JPH11152291A - Fluorine-containing siloxane compound, and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject new compound having good water repellency and useful as a fluorine-containing chemical modification agent and the like by allowing a specific hydrosilyl group-containing siloxane compound to react with an unsaturated group-having isocyanate compound in the presence of a platinum-based catalyst. SOLUTION: A new fluorine-containing siloxane compound of formula I A is a fluorine-containing organic group of formula II [R<1> and R<2> are each F or trifluoromethyl; R<3> is H or a 1-8C hydrocarbon; (k) is 0-16; (m) is 0-30; (n) is 0 or 1; (p) is 0-9; (q) is 0-1,000; Me is methyl]; R<4> is a 1-6C monovalent hydrocarbon; B is an isocyanate group of formula III ; (r) is 1-3}. The compound of the formula I is useful as a fluorine-containing chemical modifying agent having excellent water repellency and the like and having excellent chemical stability after modification, and so on. The compound of the formula I is obtained by allowing a hydroxyl group-containing siloxane compound of formula IV to react with an unsaturated grouphaving isocyanate compound of formula V in the presence of a platinum-based catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing organosilicon compound and a method for producing the same. The present invention relates to a disiloxane having an isocyanate group and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a fluorine-containing organic group is introduced into various organic compounds by using a reactive fluorine-containing organic compound having a fluorine-containing organic group, and the water repellency, oil repellency, Improvements in releasability, chemical resistance and the like have been made. The fluorine-containing organic compound used for these purposes has a highly reactive functional group so that a fluorine-containing organic group can be surely introduced into the organic compound. For this reason,
These fluorinated organic compounds have a problem of poor heat resistance and hydrolyzability.

In order to solve the above problems, attempts have been made to interpose a silicone compound between a fluorine-containing organic group and a reactive functional group.

For example, (a) JP-A-3-251589 discloses a compound in which a fluorinated organic group and an alkyl group are siloxane-bonded, and (b) JP-A-7-793 discloses a compound having a siloxane bond. A compound having a fluorine-containing organic group and an oxyalkylene group through (c) JP-A-8-1
No. 57483 discloses a chlorosilane or alkoxysilane compound similarly having a fluorine-containing organic group.

However, the compounds disclosed in the above (a) and (b) are additives or surfactants used in addition to organic substances such as polymers, and include organic substances such as polymers to be added and surfactants to be added. The compound in which a fluorine group and an alkyl group are siloxane-bonded is not chemically bonded. Therefore, depending on the use, the added compound may bleed out from an organic substance such as a polymer with the passage of time, which may cause a problem such that the effect of the addition is not maintained.

Further, the compound disclosed in (c) has a highly reactive alkoxysilane or chlorosilane as a functional group, so that the surface of a powder or metal which easily reacts with these functional groups is chemically modified. It is effective in the case. However, when an organic compound such as an organic resin is chemically modified, a carbon-oxygen-silicon bond formed by reacting an alkoxysilyl group or a chlorosilyl group of the fluorine-containing siloxane compound with the organic resin is easily hydrolyzed. Therefore, there is a problem that an organic compound such as an organic resin chemically modified by using these compounds is hydrolyzed at the binding portion during use to release a fluorine-containing siloxane compound, and the modification effect is not maintained. .

[0007]

As described above, in order to introduce a fluorine-containing organic compound into an organic compound, in particular, in order to maintain the effect semipermanently, the organic compound and the fluorine-containing organic compound are strongly combined. It is desired to modify by a chemical bond.

[0008]

Means for Solving the Problems As a result of various studies to solve the above problems, the present inventors have found that a disiloxane compound having a fluorinated organic group and an isocyanate group can be used to convert a fluorinated organic compound into an organic compound. The present invention has been found to be an extremely excellent compound as a chemical modifying agent to be introduced, and in particular, because the organic compound and the fluorine-containing organic compound form a strong chemical bond, the modifying effect can be maintained semipermanently, and the present invention is completed. It has been reached.

Accordingly, it is an object of the present invention to provide a disiloxane compound having a fluorine-containing organic group and an isocyanate group, which can modify an organic compound by a strong chemical bond, and a method for producing the same. It is in.

