JP2864191B2 - Sulfonic acid-modified silicone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sulfonic acid-modified silicone useful as a surfactant and a modifier for a coating film.

[0002]

2. Description of the Related Art Silicones obtained by replacing some methyl groups of dimethyl silicone with hydrophilic groups such as aminoalkyl groups, epoxy groups and polyether groups have conventionally been used as surfactants. For example, it is well known that polyether-modified silicone has excellent characteristics such as leveling effect, softening effect, wetting effect, emulsifying effect, and dispersing effect as a silicone surfactant as compared with an organic surfactant. ing.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sulfonic acid-modified silicone.

[0004]

That is, the present invention provides a sulfonic acid-modified silicone represented by the following formula:

[0005]

Embedded image [Where each R ¹ is independently an alkyl group having 1 to 3 carbon atoms or
Represents a phenyl group , n represents an integer of 10 to 3000, A represents a monovalent metal, a hydrogen atom or —H.X ¹ (where X ¹ represents ammonia or an amine), and R represents
Phenylene group, substituted by an alkyl group having 1 to 4 carbon atoms
Phenylene group, linear or branched alkylene having 1 to 5 carbon atoms
Group or a group represented by the following formula

Embedded image ( Where p is an integer of 1 to 5, q is 0 or 1)
R is 1 or 2 when q is 0, and when q is 1
3 ).

Here, the alkyl group having 1 to 3 carbon atoms means
It represents a methyl group, an ethyl group, or a propyl group . The value of n is 1
It is 0-3000, preferably 200-2000. The monovalent metal represented by A is preferably L
i, Na, and K. Further, X in the formula -H · ^{X 1}
If ¹ is an amine, which is represented by the general formula NR ³ _3, wherein, R ³ are each independently a hydrogen atom, preferably a linear or branched having 1-5 carbon atoms An alkyl group or a straight-chain or branched hydroxyalkyl group preferably having 1 to 5 carbon atoms and preferably having 3 or less hydroxyl groups. Examples of the amine include triethanolamine, 2-amino-2-
Methyl-1-propanol, 2-amino-2-methyl-
Examples thereof include 1,3-propanediol and monoethanolamine. R is preferably a phenylene group, having 1 carbon atom
A phenylene group substituted with an alkyl group having 1 to 4 carbon atoms,
5 to 5 alkylene groups and

[0007]

Embedded image It is. The number average molecular weight (Mn) of the sulfonic acid-modified silicone is preferably 1,000 to 200,000, particularly preferably 10,000 to 150,000.

[0008] The sulfonic acid-modified silicone of the present invention can be produced by synthesizing a silicone having a group capable of reacting with a sulfonating agent at one end, and then sulfonating the silicone.

The silicone having a group capable of reacting with a sulfonating agent at one terminal is represented by the following formula.

[0010]

Embedded image Here, R, R ¹ , and n are the same as described above, and X is a group that reacts with a sulfonating agent, for example, a halogen atom, a vinyl group,
Or a hydrogen atom bonded to an aromatic ring.

The above-mentioned silicone having a group capable of reacting with a sulfonating agent at one end includes a silicone having hydrogen bonded to Si at one end and a compound having a group capable of reacting with the sulfonating agent and a vinyl group (hydrosilyl). ) In the presence of a platinum-based catalyst.

The above-mentioned silicone having a hydrogen bonded to one terminal Si used as a raw material for the hydrosilylation reaction is represented by the following formula.

[0013]

Embedded image Here, R ¹ and n are the same as above.

The silicone having hydrogen bonded to Si at one terminal is produced by a known method. For example, the hydrogen-capped polymethylpolysiloxane as the silicone is produced by an equilibration reaction of octamethylcyclotetrasiloxane and pentamethyldisiloxane as an end cap. Preferably, the equilibration reaction is completed at a reaction temperature of 0 to 100 ° C. and a reaction time of 10 to 100 hours in an inert gas atmosphere such as nitrogen and in the presence of a hydrocarbon solvent such as hexane and benzene. The molar ratio of octamethylcyclotetrasiloxane and pentamethyldisiloxane used as raw materials is appropriately adjusted depending on the desired molecular weight of the target product.

On the other hand, a hydrosilylating agent having a group capable of reacting with a sulfonating agent and a vinyl group is represented by the following general formula.

[0016]

Embedded image (Where R is the same as above, R ² is an aryl group,
It is an alkaryl group or an aralkyl group. ), For example

[0017]

Embedded image (Here, p is an integer, and preferably 1 to 5.). The amount of the hydrosilylating agent to be used is preferably 1.0 to 5.0 in equivalent ratio to hydrogen bonded to Si in the chemical formula (3).

