JPH09241331A - Fluorosilicone oligomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fluorosilicone oligomer having high water repellency and hydrophilicity by introducing a fluoroalkyl group and a hydrophilic morpholino group into vinylsiloxane. SOLUTION: This oligomer is represented by formula I [wherein RF is (CF2 )n F or CF(CF3 )O(CF2 CF(CF3 )O)n C3 F7 (wherein (n) is an integer of 1-15; and (m) is an integer of 0-6); R1 is a lower alkyl or a lower alkoxyl; R2 is a lower alkyl; and (x) and (y) are natural numbers]. This is produced by reacting a fluoroalkanoyl peroxide represented by formula II (wherein RF is as defined in formula I) with an alkoxyvinylsilane and acryloylmorpholine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorosilicone oligomer, a method for producing the same, and a silane coupling agent comprising the fluorosilicone oligomer.

[0002]

2. Description of the Related Art It is known that a compound having a fluoroalkyl group in an organic compound has water / oil repellency and various physiological activities. In particular, fluoroalkyl group-containing silicone oligomers that have fluoroalkyl groups introduced into polysiloxanes have excellent water and oil repellency, antifouling properties, surface tension lowering properties, heat resistance, cold resistance, oil resistance, chemical resistance, and electrical resistance. Since it has a wide range of properties such as insulating properties and releasability, various compounds have been proposed (see, for example, JP-A-2-219).
829, or JP-A-2-219830), and industrially, it is very useful as a release agent, a water / oil repellency / stain resistance imparting agent for glass products, and an adhesion improving agent for resists for semiconductor devices. Further, a silicone oligomer in which a fluoroalkyl group is introduced into a methacrylic group-containing organosilicon compound is proposed in JP-A-4-342704. However, a fluorosilicone oligomer containing a morpholino group as shown in the present invention and its novel properties and usefulness are not known.

[0003]

All of the conventional fluoroalkyl group-containing silicone oligomers have a certain degree of water and oil repellency, but have a high oil repellency and at the same time, have a hydrophilic property under hydrophilic conditions. Alkyl group-containing silicone oligomers have been industrially sought. Fluoroalkyl group-containing silicone oligomers that have both oil repellency and hydrophilicity are used as fiber treatment agents that impart a soil release function that makes it easier to remove stains on textile products, as well as stain resistance and water droplet formation prevention on the glass surface. It has very high industrial utility such as a glass surface modifier that imparts a function.

For this purpose, an amphiphilic fluoroalkyl group-containing silicone oligomer having a fluoroalkyl group as a hydrophobic terminal and a polyoxyethylene unit as a hydrophilic portion has been studied as a silane coupling agent. Even if the ethylene unit is lengthened, high hydrophilicity is not obtained.

An object of the present invention is to provide a silicone oligomer having both high oil repellency and hydrophilicity, that is, a novel fluoroalkyl silicone oligomer having a fluoroalkyl group and a hydrophilic morpholino group introduced into vinyl siloxane, and a method for producing the same. is there. Furthermore, it is to provide a silane coupling agent comprising the fluorosilicone oligomer.

[0006]

According to the present invention, a fluorosilicone oligomer represented by the following general formula (A) is provided as a means for solving the above problems.

Embedded image In the formula, R _F is-(CF ₂ ) _n F (n = 1 to 15 is an integer)
Or _{-CF (CF 3) O (CF} 2 CF (CF 3) O) m
C ₃ F ₇ (m = 0 to 6 is an integer), R ₁ is a lower alkyl group or a lower alkoxy group, R ₂ is a lower alkyl group, and x and y are natural numbers.

Further, according to the present invention, as a means for solving the above-mentioned problems, a fluoroalkanoyl peroxide represented by the following general formula (B) is reacted with alkoxyvinylsilanes and acroylmorpholine. A method for producing a fluorosilicone oligomer represented by formula (A) is provided. In Formula B, R _F is-(CF ₂ ) _n F
(N = 1 to 15) or _{-CF (CF 3) O (CF} 2 C
Represented by _{F (CF 3) O) m} C 3 F 7 (m = 0~6).

