Organopolysiloxane having a perfluoropolyether block and an amino group, and method for producing the same

Abstract

To provide an organopolysiloxane that includes a perfluoropolyether block and an amino group, enables the control of the number of siloxane units in the molecule, and exhibits superior affinity for a fluorine-free organic compound, and a method for producing the same.SOLUTION: An organopolysiloxane includes a perfluoropolyether block and an amino group, with organopolysiloxane blocks positioned at least on both ends of its molecular chain. On the side chain of the organopolysiloxane block, there is at least one amino group in one molecule.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an organopolysiloxane having a perfluoropolyether block and an amino group, and a method for producing the same.

Background Art

[0002] Generally, perfluoropolyether group-containing compounds have chemical resistance, lubricity, mold release properties, water and oil repellency, etc. because their surface free energy is very low. Utilizing these properties, they are widely used industrially as lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, water and oil repellent and antifouling agents for paper, fibers, glass, resins, etc., cosmetics, protective films, etc.

[0003] However, because the surface free energy of perfluoropolyether group-containing compounds is low, their compatibility and affinity with other substances are very low. When attempting to add perfluoropolyether group-containing compounds to various industrial materials, etc. to impart the above properties, problems occur in terms of dispersion stability, reactivity, etc., and it has been difficult to incorporate perfluoropolyether group-containing compounds into various industrial materials, etc.

[0004] On the other hand, polysiloxane compounds also have properties such as water repellency, lubricity, and mold release properties because their surface free energy is low. And polysiloxane compounds have better affinity for other substances compared to perfluoropolyether compounds. Also, when subjected to various modifications, the dispersion stability is further improved. Therefore, polysiloxane compounds can be easily added to various industrial materials, etc. to impart silicone properties, and are used as additives for performance improvement 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, when the fluorine modification rate is increased for the purpose of enhancing the properties of the perfluoropolyether group, the affinity for other materials is significantly reduced. For this reason, problems may occur in terms of dispersion stability, reactivity, etc.

[0005] 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 is excellent in affinity with non-fluorine organic compounds. However, since it does not have reactive functional groups, it cannot react with or be immobilized on other materials.

[0006] In addition, perfluoropolyether-modified amino group-containing organopolysiloxanes having a perfluoropolyether group and an amino group in the siloxane side chain have also been developed (Patent Document 3). However, the perfluoropolyether-modified amino group-containing organopolysiloxane of Patent Document 3 has limited number of introducible siloxane units, and since all siloxane units have amino groups, it has been difficult to control the compatibility with non-fluorine organic compounds, control the crosslink density of the obtained cured product, and control the physical properties when used for fiber treatment, etc.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] Accordingly, an object of the present invention is to provide an organopolysiloxane having a perfluoropolyether block and an amino group, which has excellent affinity with other substances, particularly non-fluorine organic compounds, and a method for producing the same. Specifically, an object of the present invention is to provide an organopolysiloxane capable of controlling the molecular structure such as the number of each of the perfluoropolyether block and the organopolysiloxane block, and the modification rate of the amino group introduced into the side chain of the organopolysiloxane block, and a method for producing the same. [Means for Solving the Problems]

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that the following organopolysiloxane can achieve the above object, and completed the present invention.

