JPH10251348A - Fluoroalkyl group-bearing phosphoric acid derivative, its production and surface treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel phosphoric acid derivative that is prepared by indirection of fluoroalkyl groups directly via the carbon-carbon bond and is useful in cosmetics and surfactants. SOLUTION: This novel compound is represented by the formula: RF-(CH2 CR<1> L)m1 -(CH2 CR<1> R<4> )m2 -RF R<1> is H, methyl; L is C(=O)(OCH2 CHR<2> )P P(=O)(OH)2 (and its alkanolamine salt, alkali salt); R<2> is H, (chloro)methyl; p is 1-20; R<4> is a halogen, cyano; m1 is 1-5,000; m2 is 0-5,000; RF is -(CF2 )n1 X, -CF(CF3 )[OCF2 CF(CF3 )]n2 -OC3 F7 ; X is H, Cl, F; n1 is 1-10; n2 is 0-8}, typically the compound of the formula: C3 H7 - CH2- C(CH3 )-C(=O)[OCH2 CH(CH3 )]5 -OP(=O)(OH)2 }n-C3 F7 . The compound of the formula: RF-(CH2 CR<1> L)m1 --(CH2 CR<1> R<4> )m2 -RF is prepared by reaction of a peroxyfluoroalkanoyl of the formula: RFC(=O)OO(=O)CR4 with a compound of the formula: CH2 =CR<1> L and a compound of the formula: CH2 =CR<1> R<4> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel fluoroalkyl group-containing phosphoric acid derivative, a method for producing the same, and a surface treating agent.

[0002]

2. Description of the Related Art In recent years, compounds containing a fluoroalkyl group in an organic compound have attracted attention as useful compounds such as light resistance, water and oil repellency, and physiological activity.
In particular, a fluoroalkyl group-containing polymer having a fluoroalkyl group introduced into an organic compound has low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, oil repellency, mold release, In various fields because of having excellent properties such as chemical properties, for example, a surface for imparting water and oil repellency and stain resistance to surfaces of optical lenses, eyeglass lenses, glassware, paints, etc. It is considered to be useful in the fields of processing agents, cosmetics, biomaterials, raw materials for medicines and agricultural chemicals, and materials for imparting releasability. In particular, a compound having a functional group of a phosphoric acid derivative and further having a fluoroalkyl group introduced at the polymerization terminal is a material that exhibits excellent oil repellency and the like due to fluorine, and various materials such as surface treatment. It is a useful compound that is highly expected to expand into the field. However, there is no report on the synthesis of these compounds. Further, since the conventional fluoroalkyl group-containing phosphate compound is introduced through a sulfide bond that can be easily introduced, [for example, a thiol compound having a fluoroalkyl group and an unsaturated compound having a group of a phosphoric acid derivative may be used. Fluorine-containing phosphoric acid compound by Michael addition reaction; J. Fluorine Chem., 76, 193
(1996)], which has a drawback such as low weather resistance. Therefore, the development of a fluoroalkyl group-containing polymer in which a fluoroalkyl group is directly introduced at a highly stable carbon-carbon bond and furthermore, the excellent performance of an organic fluorine compound such as oil repellency is utilized is an important study. Item.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, antifogging property, antifouling property, release property, optical lens. Fluoroalkyl groups that have excellent properties such as water and oil repellency, stain resistance and chemical resistance on the surfaces of lenses for eyeglasses, glassware, paints, metal materials, etc., and are useful as cosmetics and even surfactants An object of the present invention is to provide a fluoroalkyl group-containing phosphoric acid derivative directly introduced by a carbon-carbon bond. Further, the object of the present invention is to use no reaction catalyst and special equipment,
An object of the present invention is to provide a method for producing a fluoroalkyl group-containing phosphoric acid derivative in which a fluoroalkyl group is easily introduced at a high yield and with a carbon-carbon bond.

