JP2017160340A - N, n-dichloro amino modified silicone and method for producing the same, and method for producing cyano modified silicone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide N, N-dichloro amino modified silicone, a method for producing the same and a method for producing cyano modified silicone using the silicone.SOLUTION: The present invention provides N, N-dichloro amino modified silicone represented by the following formula [1]; and a method for producing cyano modified silicone that includes making the modified silicone react with a cyclic amine with a conjugated acid having the pKa value of 6 or more, or react with a metal carboxylate in the presence of a phase transfer catalyst.SELECTED DRAWING: None

Description

  The present invention relates to N, N-dichloroamino-modified silicone, a method for producing the same, and a method for producing cyano-modified silicone.

  The cyano-modified silicone is useful in applications such as a softening agent, a release agent, a polishing agent, and a lubricant. As a method for producing a cyano-modified silicone, a method of converting a functional group from an easily available amino-modified silicone can be considered, but there is no example synthesized by this method.

  In general, as a method for converting an amino group into a cyano group, oxidation with a metal oxidant such as cobalt peroxide, nickel peroxide, osmium tetroxide, copper compound in the presence of oxygen, ruthenium compound, and the like is known. A method of synthesizing a cyano group by reacting a base with a base after chlorinating an amino group with a chlorinating agent is also known (Non-patent Documents 1 and 2).

Synlett, 2004, 12, 2180 Bull. Chem. Soc. Jpn. , 1985, 58, 1171

  However, when a reaction with a metal oxidizing agent was attempted using amino-modified silicone as a substrate, the reaction did not occur or the substrate was decomposed. In addition, there is no example in which a method of synthesizing a cyano group by activating a base after chlorinating an amino group with a chlorinating agent is applied to silicone.

  According to Non-Patent Document 1, a method using triethylamine as a base for cyanation is proposed. However, when applied to silicone, there is a problem that the viscosity is remarkably increased. Further, according to Non-Patent Document 2, a method using an excessive amount of pyridine has been proposed. However, when applied to silicone, there is a problem that the viscosity is remarkably increased. Further, when an excessive amount of base is used, the cost increases, which is not preferable.

  Accordingly, a main object of the present invention is to provide an N, N-dichloroamino-modified silicone, a method for producing the same, and a method for producing a cyano-modified silicone using the silicone.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by producing a cyano-modified silicone through a novel compound, N, N-dichloroamino-modified silicone, and have completed the present invention. .

  That is, the present invention relates to an N, N-dichloroamino-modified silicone represented by the following formula [1], a method for producing the same, a method for producing cyano-modified silicone using the same, and the like.

(In the formula [1], R ^{1 to} R ⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydroxyl group. A ¹ , A ² and A ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or the following formula [2]

[Chemical 2]
_-X-NCl 2 [2]

(In Formula [2], X is any one of a C1-C20 alkylene group, a C6-C20 aryl residue, and a C1-C20 alkoxy residue.)
The N, N-dichloroamino modified group represented by these. However, at least one of A ¹ , A ² and A ³ is an N, N-dichloroamino-modified group represented by the formula [2]. m is 10 to 10,000, and n is 0 to 100. When n = 0, at least one of A ¹ and A ² is an N, N-dichloroamino-modified group represented by the formula [2]. )

  According to the present invention, an N, N-dichloroamino-modified silicone useful as a raw material for synthesizing a cyano-modified silicone can be easily produced from an easily available amino-modified silicone. Furthermore, by using N, N-dichloroamino-modified silicone, cyano-modified silicone can be produced by a simple method without any problem of molecular weight change.

1 is a diagram showing a ¹ H NMR spectrum of N, N-dichloroamino-modified silicone obtained in Example 1. FIG. ¹ is a diagram showing a ¹ H NMR spectrum of a cyano-modified silicone obtained in Example 12. FIG. 2 is a diagram showing a ¹ H NMR spectrum of a cyano-modified silicone obtained in Comparative Example 1. FIG. 6 is a diagram showing a ¹ H NMR spectrum of a cyano-modified silicone obtained in Comparative Example 2. FIG.