[0010] 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). [Chemical Formula] [In formula (1), Rf is the following formula (2) [Chemical Formula] (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 sequence order of each repeating unit is not limited and may be random or block.) and is a perfluoropolyether block represented by W1 is the following formula (A) [Chemical Formula] (In formula (A), R 1is 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 a monovalent group having an amino group. p1 and q1 are each a number from 0 to 1,000. The sequence order of each repeating unit is not limited and may be random or block-like.) is a divalent organopolysiloxane block represented by W2 are each independently the following formula (B) [Chemical formula] (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 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 sequence order of each repeating unit is not limited and may be random or block-like.) is a monovalent organopolysiloxane block represented by 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 both 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 bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2, g is a number from 0 to 50, provided that when g is 0, q2 in the formula (B) of W2 does not become 0.) [2] The organopolysiloxane having a perfluoropolyether block and an amino group according to [1], wherein the content of the organopolysiloxane block in one molecule is 50% or more. [3] The organopolysiloxane having a perfluoropolyether block represented by Rf and an amino group is the organopolysiloxane according to [1] or [2], wherein the perfluoropolyether block is a group represented by the following formula (3). [Chemical formula] (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 (OC2F4) may be linear or branched. The sequence order of each repeating unit is not limited and may be random or block.) [4] R 2 The organopolysiloxane having a perfluoropolyether block represented by R and an amino group is the organopolysiloxane according to any one of [1] to [3], wherein the monovalent group having an amino group represented by is a group represented by the following formula (4). [Chemical formula] (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] (a) Component: a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5), and (b) Component: a polysiloxane having an amino group, and (c) Component: a fluorinated hydrocarbon solvent and are mixed, and the mixture of the (a), (b), and (c) components is (d) Component: 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 [1] to [4], which comprises a step of performing an exchange reaction between the siloxanes of the (a) component and the (b) component. [Chemical formula] [In formula (5), Rf is the perfluoropolyether block represented by the above formula (2), and W3 are each independently the following formula (A’) [Chemical formula] (In formula (A’), R 1 is the same as R 1 in the above formula (A). p1’ is a number from 0 to 1,000.) is a divalent organopolysiloxane block represented by W4 are each independently the following formula (B’) [Chemical formula] (In formula (B’), R 1 and R 1 ’ are each the same as R 1 and R 1' in the above formula (B). p2’ is a number from 0 to 1,000) is a monovalent organopolysiloxane block represented by Q is the same as Q in the above formula (1). Also, 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, and 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). [Chemical formula] (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, k is 0 or 1. p3 is a number from 0 to 1,000, and q3 is a number from 1 to 100.) [Chemical formula] (In formula (7), R 1 , i, j, and k are the same as described above. p4 is a number from 0 to 6, and q4 is a number from 1 to 8. However, 3 ≤ p4 + q4 ≤ 14.) [Advantages of the Invention]

[0011] The organopolysiloxane of the present invention has a perfluoropolyether block, a high siloxane content, and organopolysiloxane blocks at both ends of the molecular chain. Furthermore, it has an amino group in the side chain of the organopolysiloxane block. Therefore, while having a perfluoropolyether block, it is easily compatible with non-fluorine-based organic compounds, can react with epoxy compounds, etc., and also 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 in the side chain of the organopolysiloxane block. Therefore, the organopolysiloxane of the present invention is useful for applications such as surface modifiers for non-fluorine-based organic resins and fiber treatment. [Modes for Carrying Out the Invention]

[0012] Hereinafter, the present invention will be described in more detail. The organopolysiloxane of the present invention is represented by the following formula (1), and a perfluoropolyether block (Rf) and an organopolysiloxane block (W2 or W1) are present alternately. [Chemical formula] The definitions of each symbol in formula (1) are the same as described above.

[0013] Since the above organopolysiloxane block has an amino group in the side chain, it can react with and adhere to various organic compounds.

[0014] The organopolysiloxane of the above 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 at least the above lower limit value, the compatibility with the non-fluorine organic compound is excellent, and if it is at most the above upper limit value, the properties of the perfluoropolyether group are likely to be exhibited. The organopolysiloxane block content is the 1 value calculated by obtaining the molar ratio of the perfluoropolyether block Rf with a known molecular weight and the organosiloxy unit from the integration ratio of the peak derived from the alkylene of Q in the above formula (1) and the peak derived from the organic group on the silicon atom in W1 and W2 in the 1H-NMR spectrum of the organopolysiloxane of the above formula (1), and converting this molar ratio into the ratio of molecular weights. Usually, since the organopolysiloxane of the formula (1) has a distribution in its structure, the above organopolysiloxane block content is the average value per molecule.

[0015] It is preferable that one or more of the organopolysiloxane blocks W1 and W2 have a siloxane unit represented by the following formula (8).

Chemical formula

[0016] 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).

[0017]

Chemical formula

[0018] The siloxane unit having an amino group represented by the above formula (8) is present in one or more in the above formula (1), and the presence of two or more is preferable from the viewpoints of reactivity and adhesiveness with an organic compound. In the organopolysiloxane blocks W1 and W2, the siloxane units of the formula (8) may be the same or different from each other, but are preferably the same.