[0010] In order to solve the above problems, the present invention provides:
[1] The following formula (1),

[0011]

Embedded image (Where A is the following equation (2),

[0012]

Embedded image Wherein R ¹ and R ² are each a fluorine or trifluoromethyl group, and R ³ is hydrogen or a group having 1 to 1 carbon atom.
8, a linear or branched hydrocarbon group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Me is a methyl group, k is 0 to 0.
An integer of 16, m is an integer of 0 to 30, n is 0 or 1, p
Is an integer of 0 to 9, and q is an integer of 0 to 1000. B is the following formula (3),

[0013]

Embedded image And r is an integer of 1 to 3. The present invention proposes a fluorine-containing siloxane compound represented by the following formula:

Further, the present invention provides [2] the following formula (4):

[0015]

Embedded image (Where A is the following equation (2),

[0016]

Embedded image Wherein R ¹ and R ² are each a fluorine or trifluoromethyl group, and R ³ is hydrogen or a group having 1 to 1 carbon atom.
8, a linear or branched hydrocarbon group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Me is a methyl group, k is 0 to 0.
An integer of 16, m is an integer of 0 to 30, n is 0 or 1, p
Is an integer of 0 to 9, q is an integer of 0 to 1000, r is 1 to 3
Is an integer. And a siloxane compound having a hydrosilyl group represented by the following formula (5):

[0017]

Embedded image Characterized by reacting an isocyanate compound having an unsaturated group represented by the following formula in the presence of a platinum-based catalyst:

[0018]

Embedded image (Where B is the following equation (3),

[0019]

Embedded image And r is an integer of 1 to 3. A method for producing a fluorine-containing siloxane compound represented by the following formula:

Hereinafter, the present invention will be described in detail.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the fluorine-containing siloxane compound of the present invention has the following formula (1)

[0022] It is represented by

The fluorine-containing siloxane compound represented by the above formula (1) comprises a hydrosilyl group-containing siloxane compound represented by the following formula (4):

[0024]

Embedded image Isocyanate having an unsaturated group represented by the following formula (5):
The compound can be produced by reacting the compound with a platinum-based catalyst.

[0025]

Embedded image Where A is the following equation (2):

[0026]

Embedded image Wherein R ¹ and R ² are each a fluorine or trifluoromethyl group, and R ³ is hydrogen or a group having 1 to 1 carbon atom.
8, a linear or branched hydrocarbon group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Me is a methyl group, k is 0 to 0.
An integer of 16, m is an integer of 0 to 30, n is 0 or 1, p
Is an integer of 0 to 9, q is an integer of 0 to 1000, r is 1 to 3
Is an integer.

B is the following formula (3):

[0028]

Embedded image And r is an integer of 1 to 3.

The reaction between the hydrosilyl group-containing siloxane compound (4) and the isocyanate compound having an unsaturated group (5) is a hydrosilylation reaction.

In this reaction, the mixing ratio of the hydrosilyl group-containing siloxane compound (4) and the isocyanate compound having an unsaturated group (5) is 1: 1 to 1 in molar ratio.
The ratio is preferably set to 1: 2.

In the above reaction, a solvent may or may not be used. When a solvent is used, there is no particular limitation as long as the catalyst does not inhibit the catalytic action of the platinum-based catalyst or has no reactivity to the Si—H bond. Toluene, aromatic hydrocarbons such as xylene, pentane, hexane, saturated aliphatic hydrocarbons such as heptane, tetrahydrofuran,
Ethers such as diethyl ether and the like can be exemplified as commonly used solvents.

The platinum-based catalyst used in the above reaction includes:
A platinum-based catalyst used in a usual hydrosilylation reaction can be used. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, a platinum complex of divinyltetramethyldisiloxane, a platinum complex of cyclovinylmethylsiloxane,
Platinum carbonyl complexes, platinum pyridine complexes and the like are preferred,
Particularly, a platinum complex of divinyltetramethyldisiloxane and a platinum complex of cyclovinylmethylsiloxane are preferable.

The reaction temperature is preferably from room temperature to about 150 ° C. Depending on the boiling point of the raw materials, if the reaction is performed at a high temperature, the raw materials may volatilize, and if the temperature is too low, the reaction may take time to complete. For this reason, 40 ° C to 100 ° C
C is particularly preferred.

The reaction time varies depending on the reaction temperature and the like.
Generally, 3 to 24 hours are preferred.

The hydrosilyl group-containing siloxane compound (4) used in the above reaction can be obtained by reacting a fluorine-containing silane represented by the following formula (6) with chlorosilane (7).

[0036]

Embedded image

[0037]

Embedded image Note that R ¹ , R ² , R ³ , R ⁴ , Me, p, q, k, m,
n and r represent the same meaning as described above.

[0038] As the chlorosilane (7), trichlorosilane specifically, methyldichlorosilane, dimethylchlorosilane, as another R ^4, a methyl group, an ethyl group,
A chlorosilane represented by a linear or branched alkyl group such as a propyl group, a butyl group, and a hexyl group, a cyclohexyl group, a phenyl group, a phenethyl group, and the like can also be used.