(1) N, N-dichloroamino-modified silicone The N, N-dichloroamino-modified silicone of the present invention is a compound represented by the formula [1].

Here, R ^{1 to} R ⁷ are each independently any one of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydroxyl group.

A ¹ , A ² and A ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or a formula [2] The N, N-dichloroamino modified group represented by these.

[Chemical formula 4]
_-X-NCl 2 [2]

In the formula [2], X is any one of an alkylene group having 1 to 20 carbon atoms, an aryl residue having 6 to 20 carbon atoms, and an alkoxy residue having 1 to 20 carbon atoms. However, at least one of A ¹ , A ² and A ³ is an N, N-dichloroamino-modified group represented by the formula [2]. Further, at least one N, N-dichloroamino-modified group represented by the formula [2] is contained in the same molecule (that is, when n = 0, at least one of A ¹ and A ² is represented by the formula N, N-dichloroamino modified group represented by [2].)

  m is 10 to 10000, preferably 30 to 2000. When m is 10 or more, smoothness and thermal stability are good, and when it is 10,000 or less, the viscosity does not become too high and handling properties at the time of production and the like are good. n is 0 to 100, preferably 10 to 50. When n is 100 or less, the viscosity does not become too high, and the handling properties during production and the like are good.

  Specific examples of the N, N-dichloroamino-modified silicone of the present invention represented by the formula [1] include “side-chain modification” in which an N, N-dichloroamino-modified group is bonded to a side chain in polysiloxane. “Both-end modification and single-end modification” in which N, N-dichloroamino-modified group is bonded to the terminal in polysiloxane, N, N-dichloroamino-modified group is bonded to both side chain and terminal in polysiloxane. In addition, “both end side chain modification” and the like can be mentioned.

(2) Production of N, N-dichloroamino-modified silicone In the present invention, N, N-dichloroamino-modified silicone can be obtained by reacting an amino-modified silicone with a chlorinating agent.

(2-1) Amino-modified silicone The amino-modified silicone is represented by the formula [3].

R ^{1 to} R ⁷ are as described above. B ¹ , B ² and B ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or a formula [4]. It is an amino modification group represented by these.

[Chemical formula 6]
—Y—NH ₂ [4]

In Formula [4], Y is any one of a C1-C20 alkylene group, a C6-C20 aryl residue, and a C1-C20 alkoxy residue. However, at least one of B ¹ , B ² and B ³ is an amino-modified group represented by the formula [4]. In the same molecule, at least one amino-modified group represented by the formula [4] is included (that is, when n = 0, at least one of B ¹ and B ² is represented by the formula [4]. Amino-modified group.).

(2-2) Chlorinating agents As chlorinating agents, chlorine gas, sodium hypochlorite, calcium hypochlorite, hypochlorite such as t-butyl hypochlorite, trichloroisocyanuric acid (TCCA) N-chlorinated compounds such as N-chlorosuccinimide (NCS) and N-chlorohydantoin can be used. Of these, trichloroisocyanuric acid (TCCA), which is easy to handle and obtain, is preferred.

  The amount of the chlorinating agent used is preferably 2 to 100 mol of chlorine source per mol of amino group in the amino-modified silicone for N, N-dichloroation. More preferably, it is 2.1-50 mol, Most preferably, it is 2.2-30 mol. By using 2 mol or more, reaction can be advanced efficiently. By using 100 mol or less, it is possible to suppress a load on a side reaction or a treatment process after the reaction.

(2-3) Reaction The reaction temperature in the chlorination reaction may be a temperature used for normal chlorination, but is preferably −78 ° C. to 80 ° C., more preferably −40 ° C. to 50 ° C., particularly Preferably it is -20 degreeC-40 degreeC. By making the temperature higher than −78 ° C., the reaction can proceed efficiently. By making it 80 degrees C or less, a side reaction can be suppressed.