[0004]

Means for Solving the Problems In order to solve the problems associated with the prior art, the present inventors have conducted intensive studies, and as a result, useful as a surfactant represented by the general formula (1) and having a molecular weight of 3 to 1,000,000. Provided is a phosphoric acid derivative containing a fluoroalkyl group in which a natural fluoroalkyl group is directly introduced via a carbon-carbon bond (hereinafter, also referred to as a polymer in the present invention including a compound not necessarily having a repeating structure). Further, according to the present invention, a reaction catalyst and a special catalyst, characterized by reacting a fluoroalkanoyl peroxide represented by the general formula (2) with a monomer represented by the general formula (3) or (4), The present inventors have found that it is possible to provide a method for producing the polymer easily and with a high yield without using a simple apparatus, and have accomplished the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the fluoroalkyl group-containing phosphoric acid derivative according to the present invention, a method for producing the same, and a surface treating agent will be specifically described. The fluoroalkyl group-containing phosphoric acid derivative of the present invention has the following general formula (1): R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (1) ¹ independently represents a hydrogen atom or a methyl group; L is
_{C (= O) (OCH 2} CHR 2) p P (= O) (OH) 2 or alkanolamine salts such as ethanolamine salt, propanolamine salt or alkali salts such as sodium salt, potassium salt, magnesium salt shown; R ² is a hydrogen atom, a methyl group or a chloromethyl group, p represents an integer of 1 to 20; R ⁴
A halogen atom, a cyano group, -Si (R ¹⁰⁾ _3, a -C (= O) OR ⁹ or ^{-C (= O) R 6,} R 10 represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms ; R ⁹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms -
(CH ₂ ) ₃ -Si (R ¹¹ ) ₃ , R ¹¹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ⁶ is a mono or dialkylamino group having 1 to 20 carbon atoms, a pyrrolidino group, a piperidino group Or a morpholino group; m1 is 1 to 5000, m2 is 0 to 5
R _F represents-(CF ₂ ) _n1 X or -CF
(CF ₃ ) [OCF ₂ CF (CF ₃ )] _n2- OC ₃ F ₇ ; X is a hydrogen atom,
A chlorine atom or a fluorine atom, n1 is an integer of 1 to 10, n2
Represents an integer of 0 to 8. A molecular weight of 300 to
In one million fluoroalkyl group-containing phosphoric acid derivatives, the applicable fluoroalkyl group (R _F ) _is- (CF ₂ ) _n1 X
Or _{-CF (CF 3) [OCF 2} CF (CF 3)] in _n2 -OC ₃ F ₇ [wherein, n1 is 1 to 10
X represents a fluorine atom, a chlorine atom or a hydrogen atom, and n2 represents an integer of 0-8. ] Is not particularly limited, but specific examples include:

[0006] CF ₃ , 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 (C
F 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 (C
_{F 2) 10, CF (CF} 3) OC 3 F 7, CF (CF 3) [OCF 2 CF (CF 3)] - OC 3 F 7, C
F (CF ₃ ) [OCF ₂ CF (CF ₃ )] ₂ -OC ₃ F ₇ , CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] ₃
-OC ₃ F ₇ , CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] ₄ -OC ₃ F ₇ , CF (CF ₃ ) [OCF
₂ CF (CF ₃ )] ₅ -OC ₃ F ₇ , CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] ₆ -OC ₃ F ₇ , C
F (CF ₃ ) [OCF ₂ CF (CF ₃ )] ₇ -OC ₃ F ₇ , CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] ₈
-OC ₃ F _{7 and the} like. At this time, the carbon number of R _F , that is, n
When 1 and n2 are more than 10 and 8, the solubility in a solvent is undesirably reduced. Preferably n1
Is an integer of 1 to 8, and n2 is an integer of 0 to 3.

In the present invention, the fluoroalkyl group-containing phosphoric acid derivative represented by the general formula (1) is a compound in which a fluoroalkyl group (R _F ) is introduced into only one terminal of a polymer at an arbitrary ratio. You can indicate what you have included.

