JP3269135B2 - Fluoroalkyl group-containing polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fluoroalkyl group-containing polymer and a method for producing the same.

[0002]

2. Description of the Related Art A compound containing a fluoroalkyl group in an organic compound has attracted attention as a compound having useful properties such as weather resistance, water / oil repellency, and physiological activity.
In particular, fluoroalkyl group-containing polymers have excellent properties such as low surface tension, low refraction, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, mold release, and chemical resistance. Therefore, for example, the surface of synthetic materials such as biomaterials, pharmaceuticals and agricultural chemicals, adhesion improvers such as resists in the production process of semiconductor devices, optical lenses, lenses for spectacles, glass utensils, paints, etc., has water and oil repellency and stain resistance. It is useful in the field of surface treatment agents for imparting properties and the like, and materials for imparting release properties. Specifically, for example, Japanese Patent Application Laid-Open No.
No. 9 and JP-A-2-219830,
Compounds in which a fluoroalkyl group has been introduced into polysiloxane have been proposed.

[0003] However, at present, there is no known fluoroalkyl group-containing polymer having the structure as in the present invention.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low surface tension, low refraction, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, release property, water repellency, oil repellency, and stain resistance. An object of the present invention is to provide a novel fluoroalkyl group-containing polymer having excellent properties such as resistance and chemical resistance, and a method for producing the same.

Another object of the present invention is to provide a production method capable of easily obtaining a fluoroalkyl group-containing polymer in a high yield without using a reaction catalyst and a special apparatus.

[0006]

According to the present invention, a fluoroalkyl group-containing polymer represented by the following general formula ( 7 ):
(Hereinafter referred to as polymer 1).

[0007]

Embedded image [Wherein, Z ₁ represents a hydrogen atom or a methyl group, and Z ₂ and Z ₃
Are the same or different groups and represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylcarbonyloxy group, and R ₁ and R ₃ are the same or different groups and are a hydrogen atom, a halogen atom or a carbon atom. Wherein R ₂ and R ₄ are the same or different groups, and each represents a hydrogen atom, a halogen atom, a cyano group,
4 alkyl sulfonic acid, amido sulfonic acid _{group, -CO 2 R 5, -OCOR 6} , -OR 7, -CO 2 (CH 2 CH (R 3) O) m 4 -
(CH ₂ CH (R ₉ ) O) m ₅ [CH ₂ CH ₂ (CH ₂ ) m ₇ O] m ₆ (R ₁₀ ), -CO ₂ CHCH ₃ O
R ₁₁ or -CO ₂ (CH ₂ ) r-CHR ₁₂ CHR ₁₃ O (CO (CH ₂ ) sCHR ₁₄ (CH ₂ )
tCHR ₁₅ O] u-H (where R ₅ represents a hydrogen atom, sodium, potassium, ammonium, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 3 to 6 carbon atoms,
R ₆ and R ₇ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, and R ₈ , R ₉ and R ₁₀ are the same or different A hydrogen atom or a methyl group; R ₁₁ represents an alkyl group having 1 to 18 carbon atoms; m ₄ represents an integer of 1 to 20; m ₅ and m ₆ represent an integer of 0 to 20; m
₇ represents 1 or 2, R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are the same or different groups, each representing a hydrogen atom or a methyl group, r represents an integer of 0 to 2, and s and t represent Represents an integer of 0 to 3, u represents an integer of 1 to 5), and RF represents-(C
F ₂ ) n ₁ X or

Embedded image (Where X represents a fluorine atom, a chlorine atom, and a hydrogen atom, n ₁ represents an integer of ₁ to 10, and n ₂ represents an integer of 0 to 8). Further m ₁ is an integer of 1 to 1000, m ₂ is 0 to 30
00 of an integer, m ₃ is an integer of 1 to 3000, m ₈ represents 0 or 1 (case where m ₈ = 0, Z ₁ is a hydrogen atom.)]

Further, according to the present invention, difluoroalkanoyl peroxide represented by the following general formula ( 9):
Method for producing a fluoroalkyl group-containing polymer, wherein the polymerizable component B represented by the polymerizable component A and lower following general formalized 12 reacting represented by 11 is provided.

[0009]

Embedded image [In the formula, RF is (CF ₂ ) n ₁ X or

Embedded image (Where X represents a fluorine atom, a chlorine atom or a hydrogen atom; n ₁ represents an integer of 1 to 10, and n ₂ represents an integer of 0 to 8)]

[0010]