As the platinum-based catalyst, for example, an isopropyl alcohol (IPA) solution of chloroplatinic acid is used.
^-4 to 1 x ^10-5 equivalents are preferred. In the hydrosilylation reaction, an aliphatic hydrocarbon such as hexane or benzene or an aromatic hydrocarbon is preferably used as a solvent. As a preferred example of the hydrosilylation reaction, the reaction is completed in a reaction system placed under an atmosphere of an inert gas such as nitrogen at a reaction temperature of 0 to 100 ° C. and a reaction time of about 5 to 50 hours. .

Next, the silicone having a group capable of reacting with a sulfonating agent at one end produced by the hydrosilylation reaction is sulfonated to produce a sulfonic acid-modified silicone.

The sulfonating agent used here varies depending on the type of the hydrosilylating agent used in the hydrosilylation reaction, and a hydrosilylating agent having a halogen atom as a group which reacts with the sulfonating agent, for example, a chemical formula (4) or a chemical formula (4) When the compound of (5) is used, for example, Na
₂ SO ₃ and NaHSO ₃ are preferred. A hydrosilylating agent having a vinyl group as a group that reacts with the sulfonating agent,
For example, when a compound represented by the chemical formula (6) or the chemical formula (7) is used, for example, NaHSO ₃ or the like is preferable. When a hydrosilylating agent having a phenyl group as a group that reacts with the sulfonating agent, for example, a compound of the formula (8) or (9) is used, for example, H ₂ SO ₄ , HSO
₃ Cl and the like are preferred. The amount of the sulfonating agent to be used is preferably 1 to 5 in an equivalent ratio to the group X reacting with the sulfonating agent in the chemical formula (2).

In the sulfonation reaction, for example, 1,4-dioxane, dimethoxyethane, diethyl ether, tetrahydrofuran, a hydrocarbon solvent having 5 to 8 carbon atoms (such as hexane), or two or more of these solvents are used. You may mix and use. As an example of preferable reaction conditions, when the reaction system is placed under an atmosphere of an inert gas such as nitrogen and a hydrosilylating agent having a halogen atom as a group that reacts with the sulfonating agent is used, the reaction temperature is 50 ° C.
The reaction time is about 5 to 30 hours. When a hydrosilylating agent having a vinyl group or a hydrosilylating agent having a phenyl group is used, the reaction temperature is 0 to 100 ° C. and the reaction time is about 5 to 30 hours.

Alternatively, the sulfonic acid-modified silicone of the present invention can be produced by hydrosilylation of a silicone having hydrogen bonded to Si at one terminal of the chemical formula (3) in one step. Hydrosilylating agents for this are represented by the general formula:

[0023]

Embedded image (Where R is the same as above), for example

[0024]

Embedded image And the like. The amount of the compound used is preferably 1 to 5.0 in terms of an equivalent ratio to hydrogen bonded to Si at one end in the chemical formula (3). As the platinum-based catalyst, for example, a solution of chloroplatinic acid in isopropyl alcohol (IPA) or the like is used, and its addition amount is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ equivalents to the hydrosilylation agent. Also in the reaction, preferably, for example, 1,4-dioxane, dimethoxyethane, diethyl ether, tetrahydrofuran, an aliphatic hydrocarbon having 5 to 8 carbon atoms (such as hexane) or an aromatic hydrocarbon is used as a solvent, These two or more kinds may be used as a mixture. As an example of preferable reaction conditions, the reaction system is placed in an atmosphere of an inert gas such as nitrogen, the reaction temperature is 0 to 100 ° C., and the reaction time is 1 hour.
About 20 hours.

Methods for converting sulfonic acid groups into ammonium salts or amine salts are known. For example, the sulfonic acid-modified silicone in which A of the chemical formula (1) is a monovalent metal produced as described above is dissolved in hexane or heptane, and an aqueous solution of hydrochloric acid or sulfuric acid is added thereto. After acidic hydrolysis at ５０50 ° C., preferably for a reaction time of 5 minutes to 1 hour, the silicone phase is removed and the above amine is added thereto to form a sulfonic acid-modified silicone in the form of an amine salt.

The sulfonic acid-modified silicone produced in the present invention is useful as a surfactant and a modifier for a coating film.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0028]

【Example】

[0029]

Example 1 A 1-liter round bottom flask was charged with 250 parts by weight of octamethylcyclotetrasiloxane, 0.37 parts by weight of pentamethyldisiloxane, 5 parts by weight of concentrated sulfuric acid, and 300 parts by weight of toluene, and placed at room temperature under a nitrogen atmosphere. After stirring for 48 hours, the mixture was neutralized with sodium hydrogen carbonate, and low-boiling substances were removed by distillation to obtain 214 g of polymethylhydrogenpolysiloxane (yield: 86%).