  The reaction time can be appropriately selected depending on the reaction temperature, the type and amount of chlorinating agent, the reaction solvent, and the like. For example, it can be about 0.5 to 20 hours.

  The reaction solvent can be appropriately selected according to the type of chlorinating agent. When trichloroisocyanuric acid (TCCA) is used as the chlorinating agent, a solvent in which amino-modified silicone is dissolved and TCCA is partially dissolved may be used. For example, aromatic solvents such as toluene, xylene and anisole, diethyl Examples include ether solvents such as ether, diisopropyl ether, methyl t-butyl ether, tetrahydrofuran, n-dibutyl ether, cyclopentyl methyl ether, propylene glycol dimethyl ether and dioxane, and halogen solvents such as chloroform and dichloromethane. These solvents may be used alone or in combination of two or more. The usage-amount of a solvent can be suitably selected according to reaction conditions. The reaction can also be performed without using a solvent.

The fact that N, N-dichloroamino-modified silicone has been obtained can be confirmed by a known method such as ¹ H NMR.

  The obtained N, N-dichloroamino-modified silicone can be used for the next reaction as it is, or can be used for the next reaction after a purification step or the like.

  As for the purification method after completion of the chlorination reaction, a known purification method such as alkaline water washing, acid water washing, water washing, filtration, etc. is appropriately used in consideration of the physical properties of the product, the kind and amount of the chlorinating agent, the presence or absence of a solvent, etc. These techniques can be combined as needed.

(3) Production of cyano-modified silicone In the present invention, N, N-dichloroamino-modified silicone is reacted with a cyclic amine having a pKa of a conjugate acid of 6 or more, or in the presence of a phase transfer catalyst, a metal carboxylate is used. By reacting, the following formula [5]

The cyano modified silicone represented by these can be manufactured.

R ^{1 to} R ⁷ are as described above. E ¹ , E ² and E ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or a formula [6].

[Chemical Formula 8]
-Z-CN [6]

It is a cyano modified group represented by these.

In Formula [6], Z is any one of an alkylene group having 1 to 20 carbon atoms, an aryl residue having 6 to 20 carbon atoms, and an alkoxy residue having 1 to 20 carbon atoms. However, at least one of E ¹ , E ² and E ³ is a cyano-modified group represented by the formula [6]. In the same molecule, at least one cyano-modified group represented by the formula [6] is included (that is, when n = 0, at least one of E ¹ and E ² is represented by the formula [6]. Cyano modified group.).

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁷ , A ^{1 to} A ³ , B ^{1 to} B ³ and E ^{1 to} E ³ include a methyl group, an ethyl group, a propyl group, and butyl. Group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, tetradecyl group, octadecyl group, etc., or some or all of the hydrogen atoms bonded to these carbon atoms are substituted with halogen atoms, hydroxyl groups, etc. And monovalent organic groups.

  Examples of the aryl group having 6 to 20 carbon atoms include a monovalent organic group in which a phenyl group, a tolyl group, a naphthyl group, or the like or a part or all of hydrogen atoms bonded to these carbon atoms is substituted with a halogen atom, a hydroxyl group, or the like. Groups and the like. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenyloxy group, etc., or a part or all of hydrogen atoms bonded to these carbon atoms as a halogen atom, a hydroxyl group, or the like. Examples thereof include a substituted monovalent organic group.

R ^{1 to} R ⁷ , A ^{1 to} A ³ , B ^{1 to} B ^3, and E ^{1 to} E ³ may all be the same or different. X, Y, and Z are any one of an alkylene group having 1 to 20 carbon atoms, an aryl residue having 6 to 20 carbon atoms, and an alkoxy residue having 1 to 20 carbon atoms.