Embedded image [Wherein, R ₁ is a hydrogen atom, a halogen atom, or a C ₁ -C 1
5 represents an alkyl group, R ₂ represents a hydrogen atom, a halogen atom, a cyano group, an alkylsulfonic acid group having 1 to 4 carbon atoms,
Amidoalkyl sulfonic acid _{group, -CO 2 R 5, -OCOR 6} , -OR
_{7, -CO 2 (CH 2 CH} (R 8) O) m 4 - (CH 2 CH (R 9) O) m 5 [CH 2 CH 2 (CH 2)
_{m 7 O] m 6 (R} 10), - CO 2 CHCH 3 OR 11 or _{-CO 2 (CH 2) r-} CHR 12 C
HR ₁₃ O [CO (CH ₂ ) sCHR ₁₄ (CH ₂ ) tCHR ₁₅ O] u-H (however,
R ₅ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 3 to 6 carbon atoms, and R ₆ and R ₇
Are the same or different groups and each represent a hydrogen atom,
Indicates to 18 alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, R _8, R ₉ and R ₁₀ are the same or different groups, a hydrogen atom or a methyl group, R ₁₁ is 1 to carbon atoms 18 represents an alkyl group, an integer of m ₄ is from 1 to 20, an integer of m ₅ and m ₆ is 0 to 20, m ₇ represents 1 or _{2, R 12, R 13,} R 14 and R ₁₅ Are the same or different groups, each representing a hydrogen atom or a methyl group, and r is 0 to 2
S and t each represent an integer of 0 to 3, and u represents 1
Represents an integer of from 5 to 5. )]

[0011]

Embedded image [Wherein, Z ₁ represents a hydrogen atom or a methyl group, and Z ₂ and Z ₃
Represents the same or different groups, and represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylcarbonyloxy group. M ₈ represents 0 or 1, and when m ₈ = 0, Z ₁ is a hydrogen atom. ]

Hereinafter, the present invention will be described in more detail. The fluoroalkyl group-containing polymer of the present invention is the polymer 1 represented by the general formula ( 7 ). In the polymer 1, Z
₂ , when Z ₃ has 11 or more carbon atoms, R ₁ and R ₃ have 6 or more carbon atoms and m ₁ exceeds 1000, m ₂ and m ₃ are 3000
When m ₉ is 2 or more, production is difficult. When n ₁ exceeds 10, or when n ₂ exceeds 8, the solubility in the solvent decreases.

The average molecular weight of the polymer 1 is 500
To 5,000,000, and particularly preferably 500 to 10,000 in order to more remarkably exhibit the characteristics of the fluoroalkyl group. When the average molecular weight is out of the above range, production is difficult.

In the polymer 1, RF is-(CF
₂ ) n ₁ X or the following general formula 13:

[0015]

Embedded image

The above-mentioned-(CF ₂ ) n ₁ X can be specifically listed as F ₃ C-, F (CF ₂ ) _2- , F (CF ₂ ) _3- , F (CF ₂ )
_{4 -, F (CF 2)} 5 -, F (CF 2) 6 -, F (CF 2) 7 -, F
_{(CF 2) 8 -, F} (CF 2) 9 -, F (CF 2) 10 -, HCF
_{2 -, H (CF 2)} 2 -, H (CF 2) 3 -, H (CF 2) 4 -, H
_{(CF 2) 5 -, H} (CF 2) 6 -, H (CF 2) 7 -, H (CF 2) 8
−, H (CF ₂ ) ₉ −, H (CF ₂ ) ₁₀ −, ClCF ₂ −, Cl
_{(CF 2) 2 -, Cl} (CF 2) 3 -, Cl (CF 2) 4 -, Cl
_{(CF 2) 5 -, Cl} (CF 2) 6 -, Cl (CF 2) 7 -, Cl
(CF ₂ ) ₈ −, Cl (CF ₂ ) ₉ −, Cl (CF ₂ ) ₁₀ −, and the following general formula 13 is specifically listed.

[0017]

Embedded image

[0018] Examples of polymer 1, for example, by the following formula
Preferred examples include compounds represented by the following formula (wherein, m ₁ is an integer of ₁ to 1000, and m ₃ is an integer of 1 to 3000).
Number )).

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

In the production method of the present invention, the polymer 1
Can be obtained by reacting a specific difluoroalkanoyl peroxide with a specific polymerizable component.

The difluoroalkanoyl peroxide is difluoroalkanoyl 2 represented by the general formula ( 9 ). If n ₁ is 11 or more or n ₂ is 9 or more, the difluoroalkanoyl 2 cannot be used because the solubility of the difluoroalkanoyl 2 is reduced when the reaction is carried out in the presence of a solvent.

The R in the difluoroalkanoyl 2
F is the same as R F specifically enumerated in the polymer 1, and as the difluoroalkanoyl 2, specifically, for example, diperfluoro-2-methyl-3-peroxide
Oxahexanoyl, diperfluoro-2,5-peroxide
Dimethyl-3,6-dioxananoyl, diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide,
Preferred are diperfluoroheptanoyl peroxide and the like.

[0026] In the production method of the present invention, the specific polymerizable components to be reacted with the difluoro alkanoyl 2 is a polymerizable component B represented by the polymerizable component A and the general formalized 12 represented by the general formalized 11 is there.