Next, 180 parts by weight of this polymethylhydrogenpolysiloxane was dissolved in 360 parts by weight of hexane, and 1.2 parts by weight of p-chloromethylstyrene (bonded to Si at one end of the polymethylhydrogenpolysiloxane). The equivalent ratio is 4.4 with respect to the hydrogen prepared) and an IPA solution of chloroplatinic acid (2 × 10 ^-4 mol / cc) 0.001 m
l (equivalent ratio to p-chloromethylstyrene is 2.5
× 10 ⁻⁵ ) was added dropwise to the flask with stirring at 50 ° C. under a nitrogen atmosphere. After stirring for 24 hours,
After filtration, low-boiling substances were removed by distillation, and 134 g of a silicone having a chloromethylphenethyl group was obtained (yield: 7).
4%).

Further, 120 parts by weight of the obtained silicone having a chloromethylphenethyl group was dissolved in 120 parts by weight of hexane, and 1.4 parts by weight of sodium sulfite heptahydrate (equivalent ratio with respect to the chloromethylphenethyl group was 1.4% by weight). 4.6) in an autoclave under a nitrogen atmosphere.
The reaction was carried out with stirring at 0 ° C. for 24 hours. After cooling, the produced salt and unreacted sodium sulfite were separated by filtration, and the solvent was distilled off to obtain 100 g of milky oil. This oil was confirmed to be a sulfonic acid-modified silicone by an absorption attributed to a sulfonic acid group at 1180 cm ^-1 on an IR spectrum (shown in FIG. 1) (where R in chemical formula (1) was

[0032]

Embedded image A is Na, R ¹ is a methyl group, and n =
705).

[0033]

Example 2 Octamethylcyclotetrasiloxane 20
0 parts by weight, 2.98 parts by weight of pentamethyldisiloxane,
172 g of polymethyl hydrogen polysiloxane was prepared in the same manner as in Example 1 except that 4 parts by weight of concentrated sulfuric acid was used.
(86% yield).

Next, 160 parts by weight of this polymethylhydrogenpolysiloxane was dissolved in 140 parts by weight of hexane, and 5 parts by weight of p-chloromethylstyrene (hydrogen bonded to Si at one end in polymethylhydrogenpolysiloxane) The equivalent ratio is 2.0) and an IPA solution of chloroplatinic acid (2 × 10 ⁻⁴ mol / cc) 0.01 ml (p
-Equivalent ratio to chloromethylstyrene is 6.2 × 10
^-5 ) was added dropwise with stirring at room temperature under a nitrogen atmosphere. After stirring for 24 hours, the mixture was filtered, and then low-boiling substances were removed by distillation to obtain 127 g of a silicone having a chloromethylphenethyl group (yield 79%).

Further, 100 parts by weight of the obtained silicone having a chloromethylphenethyl group is dissolved in 80 parts by weight of hexane, and 5 parts by weight of sodium sulfite heptahydrate (equivalent ratio to the chloromethylphenethyl group is 2. 0)
Was charged in an autoclave under a nitrogen atmosphere, and reacted while stirring at 200 ° C. for 24 hours. After cooling, the generated salt and unreacted sodium sulfite were separated by filtration, and the solvent was distilled off to obtain 82 g of a milky oil. This oil was confirmed to be a sulfonic acid-modified silicone by absorption attributed to a sulfonic acid group at 1180 cm ^-1 on an IR spectrum (shown in FIG. 2) (R in the chemical formula (1) was represented by the chemical formula (10) Same, A was Na, R ¹ was a methyl group, n = 218).

[0036]

Example 3 Octamethylcyclotetrasiloxane 25
0 parts by weight, 0.59 parts by weight of pentamethyldisiloxane,
227 g of polymethylhydrogenpolysiloxane in the same manner as in Example 1 except that 4 parts by weight of concentrated sulfuric acid was used.
(91% yield).

Next, 160 parts by weight of this polymethylhydrogenpolysiloxane was dissolved in 200 parts by weight of hexane, and 1.5 parts by weight of p-diallylbenzene (bonded to one terminal Si in the polymethylhydrogenpolysiloxane). The equivalent ratio to hydrogen is 3.0) and 0.005 ml of an IPA solution of chloroplatinic acid (2 × 10 ⁻⁴ mol / cc)
(Equivalent ratio to p-diallylbenzene is 1.0 × 10
^-4 ) was added dropwise with stirring at room temperature under a nitrogen atmosphere at room temperature. After stirring for 12 hours, the mixture was filtered and then low-boiling substances were removed by distillation to obtain 139 g (yield: 87%) of a silicone having a 3- (p-allylphenyl) propyl group.