[0019] In the above formula (1), the organopolysiloxane block W1 is a divalent group represented by the following formula (A).

Chemical formula

[0020] 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 of 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, an octadecyl group, and the like. Examples of the aryl group having 6 to 18 carbon atoms of R 1 include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and the like. Examples of the aralkyl group having 7 to 18 carbon atoms of R 1 include a benzyl group, a 2-phenylethyl group, a 2-methyl-2-phenylethyl group, a naphthylmethyl group, a 2-naphthylethyl group, and the like. R 1 is preferably a methyl group or a phenyl group.

[0021] In the above formula (A), examples of R 2 include the same ones as those exemplified for R 2 of the formula (8).

[0022] 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 sequence order of each repeating unit is not limited and may be random or block.

[0023] Examples of the group represented by the above formula (A) include groups represented by the following formulas (9) to (14), etc., but are not limited to the following formulas.

Chemical formula

Chemical formula

[0024] In the above formula (1), the organopolysiloxane block W2 is a monovalent group represented by the following formula (B).

Chemical formula

[0025] In the above formula (B), R 1 and R 2 are the same as those exemplified 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, preferably an alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms of 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, an octadecyl group, etc. Examples of the aryl group having 6 to 18 carbon atoms of R 1 ’ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. Examples of the aralkyl group having 7 to 18 carbon atoms of R 1 ’ include a benzyl group, a 2-phenylethyl group, a 2-methyl-2-phenylethyl group, a naphthylmethyl group, a 2-naphthylethyl group, etc. More preferably, R 1 ’ is a methyl group, a butyl group, a hexyl group, an octyl group or a dodecyl group.

[0026] 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 sequence order of each repeating unit is not limited and may be random or in blocks. However, the number q1 of the siloxane units having an amino group in the above formula (A) and the number q2 of the siloxane units having an amino group in the above formula (B) do not become 0 simultaneously.

[0027] Examples of the group represented by the formula (B) include groups represented by the following formulas (15) to (19), etc., but are not limited to the following formulas. [Chemical formula] [Chemical formula]

[0028] The perfluoropolyether block Rf in the above formula (1) is represented by the following formula (2). [Chemical formula]

[0029] In the 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 each a number from 0 to 50. However, v + w + x + y = 3 to 200, preferably 10 to 50. Each repeating unit may be linear or branched, and the sequence order of each repeating unit is not limited and may be random or in blocks.

[0030] Examples of each repeating unit of the above formula (2) include the following repeating units, etc. [Chemical formula]

[0031] Among them, in the above formula (2), the perfluoropolyether block of the following formula (3) where z = 1 and x and y are 0 is preferred because it has excellent compatibility with non-fluorine-based organic compounds. [Chemical formula]

[0032] In formula (3), v and w are each a number from 0 to 200, preferably each a number from 0 to 50, provided that v + w = 3 to 200, preferably 10 to 50. The repeating unit of (OC2F4) may be linear or branched, and the sequence order of each repeating unit is not limited and may be random or block.

[0033] The perfluoropolyether block represented by the above formulas usually has a distribution in the structure, and v, w, x, and y are each the average value per molecule.

[0034] 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. Also, 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. Specifically, an ether bond, an ester bond, an amide bond, and a secondary amino group, etc. are exemplified. Specific examples of Q include the following groups, etc. [Chemical formula] (In the formula, * represents a free radical bonded to Rf, and ** represents a free radical bonded to W1 or W2.)

[0035] Among the above specific examples of Q, * -CH2OCH2CH2CH2- ** is preferred.

[0036] In the above formula (1), g is a number from 0 to 50, preferably a number from 0 to 20, more preferably a number from 0 to 10. When g is within this range, the viscosity becomes easy to handle.

[0037] [Method for producing organopolysiloxane] The present invention also relates to a method for producing an organopolysiloxane having the above perfluoropolyether block and amino group. The organopolysiloxane of the present invention can be produced, for example, by the method described below.

