JPH0940680A - New silicone having leaving group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new specific fluorine-containing silicone having a leaving group, capable of forming a soft strong coating film composition together with another monomer, etc., useful for bridging, coating, etc., in a polymer and capable of chemically modifying a surface of a material. SOLUTION: A new fluorine-containing silicone expressed by the formula [Q is a (substituted) divalent hydrocarbon; R1 to R6 are each a hydrocarbon optionally having a fluorine atom or a leaving group; at least one of R1 to R3 and at least one of R4 to R6 are leaving groups, and further a molecule has at least one fluorine atom]. Together with another monomer, etc., the silicone can form a soft strong coating film composition and enables easy chemical modification, on and of the surface of various materials such as powder or fiber. Also, it can control the physical properties of the material and is useful for bridging, coating, etc., in a polymer. The compound is obtained by adding 1,8diiodo-3,3,4,4,5,5,6,6-octafluorooctane to tetramethoxysilane, magnesium and tetrahydrofuran under refluxing to react them.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel silicone suitable for polymer crosslinking and coating.

[0002]

2. Description of the Related Art Silicone is a useful raw material for cosmetics and surface coating materials. In particular, it features excellent luster and a low coefficient of friction. However, it is difficult to control physical properties such as solubility, water repellency, oil repellency, and flexibility. Therefore, partial chemical modification of various substituents such as a hydroxyl group, an alkyl group, a fluorinated alkyl group, a phenyl group, and a sulfonyl group was attempted to control the physical properties. There are many industrial problems because it is often necessary to use dangerous and troublesome reactions such as reactions and organometallic reactions.
In addition, the physical properties themselves are remarkably different depending on the number of substituents to be introduced, and therefore there are many control problems. That is, a means for controlling physical properties by simple modification has been required. Despite the fact that excellent repellency such as water repellency and oil repellency could be imparted by the fluorination treatment, the compatibility with other components was proportionally impaired,
The range of application is limited.

[0003]

The present invention has been made in view of such a situation, and an object thereof is to provide a simple chemical modification means effective for controlling the physical properties of silicones and the like. To do.

[0004]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in search of a simple chemical modification means effective for controlling the physical properties of silicones and the like, and as a result, the following general formula (I) was obtained. The inventors have found that the compound represented by the formula makes crosslinks with polymers such as silicone, and can control the balance between the water and oil repellency and the compatibility of these polymers, and completed the invention. Hereinafter, the present invention will be described in detail.

[0005]

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(1) Compound of the present invention The compound of the present invention has a structure represented by the above general formula (I). Here, Q represents a divalent hydrocarbon group, and examples of such a hydrocarbon group include a polymethylene group and a polyphenylene group. The number of carbon atoms, substituent atoms and substituents of these hydrocarbon groups differ depending on how the physical properties are controlled, but the number of carbon atoms is preferably 1 to 20 from the viewpoint of synthetic control, In order to add water repellency and oil repellency, fluorine is preferable, and to add hydrophilicity, group VIA atoms such as oxygen atom and sulfur atom and nitrogen atom can be preferably exemplified.
As the substituent, for example, a fluorinated alkyl group or a fluorinated phenyl group is preferable in order to add water repellency and oil repellency, and in order to add partial hydrophilicity or compatibility with other components, Preferred examples include an amide group, an amino group, a hydroxyl group and a carbonyl group.

Further, in this compound, the silicon atom bonded to Q has at least one leaving group. The leaving group is a group for condensing with a part of the polymer, and for example, a halogen atom other than fluorine such as chlorine, iodine and bromine, and an alkoxy group having 1 to 4 carbon atoms can be preferably exemplified. Among these, the most preferable one is an alkoxy group having 1 to 4 carbon atoms, and among them, a methoxy group is preferable. At least one leaving group is necessary for one silicon bonded to Q, and all leaving groups other than Q may be such leaving groups.

Substituents other than Q and the leaving group of silicon bonded to Q are hydrocarbon groups which may have a fluorine atom. Examples of such a hydrocarbon group include a fluorinated aliphatic hydrocarbon group, an aliphatic hydrocarbon group, a fluorinated aromatic hydrocarbon group, and an aromatic hydrocarbon group. Of these, a methyl group, a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group and the like are preferable. The compound of the present invention is characterized by having at least one fluorine atom in one molecule. this is,
This is because the present invention aims to increase the affinity with other components without impairing the water and oil repellency of fluorine.