The fluoroalkyl group-containing phosphoric acid derivative R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (1) represented by the general formula (1) In the general formula (3), CH ₂ CRCR ¹ L (3) indicates that R ¹ represents a hydrogen atom or a methyl group, and L represents, for example, C
(= O) OCH ₂ CH ₂ OP (= O) (OH) ₂ , C (= O) OCH ₂ CH (CH ₂ Cl) OP (= O) (O
H) ₂ , C (= O) OCH ₂ CH ₂ OP (= O) (OH) O- ⁺ NH ₃ CH ₂ CH ₂ OH, C (= O)
(OCH ₂ CH ₂ ) _q OP (= O) (OH) ₂ , C (= O) (OCH ₂ CHMe) _q OP (= O) (OH) ₂
[However, q represents an arbitrary integer of 1 to 20]. ] Is not particularly limited as long as CH ₂ = C (CH ₃ ) C
(= O) OCH ₂ CH ₂ OP (= O) (OH) ₂ , CH ₂ = CHC (= O) OCH ₂ CH ₂ OP (= O)
_{(OH) 2, CH 2 =} C (CH 3) C (= O) OCH 2 CH (CH 2 Cl) OP (= O) (OH) 2,
CH ₂ = CHC (= O) OCH ₂ CH (CH ₂ Cl) OP (= O) (OH) ₂ , CH ₂ = C (CH ₃ ) C
(= O) (OCH ₂ CH (CH ₃ )) ₅ OP (= O) (OH) ₂ , CH ₂ = CHC (= O) (OCH ₂ C
H (CH ₃ )) ₅ OP (= O) (OH) ₂ , CH ₂ = C (CH ₃ ) C (= O) (OCH ₂ CH ₂ ) ₄ OP (=
O) (OH) ₂ , CH ₂ = CHC (= O) (OCH ₂ CH ₂ ) ₄ OP (= O) (OH) ₂ , CH ₂ = C (C
H ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) O- ⁺ NH ₃ CH ₂ CH ₂ OH, CH ₂ = CHC (=
O) OCH ₂ CH ₂ OP (= O) (OH) O ^{− +} NH ₃ CH ₂ CH ₂ OH and the like.

In the above general formula (4) CH ₂ CRCR ¹ R ⁴ (4), R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a halogen atom, a cyano group, Si (R ¹⁰ ) ₃ , -C (= O) OR ⁹ -C (= O) R ⁶ [
However, R ⁹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, CH ₂ CH ₂ CH ₂ Si (R ¹¹ ) ₃
R ⁶ represents an alkylamino group having 1 to 20 carbon atoms, a dialkylamino group, a pyrrolidino group, a piperidino group, a morpholino group, and R ¹⁰ and R ¹¹ represent an alkyl group having 1 to 4 carbon atoms and an alkoxy group. Show. ] Is not particularly limited, but specific examples include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate,
(Meth) acrylic acid, methyl (meth) acrylate, -t-butyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, -n (meth) acrylate
-Butyl, 2-ethylhexyl (meth) acrylate, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethoxyvinylsilane, triethoxyvinylsilane, diacetyloxymethylvinylsilane, diethoxymethylvinylsilane, triacetyloxyvinylsilane, triisopropoxyvinylsilane, trimethylvinylsilane, tri-t -Butoxyvinylsilane, ethoxydiethylvinylsilane, diethylmethylvinylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldiacetyloxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, 3-methacryloxypropyltriacetyloxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryl Propyl trimethyl silane, 3-methacryloxypropyl tri -t- butoxysilane, 3-methacryloxypropyl-ethoxy diethyl silane, 3-methacryloxypropyl diethyl methyl silane,
3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyldiacetyloxymethylsilane, 3-acryloxypropyldiethoxymethylsilane, 3-acryloxypropyltriacetyloxysilane, 3- Acryloxypropyltriisopropoxysilane, 3-acryloxypropyltrimethylsilane, 3-acryloxypropyl tri-t-butoxysilane, 3-acryloxypropylethoxydiethylsilane, 3-acryloxypropyldiethylmethylsilane, etc. it can.

In the fluoroalkyl group-containing polymer represented by the general formula (1), m1 and m2 each represent an integer of 0 to 5,000, preferably 1 to 1,000, particularly preferably 1 to 1000.
500. Here, m1 represents an integer of 1 or more. When m1 or m2 exceeds 5000, production is difficult. Further, the average molecular weight of the fluoroalkyl group-containing polymer represented by the general formula (1) is 300 to 1,000,000, and in order to make the characteristics of the fluoroalkyl group more remarkable, it is necessary to use
20200,000 is preferable, and 500,000 to 100,000 is more preferable. If the average molecular weight is less than 300, production is difficult, and if it exceeds 1,000,000, production is difficult.
The method for producing the fluoroalkyl group-containing polymer of the present invention comprises:
It is characterized by reacting a specific difluoroalkanoyl peroxide with a specific raw material monomer, and water can be added to the reaction system in order to make the reaction proceed smoothly.

The difluoroalkanoyl peroxide used in the present invention is represented by the general formula (2): R _F C (= O) OO (O =) CR _F (2) R _{F is-} (CF ₂ ) _n1 X , -CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _n2 -OC ₃ F ₇ [where n1 is an integer of 1 to 10, X is a fluorine atom, a chlorine atom,
It represents a hydrogen atom, and n2 represents an integer of 0-8. ] Is not particularly limited, but specific examples include diperfluoro-2-methyl-3-hexanoyl peroxide, perfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide,
Diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide,
Preferred are diperfluoroheptanoyl peroxide and the like.