As the polymerizable component A, specifically, for example, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate, (meth) acrylic acid, (Meth) methyl acrylate, (t) -butyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, CH ₂ = CHCO ₂ CHCH ₃ OC ₂ H ₅ , CH ₂ = CCH ₃ CO ₂ CHCH ₃ OC ₂ H ₅ , CH
₂ = CHCO ₂ CHCH ₃ OCH ₂ CH (CH ₃ ) ₂ , CH ₂ = CCH ₃ CO ₂ CHCH ₃ OCH ₂ CH (C
H ₃ ) ₂ , CH ₂ = CHCO ₂ CHCH ₃ OCH ₂ C (C ₂ H ₅ ) H (CH ₂ ) ₃ CH ₃ , CH ₂ = CCH
₃ CO ₂ CHCH ₃ OCH ₂ C (C ₂ H ₅ ) H (CH ₂ ) ₃ CH ₃ , CH ₂ = CHCO ₂ CH ₂ CH ₂ O (C
O (CH ₂ ) ₅ O) uH, CH ₂ = CCH ₃ CO ₂ CH ₂ CH ₂ O (CO (CH ₂ ) ₅ O) uH, CH ₂ =
CCH ₃ CO ₂ (CH ₂ CH ₂ O) m ₄ H (m ₄ ≠ 1), CH ₂ = CCH ₃ CO ₂ (CH ₂ CH ₂ O) m _{4
CH 3, CH 2 = CCH 3} CO 2 (CH 2 CH 2 O) m 4 (CH 2 CH (CH 3) O) m 5 H, CH 2 = C
CH ₃ CO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH (CH ₃ ) O) m ₅ CH ₃ , CH ₂ = CCH ₃ CO ₂ (C
H ₂ CH ₂ O) m ₄ (CH ₂ CH ₂ (CH ₂ ) ₂ O) m ₅ H, CH ₂ = CCH ₃ CO ₂ (CH ₂ CH ₂ O) m
₄ (CH ₂ CH ₂ (CH ₂ ) ₂ O) m ₅ CH ₃ , CH ₂ = CCH ₃ CO ₂ (CH ₂ CH (CH ₃ ) O) m
₄ (CH ₂ CH ₂ CH ₂ O) m ₆ H, CH ₂ = CCH ₃ CO ₂ (CH ₂ CH (CH ₃ ) O) m ₄ (CH ₂ CH
₂ CH ₂ O) m ₆ CH ₃ , CH ₂ = CCH ₃ CO ₂ (CH ₂ CH (CH ₃ ) O) m ₄ H, CH ₂ = CCH ₃
CO ₂ (CH ₂ CH (CH ₃ ) O) m ₄ CH ₃ , CH ₂ = CHCO ₂ (CH ₂ CH ₂ O) m ₄ H (m ₄ ≠
1), CH ₂ = CCHCO ₂ (CH ₂ CH ₂ O) m ₄ CH ₃ , CH ₂ = CHCO ₂ (CH ₂ CH ₂ O) m ₄
(CH ₂ CH (CH ₃ ) O) m ₅ H, CH ₂ = CHCO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH (CH ₃ )
O) m ₅ CH ₃ , CH ₂ = CHCO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH ₂ (CH ₂ ) ₂ O) m ₆ H, C
H ₂ = CHCO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH ₂ (CH ₂ ) ₂ O) m ₆ CH ₃ , CH ₂ = CHCO ₂
(CH ₂ CH (CH ₃ ) O) m ₄ (CH ₂ CH ₂ CH ₂ O) m ₆ H, CH ₂ = CHCO ₂ (CH ₂ CH (CH
₃ ) O) m ₄ (CH ₂ CH ₂ CH ₂ O) m ₆ CH ₃ , CH ₂ = CHCO ₂ (CH ₂ CH (CH ₃ ) O) m
₄ H, CH ₂ = CHCO ₂ (CH ₂ CH (CH ₃ ) O) m ₄ CH _{3 and the} like can be preferably exemplified (provided that m ₄ is an integer of 1 to 20, m ₅ and m ₆ are An integer of 1 to 20, and u represents an integer of 1 to 5), and when used, alone or m ₄ , m ₅ , m ₆ ,
It can be used as a mixture in which u is in the above-mentioned integer range, and further as a mixture thereof.

In the polymerizable component B, when Z ₂ and Z ₃ have 11 or more carbon atoms, production is difficult.