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[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The fluorosilicone oligomer of the present invention is a fluorosilicone oligomer represented by the general formula (A),
R _F in the formula A is — (CF ₂ ) _n F (n = 1 to 15 is an integer) or —CF (CF ₃ ) O (CF ₂ CF (CF ₃ ).
O) _m C ₃ F ₇ (m = 0 to 6 is an integer), x, y
Indicates a natural number. R _F is - when (CF _{2) n} F, it is difficult to manufacture if the number of carbon atoms is 16 or more. Also, R _F is _{-CF (CF 3) O (CF} 2 CF (CF 3) O) m C 3
Specific examples of the case represented by F ₇ are chemical formulas (C), (D), (E), (F), (G), (H), and (I). R _F is —CF (CF ₃ ) O (CF ₂ CF
When represented by (CF ₃ ) O) _m C ₃ F ₇ , the number of m is 7
In the above cases, the solubility in the solvent is lowered, which makes the production difficult.

[0009]

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[Chemical 6]

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R ₁ in the formula A is suitably a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group,
A methoxy group, an ethoxy group and an n-propoxy group,
A methoxy group is particularly preferable. Similarly, R ₂ has 1 to 1 carbon atoms.
A lower alkyl group of 5 is suitable, preferably a methyl group, an ethyl group and an n-propyl group, particularly a methyl group. The proportion of each segment represented by x and y in Formula A varies depending on the type and structure of each segment, but is generally arbitrary. A preferable ratio of each segment can be determined based on a ratio of oil repellency and hydrophilicity that the obtained oligomer shows as a result.

The number average molecular weight of the fluorosilicone oligomer of the present invention is not particularly limited, but the silane coupling agent is preferably in the range of 1,000 to 15,000. Further, the fluorosilicone oligomer represented by the general formula (1) of the present invention may contain a fluoroalkyl group R _F introduced only at one end at an arbitrary ratio. The method for producing a fluorosilicone oligomer of the present invention is characterized by reacting a specific fluoroalkanoyl peroxide with methoxyvinylsilanes and acroylmorpholine.

The fluoroalkanoyl peroxide used in the present invention is represented by the above general formula (B). In formula B, R _F is — (CF ₂ ) _n F (n = 1 to 15) or —CF
_{(CF 3) O (CF 2} CF (CF 3) O) m C 3 F 7
(M = 0 to 6 integer). R _{F in} Formula B is-(
CF ₂ ) _n F has 16 or more carbon atoms and the formula B
R _F in the _{-CF (CF 3) O (CF} 2 CF (CF 3)
O) _m C ₃ F ₇ When m is 7 or more, all fluoroalkanoyl peroxides have poor solubility in the reaction solvent and are difficult to use. When R _F in the formula B is — (CF ₂ ) _n F, a perfluoropropyl group, a perfluorohexyl group and a perfluoroheptyl group can be preferably mentioned. Also, R _{F in} formula B
There _{-CF (CF 3) O (CF} 2 CF (CF 3) O) m C
When represented by ₃ F ₇ , fluoroalkanoyl peroxide includes diperfluoro-2-methyl-3-oxahexanoyl peroxide, diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide and Preference is given to diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecinoyl peroxide.

The alkoxyvinylsilanes used in the present invention are represented by CH ₂ ═CH—Si R ₁ (OR ₂ ) ₂ .
Here, R ₁ is a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms, and is a methyl group, an ethyl group, an n-propyl group, a methoxy group, an ethoxy group or n.
A -propoxy group is preferred, and R ₂ is suitably a lower alkyl group having 1 to 5 carbon atoms, preferably a methyl group, an ethyl group and an n-propyl group. From the viewpoint of reactivity and availability, trimethoxyvinylsilane is particularly preferred as the alkoxyvinylsilane.

In the present invention, when the fluoroalkanoyl peroxide is reacted with the alkoxyvinylsilanes and the acroylmorpholine, the molar ratios of the respective charges are:
It is preferably in the range of 1: 1 to 1:10:10,
Particularly preferably, it is 1: 1 to 1: 5: 5. When the charged molar ratios of the alkoxyvinylsilanes and acroylmorpholine are less than 1 and more than 10, respectively, the yield of the desired fluorosilicone oligomer is undesirably reduced. The fluorosilicone oligomer for this purpose can be obtained by a one-step reaction in which fluoroalkanoyl peroxide, alkoxyvinylsilanes and acroylmorpholine are mixed and reacted. Further, the reaction can be carried out at normal pressure. The reaction temperature is
-20 to 150 ° C is preferable, but 0 to 100 ° C is particularly preferable in consideration of economical efficiency. If the temperature is lower than -20 ° C, a long reaction time is required. If the temperature is higher than 150 ° C, the pressure during the reaction increases, which is not preferable. The reaction time is
As an example, when the reaction temperature is 20 ° C., it can be carried out for about 10 hours, and when the reaction temperature is 50 ° C., it can be carried out for about 5 hours.