In the difluoroalkanoyl peroxide represented by the general formula (2), when n1 is 11 or more, or n2
If the value is 9 or more, the solubility of the above-mentioned difluoroalkanoyl peroxide decreases when the reaction is carried out in the presence of a solvent, so that it cannot be used. Further, R _F in the difluoroalkanoyl peroxide represented by the general formula (2) is the same as R _F listed in the polymer represented by the general formula (1). In the present invention, when reacting the difluoroalkanoyl peroxide with the monomers represented by the general formula (2) or the general formula (2) and the general formula (3), they are represented by the general formula (2). The mixing molar ratio of the monomer and the monomer represented by the general formula (3) can be any ratio, but is preferably in the range of 1: 0.01 to 100, and the difluoroalkanoyl peroxide and the general formula ( 2) or the charged molar ratio when reacting with the monomer represented by the general formula (2) and the general formula (3) is preferably in the range of 1: 0.1 to 5,000, particularly preferably 1: 1:
Preferably, it is in the range of 0.5 to 1000. When the charged molar ratio of the raw material monomer is less than 0.1, a large amount of a product resulting from the autolysis of the peroxide is generated, and when it exceeds 5,000, the desired fluoroalkyl group-containing weight is obtained. It is not preferable because the yield of the coalescence decreases.

The molecular weight of the resulting polymer can be adjusted by adjusting the charged molar ratio of the difluoroalkanoyl peroxide. That is, if the charged molar ratio of the difluoroalkanoyl peroxide is higher with respect to the monomers, a polymer having a lower molecular weight can be obtained, and if the molar ratio is lower, a polymer having a higher molecular weight can be obtained. Further, the reaction can be carried out at normal pressure, and the reaction temperature is usually in the range of -20 to 150 ° C, preferably 0 to 100 ° C. If the reaction temperature is lower than -20 ° C, the reaction time tends to be prolonged. Conversely, if it exceeds 150 ° C, the pressure during the reaction increases and the reaction operation is difficult, which is not preferable. Further, the reaction time can be generally in the range of 30 minutes to 20 hours, but it is desirable to set conditions so that it is practically 1 to 10 hours.

In the production method of the present invention, the desired fluoroalkyl group-containing polymer can be directly obtained by a one-step reaction by reacting the fluoroalkanoyl peroxide with the monomers under the various reaction conditions. However, in the reaction of the fluoroalkanoyl peroxide, it is preferable to add water to the monomer represented by the general formula (3) in an amount of 1 to 90% by weight to dissolve the monomers and use the resultant in the reaction. At the time of the reaction, a known additive such as a dispersant may be used in an appropriate ratio for the reaction. If water is not used in this reaction, it tends to be generally difficult to obtain the desired polymer in good yield. Further, it is preferable to use an organic solvent in order to carry out the reaction more smoothly. As the organic solvent, a halogenated aliphatic solvent and a halogenated aromatic solvent are 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, , 1,2-trichlorotrifluoroethane,
1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-
1,3-dichloropropane, benzotrifluoride, hexafluoroxylene, pentafluorobenzene and the like can be used. Particularly, industrially, 1,1,1,2,2
-Pentafluoro-3,3-dichloropropane, 1,
Solvents such as 1,2,2,3-pentafluoro-1,3-dichloropropane and benzotrifluoride or a mixed solvent in which these solvents are mixed at an arbitrary ratio (for example, AK225
Asahi Glass Co., Ltd.) is preferred. When the solvent is used, it is usually desirable that the concentration of the fluoroalkanoyl peroxide in the solvent is about 0.1 to 30% by weight.

The fluoroalkyl group-containing polymer represented by the above general formula (1) of the present invention generally shows solubility in water at a low concentration, and furthermore, is soluble in organic compounds such as methanol, ethanol, dimethylformamide and dimethylsulfoxide. It also tends to show solubility at low concentrations in solvents. Therefore, it is also useful as a novel fluorine-based surfactant. The polymer represented by the general formula (1) obtained by the production method of the present invention can be purified by a known method such as a reprecipitation method, column chromatography, and dialysis.

[0016]

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.

