxane of the above formula (1) and does not dissolve the by-product cyclic polysiloxane having amino groups to the reaction product, filtering the mixture, and distilling off the non-fluorine-based organic solvent that was added.

The above-mentioned (f) component: non-fluorinated organic solvent may, for example, be aromatic hydrocarbons such as toluene, xylene, mesitylene, etc.; aliphatic hydrocarbons such as hexane, heptane, decane, n-tetradecane, etc.; ketones such as diisopropyl ketone, diisobutyl ketone, etc.; esters such as butyl acetate, isobutyl acetate, etc. For the purpose of increasing the boiling point, n-tetradecane, which has a high boiling point and is compatible with the (a) component: perfluoropolyether-organopolysiloxane block copolymer represented by the above formula (5) and the polysiloxanes of the (b) and (e) components, is preferred. For the purpose of separating and purifying the organopolysiloxane of the above formula (1) from the by-product cyclic polysiloxane having amino groups, is preferred, and an aliphatic hydrocarbon in which the organopolysiloxane of the above formula (1) is easily soluble and the cyclic polysiloxane having amino groups is difficult to dissolve is preferred, and hexane, which has a low boiling point and is easy to distill off, is more preferred.

Component (f): The amount of non-fluorinated organic solvent used is not particularly limited as long as it is an amount that allows the exchange reaction between siloxanes to proceed and an amount that allows separation of the organopolysiloxane of formula (1) above from the by-product cyclic polysiloxane having amino groups, but it is preferably 10 to 300% by mass based on the total of components (a), (b), (d), and (e).

In the above manufacturing method, the reaction temperature is not particularly limited as long as it is a temperature at which the exchange reaction between the siloxane of component (a): perfluoropolyether-organopolysiloxane block copolymer and the siloxanes of components (b) and (e) proceeds, but it is preferably 90 to 180°C. If the reaction temperature is equal to or higher than the lower limit, the reaction tends to proceed quickly, and if the reaction temperature is equal to or lower than the upper limit, side reactions are unlikely to occur.

In the above manufacturing method, the reaction time is not particularly limited as long as it is the time required for the exchange reaction between the siloxanes of component (a) and components (b) and (e) to reach equilibrium, but it is preferably 0.5 to 12 hours.

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

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, the number of repeating units g is ^{a value} calculated from the integral value M derived from Si in the Si(R ^1' ) ₃ -O- structure based on the above formula (1) in the 29 Si-NMR spectrum and the integral value M' derived from Si in the -Q-Si(R ¹ ) ₂ -O- structure based on the above formula (1), and g = (M'/M) -1.

Example 1 Synthesis of Organopolysiloxane (1-1) 3.3 g of perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5-1) synthesized according to Japanese Patent No. 4,900,854, 0.25 g of a mixture of polysiloxanes having amino groups represented by the following formulas (6-1) and (7-1), 2.4 g of 1,3-bis(trifluoromethyl)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 placed in a reaction vessel and stirred for 6 hours at 150° C. under a nitrogen atmosphere. Next, the mixture in the reaction vessel was cooled to 100° C., and 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 2.6 g of a pale yellow, semitransparent liquid product.

The results of measuring the NMR spectra of the products obtained 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 that 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), 0.30 g of a mixture of polysiloxanes having amino groups represented by the following formulas (6-2) and (7-2), 2.4 g of 1,3-bis(trifluoromethyl)benzene, and 0.32 g of polysiloxane having a silanolate structure represented by the following formula (23-2) were placed in a reaction vessel and 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 the solvents 1,3-bis(trifluoromethyl)benzene and n-tetradecane were distilled off under reduced pressure, 5.0 g of n-hexane was added, the solution was filtered, and cyclic polysiloxanes having amino groups that were insoluble in n-hexane were removed. The n-hexane was distilled off under reduced pressure to obtain 2.3 g of a white translucent liquid product.

The results of measuring the NMR spectra of the products obtained 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 that 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), 0.35 g of a mixture of polysiloxanes having amino groups represented by the above formulas (6-1) and (7-1), 2.6 g of 1,3-bis(trifluoromethyl)benzene, 1.3 g of n-tetradecane, and 0.042 g of polysiloxane having a silanolate structure represented by the above formula (23-1) were placed in a reaction vessel and stirred for 6 hours at 150° C. under a nitrogen atmosphere. The mixture in the reaction vessel was then cooled to 100° C., and 0.013 g of 2-chloroethanol was added to the reaction vessel for the purpose of neutralizing the silanolate, followed by stirring 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 2.7 g of a pale yellow, semitransparent liquid product.