[0038] (a) Component: A perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5), (b) Component: A polysiloxane having an amino group, and (c) Component: A fluorinated hydrocarbon solvent are mixed, and the mixture of the (a), (b) and (c) components is in the presence of (d) Component: A base catalyst, By carrying out an exchange reaction between the siloxanes of the (a) component and the (b) component, the organopolysiloxane represented by the above formula (1) can be obtained.

[0039] [Chemical formula]

[0040] (a) Component: The perfluoropolyether-organopolysiloxane block copolymer represented by formula (5) can be produced using the method described in Patent No. 4,900,854 and the like.

[0041] Specifically, an organohydrogenpolysiloxane having one hydrosilyl group at one end for inducing W4, and one or more organohydrogenpolysiloxanes having one hydrosilyl group at each end for inducing W3 and / or W4, and a compound having a group Q' with unsaturated groups 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 each end and a compound represented by the following formula (20) are subjected to a hydrosilylation reaction, a non-substituted or substituted terminal unsaturated hydrocarbon having 1 to 18 carbon atoms is further 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.

[0042]

Chemical formula

[0043] In the above formula (20), Rf is a perfluoropolyether block represented by the above formula (2), and Q' is a group containing an unsaturated group at the terminal, for example, as shown below.

[0044]

Chemical formula

[0045] In the above formula (5), Rf is a perfluoropolyether block represented by the above formula (2).

[0046] In formula (5), the organopolysiloxane block W3 is a divalent group independently represented by the following formula (A') respectively.

Chemical formula

[0047] In the above formula (A'), R 1is 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, more preferably a number from 0 to 200.

[0048] In the above formula (5), the organopolysiloxane block W4 is a monovalent group represented by the following formula (B’). [Chemical formula]

[0049] 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 a number from 0 to 500, more preferably a number from 0 to 200.

[0050] 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. Also, 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. Specifically, an ether bond, an ester bond, an amide bond, and a secondary amino group, etc. are exemplified. Specific examples of Q include the following groups, etc.

[0051] [Chemical formula] (In the formula, * represents a free group bonded to Rf, and ** represents a free group bonded to W3 or W4.)

[0052] Among the specific examples of the above Q, in terms of the ease of linking the organopolysiloxane block and the perfluoropolyether block, * -CH2OCH2CH2CH2- ** is preferred.

[0053] In the above formula (5), g’ is a number from 0 to 50, preferably a number from 0 to 20, more preferably a number from 0 to 10. When g’ is within this range, the viscosity becomes easy to handle.

[0054] In formula (5), examples of the organohydrogenpolysiloxane having one hydrosilyl group at one end for inducing W4 include, but are not limited to, the following siloxanes and the like.

[0055]

Chemical formula

[0056] In the above formula (5), examples of the organohydrogenpolysiloxane having one hydrosilyl group at each end for inducing W3 and / or W4 include, but are not limited to, the following siloxanes and the like.

[0057]

Chemical formula

[0058] 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).

[0059]

Chemical formula

[0060]

Chem.

[0061] Examples of the polysiloxane represented by the above formula (6) include, but are not limited to, polysiloxanes of the following formulae.

[0062]

Chem.

[0063] Examples of the polysiloxane represented by the above formula (7) include, but are not limited to, polysiloxanes of the following formulae.

[0064]

Chem.

[0065] (c) Component: The fluorinated hydrocarbon solvent is necessary to dissolve the (a) component: perfluoropolyether-organopolysiloxane block copolymer, the (b) component: polysiloxane having an amino group, and the (d) component: base catalyst to promote the exchange reaction between siloxanes. The (c) component: fluorinated hydrocarbon solvent is not particularly limited as long as it does not deactivate the (d) component: base catalyst, but a high-boiling-point one is preferred for performing 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, 1,3-bis(trifluoromethyl)benzene, which has good compatibility between the (a) component: perfluoropolyether-organopolysiloxane block copolymer represented by the above formula (5) and the (b) component: polysiloxane, is preferred.

[0066] (c) Component: The amount of the fluorinated hydrocarbon solvent used is not particularly limited as long as the above (a) component, (b) component, and (d) component are compatible, but it is preferably 10 to 300% by mass based on the total of the (a) component, (b) component, and (d) component.