Examples of the polymerizable component B include, for example, trimethoxyvinylsilane, triethoxyvinylsilane, diacetyloxymethylvinylsilane, diethoxymethylvinylsilane, triacetyloxyvinylsilane, triisopropoxyvinylsilane, trimethylvinylsilane, trimethylvinylsilane, t-butoxyvinylsilane, ethoxydiethylvinylsilane, diethylmethylvinylsilane, 3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropyltriethoxysilane, 3-
Methacryloxypropyldiacetyloxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, 3-methacryloxypropyltriacetyloxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltrimethylsilane,
3-methacryloxypropyltri-t-butoxysilane, 3-methacryloxypropylethoxydiethylsilane, 3-methacryloxypropyldiethylmethylsilane, 3-acryloxypropyltrimethoxysilane,
-Acryloxypropyltriethoxysilane, 3-acryloxypropyldiacetyloxymethylsilane, 3-
Acryloxypropyldiethoxymethylsilane, 3-acryloxypropyltriacetyloxysilane, 3-acryloxypropyltriisopropoxysilane, 3-acryloxypropyltrimethylsilane, 3-acryloxypropyltri-t-butoxysilane, 3- Acryloxypropylethoxydiethylsilane, 3-acryloxypropyldiethylmethylsilane and the like can be preferably mentioned.

In the production method of the present invention, the molar ratio of the charged difluoroalkanoyl 2 to the polymerizable component A and the polymerizable component B is such that the ratio of the fluoroalkanoyl 2: the polymerizable components A and B is 1 : 0.1 ~
It is preferably in the range of 5000, especially 1: 0.5
It is preferably in the range of ~ 1000. When the charged molar ratio of the polymerizable components A and B is less than 0.1, a large amount of a product due to peroxide self-decomposition is produced, which is not industrially preferable. Is not preferred because the yield of the desired polymer 1 decreases.
When a mixture of the polymerizable component A and the polymerizable component B is used as the polymerizable component, the charged molar ratio of the polymerizable component A and the polymerizable component B is not particularly limited,
1: It is desirable to be in the range of 0.01 to 100. Further, the molecular weight of the obtained polymer 1 can be adjusted by adjusting the charged molar ratio of the difluoroalkanoyl 2. That is, if the charged molar ratio of the difluoroalkanoyl 2 is increased, a polymer having a low molecular weight can be obtained,
If the charged molar ratio of the difluoroalkanoyl 2 is reduced, a polymer having a high molecular weight can be obtained.

In the production method of the present invention, the reaction between the difluoroalkanoyl 2 and the specific polymerizable component can be carried out at normal pressure.
Preferably -20 to + 150 ° C, particularly preferably 0 to 1
It is in the range of 00 ° C. When the reaction temperature is lower than -20 ° C, a long time is required for the reaction, and when it is higher than + 150 ° C, the pressure at the time of the reaction is increased, which is not preferable because the reaction operation becomes difficult. Furthermore, the reaction time is preferably in the range of 30 minutes to 20 hours, and it is particularly preferable to carry out the reaction in the range of 1 to 10 hours industrially.

In the production method of the present invention, the desired polymer 1 is directly obtained by a one-step reaction by reacting the difluoroalkanoyl 2 with the polymerizable components A and B under the various reaction conditions. Can be
It is preferable to use a solvent in order to handle and react the difluoroalkanoyl 2 more smoothly. As the solvent, a halogenated aliphatic solvent is particularly preferable, and specifically, for example, methylene chloride, chloroform,
2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-
Difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,
1,3-tetrachlorotetrafluoropropane, 1,
1,1-trichloropentafluoropropane, 1,1,
2-trichlorotrifluoroethane, 1,1,1,2,2
2-pentafluoro-3,3-dichloropropane, 1,
1,2,2,3-pentafluoro-1,3-dichloropropane and the like can be used.
1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3
-Dichloropropane and 1,1,2-trichlorotrifluoroethane are preferred. When the solvent is used, the difluoroalkanoyl 2 in the solvent is used.
Is preferably 0.5 to 30% by weight based on the whole solution.

The product obtained by the production method of the present invention is produced as a mixed product in which, in addition to the polymer 1, the product of the above general formula ( 7) in which only one terminal is an RF group is somewhat mixed. Depending on the application, such a mixed product can be used for various applications without performing the purification step described below.

The reaction product obtained by the production method of the present invention can be purified by a known method such as a reprecipitation method.

[0035]

Industrial Applicability The fluoroalkyl group-containing polymer of the present invention is a novel compound. Since the fluoroalkyl group is bonded not directly through an ester bond but directly through a carbon-carbon bond, properties derived from the fluoroalkyl group are obtained. Can be maintained for a long time, and is a compound having high weather resistance. Therefore, as a compound having characteristics such as low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, release property, defoaming property, chemical resistance, especially pharmaceuticals, agricultural chemicals, etc. Synthetic intermediates, adhesion improvers such as resists for semiconductor devices, paints, optical lenses, eyeglass lenses, glassware,
It can be used as a surface treatment agent for imparting water and oil repellency and stain resistance to the surface of a biomaterial or the like, a sealant, and a material that imparts releasability. In particular, the fluoroalkyl group-containing polymer having a functional group such as a silyl group, a hydroxyl group, an epoxy group, or a carboxylic acid group in the present invention is effective as a curing site to further enhance the adhesion to a substrate. Further, according to the production method of the present invention, a fluoroalkyl group-containing polymer can be produced by a one-step reaction in a short time with good yield and without using a reaction catalyst and a special apparatus.