Example 1 10 containing 1.68 g (8.00 mmol) of a monomer represented by the following formula:
Weight% aqueous solution, CH_Two= C (CH_Three) C (= O) OCH_TwoCH_TwoOP (= O) (OH)_Two Perfoxide dissolved in 50 g of AK-225 (made by Asahi Glass Co., Ltd.)
1.10 g (4.01 mmol) of luorobutyryl was added, and the mixture was added under nitrogen stream.
The reaction was carried out at 5 ° C for 5 hours. After the reaction, the solvent is removed and the product is
Dissolve in methanol, reprecipitate in methanol-ethyl acetate
And the oligomers are filtered and dried in vacuo at room temperature.
As a result, a product was obtained in a yield of 22%. The resulting generation
Gel molecular permeation chromatography
(Hereinafter abbreviated as GPC), Mn = 29000, Mw / Mn =
1.15 (where Mn is the number average molecular weight and Mw is the weight average molecular weight
is there. ), Infrared spectroscopy (hereinafter abbreviated as IR) and nuclear magnetic
Qi resonance method (below¹H-NMR,¹⁹Analyzed by F-NMR)
(See below), the compound represented by the structural formula (5)
Phosphoric acid derivative containing fluoroalkyl group containing
It was a conductor (referred to as polymer A). R_F-[CH_Two-C (CH_Three) C (= O) (OCH_TwoCH (CH_Three))_FiveOP (= O) (OH)_Two]_n-R_F (5) where R_FIs -C_ThreeF₇ ¹ H-NMR (D_TwoO) δ: 0.72 to 1.48 (CH_Three), 1.77-2.14 (C
H_Two), 4.01 to 4.25 (CH_Two)¹⁹ F-NMR (D_TwoO, ext.CF_ThreeCOOH) δ: -5.09 (CF_Three), -43.20
(CF_Two), -52.26 (CF_Two) IR: 988 (P-O), 1230 (CF_Two), 1320 (CF_Three), 1718 (C = O),
3471 (OH)

Example 2 10 containing 2.17 g (8.00 mmol) of a monomer represented by the following formula:
In a weight% aqueous solution, CH ₂ = C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) O ^{− +} NH ₃ CH ₂ CH ₂ OH AK-225 (manufactured by Asahi Glass Co., Ltd.) 1.10 g (4.01 mmol) of perfluorobutyryl peroxide dissolved in 50 g were added, and the mixture was added under a nitrogen stream.
The reaction was performed at 0 ° C. for 5 hours. After the reaction, the solvent was removed, the product was dissolved in water, reprecipitated in a water-methanol system, and the oligomers were further filtered and vacuum dried at room temperature to obtain the product in a yield of 22%. . As a result of analysis in the same manner as in Example 1, it was found to be a fluoroalkyl group-containing phosphoric acid derivative having the compound represented by the structural formula (6) as a constitutional unit (hereinafter referred to as polymer B). R _F- [CH ₂ -C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) O- ⁺ NH ₃ CH ₂ CH ₂ OH _n- R _F (6) In the formula, R _F was -C ₃ F ₇ , and Mn = 28000 and Mw / Mn = 1.10 according to GPC.

Example 3 A 10% by weight aqueous solution containing 2.52 g (11.99 mmol) of a monomer represented by the following formula was added to CH ₂ 10C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH ₂ ) 2.82 g (19.98 mmol) of acryloylmorpholine dissolved in 45 g of AK-225 (manufactured by Asahi Glass Co., Ltd.) were added, and AK-225 was further added.
1.10 g (4.01 mmol) of perfluorobutyryl peroxide dissolved in 10 g (manufactured by Asahi Glass Co., Ltd.) was added, and the mixture was heated at 40 ° C. for 5 hours under a nitrogen stream.
r Reacted. After the reaction, the solvent was removed, the product was dissolved in methanol, reprecipitated with water-tetrahydrofuran system, and the oligomers were filtered and dried in vacuo at a constant temperature to obtain a product in a yield of 5%. . As a result of analysis in the same manner as in Example 1, it was found to be a fluoroalkyl group-containing phosphoric acid copolymer (polymer C 2) containing the compound represented by the structural formula (7) as a constitutional unit. R _F- [ACMO] _x- [CH ₂ -C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) ₂ ] _y -R _F (7) where R _F is -C ₃ F ₇ , ACMO indicates a repeating unit derived from acryloylmorpholine. The ratio of x and y in the structural formula (7) based on the ¹ H-NMR analysis result was 61:39. GPC measurement resulted in Mn = 72000 and Mw / Mn = 1.38.