(2) Method for producing the compound of the present invention The method for producing the compound of the present invention can be constructed by combining ordinary reactions. For example, a method of reacting a hydrocarbonodiene represented by the general formula (III) with an alkoxythioalkylsilane, a general formula (I
V), a method of generating a Grignard reagent from a dihalogenohydrocarbon and condensing it with an alkoxysilane, a method of condensing a hydrocarbonodiisocyanate represented by the general formula (V) with a hydroxyalkylalkoxysilane, a general formula ( Examples thereof include a method of condensing a dihalogenohydrocarbon represented by VI) and a thioalkylalkoxysilane in the presence of an alkali catalyst, and a method of using a compound in which the alkoxy group of the compound in the above reaction is replaced with a halogen atom, instead of the alkoxysilane. it can. These reactions may be performed under generally known reaction conditions.

[0010]

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[0011]

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[0012]

[Chemical 6]

[0013]

[Chemical 7]

(3) Fields of application of the compound of the present invention Since the compound of the present invention has a leaving group, it reacts with a part of the surface of powder, metal, wood, fiber or polymer compound to give a surface. It is suitable for modifying its surface because it forms a film bonded to the. Further, since it condenses with a polymer such as a hydroxyl group or a carbonyl group of polyvinyl alcohol, cellulose, polyacrylic acid, etc., it is useful as a surface treatment of these or as a grafting agent for these polymers. Further, since there are at least two leaving groups, the physical properties of the resulting polymer can be changed by adding the compound of the present invention together with the monomer when the polymer is prepared by polymerization. When the compound of the present invention is used for the purpose of controlling the physical properties as described above, one kind selected from the compounds of the present invention may be used alone, or two or more kinds may be used in combination. Thus, when the compound of the present invention is used for surface treatment or modification of a polymer or the like, these compositions have the general formula (I
It has a partial structure represented by I), which contributes to reforming.

[0015]

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[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, focusing on the modes for carrying out the invention, but the present invention is not limited to these Examples. Needless to say.

Example 1 Production Example 150 g of tetramethoxysilane, 7 g of magnesium and 300 ml of tetrahydrofuran (THF) were weighed in a flask and heated under reflux. 1,8-diiodo-3,3,4,5,5,5 dissolved in 100 ml of THF
50 g of 6,6-octafluorooctane was slowly added dropwise, and the mixture was heated under reflux for 24 hours. The reaction solution was filtered to remove insolubles and then concentrated to obtain 37 g of 1,8-bis (trimethoxysilyl) -3,3,4,4,5,5,6,6-octafluorooctane (Compound 1). Obtained. IR of this thing
The spectrum and the NMR spectrum supported this structure.

[0018]

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Example 2 Production Example 40 g of phenyltrimethoxysilane, 7 magnesium
g, 1,8-diiodo-3,3,4,4,5,5,6
50 g of 6-octafluorooctane was treated as in Example 1 to give 1,8-bis (dimethoxyphenylsilyl).
32 g of -3,3,4,4,5,5,6,6-octafluorooctane (Compound 2) was obtained. Spectral data supported this structure.

[0020]

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Example 3 Production Example 1360 g of methyltrimethoxysilane and 7 of magnesium
g, 1,8-diiodo-3,3,4,4,5,5,6
50 g of 6-octafluorooctane was treated as in Example 1 to give 1,8-bis (dimethoxymethylsilyl)-
35 g of 3,3,4,4,5,5,6,6-octafluorooctane (Compound 3) was obtained. Spectral data supported this structure.

[0022]

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Example 4 Production Example 120 g of dimethoxydimethylsilane and 7 of magnesium
g, 1,8-diiodo-3,3,4,4,5,5,6
50 g of 6-octafluorooctane was treated as in Example 1 to give 1,8-bis (dimethylmethoxysilyl)-
29 g of 3,3,4,4,5,5,6,6-octafluorooctane (Compound 4) was obtained. Spectral data supported this structure.

[0024]

[Chemical 12]

Example 5 Production Example 176 g of diethoxydiethylsilane, 7 magnesium
g, 1,8-diiodo-3,3,4,4,5,5,6
50 g of 6-octafluorooctane was treated as in Example 1 to give 1,8-bis (diethylethoxysilyl)-
24 g of 3,3,4,4,5,5,6,6-octafluorooctane (Compound 5) was obtained. Spectral data supported this structure.