[0036]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0037]

Example 1 1.5 g (15 mmol) of methyl methacrylate
And 2.2 g (15 mmol) of trimethoxyvinylsilane,
1,1,2 containing diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide (5.0 g, 5 mmol)
-150 g of trichlorotrifluoroethane solution are added,
The reaction was performed at 30 ° C. for 5 hours under a nitrogen atmosphere. After the completion of the reaction, the reaction solvent was removed, followed by drying under vacuum to obtain 6.9 g of a product. Gel permeation chromatography of the product obtained, IR, ¹⁹ F-NM
As a result of performing R, it was a fluoroalkyl group-containing silicone polymer represented by the following structural formula . The analysis results are shown below. The obtained polymer is added with acetic acid to adjust the pH.
It was dissolved in a 95% by weight aqueous ethanol solution adjusted to 5.5 to prepare a 2% by weight solution. Next, a film was formed on a glass substrate by a dip coating method using the obtained solution, and a heat treatment was performed at 120 ° C. for 10 minutes.
The contact angle was measured. Table 1 shows the results.

[0038]

Embedded image Molecular weight: Mn = 1300 (Mw / Mn = 1.00) ¹⁹ F
-NMR (CDCl _3, external standard CF ₃ COOH) .delta.
3.35 to -9.99 (26F), -54.09 to -6
9.51 (8F), IR (cm ^-1 ) 1730 (C = O), 1
230 (CF ₂ ), 1330 (CF ₃ ) m ₁ : m ₃ = 5: 1

[0039]

EXAMPLE 2 3.2 g (5.0 g) of diperfluoro-2-methyl-3-oxahexanoyl peroxide was converted from diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide.
The reaction was carried out in the same manner as in Example 1 except that the yield was 5.2 mmol, and 5.2 g of a polymer represented by the following structural formula was obtained. The analysis results are shown below. The contact angle was measured in the same manner as in Example 1. Table 1 shows the results.

[0040]

Embedded image Molecular weight: Mn = 1250 (Mw / Mn = 1.00) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.33 to -9.89 (16F), -54.14 to -5
6.70 (6F) IR (cm ^-1 ) 1730 (C = O), 12
30 (CF ₂ ), 1335 (CF ₃ ) m ₁ : m ₃ = 5: 1

[0041]

Example 3 Diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide was converted to 3.2 g (5.0 mmo) of diperfluoro-2-methyl-3-oxahexanoyl peroxide.
l), and the charged amount of methyl methacrylate is 0.5 g.
(5 mmol) and the reaction was carried out in the same manner as in Example 1 except that the charged amount of trimethoxyvinylsilane was changed to 0.74 g (5 mmol), thereby obtaining 4.2 g of a polymer represented by the following structural formula . The analysis results are shown below. Examples
The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0042]

Embedded image Molecular weight: Mn = 1450 (Mw / Mn = 1.00) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.30 to -9.77 (16F), -54.0 to -5
6.75 (6F) IR (cm ^-1 ) 1730 (C = O), 12
30 (CF ₂ ), 1335 (CF ₃ ) m ₁ : m ₃ = 5: 1

[0043]

Example 4 Diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide was converted to diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide. The reaction was carried out in the same manner as in Example 1 except that the charged amount of methyl methacrylate was 0.5 g (5 mmol) and the charged amount of trimethoxyvinylsilane was 0.74 g (5 mmol).
7.5 g of a polymer represented by the formula was obtained. The analysis results are shown below. The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0044]

Embedded image Molecular weight: Mn = 1800 (Mw / Mn = 1.01) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.49 to -9.54 (36F), -54.21 to -6
9.39 (10F) IR (cm ^-1 ) 1735 (C = O), 1
235 (CF ₂ ), 1330 (CF ₃ ) m ₁ : m ₃ = 5: 1

[0045]

Example 5 Diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide was changed to 3.7 g (5 mmol) of diperfluoroheptanoyl peroxide, and the charged amount of methyl methacrylate was 0.5 g (5 mmol). ), And the reaction was carried out in the same manner as in Example 1 except that the charged amount of trimethoxyvinylsilane was changed to 0.74 g (5 mmol), to obtain 4.8 g of a polymer represented by the following structural formula . The analysis results are shown below. The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0046]

Embedded image Molecular weight: Mn = 810 (Mw / Mn = 1.00) ¹⁹ F-
NMR (CDCl ₃ , external standard CF ₃ COOH) δ-2.
90 (6F), -29.00 (4F), -43.29 to -4
9.22 (16F) IR (cm ^-1 ) 1735 (C = O), 1
240 (CF ₂ ), 1330 (CF ₃ ) m ₁ : m ₃ = 6: 1

[0047]

Example 6 The amount of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was 2.5 g.
(2.5 mmol), the same as Example 1 , except that the charged amount of methyl methacrylate was 0.75 g (7.5 mmol) and the trimethoxyvinylsilane was 3.72 g (15 mmol) of 3-methacryloxypropyltrimethoxysilane. To give 6.2 g of a polymer represented by the following structural formula . The analysis results are shown below. Examples
The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0048]