EXAMPLE 4 A 10% by weight aqueous solution containing 2.14 g (10.17 mmol) of a monomer represented by the following formula was added to CH ₂ CC (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH ₂ ) 2.39 g (16.93 mmol) of acryloylmorpholine dissolved in 45 g of AK-225 (manufactured by Asahi Glass Co., Ltd.) was added, and further perfluoro-2-peroxide dissolved in 10 g of AK-225 (manufactured by Asahi Glass Co., Ltd.)
20 g (3.39 mmol) of methyl-3-oxahexanoyl were added,
When the reaction and purification were carried out in the same manner as in Example 3, the product was obtained in a yield of 6%. As a result of analysis in the same manner as in Example 1, a fluoroalkyl group-containing phosphoric acid copolymer having the compound represented by the structural formula (8) as a constitutional unit (Polymer D)
Met. R _F- [ACMO] _x- [CH ₂ -C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) ₂ ] _y -R _F (8) where R _F is -CF (CF ₃ ) OC ₃ F ₇ and ACMO represent repeating units derived from acryloylmorpholine. The ratio of x and y in the structural formula (8) based on the analysis result of ¹ H-NMR was 40:60. GPC
As a result of the measurement, Mn = 63000 and Mw / Mn = 1.21.

Example 5 A 10% by weight aqueous solution containing 1.89 g (8.99 mmol) of a monomer represented by the following formula was added to CH ₂ CC (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH ₂ ) 2.12 g (15.02 mmol) of acryloylmorpholine dissolved in 45 g of AK-225 (manufactured by Asahi Glass Co., Ltd.) was added, and perfluoro-2,5 peroxide dissolved in 10 g of AK-225 (manufactured by Asahi Glass Co., Ltd.)
-3.19 g of dimethyl-3,6-dioxano nanoyl (3.00mmo
l) was added, and the reaction and purification were carried out in the same manner as in Example 3. As a result, a product was obtained in a yield of 11%. As a result of analysis in the same manner as in Example 1, it was found to be a fluoroalkyl group-containing phosphoric acid copolymer (polymer E) containing the compound represented by the structural formula (9) as a constituent unit. R _F- [ACMO] _x- [CH ₂ -C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) ₂ ] _y -R _F (9) where R _F is -CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OC ₃ F ₇ , ACMO represents a repeating unit derived from acryloylmorpholine. The ratio of x and y in the structural formula (9) from the result of ¹ H-NMR analysis was 35:65. GPC measurement resulted in Mn = 84000 and Mw / Mn = 1.02.

EXAMPLE 6 CH ₂ CC (CH ₃ ) C (8.9O) OCH ₂ CH ₂ OP (= O) (OH) was added to a 10% by weight aqueous solution containing 1.89 g (8.99 mmol) of a monomer represented by the following formula. ₂ 0.89 g (8.98 mmol) of N, N-dimethylacrylamide dissolved in 45 g of AK-225 (manufactured by Asahi Glass Co., Ltd.) was added.
3. Perfluoro-2,5-dimethyl-3,6-dioxananoyl 3.19 g (3.00 g) dissolved in 10 g of 5 (manufactured by Asahi Glass Co., Ltd.)
mmol), and the reaction and purification were carried out in the same manner as in Example 1. As a result, a product was obtained in a yield of 30%. As a result of analysis in the same manner as in Example 1, it was found to be a fluoroalkyl group-containing phosphoric acid copolymer having the compound represented by Structural Formula (10) as a constitutional unit (Polymer F). R _F- [CH ₂ -CH (= O) N (CH ₃ ) ₂ ] _x- [CH ₂ -C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) ₂ ] _y -R _F (10) wherein R _F is —CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OC ₃ F ₇ , the ratio of x and y in the structural formula (X) from the result of ¹ H-NMR analysis. Was 60:40.
GPC measurement resulted in Mn = 81000 and Mw / Mn = 1.08.