[0067] (d) Component: The base catalyst is not particularly limited as long as it can hydrolyze the siloxane bonds of the above (a) component and (b) component, but a polysiloxane having a silanolate structure with good compatibility with the above (a) component and (b) component is preferred.

[0068] Examples of the above (d) component: base catalyst include, but are not limited to, polysiloxanes having a silanolate structure of the following formula.

[0069]

Chemical formula

[0070] In the method for producing the organopolysiloxane of the above formula (1), if necessary, one or more selected from the polysiloxanes represented by the following formula (21) and the following formula (22) may be added as component (e) to perform an exchange reaction between siloxanes. By adding component (e) and reacting, it is possible to control the number of organosiloxy units in the above formula (1), and it becomes easier to control the compatibility with non-fluorine-based organic compounds.

[0071] [Chemical formula] (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.)

[0072] [Chemical formula] (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.)

[0073] Among the component (e), the cyclic polysiloxane represented by the formula (21) is preferred, and in particular, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are preferred.

[0074] In the method for producing the organopolysiloxane of the above formula (1), for the purpose of raising the boiling point and separating and purifying the organopolysiloxane of the above formula (1) from the cyclic polysiloxane having an amino group as a by-product, an optional component (f): a non-fluorinated organic solvent may be added. This reaction is possible even in the presence of only the component (c): a fluorinated hydrocarbon solvent. However, by adding the non-fluorinated organic solvent of the component (f) to raise the boiling point, the temperature can be easily raised, and the exchange reaction between siloxanes and the decomposition reaction of the component (d): a base catalyst may be able to proceed efficiently. Further, a non-fluorinated organic solvent that dissolves the organopolysiloxane of the above formula (1) and does not dissolve the cyclic polysiloxane having an amino group as a by-product is added to the reaction product and filtered, and the added non-fluorinated organic solvent is distilled off, whereby the organopolysiloxane of the above formula (1) can be purified.

[0075] Examples of the above component (f): non-fluorinated organic solvents include aromatic hydrocarbons such as toluene, xylene, and mesitylene; aliphatic hydrocarbons such as hexane, heptane, decane, and n-tetradecane; ketones such as diisopropyl ketone and diisobutyl ketone; and esters such as butyl acetate and isobutyl acetate. For the purpose of raising the boiling point, n-tetradecane, which has good compatibility between the component (a): the perfluoropolyether-organopolysiloxane block copolymer represented by the above formula (5) and the polysiloxanes of the components (b) and (e) and has a high boiling point, is preferred. 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, aliphatic hydrocarbons in which the organopolysiloxane of the above formula (1) is easily dissolved and the cyclic polysiloxane having an amino group is hardly dissolved are preferred, and hexane, which has a low boiling point and is easily distilled off, is more preferred.

[0076] (f) Component: The amount of the non-fluorine-based 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 can separate the organopolysiloxane of the above formula (1) and the cyclic polysiloxane having an amino group as a by-product. However, it is preferably 10 to 300% by mass based on the total of components (a), (b), (d), and (e).

[0077] In the above production 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. However, it is preferably 90 to 180°C. If the reaction temperature is at or above the above lower limit value, the reaction easily proceeds rapidly, and if it is at or below the above upper limit value, side reactions are less likely to occur.

[0078] In the above production method, the reaction time is not particularly limited as long as it is a time at which the exchange reaction between the siloxanes of component (a) and components (b) and (e) reaches an equilibrium state. However, it is preferably 0.5 to 12 hours.

[0079] The organopolysiloxane of the above formula (1) obtained by the above production method usually has a distribution in its structure, and in formula (1), g is an average value per molecule.

Examples

[0080] Hereinafter, examples and comparative examples will be shown to specifically explain the present invention, but the present invention is not limited to the following examples. In the following examples, the repeating unit number g is 29 in the Si-NMR spectrum, the integrated value M derived from Si of the Si(R 1' )3-O-structure based on the above formula (1) and the integrated value M' derived from Si of the -Q-Si(R 1 )2-O-structure based on the above formula (1), and g = (M' / M) - 1.