Embedded image Molecular weight: Mn = 5600 (Mw / Mn = 1.61) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.30 to -9.94 (26F), -54.11 to -6
9.44 (8F) IR (cm ^-1 ) 1730 (C = O), 12
40 (CF ₂ ), 1330 (CF ₃ ) m ₁ : m ₃ = 1: 1

[0049]

Example 7 1.65 g of diperfluoro-2-methyl-3-oxahexanoyl peroxide was prepared by converting diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide to 1.65 g (2.
In 5 mmol), also the charge of methyl methacrylate 0.75 g (7.5 mmol), except that the trimethoxyvinylsilane 3-methacryloxypropyl trimethoxy silane 3.72 g (15 mmol) are in the same manner as in Example 1 The reaction was carried out to obtain 5.0 g of a polymer represented by the following structural formula . The analysis results are shown below. The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0050]

Embedded image Molecular weight: Mn = 5000 (Mw / Mn = 1.74) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.31 to -9.90 (16F), -54.0 to 56.
66 (6F) IR (cm ^-1 ) 1730 (C = O), 1230
(CF ₂ ), 1330 (CF ₃ ) m ₁ : m ₃ = 1: 1

[0051]

Example 8 Diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide was charged in an amount of 5.0 g (5 g).
mmol), methyl methacrylate to 2.0 g (15 mmol) of 2-hydroxyethyl methacrylate, and 2.2 g (15 mmol) of trimethoxyvinylsilane to be charged.
The reaction was carried out in the same manner as in Example 1 except that 5.9 g of a polymer represented by the following structural formula was obtained. The analysis results are shown below. The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0052]

Embedded image Molecular weight: Mn = 3400 (Mw / Mn = 1.20) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.49 to -9.90 (26F), -54.0 to -6
9.50 (8F) IR (cm ^-1 ) 1730 (C = O), 12
40 (CF ₂ ), 1330 (CF ₃ ) m ₁ : m ₃ = 6: 1

[0053]

EXAMPLE 9 3.3 g (5 mmol) of diperfluoro-2-methyl-3-oxahexanoyl peroxide was prepared by converting diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
l), the reaction was carried out in the same manner as in Example 1 except that the amount of methyl methacrylate was changed to 2.0 g (15 mmol) of 2-hydroxyethyl methacrylate and the amount of trimethoxyvinylsilane was changed to 2.2 g (15 mmol). Structural formula
The in represented by polymer was obtained Yield 5.1 g. The analysis results are shown below. The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0054]

Embedded image Molecular weight: Mn = 2100 (Mw / Mn = 1.12) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.30 to -9.96 (16F), -54.14 to 56.
44 (6F) IR (cm ^-1 ) 3450 (OH), 1730
(C = O), 1230 (CF ₂ ), 1340 (CF ₃ ) m ₁ : m
₃ = 5: 1

[0055]

Example 10 Diperfluoro-2,5-dimethyl-3,6-dioxano nanoyl peroxide was converted to diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide. To 61 g (5 mmol) and methyl methacrylate was added 2-hydroxyethyl methacrylate 2.0
The reaction was carried out in the same manner as in Example 1 except that the amount of trimethoxyvinylsilane was changed to 2.2 g (15 mmol), thereby obtaining 7.1 g of a polymer represented by the following structural formula . . The analysis results are shown below. The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0056]

Embedded image Molecular weight: Mn = 3900 (Mw / Mn = 1.21) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.58 to -9.75 (36F), -54.0 to -6
9.71 (10F) IR (cm ^-1 ) 3450 (OH), 17
30 (C = O), 1240 (CF ₂ ), 1335 (CF ₃ )
m ₁ : m ₃ = 4: 1

[0057]

EXAMPLE 11 The amount of diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide was adjusted to 5.0 g.
(5 mmol), and the same as Example 1 except that methyl methacrylate was 2.0 g (15 mmol) of 2-hydroxyethyl methacrylate and trimethoxyvinylsilane was 3.7 g (15 mmol) of 3-methacryloxypropyltrimethoxysilane. The reaction was carried out to obtain 5.8 g of a polymer represented by the following structural formula . The analysis results are shown below. The contact angle was measured in the same manner as in Example 1 .
Table 1 shows the results.

[0058]

Embedded image Molecular weight: Mn = 5300 (Mw / Mn = 1.62) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.40 to -9.91 (26F), -54.19 to -6
9.50 (8F) IR (cm ^-1 ) 3450 (OH), 173
0 (C = O), 1240 (CF ₂ ), 1330 (CF ₃ ) m1:
m ₃ = 4: 1

[0059]

Example 12 Diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide was converted to diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide. To 61 g (5 mmol) and methyl methacrylate was added 2-hydroxyethyl methacrylate 2.0
To g (15 mmol), toshimethoxyvinylsilane was added to 3.7 g (15 mmol) of 3-methacryloxypropylmethoxysilane.
The reaction was carried out in the same manner as in Example 1 except that 6.9 g of a polymer represented by the following structural formula was obtained. The analysis results are shown below. The contact angle was measured in the same manner as in Example 1 . Table 1 shows the results.