[0026]

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Example 6 Production Example 8 g of the compound 1 of Example 1, 1 g of magnesium and 3 g of 3-iodo-1,1,1-trifluoropropane were condensed by the Grignard reaction as in Example 1 and purified by a silica gel column. 2 g of 1,8-bis (dimethoxy (3,
3,3-trifluoropropyl) silyl) -3,3
4,4,5,5,6,6-octafluorooctane (Compound 6) was obtained. Spectral data supported this structural formula.

[0028]

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Example 7 Preparation Example 8 g of the compound 2 of Example 2, 1 g of magnesium and 6 g of 1-iodo-3,3,3-trifluoropropane are treated as in Example 6 and treated with 3 g of 1,8-bis. (Methoxyphenyl (3,3,3-trifluoropropyl) silyl)-
3,3,4,4,5,5,6,6-octafluorooctane (Compound 7) was obtained. Spectral data supported this structural formula.

[0030]

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Example 8 Production Example 40 g of 3-mercaptopropyltrimethoxysilane was dissolved in 500 ml of absolute ethanol, 14 g of sodium ethoxide was added, and the mixture was stirred at room temperature for 10 minutes. This one
36 g of 1,4-dibromooctafluorobutane dissolved in 00 ml was added dropwise, and the mixture was heated under reflux for 24 hours. After cooling the reaction solution, the precipitate was removed by filtration, concentrated, and subjected to silica gel column chromatography (eluting solvent; benzene:
Methanol = 100: 0 → 50:50) and purified to 38
g of 1,4-bis (3- (trimethylsilyl) propylthio) perfluorobutane (Compound 8) was obtained. Spectral data supported this structure.

[0032]

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Example 9 Production Example 40 g of 3-mercaptopropyltrimethoxysilane was dissolved in 500 ml of absolute ethanol, 14 g of sodium ethoxide was added, and the mixture was stirred at room temperature for 10 minutes. This one
56 g of 1,8-dibromoperfluorooctane dissolved in 00 ml was added dropwise, and the mixture was heated under reflux for 24 hours. After cooling the reaction solution, the precipitate was removed by filtration, concentrated, and subjected to silica gel column chromatography (eluting solvent; benzene:
Methanol = 100: 0 → 50:50) and purified to 46
g of 1,8-bis (3- (trimethoxysilyl) propiothio) perfluorooctane (Compound 9) was obtained. Spectral data supported this structure.

[0034]

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Example 10 Preparation Example 30 g of 3-aminopropyltriethoxysilane was added to 30 g.
It was dissolved in 0 ml of triethylamine and 300 ml of THF, and 100 ml of a 10% solution of tetrafluorosuccinyl chloride in THF was added dropwise under ice cooling, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. The deposited precipitate was removed by filtration, concentrated, and subjected to silica gel column chromatography (elution solvent; benzene: methanol = 100: 0 → 5).
0:50) to obtain 11 g of tetrafluorosuccinyl bis (3- (trimethoxysilyl) propyl) amide (Compound 10). Spectral data supported this structure.

[0036]

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Example 11 Production Example 5 g of allylamine was dissolved in 200 ml of triethylamine and 200 ml of THF, and 100 ml of a 10% solution of tetrafluorosuccinyl chloride in THF was cooled with ice.
Was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. The deposited precipitate was removed by filtration and concentrated, and this was dissolved in 100 ml of benzene. To this, about 100 mg of 2,2'-azobis (isobutyronitrile) was added, and further 20 g of 3-mercaptopropyltrimethoxysilane was dissolved in 200 ml of benzene and added dropwise. This was heated under reflux for 12 hours, concentrated, and subjected to silica gel column chromatography (elution solvent; benzene: methanol =
1: 0 → 50: 50) to obtain 7 g of tetrafluorosuccinyl bis (3- (3- (trimethoxysilyl) propylthio) propyl) amide (Compound 11). Spectral data supported this structure.