[0081] [Example 1] Synthesis of Organopolysiloxane (1-1) Into a reaction vessel, 3.3 g of a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5-1) synthesized according to Patent No. 4,900,854, 0.25 g of a mixture of polysiloxanes having amino groups represented by the following formula (6-1) and the following formula (7-1), 2.4 g of 1,3-bis(trifluoromethyl)benzene, 1.2 g of n-tetradecane, and 0.077 g of a polysiloxane having a silanolate structure represented by the following formula (23-1) were placed, 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 1,3-bis(trifluoromethyl)benzene and n-tetradecane as solvents, and an excess amount of 2-chloroethanol were distilled off under reduced pressure to obtain 2.6 g of a pale yellow translucent liquid product.

[0082] [Chemical formula]

[0083] The measurement results of the NMR spectra of the obtained product are shown in Tables 1 to 3. [Table 1] [Table 2] [Table 3]

[0084] From the above results, it was found that the product has a structure represented by the following formula (1-1) and the content of the organopolysiloxane block in the molecule is 78%. [Chemical formula]

[0085] [Example 2] Synthesis of Organopolysiloxane (1-2) Into a reaction vessel, 3.0 g of a 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 formula (6-2) and the following formula (7-2), 2.4 g of 1,3-bis(trifluoromethyl)benzene, and 0.32 g of a polysiloxane having a silanolate structure represented by the following formula (23-2) were placed, 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 the mixture was stirred at 150 °C for 2 hours to decompose the base catalyst. After distilling off 1,3-bis(trifluoromethyl)benzene and n-tetradecane, which are solvents, under reduced pressure, 5.0 g of n-hexane was added, and the solution was filtered to remove the cyclic polysiloxane having amino groups that is insoluble in n-hexane. n-Hexane was distilled off under reduced pressure to obtain 2.3 g of a white translucent liquid product.

[0086] [Chemical formula]

[0087] The measurement results of the NMR spectra of the obtained product are shown in Tables 4 to 6. [Table 4] [Table 5] [Table 6]

[0088] From the above results, it was found that the product has a structure represented by the following formula (1-2) and the content of the organopolysiloxane block in the molecule is 79%. [Chemical formula]

[0089] [Example 3] Synthesis of Organopolysiloxane (1-3) 3.5 g of a 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 formula (6-1) and the above formula (7-1), 2.6 g of 1,3-bis(trifluoromethyl)benzene, 1.3 g of n-tetradecane, and 0.042 g of a polysiloxane having a silanolate structure represented by the above formula (23-1) were placed in a reaction vessel and stirred at 150° C. for 6 hours under a nitrogen atmosphere. Next, the mixture in the reaction vessel was cooled to 100° C., and 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 1,3-bis(trifluoromethyl)benzene and n-tetradecane as solvents, and an excess amount of 2-chloroethanol were distilled off under reduced pressure to obtain 2.7 g of a pale yellow translucent liquid product.

[0090] [Chemical formula]

[0091] The measurement results of the NMR spectra of the obtained product are shown in Tables 7 to 9. [Table 7] [Table 8] [Table 9]

[0092] From the above results, it was found that the product has a structure represented by the following formula (1-3) and the content of the organopolysiloxane block in the molecule is 55%. [Chemical formula]

[0093] [Comparative Example 1 (content of organopolysiloxane block in molecule: 23%)] Into a reaction vessel, 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, 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. 1,3-Bis(trifluoromethyl)benzene as the solvent and the excess amount of allylamine were distilled off under reduced pressure to obtain 20.8 g of an organopolysiloxane represented by the following formula (25).

[0094] [Chemical formula]

[0095] [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-fluorinated organic compound, and the mixed solution was visually observed to evaluate the solubility according to the following criteria. Evaluation criteria ○: The mixed solution is transparent. △: The mixed solution is slightly turbid. ×: The mixed solution is white turbid or separated into two phases.

[0096] [Table 10]

[0097] From the results in Table 10, it was found that the organopolysiloxane having a perfluoropolyether block and an amino group of the present invention is superior in solubility to non-fluorinated organic compounds than the organopolysiloxane of the Comparative Example having a low siloxane content.