[0060]

Embedded image Molecular weight: Mn = 5950 (Mw / Mn = 1.48) ¹⁹ F
-NMR (CDCl ₃ , external standard CF ₃ COOH) δ-
3.59 to -9.81 (36F), -54.19 to -6
9.23 (10F) IR (cm ^-1 ) 3450 (OH), 17
30 (C = O), 1240 (CF ₂ ), 1330 (CF ₃ )
m ₁ : m ₃ = 5: 1

[0061]

Comparative Example 1 The contact angle of an untreated glass plate was measured in the same manner as in Example 1 . Table 1 shows the results.

[0062]

[Table 1]

[0063]

Embodiment 13 CH ₂ ＣC (CH ₃ ) CO ₂ (CH ₂ CH ₂ O) ₂
In 1.74 g (10 mmol) of H and 1.48 g (10 mmol) of trimethoxyvinylsilane, diperfluoro-peroxide was added.
2,5-dimethyl-3,6-dioxananoyl 9.
80 g of a 1,1,2-trichlorotrifluoroethane solution containing 9 g (10 mmol) was added, and the mixture was reacted at 30 ° C. for 7 hours under a nitrogen atmosphere. After completion of the reaction, the white powder component was filtered, dried under vacuum, and purified to obtain a white powder product in a yield of 0.4 g. Then, the reaction solvent in the filtrate was removed, and the filtrate was dried under vacuum to obtain 12.3 g of a colorless liquid product. The obtained product was a polymer represented by the following structural formula .

[0064]

Embedded image m ₁ : m ₃ = 5: 2, white powder product: yield 0.4 g, molecular weight:
Mn = 8800 (Mw / Mn = 1.39), m ₁ : m ₃ = 5: 2, liquid product: yield 12.3 g, molecular weight: Mn = 1500 (Mw / Mn = 1.0)
9), IR (cm ^-1 ): 3450 (OH), 1725 (C = O), 1330 (CF ₃ ), 1240
(CF ₂ ) ¹⁹ F-NMR (CDCl ₃ , δ −3.12 to −9.00 (26F), −
54.12 to -69.00 (8F) External standard CF ₃ CO ₂ H)

[0065]

Example 14 Diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide was replaced by diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide The reaction was carried out in the same manner as in Example 13 except that
Thus, a colorless liquid product was obtained in a yield of 13.9 g. The obtained product was a polymer represented by the following structural formula .

[0066]

Embedded image m ₁ : m ₃ = 4: 1 white powder product: yield 0.7 g molecular weight:
Mn = 10100 (Mw / Mn = 1.41), m 1: m 3 = 4: 1 liquid product: yield 13.9g molecular weight: Mn = 2100 (Mw / Mn = 1.0
4) IR (cm ^-1 ): 3450 (OH), 1725 (C = O), 1335 (CF ₃ ), 1240
(CF ₂ ) ¹⁹ F-NMR (CDCl ₃ , δ−3.59 to −9.32 (36F), −5
4.11 to -68.91 (10F) External standard CF ₃ CO ₂ H)

[0067]

Example 15 Instead of trimethoxyvinylsilane, 3
The reaction was carried out in the same manner as in Example 13 except that methacryloxypropyltrimethoxysilane was used. The yield was 0.6 g for a white powder product and 1 for a colorless liquid product.
2.9 g were obtained. The obtained product was a polymer represented by the following structural formula .

[0068]

Embedded image m ₁ : m ₃ = 10: 9 White powder product: Yield 0.6 g Molecular weight:
Mn = 12000 (Mw / Mn = 1.41), m1: m3 = 10: 9 Liquid product: yield 12.9 g Molecular weight: Mn = 2900 (Mw / Mn =
1.19) IR (cm ^-1 ): 3450 (OH), 1730, 1725 (C = O), 1330 (CF
₃ ), 1240 (CF ₂ ) ¹⁹ F-NMR (CDCl ₃ ,: δ −3.11 to −9.29 (2
6F), −54.19 to −69.99 (8F) External standard CF ₃ CO ₂ H)