  In the present specification, the “residue” refers to a group having a structure in which one hydrogen atom is removed from a predetermined group.

  Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, a decylene group, a tetradecylene group, an octadecylene group, and the like, or a hydrogen atom bonded to these carbon atoms. And divalent organic groups in which a part or all of these are substituted with halogen atoms, hydroxyl groups, and the like.

  As the aryl residue having 6 to 20 carbon atoms, for example, a phenyl residue, a tolyl residue, a naphthyl residue or the like, or part or all of the hydrogen atoms bonded to these carbon atoms are substituted with a halogen atom, a hydroxyl group, or the like. And divalent organic groups.

  Examples of the alkoxy residue having 1 to 20 carbon atoms include a methoxy residue, an ethoxy residue, a propoxy residue, a butoxy residue, a phenyloxy residue, etc., or a part or all of hydrogen atoms bonded to these carbon atoms. And divalent organic groups substituted by halogen atoms, hydroxyl groups, and the like.

  m is 10 to 10000, preferably 30 to 2000. When m is 10 or more, smoothness and thermal stability are good, and when it is 10,000 or less, the viscosity does not become too high and handling properties at the time of production and the like are good. n is 0-100, Preferably it is 0-50. When n is 100 or less, the viscosity does not become too high, and the handling properties during production and the like are good.

(3-1) Catalyst In the present invention, the catalyst used for producing cyano-modified silicone from N, N-dichloroamino-modified silicone is preferably a phase transfer catalyst. As the phase transfer catalyst, a known catalyst can be used, and examples thereof include quaternary ammonium salts, quaternary phosphonium salts, crown ethers, cryptands, chain polyethers and the like. These catalysts may be used individually by 1 type, or may use 2 or more types together.

  The amount of the phase transfer catalyst used is preferably 0.0001 to 100 mol, more preferably 0.001 to 10 mol, per mol of N, N-dichloroamino group in the N, N-dichloroamino-modified silicone. A high reaction rate can be obtained by setting the amount of the phase transfer catalyst used to 0.0001 mol or more. By making the usage-amount of a phase transfer catalyst 100 mol or less, cost and the load to the process process after reaction can be suppressed.

(3-2) Metal carboxylate As the metal carboxylate, for example, acetate, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, acetic acid Examples thereof include copper, manganese acetate, cobalt acetate, and nickel acetate.

  Further, for example, potassium salts include potassium formate, potassium propionate, potassium butyrate, potassium valerate, potassium caproate, potassium caprylate, potassium methacrylate and the like, alkali metal salts of aliphatic carboxylic acids such as potassium benzoate, etc. Examples include alkali metal salts of aromatic carboxylic acids.

  The metal carboxylate may be an anhydride or a hydrate. These metal carboxylates may be used alone or in combination of two or more. Of these, sodium acetate, potassium acetate, magnesium acetate, and calcium acetate are preferred because they are inexpensive and easy to use industrially.

  The amount of the metal carboxylate used is preferably 2 to 15 mol, more preferably 2.5 to 10 mol, per mol of N, N-dichloroamino group in the N, N-dichloroamino-modified silicone. By setting the amount of metal carboxylate used to 2 mol or more, a sufficient reaction rate can be obtained. By making the usage-amount of metal carboxylate 15 mol or less, the load to the side reaction or the process process after reaction can be suppressed.

(3-3) Cyclic amine having a pKa value of 6 or more In the present invention, a cyano-modified silicone can also be obtained by reacting an N, N-dichloroamino-modified silicone with a cyclic amine having a pKa value of a conjugate acid of 6 or more. Can be manufactured.

  Examples of the cyclic amine having a pKa value of 6 or more include morpholines such as morpholine (8.4) and N-methylmorpholine (7.4), imidazoles such as imidazole (7.0), 1,4-diazabicyclo [ 2.2.2] Bicyclic amines such as octane (DABCO) (8.8), quinuclidine (11.0), aromatic amines such as 4-dimethylaminopyridine (DMAP) (9.2), Rings such as 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (12.5), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) (12.7) And formula amidines. The numerical value in () represents the pKa value.