EXAMPLE 7 A 10% by weight aqueous solution containing 1.42 g (6.76 mmol) of a monomer represented by the following formula was added to CH ₂ CC (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH _2. Perfluoro-2,5-dimethyl-3,6-dioxano nanoyl 3.19 g dissolved in 50 g of AK-225 (Asahi Glass Co., Ltd.)
(3.00 mmol) was added, and the reaction and purification were carried out in the same manner as in Example 1. As a result, a product was obtained in a yield of 10%. Example 1
As a result of analysis in the same manner as in the above, it was found to be a fluoroalkyl group-containing phosphoric acid derivative containing the compound represented by the structural formula (11) as a constitutional unit (polymer G). _{R F - [CH 2 -C (} CH 3) C (= O) (OCH 2 CH (CH 3)) 5 OP (= O) (OH) 2] n -R F (11) formula R _F is - CF was _{(CF 3) OCF 2 CF (} CF 3) OC 3 F 7, the results were measured by GPC Mn = 39000, Mw / Mn = 1.18.

Example 8 A 10% by weight aqueous solution containing 1.63 g (6.01 mmol) of a monomer represented by the following formula was added to CH ₂ CC (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH ) O- ⁺ NH ₃ CH ₂ CH ₂ OH 3.19 g of perfluoro-2,5-dimethyl-3,6-dioxano nanoyl peroxide dissolved in 50 g of AK-225 (manufactured by Asahi Glass Co., Ltd.)
(3.00 mmol), and the reaction and purification were carried out in the same manner as in Example 2. As a result, a product was obtained in a yield of 18%. Example 1
As a result of analysis in the same manner as in the above, it was found to be a fluoroalkyl group-containing phosphoric acid derivative having the compound represented by the structural formula (12) as a constitutional unit (polymer H 2). R _F- [CH ₂ -C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) O- ⁺ NH ₃ CH ₂ CH ₂ OH] _n -R _F (12) _F is -CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OC ₃ F ₇ , GPC measurement result
Mn = 35000, Mw / Mn = 1.15.

Comparative Example 1 A 10% by weight aqueous solution containing 1.26 g (6.00 mmol) of a monomer represented by the following formula was added to CH ₂ CHC (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH ₂ ) V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 50 g of purified water
When 33 g (1.22 mmol) was added and the reaction and purification were carried out in the same manner as in Example 2, the product was obtained in a yield of 30%. As a result of analysis in the same manner as in Example 1, it was found to be a phosphoric acid polymer having the compound represented by Structural Formula (13) as a structural unit (Comparative Polymer A). -[CH ₂ -C (CH ₃ ) C (= O) (OCH ₂ CH (CH ₃ )) ₅ OP (= O) (OH) ₂ ] _n- (13) GPC measurement result Mn = 28000, Mw / Mn = 1.32.

Comparative Example 2 In a 10% by weight aqueous solution containing 2.17 g (8.00 mmol) of a monomer represented by the following formula, CH ₂ CC (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH ) O- ⁺ NH ₃ CH ₂ CH ₂ OH V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 50 g of purified water.
When 43 g (1.59 mmol) was added and the reaction and purification were carried out in the same manner as in Example 2, the product was obtained in a yield of 31%. As a result of analysis in the same manner as in Example 1, it was found to be a phosphoric acid polymer having the compound represented by Structural Formula (14) as a constituent unit (Comparative Polymer B). -[CH ₂ -C (CH ₃ ) C (= O) OCH ₂ CH ₂ OP (= O) (OH) O- ⁺ NH ₃ CH ₂ CH ₂ OH _n- (14) As a result of GPC measurement, Mn = 21000 and Mw / Mn = 1.26.

Effect Example 1 As a result of measuring the surface tension of an aqueous solution of the polymers A, B, C, D, E, and F at 30 ° C. by the Wilhelmi method, the surface tension of water was reduced by adding a small amount. Whereas the surface tension value of the added water is 71 mN / m, the surface tension of the 10 g / L aqueous oligomer solution is 20 mN / m, 30 mN / m, 45 mN / m, and 20 mN / m, respectively.
m, 19 mN / m and 16 mN / m. Further, polymers A and D
, E, and F show a discontinuous change in surface tension depending on the addition concentration, and the concentration, that is, the concentration that forms an aggregate in an aqueous solution (corresponding to the critical micelle concentration) is 1 g / L and 0.6 g, respectively.
/ L, 7 g / L and 0.08 g / L. These oligomers were easily dissolved in purified water. In contrast, the comparative polymer
The surface tensions of the aqueous solutions A and B were measured in the same manner, but hardly decreased, and the value was 61 mN / m for the 10 g / L aqueous oligomer solution.