Further, 120 parts by weight of the obtained silicone having a 3- (p-allylphenyl) propyl group was dissolved in 120 parts by weight of hexane, and 1 part by weight of sodium hydrogen sulfate (3- (p-allylphenyl) propyl group) was dissolved. The reaction was carried out under a nitrogen atmosphere while stirring at 50 ° C. for 24 hours. Unreacted sodium hydrogen sulfate was separated by filtration, and the solvent was distilled off to obtain 96 g of milky white oil. This oil was confirmed to be a sulfonic acid-modified silicone by absorption attributable to a sulfonic acid group at 1180 cm ^-1 on an IR spectrum (shown in FIG. 3) (where R in chemical formula (1) was

[0039]

Embedded image A is Na, R ¹ is a methyl group, and n =
389).

[0040]

Example 4 Octamethylcyclotetrasiloxane 20
0 parts by weight, 1.18 parts by weight of pentamethyldisiloxane,
162 g of polymethyl hydrogen polysiloxane in the same manner as in Example 1 except that 5 parts by weight of concentrated sulfuric acid was used.
(81% yield).

Next, 100 parts by weight of a 1: 1 mixed solution of toluene and tetrahydrofuran and 3.3 parts by weight of sodium p-styrenesulfonate (based on hydrogen bonded to Si at one end in polymethyl hydrogen polysiloxane) The equivalent ratio is 2.6) and 0.005 ml of an IPA solution of chloroplatinic acid (2 × 10 ⁻⁴ mol / cc) (the equivalent ratio is 6.3 × 10 ^{4 with} respect to sodium p-styrenesulfonate).
^-5 ) was added dropwise to a mixture of 150 parts by weight of the obtained polymethylhydrogenpolysiloxane and 100 parts by weight of hexane at 50 ° C. with stirring in a nitrogen atmosphere. After stirring for 10 hours, the mixture was filtered and then low-boiling substances were removed by distillation to obtain 108 g of milky oil. This oil was confirmed to be a sulfonic acid-modified silicone by an absorption attributed to a sulfonic acid group at 1180 cm ^-1 on an IR spectrum (shown in FIG. 4) (R in chemical formula (1) is p-phenylene. , A was Na, R ¹ was a methyl group, and n = 533).

[0042]

Example 5 50 g of the sulfonic acid-modified silicone prepared in Example 1 was dissolved in 50 ml of hexane, and 1N HCl was added.
The reaction was carried out at room temperature for 20 minutes while stirring with 50 ml of the aqueous solution. After the reaction, the silicone phase was taken out, 1 g of triethanolamine was added, and the mixture was reacted with stirring for 30 minutes.
The unreacted portion was distilled off to obtain 48 g of milky white oil. This oil had a 3350 in the IR spectrum (shown in FIG. 5).
Since an absorption band attributable to a hydroxyethyl group is shown around cm ⁻¹ , it was confirmed that the product was a sulfonic acid-modified silicone in the form of a salt with triethanolamine sulfonic acid.

[0043]

As described above, according to the present invention, a novel sulfonic acid-modified silicone useful as a surfactant and a modifier for a coating film is provided.

[Brief description of the drawings]

FIG. 1 is a chart of an IR spectrum of a sulfonic acid-modified silicone obtained in Example 1 after washing with water.

FIG. 2 is a chart of an IR spectrum of a sulfonic acid-modified silicone obtained in Example 2 after washing with water.

FIG. 3 is a chart of an IR spectrum of the sulfonic acid-modified silicone obtained in Example 3 after washing with water.

FIG. 4 is a chart of an IR spectrum of the sulfonic acid-modified silicone obtained in Example 4 after washing with water.

FIG. 5 is a chart of an IR spectrum of a sulfonic acid-modified silicone obtained in Example 5 after washing with water.

Claims (1)

(57) [Claims] 1. A sulfonic acid-modified silicone represented by the following formula: [Where each R ¹ is independently an alkyl group having 1 to 3 carbon atoms or
Represents a phenyl group , n represents an integer of 10 to 3000, A represents a monovalent metal, a hydrogen atom or —H.X ¹ (where X ¹ represents ammonia or an amine), and R represents
Phenylene group, substituted by an alkyl group having 1 to 4 carbon atoms
Phenylene group, linear or branched alkylene having 1 to 5 carbon atoms
Or a group represented by the following formula : ( Where p is an integer of 1 to 5, q is 0 or 1)
R is 1 or 2 when q is 0, and when q is 1
3 ).