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takeo Matsumoto 2-14-9 Higashi, Tsukuba City, Ibaraki Prefecture (72) Inventor Masayo Nakayama 1132-9, Ekuni, Tsuchiura City, Ibaraki Prefecture (56) References JP-A-62-59610 (JP, A) JP-A-58-189210 (JP, A) JP-A-5-131130 (JP, A) JP-A-5-311149 (JP, A) JP-A-5-339538 (JP, A) JP-A-6-16780 (JP, A) JP-A-6-65261 (JP, A) JP-A-6-32842 (JP, A) JP-A-6-56962 (JP, A) JP, B1) JP-T 7-504224 (JP, A) US Patent 2,596,930 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/00-4/82 CA (STN ) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A molecular weight of 500 represented by the following general formula 1.
~ 5,000,000 fluoroalkyl group-containing polymers. Embedded image [Wherein, Z ₁ represents a hydrogen atom or a methyl group, and Z ₂ and Z ₃
Are the same or different groups and represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylcarbonyloxy group, and R ₁ and R ₃ are the same or different groups and are a hydrogen atom, a halogen atom or a carbon atom. Wherein R ₂ and R ₄ are the same or different groups, and each represents a hydrogen atom, a halogen atom, a cyano group,
4 alkyl sulfonic acid, amido sulfonic acid _{group, -CO 2 R 5, -OCOR 6} , -OR 7, -CO 2 (CH 2 CH (R 3) O) m 4 -
(CH ₂ CH (R ₉ ) O) m ₅ [CH ₂ CH ₂ (CH ₂ ) m ₇ O] m ₆ (R ₁₀ ), -CO ₂ CHCH ₃ O
R ₁₁ or -CO ₂ (CH ₂ ) r-CHR ₁₂ CHR ₁₃ O (CO (CH ₂ ) sCHR ₁₄ (CH ₂ )
tCHR ₁₅ O] u-H (where R ₅ represents a hydrogen atom, sodium, potassium, ammonium, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 3 to 6 carbon atoms,
R ₆ and R ₇ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, and R ₈ , R ₉ and R ₁₀ are the same or different A hydrogen atom or a methyl group; R ₁₁ represents an alkyl group having 1 to 18 carbon atoms; m ₄ represents an integer of 1 to 20; m ₅ and m ₆ represent an integer of 0 to 20; m
₇ represents 1 or 2, R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are the same or different groups, each representing a hydrogen atom or a methyl group, r represents an integer of 0 to 2, and s and t represent Represents an integer of 0 to 3, u represents an integer of 1 to 5), and RF represents-(C
F ₂ ) n ₁ X or (Where X represents a fluorine atom, a chlorine atom, and a hydrogen atom, n ₁ represents an integer of ₁ to 10, and n ₂ represents an integer of 0 to 8). Further m ₁ is an integer of 1 to 1000, m ₂ is 0 to 30
00 of an integer, m ₃ is an integer of 1 to 3000, m ₈ represents 0 or 1 (case where m ₈ = 0, Z ₁ is a hydrogen atom.)] 2. A peroxide-difluoro alkanoyloxy represented by the following general formalized 3, reacting a polymerizable component B represented by the polymerizable component A and lower following general formalized 6 represented by the following general formalized 5 The method for producing a fluoroalkyl group-containing polymer according to claim 1, wherein Embedded image [In the formula, RF is (CF ₂ ) n ₁ X or (Where X represents a fluorine atom, a chlorine atom or a hydrogen atom. N ₁ represents an integer of 1 to 10, and n ₂ represents an integer of 0 to 8)]. [Wherein, R ₁ is a hydrogen atom, a halogen atom, or a C ₁ -C 1
5 represents an alkyl group, R ₂ represents a hydrogen atom, a halogen atom, a cyano group, an alkylsulfonic acid group having 1 to 4 carbon atoms,
Amidoalkyl sulfonic acid _{group, -CO 2 R 5, -OCOR 6} , -OR
_{7, -CO 2 (CH 2 CH} (R 8) O) m 4 - (CH 2 CH (R 9) O) m 5 [CH 2 CH 2 (CH 2)
_{m 7 O] m 6 (R} 10), - CO 2 CHCH 3 OR 11 or _{-CO 2 (CH 2) r-} CHR 12 C
HR ₁₃ O [CO (CH ₂ ) sCHR ₁₄ (CH ₂ ) tCHR ₁₅ O] u-H (however,
R ₅ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 3 to 6 carbon atoms, and R ₆ and R ₇
Are the same or different groups and each represent a hydrogen atom,
Indicates to 18 alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, R _8, R ₉ and R ₁₀ are the same or different groups, a hydrogen atom or a methyl group, R ₁₁ is 1 to carbon atoms 18 represents an alkyl group, an integer of m ₄ is from 1 to 20, an integer of m ₅ and m ₆ is 0 to 20, m ₇ represents 1 or _{2, R 12, R 13,} R 14 and R ₁₅ Are the same or different groups, each representing a hydrogen atom or a methyl group, and r is 0 to 2
S and t each represent an integer of 0 to 3, and u represents 1
Represents an integer of from 5 to 5. )] [Wherein, Z ₁ represents a hydrogen atom or a methyl group, and Z ₂ and Z ₃
Represents the same or different groups, and represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylcarbonyloxy group. M ₈ represents 0 or 1, and when m ₈ = 0, Z ₁ is a hydrogen atom. ]