Effect Example 2 A stainless steel plate (SUS304) was treated with diethyl ether, purified water,
The surface is cleaned by ultrasonic cleaning with chloroform for one day each for a total of three days, and then the polymers F, G, H, and the comparative polymer A
, B in a 1% by weight methanol solution and dried in a dryer at 150 ° C. for 30 minutes, followed by Soxhlet extraction with methanol for 2 hours to remove excess polymer adhering to the surface. Further, the solvent is completely removed by heating at 100 ° C. with a vacuum dryer, and a treated stainless plate is prepared. Place the prepared plate in a constant temperature and humidity room (23 ° C, 50% relative humidity)
To prepare a measurement sample for 2 days.

When the contact angles of 1-dodecane and purified water of the measurement sample were measured by a liquid method, the following results were obtained. Untreated plate (washing only) 1-dodecane contact angle: 0 degrees Contact angle with purified water: 63 degrees Polymer F treated plate 1-dodecane contact angle: 11 degrees Purified water contact angle: 79 degrees Polymer G treated plate 1-dodecane Contact angle: 26 degrees Purified water contact angle: 75 degrees Polymer H treated plate 1-dodecane contact angle: 26 degrees Purified water contact angle: 89 degrees Comparative polymer A treated plate 1-dodecane contact angle: 0 degrees Purified water contact angle : 52 degrees Comparative polymer B treated plate 1-dodecane contact angle: 0 degrees Purified water contact angle: 59 degrees Polymer F, G, H treatment has high water and oil repellency. On the other hand, Comparative Polymers A and B treatments had low water repellency and conversely had a lower water contact angle than the untreated plate, and the contact angle of 1-dodecane was 0 °, indicating no oil repellency.

[0030]

Industrial Applicability The fluoroalkyl group-containing polymer of the present invention is a novel compound. Since the fluoroalkyl group is directly bonded not by a sulfide bond but by a carbon-carbon bond, it has a property derived from the fluoroalkyl group. It is a compound that can be maintained for a long time and has high weather resistance. Therefore, as a new fluoropolymer surfactant, it has properties such as low surface tension, low refraction, heat resistance, cold resistance, oil resistance, electrical insulation, antifogging, antifouling, and chemical resistance. As a compound having a surface treatment agent having hydrophilic properties and imparted properties such as oil repellency and stain resistance, further aluminum,
It can be used as a metal material such as stainless steel, a paint, an optical lens, a lens for spectacles, a material for a surface of a glass device, and a raw material for cosmetics.

Further, according to the production method of the present invention, a fluoroalkyl group-containing polymer can be produced by a one-step reaction easily in a short time with good yield and without using a reaction catalyst and a special apparatus.

Claims (3)

[Claims] 1. A compound represented by the following general formula (1): R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (1) wherein R ¹ is independently a hydrogen atom or Represents a methyl group; L is
C (= O) (OCH ₂ CHR ² ) _p P (= O) (OH) ₂ or an alkanolamine salt or an alkali salt thereof; R ² represents a hydrogen atom, a methyl group or a chloromethyl group, and p represents 1 to Indicates an integer of 20;
R ⁴ is a halogen atom, a cyano group, -Si (R ¹⁰ ) ₃ , -C (= O) OR ⁹
Or -C (= O) R ⁶ , R ¹⁰ represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms; R ⁹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxy having 2 to 6 carbon atoms. An alkyl group or
-(CH ₂ ) ₃ -Si (R ¹¹ ) ₃ , R ¹¹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ⁶ is a mono or dialkylamino group having 1 to 20 carbon atoms, a pyrrolidino group, a piperidino M1 represents 1 to 5000, m2 represents 0 to 5
R _F represents-(CF ₂ ) _n1 X or -CF
(CF ₃ ) [OCF ₂ CF (CF ₃ )] _n2- OC ₃ F ₇ ; X is a hydrogen atom,
A chlorine atom or a fluorine atom, n1 is an integer of 1 to 10, n2
Represents an integer of 0 to 8. A molecular weight of 300 to
1 million phosphoric acid derivatives containing fluoroalkyl groups. 2. A fluoroalkanoyl peroxide represented by the following general formula (2) R _F C (= O) OO (O =) CR _F (2) (where R _F is as defined above) and Reaction of the general formula (3) CH ₂ = CR ¹ L (3) and the following general formula (4) CH ₂ = CR ¹ R ⁴ (4) (wherein R ¹ , L and R ⁴ are as described above) 2. The method for producing a fluoroalkyl group-containing phosphoric acid derivative according to claim 1, wherein 3. A surface treating agent containing the fluoroalkyl group-containing phosphoric acid derivative according to claim 1 as an active ingredient.