As a solvent for carrying out the reaction, halogenated aliphatic solvents can be widely used.
225 (1,1-dichloro-2,2,3,3,3-pentafluoropropane: 1,3-dichloro-1,2,2
3,3-pentafluoropropane = 1: 1.35 manufactured by Asahi Glass Co., Ltd.), chloroform, methylene chloride, bis (trifluoromethyl) benzene, benzotrifluoride,
Hexafluorobenzene and the like can be used.
The concentration of the fluoroalkanoyl peroxide in the reaction solvent is desirably 0.5 to 30% by weight. The product obtained by the production method of the present invention is a known purification method such as reprecipitation method, distillation, gel filtration chromatography (GPC).
It is possible to purify by

[0016]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 2.13 g (5 m of diperfluorobutyryl peroxide
mol) to AK-225 (1,1-dichloro-2,2,3,
3,3-pentafluoropropane: 1,3-dichloro-
1,2,2,3,3-pentafluoropropane = 1: 1.
35 Dissolved in 21 g of Asahi Glass Co., Ltd., 2.22 g (15 mmol) of trimethoxyvinylsilane and acryloylmorpholine 2.
12 g (15 mmol) was added to a mixture prepared by dissolving 62 g of AK-225, and the mixture was stirred at 45 ° C. for 3 hours under a nitrogen stream. After the completion of the reaction, the concentrate obtained by removing the reaction solvent was purified by a reprecipitation method using a system of AK-225 and hexane, then the solvent was removed, and vacuum drying was performed to obtain 3.1 g of a purified product. This purified product is
When analyzed by R, ¹ H-NMR and ¹⁹ F-NMR, it was a fluorosilicone oligomer having a compound represented by the following structural formula (J) as a constitutional unit. Table 1 shows the analysis results. Table 2 shows the ratio between x and y in the formula K obtained from the ¹ H-NMR measurement results.

[0017]

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[0018]

[Table 1] Number average molecular weight: 2720 ¹ H-NMR (CDCl ₃ ) δ: 0.77 to 2.80 (CH ₂ , CH), 1.96
_{(CH 3), 3.20~3.98 (CH} 2) 19 F-NMR (CDCl 3, ext.CF 3 COOH) δ: -1.58 (6F), -
36.73 (4F),-44.53 (4F) IR (cm ^-1 ): 1631 (C = O), 1335 (CF ₃ ), 1230 (CF ₂ ),
1115 (-O-)

Example 2 Diperfluorobutyryl peroxide 5 mmol was replaced with diperfluoroheptanoyl peroxide 5 mmol
The reaction was performed in the same manner as in Example 1 except that (3.63 g) was changed to obtain 3.3 g of a fluorosilicone oligomer having a compound represented by the following structural formula (K) as a constitutional unit.

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(Example 3) 5 mmol of diperfluorobutyryl peroxide was replaced with 5 mmol of diperfluorooctanoyl peroxide.
(4.13 g) was reacted in the same manner as in Example 1 except that the same amount of benzotrifluoride was used as the reaction solvent AK-225, and a compound represented by the following structural formula (L) was used as a structural unit. As a result, 3.1 g of fluorosilicone oligomer was obtained.

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Example 4 A reaction was carried out in the same manner as in Example 1 except that 5 mmol (3.29 g) of diperfluoro-2-methyl-3-oxahexanoyl peroxide was used instead of 5 mmol of diperfluorobutyryl peroxide. , R _{F of the} general formula (A) is −
To obtain a fluorosilicone oligomer 1.8g to CF (CF ₃₎ OC ₃ constituting unit a compound represented by F _7. The number average molecular weight of this product is shown in Table 2. Also, ¹ H−
Table 2 shows the ratio of x and y in the formula K obtained from the measurement result of NMR.