[0038]

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Example 12 Production Example To 35 g of 1- (trimethoxysilyl) -3- (2- (trimethoxysilyl) ethylthio) propane was added 150 ml of diethyl ether, and 27 g of ethylmagnesium bromide was added to 100 ml of diethyl ether under ice cooling. The solution dissolved in was added dropwise. Raise the temperature to room temperature,
The mixture was stirred at room temperature for 24 hours. The precipitate was removed by filtration, concentrated, and subjected to silica gel column chromatography (eluting solvent;
Benzene: methanol = 100: 0 → 50: 50) and purified by 1- (dimethoxyethylsilyl) -3- (2-
(Dimethoxyethylsilyl) ethylthio) propane 21
g was obtained. To this product, 150 ml of diethyl ether was added and dissolved, and 28 g of 3-iodo-1,1,1-trifluoropropane, 3 g of magnesium and 200 ml of diethyl ether were added dropwise under ice cooling and the mixture was heated under reflux for 10 hours. After cooling the reaction solution, the precipitate was removed by filtration,
Concentrate and silica gel column chromatography (eluting solvent; benzene: methanol = 100: 0 → 50: 50)
Purified by 1- (ethyldimethoxysilyl) -3- (2
19- (ethylmethoxy-3,3,3-trifluoropropylsilyl) ethylthio) propane (Compound 12)
g was obtained. Spectral data supported this structure.

[0040]

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Example 13 Production Example 1- (trimethoxysilyl) -3-as in Example 12.
From (2- (trimethoxysilyl) ethylthio) propane 3.5 g and phenylmagnesium bromide 4 g,
1- (dimethoxyphenylsilyl) -3- (2- (dimethoxyphenylsilyl) ethylthio) propane was added to which 2.2 g of 3-iodo-1,1,1-trifluoropropane and 0.3 g of magnesium were added. 2 g of 1- (2- (methoxyphenyl-3,3,3-trifluoropropylsilyl) was reacted with the Grignard reagent derived from
Ethylthio) -3- (methoxyphenyl-3,3,3-
Trifluoropropylsilyl) propane (Compound 13)
I got Spectral data supported this structure.

[0042]

[Chemical 21]

Example 14 Production Example 0.8 g of magnesium, 14 g of methyltrimethoxysilane, about 100 mg of iodine and 100 ml of THF were weighed and heated to reflux, and 2.4 g of 1,4-dibromobenzene was added to 100 ml of the mixture. A solution of the above in THF was added dropwise, and the mixture was heated under reflux for 24 hours. After completion of the reaction, the precipitate was removed by filtration, concentrated, and subjected to silica gel column chromatography (elution solvent; benzene: methanol = 100: 0 → 5).
0:50) to give 1,4-bis (dimethoxymethylsilyl) benzene, which was treated with a Grignard reagent derived from perfluorobutyl iodide as in Examples 12 and 13 to give 1.6 g of 1 , 4-bis (methoxymethylperfluorobutylsilyl) benzene (Compound 14) was obtained. Spectral data supported this structure.

[0044]

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Example 15 Production Example 0.8 g of magnesium, 15 g of tetramethoxysilane, about 100 mg of iodine and 100 ml of THF were weighed, heated and refluxed, and 1,4-dibromo-2 dissolved in 100 ml of THF was added thereto. -Trifluoromethylbenzene 3
g was added dropwise, and heating under reflux was continued for another 24 hours. After the reaction was completed, the precipitate was removed by filtration, concentrated, and subjected to silica gel column chromatography (elution solvent; benzene: methanol =
1: 0 → 50:50) to obtain 1,4-bis (trimethoxysilyl) -2-trifluoromethylbenzene (Compound 15) (2 g). Spectral data supported this structure.

[0046]

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Example 16 Production Example 1,6-dihydroxy-2,2,3,3,4,4,5
26 g of 5-octafluorohexane, 50 g of 3- (triethoxysilyl) propylisocyanate and 50 of THF
0 ml was weighed and heated under reflux for 24 hours to add a hydroxyl group to the carbonyl of isocyanate. The reaction solution was cooled and then concentrated, and silica gel column chromatography (eluting solvent; benzene: methanol = 100: 0 → 50: 50).
Purified with 12 g of 1,6-bis (3- (triethoxysilyl) propylaminocarboxy) -2,2,3,
3,4,4,5,5-octafluorohexane (Compound 16) was obtained. Spectral data supported this structure.