  These may be used alone or in combination of two or more. Among these, from the viewpoint of reaction rate, it is preferable to use a cyclic amine having a pKa value of 8.5 or more. Examples of such a compound include 1,4-diazabicyclo [2.2.2] octane (DABCO), Quinuclidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) are preferred. .

  The amount of cyclic amine having a pKa value of 6 or more is preferably 2 to 15 mol, more preferably 2.5 to 10 mol, per mol of N, N-dichloroamino group in the N, N-dichloroamino-modified silicone. . A sufficient reaction rate can be obtained by setting the usage amount of the cyclic amine having a pKa value of 6 or more to 2 mol or more. By making the usage-amount of the cyclic amine whose pKa value is 6 or more into 15 mol or less, the load to the side reaction or the processing process after reaction can be suppressed.

(3-4) Reaction The reaction temperature in the cyanation reaction can be appropriately selected according to the type of base, the amount used, and the reaction solvent. The reaction temperature is preferably −40 ° C. to 180 ° C., more preferably −20 ° C. to 150 ° C., and particularly preferably 0 ° C. to 120 ° C. By setting the temperature to −40 ° C. or higher, the reaction can be efficiently performed. A side reaction can be suppressed by setting it as 180 degrees C or less.

  The reaction time can be appropriately selected according to the reaction temperature, the type and amount of base used, and the reaction solvent. For example, it can be about 0.5 to 20 hours.

  The reaction solvent may be any solvent in which N, N-dichloroamino-modified silicone is dissolved and does not contain active hydrogen. For example, aromatic solvents such as toluene, xylene and anisole, diethyl ether, diisopropyl ether, methyl t-butyl ether, tetrahydrofuran, n-dibutyl ether, cyclopentyl methyl ether, propylene glycol dimethyl ether, dioxane and other ether solvents, chloroform, dichloromethane And halogen-based solvents such as These solvents can be used alone or in a combination of two or more. The usage-amount of a solvent can be suitably selected according to reaction conditions etc. Further, the reaction can be carried out without using a solvent.

The formation of cyano-modified silicone can be confirmed by a known method such as ¹ H NMR, for example.

  The obtained cyano-modified silicone can be purified as necessary. Regarding the purification method after completion of the cyanation reaction, a known purification method such as alkaline water washing, acid water washing, water washing, filtration, etc. should be used in consideration of the physical properties of the product, the type and amount of base, the presence or absence of a solvent, etc. These methods can be appropriately combined as necessary.

  The cyano-modified silicone can be used as a softening agent, a release agent, a polishing agent, a lubricant, and the like. The application is not limited to this.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples.

Reaction tracking was performed by ¹ H NMR (270 MHz, CDCl ₃ ). The viscosity was measured at 25 ° C. using an E-type viscometer (VISCONEC EMD manufactured by Tokimec).

[Example 1]
In a glass flask equipped with a stirrer, thermometer, and Jimroth condenser, amino-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-8585, amino equivalent: 6000 g / mol, viscosity: 150 mPa · s, R ^{1 to} R ⁷ in formula [3] are methyl groups, B ¹ and B ² are methyl groups, B ³ is an amino-modified group, m is 120 on average, n is 1.5 on average, and Y in formula [4] is propylene Base group) 6.00 g, trichloroisocyanuric acid (TCCA) 0.209 g (0.900 mmol, 0.9 equivalent to amino group), toluene 10.0 mL (0.1 M relative to amino group), Stir at 25 ° C. for 1 hour.