Example 5 5 mmol of diperfluoro-2-methyl-3-oxahexanoyl peroxide was replaced with 5 mmol (4.95 g) of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide. Other than the above, the reaction is carried out in the same manner as in Example 4, and R _{F of the} general formula (A) is —CF (CF
_{3) O (CF2CF (CF 3} ) O) fluorosilicone oligomer as constituent units compound represented by C ₃ F ₇
I got 2.4g. The number average molecular weight of this product is shown in Table 2. Table 2 shows the ratio between x and y in the formula K obtained from the ¹ H-NMR measurement results.

Example 6 5 mmol of diperfluoro-2-methyl-3-oxahexanoyl peroxide was replaced with 6 mmol (7.93) of diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecinoyl peroxide. g), trimethoxyvinylsilane 15 mmol was replaced with 18 mmol (2.67 g), and acryloylmorpholine 15 mmol was replaced with 18 mmol (2.54 g), respectively. R _F is _{-CF (CF 3) O (CF} 2 CF (CF
₃ ) 3.7 g of a fluorosilicone oligomer having a compound represented by O) ₂ C ₃ F ₇ as a constitutional unit was obtained. The number average molecular weight of this product is shown in Table 2. In addition, ¹ H-NMR
Table 2 shows the ratio of x and y in the formula K obtained from the measurement result of.

[0024]

[Table 2]

(Effect Example 1) The fluorosilicone oligomers prepared in Examples 1 and 4 to 6 were used as a tetrahydrofuran solution, 1N acetic acid was added thereto, and a slide glass was dipped in the solution to form a glass surface in Examples 1 and 4 ~
A fluorosilicone oligomer 6 coating was formed.
The contact angles of dodecane and water on the coating film surface of this glass were measured using a contact angle meter CA-DT • A type manufactured by Kyowa Interface Science Co., Ltd., and the results are shown in Table 3. The contact angle of water was measured over time after placing water on the coating film surface. The fluorosilicone oligomer of the present invention showed excellent oil repellency on the glass surface, as is clear from the contact angle of dodecane in Table 3.
On the other hand, the contact angle of water decreased with the passage of time and became 0 after 30 minutes, and the initial high water repellency turned hydrophilic.

[0026]

[Table 3]

[0027]

INDUSTRIAL APPLICABILITY The fluorosilicone oligomer of the present invention is a novel compound, which exhibits high oil repellency in a hydrophobic environment, but changes from water repellency to hydrophilicity in a hydrophilic environment over a short period of time. have. Also, it has the same excellent oil repellency, surface tension reduction, heat resistance, cold resistance, and oil resistance as conventional fluorosilicone oligomers.
In addition to a wide range of properties such as chemical resistance and releasability, it also has hydrophilic properties, so surface modifiers such as optical lenses, eyeglass lenses, glass equipment, window glass for vehicles, and dirt on textile products. It can be used as a fiber treatment agent that has a soil release function that makes it easier to remove, as well as building civil engineering agents and medical materials. It is also very useful as a silane coupling agent.

The fluorosilicone oligomer can be easily produced by the one-step reaction in a short time by the production method of the present invention.

Claims (5)

[Claims] 1. A fluorosilicone oligomer represented by the following general formula (1). Embedded image R _F [In the formula, R _F is — (CF ₂ ) _n F or —CF
(CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _m C ₃ F ₇
(Wherein n is an integer of 1 to 15 and m is an integer of 0 to 6), R ₁ is a lower alkyl group or a lower alkoxy group, R ₂ is a lower alkyl group, and x and y are natural numbers. Show] 2. R _F is C ₃ F ₇ , C ₆ F ₁₃ , C ₇ F ₁₅ or --CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _m.
The fluorosilicone oligomer according to claim 1, which is C ₃ F ₇ (m = 0, 1, 2). 3. A fluorosilicone oligomer represented by the general formula (1), which comprises reacting fluoroalkanoyl peroxide represented by the following general formula (2) with alkoxyvinylsilanes and acroylmorpholine. Embedded image [In the formula, R _F is-(CF ₂ ) _n F or -CF (
_{CF 3) O (CF 2 CF} (CF 3) O) m C 3 F 7 ( wherein, n represents an integer of 1 to 15, m is an integer of 0 to 6)] 4. R _F is C ₃ F ₇ , C ₆ F ₁₃ , C ₇ F ₁₅ or —CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _m.
The method for producing a fluorosilicone oligomer according to claim _{3, wherein} C ₃ F ₇ (m = 0, 1, 2). 5. The silane coupling agent comprising the fluorosilicone oligomer according to claim 1, which has a number average molecular weight of 1,000 to 15,000.