[0048]

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Example 17 Preparation Example 45 g of 1,9-dihydroxy-1 were prepared as in Example 16.
H, 1H, 9H, 9H-perfluorodecane and 3- (triethoxysilyl) propylisocyanate 50 to 23 g of 1,9-bis (3- (triethoxysilyl) propylaminocarboxy) -1H, 1H ,, 9H, 9H
-Perfluorodecane (Compound 17) was obtained. Spectral data supported this structure.

[0050]

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Example 18 Test Example A glass surface was treated with the silicone of the present invention of Examples 1 to 17 above. That is, it is dissolved in THF to a concentration of 10%, sprayed on the glass surface,
It was treated overnight at 0 ° C. As a control, a normal fluoroalkylalkoxy silicone was used. The degree of repellency when olive oil was poured into this treated glass (oil repellency test) and the degree of repellency when water was poured (water repellency test) were evaluated according to the criteria of +: good, ±: neither, or −: bad. . The results are shown in Table 1. From this, it is understood that the treatment with the compound of the present invention is excellent in water repellency and oil repellency.

[0052]

[Table 1]

Example 19 Test Example Cotton was treated using the silicones of the present invention of Examples 1 to 17 above. That is, cotton was sprayed with a 10% THF solution of the silicone of the present invention and treated at 60 ° C. in a vacuum for 3 days. As a control, a fluoroalkylalkoxy silicone was similarly used and treated. The treated cotton cloth was subjected to dry cleaning and normal washing with a laundry detergent 5 times each, and then the water repellency when water was applied and the oil repellency when olive oil was applied were examined. The judgment criteria were the same as in Example 18. Table 2 shows the results. From this, it is understood that the treatment of the silicone of the present invention is stronger than that of the conventional fluoroalkylalkoxy silicone. In addition, Table 2 also shows a sensory test (hand feel) of the cotton cloth immediately after the treatment, but it can be seen that the treatment with the treatment agent of the present invention can change the physical properties of the treated object in various ways. That is, the physical properties of the object to be treated can be controlled by the types of treating agents and their combinations.

[0054]

[Table 2]

Example 20 Test Example Powders were treated using the silicones of the present invention of Examples 1 to 17 above. That is, talc contains 20% of talc weight.
The silicone was dissolved in 10 times the amount of THF for coating, the solvent was removed under reduced pressure, and the surface was baked at 200 ° C. for 10 hours. A normal fluoroalkylalkoxy silicone was used as a control. The treated powder thus obtained was packed in a mold and pressed, and water and olive oil were poured onto the surface of the press, and the water repellency and oil repellency were examined by checking the contact angle. The results are shown in Table 3. From this, it is understood that the treated powder of the present invention has an excellent surface treatment action. In addition, the sensory test results of this treated powder are also shown in Table 3. From this, it is understood that the surface properties of the powder can be variously changed by the silicone of the present invention, and the physical properties of the powder can be controlled.

[0056]

[Table 3]

Example 21 Test Example The silicone of Example 1 above was made into a 10% THF solution,
The polyurethane resin plate was sprayed and treated in vacuum at 60 ° C. for 3 days. The water repellency and oil repellency of this treated plate were improved.

Example 22 Test Example The silicone of Example 10 was made into a 10% THF solution,
It was sprayed on a lauan plate and treated in vacuum at 60 ° C. for 3 days. The treated lauan plate had improved luster, water repellency and oil repellency.

[0059]

According to the silicone of the present invention, the chemical modification of the surface of various materials such as powder and fiber can be easily carried out and the physical properties thereof can be controlled.

Claims (9)

[Claims] 1. A fluorine-containing silicone represented by the general formula (I). Embedded image 2. The silicone according to claim 1, wherein the leaving group is an alkyloxy group having 1 to 4 carbon atoms. 3. A composition comprising one or more silicones according to claim 1 or 2. 4. The composition according to claim 3, which is used as a coating. 5. The composition according to claim 3, which is used for crosslinking a polymer. 6. A method for crosslinking a polymer, which comprises reacting the polymer with one or more kinds of the silicone according to claim 1 or 2 by removing a leaving group. 7. A composition having a structure of general formula (II) in a partial structure. Embedded image 8. The composition according to claim 7, which is obtained by reacting the compound represented by formula (I) with a material to be coated. 9. The composition according to claim 7, which is obtained by reacting a compound represented by the general formula (I) with a polymer.