After completion of the reaction, filtration was performed, and then the filtrate was concentrated under reduced pressure to obtain 6.00 g (viscosity: 149 mPa · s) of N, N-dichloroamino-modified silicone. The reaction was traced by ¹ H NMR (270 MHz, CDCl ₃ ), and it was confirmed that N, N-dichloroamino-modified silicone was produced. The reaction yield was 100%. ^{The 1} H NMR spectrum is shown in FIG. Moreover, when it decomposed | disassembled by the alkali melting method and the content chlorine was quantified by the ion chromatography, it was 10900 microgram / g.

[Examples 2 to 9]
The experiment was conducted in the same manner as in Example 1 except that the solvent, reaction time, and TCCA amount used in Example 1 were changed to those shown in Table 1. The results are also shown in Table 1.
(In Table 1, MTBE: methyl t-butyl ether, THF: tetrahydrofuran, nBu ₂ O: n-dibutyl ether, IPE: diisopropyl ether, CPME: cyclopentyl methyl ether).

  [Example 10] A glass flask equipped with a stirrer, a thermometer, and a Dimroth condenser tube was charged with 3.00 g of the same amino-modified silicone as in Example 1 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-8585). , N-chlorosuccinimide (NCS) 0.180 g (1.40 mmol, 2.7 equivalents relative to the amino group) and dichloromethane 5.0 mL (0.1 M relative to the amino group) were charged and stirred at 25 ° C. for 8 hours. did. The reaction yield was 100%.

[Example 11]
To a glass flask equipped with a stirrer, a thermometer, and a Dimroth condenser, 3.00 g of the same amino-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-8585) as in Example 1 7 mL and 5.0 mL of cyclopentyl methyl ether (CPME) (0.1 M with respect to the amino group) were charged and ice-cooled. Subsequently, 1.7 mL of 5% sodium hypochlorite aqueous solution (NaOCl 1.25 mmol, 2.5 equivalents relative to the amino group) was added dropwise, and the mixture was stirred for 3 hours under ice cooling. The reaction yield was 100%.

[Example 12]
To a glass flask equipped with a stirrer, a thermometer, and a Dimroth condenser, 3.00 g of N, N-dichloroamino-modified silicone obtained in Example 1, 0.245 g (2.50 mmol, N, N— 5 equivalents to the dichloroamino group), 0.083 g (0.25 mmol, 0.5 equivalents to the N, N-dichloroamino group) tetrabutylammonium bromide, 5.0 mL toluene (N, N-dichloroamino group) 0.1M) and stirred at 90 ° C. for 2 hours.

  After completion of the reaction, the reaction mixture was cooled to room temperature, 10% by mass aqueous potassium carbonate was added, and the mixture was stirred for 1 hour. After separating the aqueous layer, the obtained organic layer was washed with saturated brine, and subsequently magnesium sulfate was added and dried.

After filtration, the filtrate was concentrated under reduced pressure to obtain 2.45 g (viscosity: 150 mPa · s) of cyano-modified silicone. The reaction was traced by ¹ H NMR (270 MHz, CDCl ₃ ) to confirm that cyano-modified silicone was produced. The reaction yield was 100%. ^{The 1} H NMR spectrum is shown in FIG.

[Examples 13 to 20, Comparative Examples 1 to 4]
The experiment was conducted in the same manner as in Example 12 except that the bases, amounts, phase transfer catalysts and solvents used in Example 12 were those described in Table 2. The results are also shown in Table 2.
(In Table 2, nBu ₄ NBr: tetrabutylammonium bromide, 18-crown-6: 1, _4, 7, 10, 13, 16-hexaoxacyclooctadecane, PEG 300: polyethylene glycol 300, MTBE: methyl t-butyl ether, nBu ₂ O: n-dibutyl ether, CPME: cyclopentyl methyl ether)

In Comparative Examples 1 and 2, when alkoxide was used as the base, only a cyano-modified silicone having a low viscosity was obtained. ^{From the 1} H NMR spectrum, insertion of a methoxy group or t-butoxy group, that is, decomposition of the siloxane bond was confirmed, and it was revealed that the molecular weight was reduced by decomposition of the main chain. The ¹ H NMR spectrum of the cyano-modified silicone obtained in Comparative Example 1 is shown in FIG. 3, and the ¹ H NMR spectrum of the cyano-modified silicone obtained in Comparative Example 2 is shown in FIG.