Further, as a method for producing the hydrosilyl group-containing siloxane compound (4), a cyclic monomer represented by the following formula (8) is prepared by using a fluorine-containing lithium silanolate represented by the following formula (9) as a starting material. It can also be obtained by performing polymerization and terminating the polymerization with chlorosilane (7).

[0040]

Embedded image

[0041]

Embedded image Here, R ¹ , R ² , R ³ , R ⁴ , Me, p, k, m, and n have the same meaning as described above.

A different method for producing the hydrosilyl group-containing siloxane compound (4) besides the above-mentioned production method is disclosed in, for example, Japanese Patent Publication No. 6-792. Naturally, the hydrosilyl group-containing siloxane compound used in the present invention is used. The production method of the compound is not particularly limited to the above production method.

Specific examples of the hydrosilyl group-containing siloxane compound (4) used in the present invention are as follows, but the present invention is not limited thereto.

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

EXAMPLE 1 (Production of fluorine-containing disiloxane) In a 500 ml three-necked flask, 39.7 g (0.39 mol) of triethylamine, 47.2 g (2.62 mol) of pure water and 77.4 g of tetrahydrofuran were added. The mixture was charged and stirred with a stirrer while cooling to 5 ° C. with ice water. 50.0 g of 3,3,3-trifluoropropyldimethylchlorosilane (0.26
Mol) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further stirred for 1 hour while maintaining the reaction temperature at 10 ° C or lower. After acetic acid was added to make the solution acidic, 500 ml of hexane was added to the reaction solution for extraction. After the extract was washed with water, the extract was dried using anhydrous magnesium sulfate.

To the dried extract, 39.7 g (0.39 mol) of triethylamine was added, and the mixture was cooled to 5 ° C. with ice water. 23. Dimethylchlorosilane under a nitrogen atmosphere
6 g (0.26 mol) was added dropwise over 2 hours, and the mixture was further stirred for 2 hours, and then neutralized with dilute hydrochloric acid.

The obtained reaction mixture was washed with water, dried over anhydrous magnesium sulfate, and represented by the following formula (10).
(3,3-trifluoropropyl) -1,1,3,3-tetramethyldisiloxane was obtained. As a result of quantification by an internal standard method using a gas chromatograph (GC), the yield was 99%.

[0050]

Embedded image (Production of disiloxane containing isocyanate group) In a 100 ml three-necked flask equipped with a cooling device and a stirring device, the above-prepared 1- (3,3,3-trifluoropropyl) -1,1,3,3- 1/5 parts by weight of tetramethyldisiloxane solution (disiloxane content: 12.0 g (0.0
51 mol)), 11.5 g (0.0571 mol) of 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex 3 42% by weight xylene solution
and heated to 50 ° C. After heating and stirring for 6 hours, low boiling components were distilled off at 150 ° C./3 mmHg.
7 g of the product were obtained. This infrared absorption spectrum, 1H-
When the NMR spectrum was measured, the following results were obtained. Infrared absorption spectrum: shown in FIG. 1H-NMR spectrum: shown in FIG.

From the above results, it was confirmed that the obtained substance was an isocyanate group-containing disiloxane represented by the following formula (11). 97% yield.

[0052]

Embedded image Example 2 (Production of fluorine-containing siloxane) In a 500 ml four-necked flask equipped with a stirrer and a dropping funnel, 21.1 g (0.209 mol) of triethylamine and 25.0 g of pure water were placed.
(1.39 mol), 100 g of tetrahydrofuran, and 75.0 g of (heptadecafluoro-1,1,2,2-tetrahydrodecyl) dimethylchlorosilane under ice water.
(0.139 mol) was added dropwise. After completion of the dropwise addition, the mixture was further stirred for 1.5 hours while maintaining the reaction temperature at 10 ° C or lower.
GC analysis confirmed that the chlorosilane was completely hydrolyzed. After adding an aqueous acetic acid solution to make the solution acidic, 180 g of hexane was added to the solution to extract the desired silanol. The extract is saturated aqueous sodium hydrogen carbonate,
Then, after washing with pure water, it was dried using anhydrous magnesium sulfate.

After distilling off the solvent using an evaporator,
Distillation was carried out under reduced pressure of 84.5-87.5 ° C./2 mmHg, and 44.3 g of heptadecafluoro-1,1,2,2 was obtained.
A pure solid of-(tetrahydrodecyl) dimethylsilanol was obtained. Yield 61%.