[0098] [Comparative Example 2] The exchange reaction between siloxanes was carried out in the same manner as in Example 1 except that the reaction was carried out without a solvent, without using 2.4 g of 1,3-bis(trifluoromethyl)benzene as the reaction solvent and 1.2 g of n-tetradecane. However, the reaction did not proceed, and the residual of the polysiloxane having an amino group represented by the above formula (6-1) as the reaction raw material was confirmed.

[0099] [Comparative Example 3] The 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, and 2.7 g of a non-uniform liquid product composed of a highly viscous turbid layer and a slightly turbid layer with low viscosity was obtained. The residual of the polysiloxane having an amino group represented by the above formula (6-1) as the reaction raw material could not be confirmed. The above highly viscous turbid layer was hardly soluble in toluene, and the above low-viscosity slightly turbid layer was easily soluble in toluene.

[0100] From the above, in Example 1 in which the reaction was carried out in a fluorinated hydrocarbon solvent, an organopolysiloxane having an amino group into which a perfluoropolyether block was 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 could not be obtained. Further, in Comparative Example 3 in which the reaction was carried out in a non-fluorinated organic solvent, an organopolysiloxane having an amino group into which a perfluoropolyether block was non-uniformly introduced was obtained. From these facts, it is clear that a fluorinated hydrocarbon solvent is necessary to make the reaction proceed uniformly.

[0101] The organopolysiloxane having a perfluoropolyether block and an amino group of the present invention is easy to control the number of each of the perfluoropolyether block and the organopolysiloxane block and the number of siloxane units having an amino group. Therefore, it is also possible to control the compatibility, the crosslink density of the cured product, and the adhesion to fibers and the like, and it is useful for applications such as a surface modifier for non-fluorinated organic resins and a fiber treating agent.

Claims

1. An organopolysiloxane having a perfluoropolyether block and an amino group, represented by the following formula (1), wherein the content of the organopolysiloxane block in one molecule is 50% by mass or more. 【Chemical 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 numbers from 0 to 200, and v + w + x + y = 3 to 200. Also, each repeating unit may be linear or branched. The sequence order of each repeating unit is not limited and may be random or block-like.) is a perfluoropolyether block represented by, W1 is the following formula (A) [Chemical 3] (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. R 2 is independently a monovalent group having an amino group. p1 and q1 are each a number from 0 to 1,000. The sequence order of each repeating unit is not limited and may be random or block.) is a divalent organopolysiloxane block represented by, W2 is each independently the following formula (B) [Chemical Formula 4] (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 sequence 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 in the above formula (A) and the number q2 of the siloxane units having an amino group in the above formula (B) do not both 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 bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2, g is a number from 0 to 50, but when g is 0, q2 in the 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). 【Chemical Formula 5】 (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.)

3. R 2 The monovalent group having an amino group represented by the following formula (4), the organopolysiloxane having a perfluoropolyether block and an amino group according to claim 1. 【Chemical Formula 6】 (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.)

4. Component (a): A perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5), Component (b): A polysiloxane having an amino group, Component (c): A fluorinated hydrocarbon solvent are mixed, and the mixture of components (a), (b), and (c) is Component (d): In the presence of a base catalyst A process for producing an organopolysiloxane having a perfluoropolyether block and an amino group according to any one of Claims 1 to 3, which comprises performing an exchange reaction between the siloxanes of components (a) and (b). 【Chemical Formula 7】 [In formula (5), Rf is the perfluoropolyether block represented by the above formula (2), and W3 is each independently the following formula (A') 【Chemical Formula 8】 (In formula (A'), R 1 is the same as R in the above formula (A). p1' is a number from 0 to 1,000.) 1 ​ is a divalent organopolysiloxane block represented by, W4 are each independently a monovalent organopolysiloxane block represented by the following formula (B') 【Chemical Formula 9】 (In formula (B'), R 1 and R 1 ' are respectively the same as R 1 and R 1 ' in the said formula (B). p2' is a number from 0 to 1,000) and, Q is the same as Q in the formula (1). Further, 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, and g' is a number from 0 to 50. ] **Claim 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). 【Chemical Formula 10】 (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 defined 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.) 【Chemical 11】 (In formula (7), R 1 , i, j, and k are the same as described above. p4 is a number from 0 to 6, and q4 is a number from 1 to 8. However, 3 ≤ p4 + q4 ≤ 14.)

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