  In Comparative Examples 3 and 4, even when hydroxide was used as the base, the viscosity of the obtained cyano-modified silicone was very low, and the molecular weight was reduced due to decomposition of the main chain.

[Example 21]
In a glass flask equipped with a stirrer, a thermometer, and a Dimroth condenser, 3.00 g of N, N-dichloroamino-modified silicone obtained in Example 1, 1,8-diazabicyclo [5.4.0] undecene- 7 (DBU) 0.381 g (2.50 mmol, 5 equivalents relative to the N, N-dichloroamino group) and MTBE 5.0 mL were charged and stirred at 25 ° C. for 1 hour.

After completion of the reaction, a 5 mass% oxalic acid aqueous solution was added and stirred for 1 hour. After separating the aqueous layer, the obtained organic layer was washed with saturated brine, and subsequently magnesium sulfate was added and dried. After filtration, the filtrate was concentrated under reduced pressure to obtain 2.17 g (viscosity: 124 mPa · s) of cyano-modified silicone. The reaction was traced by ¹ H NMR (270 MHz, CDCl ₃ ) to confirm that cyano-modified silicone was produced. The reaction yield was 100%.

[Examples 22 to 23, Comparative Examples 5 to 7]
The same procedure as in Example 21 was performed except that the base and solvent used in Example 21 were those shown in Table 3. The results are also shown in Table 3. (In Table 3: DBU: 1,8-diazabicyclo [5.4.0] undecene-7, DABCO: 1,4-diazabicyclo [2.2.2] octane, DMAP: 4-dimethylaminopyridine, Et ₃ N : Triethylamine, MTBE: methyl t-butyl ether, THF: tetrahydrofuran)

  In Comparative Examples 5 to 7, it was suggested that high-viscosity cyano-modified silicone was obtained and the molecular weight was increased (the cyano-modified silicone was polymerized).

[Examples 24-28]
The experiment was performed in the same manner as in Example 1 except that the amino-modified silicone used in Example 1 was the same as that described in Table 4. Subsequently, the obtained N, N-dichloroamino-modified silicone was reacted in the same manner as in Example 12 to obtain a cyano-modified silicone. The results are also shown in Table 4.

[Example 29]
In a glass flask equipped with a stirrer, a thermometer and a Dimroth condenser, an amino-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-864, amino equivalent: 3800 g / mol, viscosity: 1850 mPa · s, formula [ 3] R ^{1 to} R ⁷ are methyl groups, B ¹ and B ² are methyl groups, B ³ is an amino-modified group, m is 430 on average, n is 8.7 on average, and Y in formula [4] is a propylene group Things) 2000 g, trichloroisocyanuric acid (TCCA) 110 g (0.474 mol, 0.9 equivalent to amino group), MTBE 5260 mL (0.1 M to amino group) were charged and stirred at 25 ° C. for 3 hours. Subsequently, 354 g (3.158 mol, 6 equivalents relative to the N, N-dichloroamino group) of 1,4-diazabicyclo [2.2.2] octane (DABCO) was added, and the mixture was stirred at 50 ° C. for 19.5 hours.
Filtration was performed after completion of the reaction, and the filtrate was washed with a 10% by mass ammonium chloride aqueous solution and then with saturated saline, and dried by adding magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure to obtain 1617 g (viscosity: 2270 mPa · s) of cyano-modified silicone. The results are also shown in Table 4.

1 methoxy group 2 t-butoxy group

Claims (4)

N, N-dichloroamino-modified silicone represented by the following formula [1].
(In the formula [1], R ^{1 to} R ⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydroxyl group. A ¹ , A ² and A ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or the following formula [2]
[Chemical 2]
_-X-NCl 2 [2]
(In Formula [2], X is any one of a C1-C20 alkylene group, a C6-C20 aryl residue, and a C1-C20 alkoxy residue.)
The N, N-dichloroamino modified group represented by these. However, at least one of A ¹ , A ² and A ³ is an N, N-dichloroamino-modified group represented by the formula [2]. m is 10 to 10,000, and n is 0 to 100. When n = 0, at least one of A ¹ and A ² is an N, N-dichloroamino-modified group represented by the formula [2]. ) Following formula [3]
(In Formula [3], R ^{1 to} R ⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydroxyl group. B ¹ , B ² and B ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or the following formula [4]
[Chemical formula 4]
—Y—NH ₂ [4]
(In Formula [4], Y is any one of a C1-C20 alkylene group, a C6-C20 aryl residue, and a C1-C20 alkoxy residue.)
It is an amino modification group represented by these. However, at least one of B ¹ , B ² and B ³ is an amino-modified group represented by the formula [4]. m is 10 to 10,000, and n is 0 to 100. When n = 0, at least one of B ¹ and B ² is an amino-modified group represented by the formula [4]. Amino-modified silicone represented by
Including a step of reacting with a chlorinating agent,
Following formula [1]
(In the formula [1], R ^{1 to} R ⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydroxyl group. A ¹ , A ² and A ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or the following formula [2]
[Chemical formula 6]
_-X-NCl 2 [2]
(In Formula [2], X is any one of a C1-C20 alkylene group, a C6-C20 aryl residue, and a C1-C20 alkoxy residue.)
The N, N-dichloroamino modified group represented by these. However, at least one of A ¹ , A ² and A ³ is an N, N-dichloroamino-modified group represented by the formula [2]. m is 10 to 10,000, and n is 0 to 100. When n = 0, at least one of A ¹ and A ² is an N, N-dichloroamino-modified group represented by the formula [2]. )
A method for producing an N, N-dichloroamino-modified silicone represented by the formula: Following formula [1]

(In the formula [1], R ^{1 to} R ⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydroxyl group. A ¹ , A ² and A ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or the following formula [2]
[Chemical Formula 8]
_-X-NCl 2 [2]
(In Formula [2], X is any one of a C1-C20 alkylene group, a C6-C20 aryl residue, and a C1-C20 alkoxy residue.)
The N, N-dichloroamino modified group represented by these. However, at least one of A ¹ , A ² and A ³ is an N, N-dichloroamino-modified group represented by the formula [2]. m is 10 to 10,000, and n is 0 to 100. When n = 0, at least one of A ^{1 and} A ² is an N, N-dichloroamino-modified group represented by the formula [2]. )
N, N-dichloroamino-modified silicone represented by
A step of reacting a cyclic acid having a pKa value of the conjugate acid of 6 or more, or a step of reacting with a metal carboxylate in the presence of a phase transfer catalyst.
Following formula [5]
(In Formula [5], R ^{1 to} R ⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydroxyl group. E ¹ , E ² and E ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a hydrogen atom, or the following formula [6]
[Chemical Formula 10]
-Z-CN [6]
(In Formula [6], Z is any one of a C1-C20 alkylene group, a C6-C20 aryl residue, and a C1-C20 alkoxy residue.)
It is a cyano modified group represented by these. However, at least one of E ¹ , E ² and E ³ is a cyano-modified group represented by the formula [6]. m is 10 to 10,000, and n is 0 to 100. When n = 0, at least one of E ¹ and E ² is a cyano modified group represented by the formula [6]. )
A method for producing a cyano-modified silicone represented by the formula:   A method for producing a cyano-modified silicone according to claim 3, wherein an N, N-dichloroamino-modified silicone is produced by the method according to claim 2, and the N, N-dichloroamino-modified silicone is used.