The results of measuring the NMR spectra of the products obtained 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 that the organopolysiloxane block content in the molecule was 55%.

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

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

The results in Table 10 show that the organopolysiloxane of the present invention having a perfluoropolyether block and an amino group has better solubility in non-fluorinated organic compounds than the comparative organopolysiloxane having a lower siloxane content.

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

[Comparative Example 3]
An exchange reaction between siloxanes 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 the reaction solvent, to obtain 2.7 g of a heterogeneous liquid product consisting of a high-viscosity opaque layer and a low-viscosity slightly opaque layer. No remaining amino group-containing polysiloxane represented by the above formula (6-1), which is the reaction raw material, was confirmed.
The high-viscosity opaque layer was poorly soluble in toluene, whereas the low-viscosity slightly opaque layer was easily soluble in toluene.

From the above, in Example 1, where the reaction was carried out in a fluorinated hydrocarbon solvent, an organopolysiloxane having amino groups with perfluoropolyether blocks uniformly introduced was obtained. In contrast, in Comparative Example 2, where the reaction was carried out in the absence of a solvent, no organopolysiloxane having perfluoropolyether blocks and amino groups was obtained. Moreover, in Comparative Example 3, where the reaction was carried out in a non-fluorinated organic solvent, an organopolysiloxane having amino groups with perfluoropolyether blocks non-uniformly introduced was obtained. From these facts, it is clear that a fluorinated hydrocarbon solvent is necessary to make the reaction proceed uniformly.

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

Claims (5)

The organopolysiloxane has a perfluoropolyether block and an amino group, and is represented by the following formula (1), and the organopolysiloxane has a content of the organopolysiloxane block in one molecule of 50 mass% or more.

[In formula (1),
Rf is represented by 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. Each repeating unit may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.)
is a perfluoropolyether block represented by
W1 is represented by the following formula (A):

(In formula (A), ^R1 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. ^R2 is independently 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.)
is a divalent organopolysiloxane block represented by
W2 each independently represents the following formula (B):

(In formula (B), 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 ² is independently a monovalent group having an amino group. 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. 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.)
is a monovalent organopolysiloxane block represented by
However, the number q1 of the siloxane units having an amino group of the above formula (A) and the number q2 of the siloxane units having an amino group of the above formula (B) are not 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 bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2;
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 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, with the proviso that v+w=3 to 200. The repeating unit of (OC ₂ F ₄ ) may be linear or branched. The arrangement order of the repeating units is not limited and may be random or block.)
2. The organopolysiloxane having a perfluoropolyether block and an amino group according to claim 1, wherein the monovalent group having an amino group represented ^by R2 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),
Component (b): a polysiloxane having an amino group;
4. A method for producing an organopolysiloxane having perfluoropolyether blocks and amino groups according to any one of claims 1 to 3, comprising the steps of mixing component (c) with a fluorinated hydrocarbon solvent, and subjecting the mixture of components (a), (b) and ( c ) to an exchange reaction between the siloxanes of component (a) and component (b) in the presence of component (d): a base catalyst.

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

(In formula (A'), ^R1 is the same as ^R1 in formula (A). p1' is a number from 0 to 1,000.)
is a divalent organopolysiloxane block represented by
W4 each independently represents the following formula (B'):

(In formula (B'), ^R1 and ^R1 ' are the same as ^R1 and ^R1 ' in formula (B), respectively. p2' is a number from 0 to 1,000.)
is a monovalent organopolysiloxane block represented by
Q is the same as Q in the formula (1). In addition, in the formula (5), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W3, or the silicon atom at the end of W4,
g' is a number from 0 to 50.
5. The method for producing an organopolysiloxane having a perfluoropolyether block and an amino group according to claim 4 , wherein the component (b) is at least one selected from polysiloxanes having an amino group represented by the following formula (6) or the following formula (7):

(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 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, j is a number from 1 to 4, and 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, with the proviso that 3≦p4+q4≦14.)