Under a nitrogen atmosphere, 42.0 g (0.0804 mol) of the above silanol dissolved in 100 g of tetrahydrofuran was charged into a 300 ml four-necked flask equipped with a stirrer. 52. Under ice cooling, paying attention to temperature rise.
2 ml of a butyl lithium hexane solution (1.54 mol /
l) was added dropwise. Thereafter, the mixture was stirred for 1 hour to induce lithium silanolate.

Hexamethylcyclotrisiloxane 450
g (2.25 mol) of a tetrahydrofuran solution 400 g was charged into a 2000 ml four-necked flask equipped with a stirrer. While maintaining the temperature at 20 ° C. on a water bath, the entire amount of the lithium silanolate solution was added under a nitrogen atmosphere to initiate living polymerization.

After 3 hours, 80% of the hexamethylcyclotrisiloxane has been consumed.
After adding 2 g of dimethylchlorosilane (0.161 mol) and 16.3 g (0.161 mol) of triethylamine, stirring was further continued overnight, and then the polymerization was stopped. Next, the obtained reaction mixture was washed sequentially with an aqueous acetic acid solution, a saturated aqueous sodium hydrogen carbonate solution and pure water, and then dried over anhydrous magnesium sulfate. Thereafter, low boiling components were distilled off at 130 ° C./2 mmHg to obtain 399 g of a fluorine-containing siloxane compound having a hydrosilyl group represented by the following formula (12).
Here, s is an integer and is estimated to be about 80 to 90.

[0057]

Embedded image (Production of isocyanate group-containing siloxane) cooling device,
In a 100 ml three-necked flask equipped with a stirrer,
30.0 g of the fluorine-containing siloxane compound having a hydrosilyl group produced by the above method and 3-isopropenyl-
1.33 g of α, α-dimethylbenzyl isocyanate
(0.0066 mol) and heated to 70 ° C.
Then, a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex 3% by weight xylene solution 42
Then, the mixture was heated and stirred at 70 ° C. for 6 hours. After confirming the disappearance of the Si-H group by measuring the infrared absorption spectrum of the reaction mixture, low boiling components were distilled off at 150 ° C./3 mmHg to obtain 31.0 g of a product. This infrared absorption spectrum was measured. FIG. 3 shows the infrared absorption spectrum.

From the above results, it was confirmed that the obtained substance was an isocyanate group-containing disiloxane represented by the following formula (13). Yield 100%.

[0059]

Embedded image

[0060]

The isocyanate-containing siloxane compound obtained as described above has a highly reactive isocyanate group and fluorine having excellent water and oil repellency, mold release properties and chemical resistance. It can be used to improve the properties of organic substances. Particularly, those which form a stable chemical bond with an organic substance having a functional group having high reactivity with isocyanate, for example, a hydroxyl group, an amino group, an amide group, a carboxyl group, etc., and the effect of which is semi-permanent. It is.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the compound obtained in Example 1.

FIG. 2 is a 1H-NMR spectrum of the compound obtained in Example 1.

FIG. 3 is an infrared absorption spectrum of an isocyanate group-containing siloxane compound obtained in Example 2.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code FI C07F 7/18 C07F 7/18 X C08G 77/24 C08G 77/24 // C07B 61/00 300 C07B 61/00 300

Claims (2)

[Claims] [Claim 1] The following formula (1): (Where A is the following formula (2): Wherein R ¹ and R ² are each a fluorine or trifluoromethyl group, and R ³ is hydrogen or a group having 1 to 1 carbon atom.
8, a linear or branched hydrocarbon group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, k is an integer of 0 to 16, m is an integer of 0 to 30, n is 0 or 1. , P is an integer from 0 to 9,
q is an integer of 0 to 1000. B is the following formula (3): And r is an integer of 1 to 3. A fluorine-containing siloxane compound represented by the formula: 2. The following formula (4): (Where A is the following formula (2): Wherein R ¹ and R ² are each a fluorine or trifluoromethyl group, and R ³ is hydrogen or a group having 1 to 1 carbon atom.
8, a linear or branched hydrocarbon group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, k is an integer of 0 to 16, m is an integer of 0 to 30, n is 0 or 1. , P is an integer from 0 to 9,
q is an integer of 0 to 1000, and r is an integer of 1 to 3. )
And a hydrosilyl group-containing siloxane compound represented by the following formula (5): Characterized by reacting an isocyanate compound having an unsaturated group represented by the following formula in the presence of a platinum-based catalyst: (Where B is the following formula (3): Is an isocyanate-containing group represented by A method for producing a fluorine-containing siloxane compound represented by the formula: